Chemical and mineralogical investigations on deep sea manganese nodules from the Southern Ocean

Deep sea manganese nodules from the Southern Ocean have been studied using chemical analysis, X-ray diffraction, optical mineragraphic and electron probe microanalysis techniques. The nodules were lower in manganese, iron and associated elements than the average grade of manganese nodules from other localities. A number of chemical relationships have been observed. Nickel, copper, cobalt, barium, zinc, molybdenum, strontium, sulphur and phosphorus are associated with the manganese rich phases and titanium with the iron rich phases. X-ray diffraction analysis and electron probe microanalysis results indicate that the manganese phases are similar to the disordered -MnO₂ and manganite phases reported by other workers.

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Zusammenfassung Tiefsee-Manganknollen aus dem südlichen Ozean wurden mit Hilfe von chemischen Analysen, Röntgenbeugung, mikroskopischer Untersuchung und Anwendung von Mikroelektronensonden untersucht. Die Knollen enthielten weniger Mangan, Eisen und Begleitelemente als das Durchschnittsquantum in Manganknollen aus anderen Gebieten. Eine Anzahl chemischer Ähnlichkeiten wurde beobachtet. Nickel, Kupfer, Kobalt, Barium, Zink, Molybdän, Strontium, Schwefel und Phosphor treten gemeinsam mit den manganreichen Erscheinungsformen, und Titan zusammen mit den eisenreichen auf. Ergebnisse der Röntgenbeugungsanalyse und Mikroelektronensondenuntersuchung ergaben, daß die Manganphasen Ähnlichkeit haben mit ungeordneten -MnO₂ und manganitischen Erscheinungsformen, über die andere Wissenschaftler berichtet haben.

     

太平洋富稀土深海沉积物中稀土元素赋存载体研究

太平洋深海沉积物中富含稀土(含Y,简称REY),尤其是(含)沸石粘土,其主要由粘土组分、沸石、鱼牙骨、微结核及生物残渣等组成,目前对于该类稀土矿床中REY的赋存载体存在争议。本文在中、西太平洋选取两个富REY的沸石粘土样品利用地球化学和矿物学对稀土赋存状态进行定量研究。矿物微区成分表明,鱼牙骨主要成分为磷灰石,含有最高的REY含量,为2497×10~(- 6)~18623×10~(- 6),微结核和沸石颗粒含有较低的REY含量,分别为246×10~(- 6)~333×10~(- 6)和29.36×10~(- 6)~256×10~(- 6)。通过三种矿物相在沉积物63~250μm粒级组分中各自所占质量比例,计算得出磷灰石对REY的贡献率可达90%以上,说明此粒级中磷灰石为主要REY赋存载体,然而相对全岩总的REY含量,该粒级中磷灰石的贡献仍较小。通过对全岩和粉砂级组分(小于63μm)主微量地球化学分析和XRD矿物相分析表明,2个样品中REY主要存在于粉砂级组分中,其中的磷灰石对全岩REY的贡献最高均可达70%左右。另外通过对粘土组分(2μm)研究发现2个样品粘土组分的REY含量相似,分别为530×10~(- 6)和631×10~(- 6),粘土组分对全岩沉积物的REY贡献意义不大,对整个沉积物REY而言其贡献率仅为2%~5%左右。因此认为磷灰石为整个沸石粘土中REY主要赋存载体。     

Rare earth elements and strontium isotopes of polymetallic nodules from southeastern Pacific Ocean

Rare earth element (REE) distributions and ⁸⁷Sr/⁸⁶Sr ratios were determined for nodule crusts and associated surface sediments collected in the southeastern Pacific Ocean between South America and the Tuamotu archipelago. The shale-normalized patterns of the REE from the surface sediments show pronounced negative anomalies in Ce which indicate a marine origin. One ⁸⁷Sr/⁸⁶Sr ratio also has a value characteristic for seawater strontium. REE patterns from the nodule crusts, when normalized to shales, seawater or associated surface sediment, show that a marine origin can also be proposed for the oxy-hydroxides. Only the Ce shows a systematic scatter, which could be the result of fluctuations in the oxidation-reduction conditions during nodule growth. The marine origin for REE is corroborated by the ⁸⁷Sr/⁸⁶Sr ratios which average 0 · 70905 ± 0 · 00019 (2σ), a value close to the seawater ⁸⁷Sr/⁸⁶Sr ratio of 0·70910 ± 0 · 00035. If the major metals of the polymetallic nodules have the same origin as these trace elements, then a direct precipitation from seawater can be postulated for the crusts studied here.     

太平洋中部富REY深海沉积物的地球化学特征及化学分类

赋存于深海沉积物中的稀土资源是一种潜在的稀土资源。对太平洋中部30个重力活塞柱状样中的1 275个深海沉积物样品的常量、稀土化学分析数据进行了系统研究。在涂片鉴定的基础上,采用Ca O和Al2O3含量把太平洋中部深海沉积物划分为钙质软泥类沉积物、硅质软泥类沉积物、深海黏土类沉积物三种成因类型;这三种类型沉积物的稀土分布模式相似,表现为明显的Ce负异常,一定程度的重稀土元素富集和Y正异常,深海黏土类沉积物的ΣREY明显偏高。采用主要元素(包括Ca O/P2O5比值)与REY的关系图可以有效地判别不同成因类型沉积物的混合状况。太平洋中部富P、富含沸石的深海黏土类沉积物是最有利的富REY的深海沉积物类型。太平洋中部深海沉积物REY富集的主要原因是由于深海沉积物中混入了过量的(鱼牙骨碎屑状)磷灰石组分,而钙质生物组分和硅质生物组分的加入对REY含量起了明显的稀释作用。     

太平洋富钴结壳中碲元素的地球化学特征及其富集机制探讨

文章通过对采自太平洋海域不同海山上68个结壳样品中Te元素地球化学特征的研究,探讨了富钴结壳中控制Te元素富集的古海洋氧化还原环境及其富集机制。分析表明,太平洋海域中大多数结壳的w（Te）变化于13.4×10^-6~115.8×10^-6,平均50×10^-6,是海水w（Te）的10⁹倍;结壳中w（Te）与Mn/Fe比值呈正相关,相关系数为0.51;与Fe呈负相关,相关系数为-0.61,显示结壳中Te与Co有类似的地球化学特征。古海水氧化还原环境的改变是控制结壳中Te元素含量变化的重要因素;能反映古海水氧化还原环境的Ce异常与结壳中Te含量基本呈同步变化趋势,Te含量具有随古海水氧化程度减弱而降低的特征。结壳中Te元素的富集主要受控于其内的Mn/Fe比值。Te元素的富集机制除被海水中带微弱正电荷的FeOOH胶体以库伦静电吸附外,还可能与δ-MnO₂表面上以一种表面络合物方式的富集机制有关。Te进入结壳的存在形式及其在不同古海洋环境中的富集机制还有待进一步研究和探讨。     

中太平洋多金属结壳的地球化学特征

采用XRF和ICP AES法对中太平洋CA等6座海山的4 0多个站位的多金属结壳中化学元素进行测试与分析, 并结合其他资料对调查区结壳主要成矿元素的含量组成、特征变化、元素间的相关关系以及结壳与水深、地形等重要环境因子进行探讨.研究表明太平洋海山结壳中元素丰度特征具有多种变化类型, 中太平洋结壳主成分和成矿元素丰度明显高于马绍尔群岛, 而与西北太平洋、麦哲伦海山相近; 中太平洋结壳化学元素相关关系分析表明: Ca与P、Al与K呈显著正相关性; Mn与Al呈显著负相关性.研究还发现中太平洋结壳富Co(0.6 3%)而贫Cu(0.1 1 %)及高Fe(1 6.9%)低Mn(2 1.3%)的分布特征, 与深海多金属结核在含量分布特征上存在较大差异.与多金属结核相比: 结壳中Mn组元素含量显著降低, Fe组元素含量和稀土总量明显增大, 尤其是Co和REEs的变化最为突出。      

太平洋CC区西部沉积物地球化学特征及其成因

对太平洋CC区西部7根沉积物短柱样的常微量元素进行浓度测试,以了解沉积物元素时空分布特征及其来源和控制因素.与上地壳元素平均值(UCC)相比,研究区沉积物中MnO、P2O5、Co、Ni、Cu、Mo、Ba明显富集,Al2O3、K2O、Fe2O3、CaO、Sr等亏损.聚类和因子分析表明研究区沉积物元素有4种来源,其中Al2...     

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...     

中太平洋WX海山富钴结壳磷酸盐矿物学研究及成因类型分析

大洋富钴结壳普遍发生磷酸盐化,磷酸盐化对富钴结壳的各种属性存在显著影响,而磷酸盐的成因问题一直没有得到很好解决。中太平洋WX海山富钴结壳老壳层中发育着两期磷酸盐化事件所产生的上下两层磷酸盐,本文运用反光显微镜、扫描电子显微镜、电子探针、微量粉晶X衍射等手段分别对其进行了矿物学特征观察和测试,研究了老壳层上下两层磷酸盐特征并探讨其可能成因。上层磷酸盐由大量形态结构清楚的磷酸质有孔虫和超微化石以及非生物碳氟磷灰石(CFA)组成,成分均一,杂质少,表现出生物成因和原生自沉积特点;下层磷酸盐变化复杂,具有特征的交代结构,混杂较高的Si、Al、K、Fe成分,显示以磷酸盐交代碳酸盐成因为主。这表明不同磷酸盐化期形成的磷酸盐有不同的成因类型。     

Geochemical and mineralogical composition of black weathering crusts on limestones from seven different European countries

Twenty-seven samples of black weathering crust and host carbonates were studied from seven European countries (Germany, Hungary, Belgium, Czech Republic, France, Italy and Poland) representing 11 different sites. The samples were collected for sites for which long-term air pollution records are available. The mineralogical analyses (XRD, polarizing microscopy, SEM) have shown that despite decreasing SO₂ emissions crust samples are still very rich in gypsum. Further, in all host rock samples gypsum was also detected. Good correlations (R² > 0.9) were also found between water-soluble calcium and gypsum content and between sulphate and gypsum content both for black crusts and host rocks. The black gypsum crusts are four or five times richer in sulphate than the host rock. The conductivity of dissolved crust and host rock samples also shows a positive correlation with gypsum content of the samples. LA-ICP-MS analyses allowed the detection of high Pb-levels in black crusts and a negative shift in lead concentration at the crust/host rock transition. The lead content of the host rock is 2–5 mg/kg, while that of the crust is 3–25 mg/kg in the sample collected from Germany, while in the Belgian sample these values are 2–14 mg/kg and 80–870 mg/kg for the host rock and crust, respectively. The GC–MS technique allowed to detect the PAH content of black crusts and host rocks. The former one contains 0.6–15.6 (102.5) mg/kg, while in the host rock values between 0.2 and 2.4 mg/kg were found. The present study suggests that still large amounts of air pollution-related minerals and organic pollutants are found in the black weathering crusts of European carbonate buildings despite decreasing trends in air pollution.     

西北太平洋深海底栖有孔虫DNA分子多样性与群落组成特点的初步研究

深海蕴藏着丰富的自然资源,是目前世界各国争相探索的战略要地。本工作以底栖有孔虫为研究对象,研究了它在西北太平洋深海（水深4080 m至5830 m）的DNA分子多样性和群落组成特点。我们共采集了11个站位的表层沉积物,提取了样品中的总基因组DNA,利用有孔虫特异性引物扩增了其中的有孔虫DNA,应用高通量测序技术对获得的有孔虫DNA片段测序。最终,共获得1536个操作分类单元（operational taxonomic units,简称OTUs）,有1330个OTUs成功注释到有孔虫,其中721个（约54%）有孔虫OTUs属于起源最早但研究较少的软壳类单房室有孔虫。有孔虫OTUs注释结果的Identity值的平均值为92.9%,Identity值大于或等于97%的OTUs仅占20.6%,Identity值小于95%的OTUs占63.1%,说明西北太平洋深海底栖有孔虫与目前检获到的有孔虫之间存在较明显的遗传差异性,该海区极可能蕴藏着大量至今未被发现的"新物种"甚至新的高级分类阶元。在我们获得的有孔虫属中,有1/ 3呈典型的斑块性分布,且站位间的有孔虫群落结构也存在明显差异。本工作是国内利用高通量测序技术对西北太平洋深海底栖有孔虫开展调查的首次尝试,旨在为探索有孔虫的全球地理分布模式、开发和利用深海资源等工作提供分子生态和分子遗传数据支持。

     

An appraisal of an iterative construction of the endmembers controlling the composition of deep-sea manganese nodules from the Central Indian Ocean Basin

This paper describes an estimation of endmember compositions followed by the assessment of those results by log-ratio variance analysis. As an appraisal, it deals only with the first objective of an endmember analysis namely, to identify endmembers if they exist by estimating their compositions. Following the creation of the endmember estimates, the computation of an array of log-ratio variances was a key innovation in this type of study. Log-ratio variances revealed intrinsic linear associations between the dominant elements on each of the estimated endmember compositions, largely confirming the endmember analysis. The dataset under study contained the concentrations of 16 elements in 93 samples of deep-sea manganese nodules from the Central Indian Ocean Basin. Many previous analyses of these nodules were undertaken to assess the economic potential of the deposits. This study by contrast, quantified the inter-element associations that account for the nodule compositions. Four endmembers were identified. The elements loaded on each were: (1) Mn, Zn, Ni, Cu, Mn-rich, (2) Fe, Ti, P, Co, Fe-rich, (3) Si, Al, Na, K, clay minerals, (3) Mg, ultramafic material, possibly including Mn, Cr, V, Ca, Na. These latter elements were also detected by their log-ratio variances to be associated with Mg on the 4th endmember.     

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。     

基于高斯混合模型的太平洋深海盆地多金属结核成因分类

多金属结核类型成因分类是海底矿产资源关注的重要地质问题,诸多学者一直探索利用多金属结核地球化学特征进行多金属结核成因判别。近年来,随着大数据分析方法的应用,为探索利用机器学习技术进行多金属结核地球化学特征进行成因分类提供了很好的思路和方法。本文基于多年调查研究获取的太平洋多金属结核地球化学数据,利用高斯混合模型聚类分析技术,实现了太平洋深海盆地多金属结核成因分类,并对水成型结核进行了进一步判别分析,共划分出成岩型、混合型、水成Ⅰ型和水成Ⅱ型四类成因多金属结核,为太平洋深海找矿突破和资源评价提供重要依据。同时,不同成因类型结核空间预测结果显示,西北太平洋海域是水成Ⅰ型富钴多金属结核的主要分布区域之一,主要分布在马尔库斯—威克海山群、麦哲伦海山群北部、马绍尔海山群和中太平洋海山群西南部的山间盆地,以及附近的皮嘉费他海盆和中太平洋海盆西北部,是未来西太平洋富钴多金属结核资源找矿突破需要关注的关键海域。     

Assessment of acoustic backscatter intensity surveying on deep-sea ferromanganese crust: Constraints from Weijia Guyot,western Pacific Ocean

Near-bottom observation data from the manned deep submersible Jiaolong with high-precision underwater positioning data from Weijia Guyot, Magellan Seamounts in the Western Pacific Ocean are reported. Three substrate types were identified: Sediment, ferromanganese crust, and ferromanganese crust with a thin cover of sediment. The ferromanganese crusts show clear zoning and their continuity is usually disturbed by sediments on areas of the mountainside with relatively gentle slope gradients. The identified substrate spatial distributions correspond to acoustic backscatter intensity data, with regions of high intensity always including crust development and regions of low intensity always having sediment. Therefore, acoustic backscatter intensity surveying appears useful in the delineation and evaluation of crust resources, although further more work is needed to develop a practicable methodology.     

Geochemical and mineralogical aspects of sulfide mine tailings

Tailings generated during processing of sulfide ores represent a substantial risk to water resources. The oxidation of sulfide minerals within tailings deposits can generate low-quality water containing elevated concentrations of SO₄, Fe, and associated metal(loid)s. Acid generated during the oxidation of pyrite [FeS₂], pyrrhotite [Fe_(1−x)S] and other sulfide minerals is neutralized to varying degrees by the dissolution of carbonate, (oxy)hydroxide, and silicate minerals. The extent of acid neutralization and, therefore, pore-water pH is a principal control on the mobility of sulfide-oxidation products within tailings deposits. Metals including Fe(III), Cu, Zn, and Ni often occur at high concentrations and exhibit greater mobility at low pH characteristic of acid mine drainage (AMD). In contrast, (hydr)oxyanion-forming elements including As, Sb, Se, and Mo commonly exhibit greater mobility at circumneutral pH associated with neutral mine drainage (NMD). These differences in mobility largely result from the pH-dependence of mineral precipitation–dissolution and sorption–desorption reactions. Cemented layers of secondary (oxy)hydroxide and (hydroxy)sulfate minerals, referred to as hardpans, may promote attenuation of sulfide-mineral oxidation products within and below the oxidation zone. Hardpans may also limit oxygen ingress and pore-water migration within sulfide tailings deposits. Reduction–oxidation (redox) processes are another important control on metal(loid) mobility within sulfide tailings deposits. Reductive dissolution or transformation of secondary (oxy)hydroxide phases can enhance Fe, Mn, and As mobility within sulfide tailings. Production of H₂S via microbial sulfate reduction may promote attenuation of sulfide-oxidation products, including Fe, Zn, Ni, and Tl, via metal-sulfide precipitation. Understanding the dynamics of these interrelated geochemical and mineralogical processes is critical for anticipating and managing water quality associated with sulfide mine tailings.