Mineralogy and composition of manganese crusts and nodules and sediments from the Manihiki plateau and adjacent areas: Results of HMNZS Tui Cruises

Forty‐four sediment samples and 23 Mn crusts and Mn nodules have been analyzed for several elements in order to characterize their geochemical nature. Most of the Mn crusts and Mn nodules are of hydrogenous origin, although one crust (U375) from the flanks of the Rarotonga volcano is thought to be of hydrothermal origin. δ‐MnO₂ is the principal Mn mineral in the crusts, whereas todorokite and birnessite occur in addition to δ‐MnO₂ in the nodules. The sediments can be divided into carbonates, with calcite as the dominant phase, and deep‐sea clay, consisting mainly of illite and smectite.     

西北太平洋多金属结核铂族元素地球化学特征

Polymetallic nodules and cobalt (Co)-rich crusts are enriched in platinum-group elements (PGEs),especially platinum (Pt) and may be important sinks of PGEs.At present,little information is available on PGEs in polymetallic nodules,and their geochemical characteristics and the causes of PGEs enrichment are unclear.Here PGEs of polymetallic nodules from abyssal basin in the Marcus-Wake Seamount area of the Northwest Pacific Ocean are reported and compared with the published PGEs data of polymetallic nodules and Co-rich crusts in the Pacific.The total PGEs (ΣPGE) content of polymetallic nodules in study area is 258×10~(–9) in average,markedly higher than that of Clarion-Clipperton Zone (CCZ) nodules (ΣPGE=127×10~(–9)) and lower than that of Co-rich crusts in the Marcus-Wake Seamount (ΣPGE=653×10~(–9)),similar to that of Co-rich crusts in the South China Sea(ΣPGE=252×10~(–9)).The CI chondrite-normalized PGEs patterns in different regions of polymetallic nodules and cobalt-rich crusts are highly consistent,with all being characterized by positive Pt and negative Pd anomalies These results,together with those of previous studies,indicate that PGEs in polymetallic nodules and Co-rich crusts are mainly derived directly from seawater.Pt contents of polymetallic nodules from the study area are negatively correlated with water depth,and Pt/ΣPGE ratios in nodules there are also lower than those of the Corich crusts in the adjacent area,indicating that sedimentary water depth and oxygen fugacity of ambient seawater are the possible important controlling factors for Pt accumulation in crusts and nodules.     

东太平洋海底结核及相关沉积物的稀土元素地球化学特征

海底多金属结核多分布于沉积物表面,而且二者之间关系密切.宏观上,结核的丰度、品位、形态及分布规律与海底地形、地层结构、沉积厚度及沉积物类型有密切关系[1,2];微观上,结核和相关沉积物的元素组成有一定的联系[3~7]1).     

九州-帕劳海脊南段共生多金属结核与富钴结壳地球化学特征及其资源意义

深海多金属结核与富钴结壳富含Mn、Co、Ni、Cu及稀土等元素,极具资源潜力,因而广受关注。选择采集自九州-帕劳海脊南段水深约3 000 m的6个多金属结核和2个富钴结壳样品进行地球化学特征研究。结果显示本区样品Mn/Fe比值为0.88～1.07,Co及稀土元素含量高,与库克群岛多金属结核元素特征相似,表现出典型的水成成因特征。与其他地区水成结核、结壳相比,样品具有较高的Ca含量,可能和其所在位置海脊部位水深较浅、位于碳酸盐补偿深度（CCD）以上有关。样品表现出Y负异常、Nd含量高等水成结核的特点,但微弱的Ce正异常特征与其他地区水成多金属结核/壳的强烈Ce正异常特征不同,这表明其生长于弱氧化环境。本区结核分布在CCD以上,最小溶氧层（OMZ）以下,是一种水成成因、贫氧生长的新型多金属结核,其物质来源、成矿模式将为揭示多金属结核的形成分布规律提供一条全新的认识途径。同时研究区结核、结壳Co及稀土元素含量较高,且分布位置较浅,易于开采,具有一定的资源潜力。     

太平洋徐福海山富钴结壳稀土元素和铂族元素赋存状态研究

利用等离子体发射光谱法、等离子体质谱法以及相态分析手段,对太平洋徐福海山富钴结壳稀土和铂族元素地球化学特征、赋存状态及富集机制进行研究。结果表明,富钴结壳稀土和铂族元素明显富集,其稀土总量为1 842～2 854 μg/g,铂族总量为144～1 180 ng/g,老壳层中稀土和铂族元素含量明显高于新壳层,这可能与老壳层发生磷酸盐化作用有关。轻稀土元素含量明显高于重稀土元素含量,呈现Ce正异常而Eu无异常,具有明显Ce富集特征。铂族元素之间发生了明显分异作用,PPGE含量明显高于IPGE,表现出明显Pt正异常而Pd负异常,具有明显Pt富集而Pd亏损特征。稀土元素赋存状态显示,新壳层中稀土元素主要赋存于铁氧化物相,其富集比例为65.40%～70.05%,老壳层中稀土元素主要赋存于残渣态,富集比例为62.27%～65.77%,这可能与残渣态中磷酸盐有关。铂族元素赋存状态显示,新壳层和老壳层中铂族元素都主要赋存于铁氧化物相,其富集比例为63.66%～69.51%,残渣态(29.20%～34.68%)对铂族元素也有一定的富集能力。富钴结壳稀土和铂族元素的富集推测为铁氧化物胶体粒子的吸附作用,受海水氧化性环境影响,可溶性Ce³⁺和Pt²⁺分别被氧化成不溶性Ce⁴⁺和Pt⁴⁺,沉淀被吸附到铁氧化物相中,从而造成富钴结壳稀土和铂族元素的富集。     

西盘古海盆锰结核的元素地球化学特征及生长机制

通过对西盘古海盆(Cipangu Basin)15个锰结核样品开展系统的形态结构、显微构造、矿物组成、常微量元素和稀土元素含量特征差异性研究,进而探讨该区锰结核的成因类型和生长机制。西盘古海盆锰结核外观为椭球状或连生体状,表面光滑,组成矿物主要有水羟锰矿、石英、钙长石和石盐;其稀土元素配分模式图表现出明显的Ce正异常、Y负异常和轻稀土富集特征。样品Mn/Fe比值均<2.5,与Ni、Cu正相关,且Mn与Cu、Co和Ni高度正相关,这表明因Cu2+、Ni2+、Co2+更易占据层板结构锰氧八面体MnO6的空位而在锰矿物表面富集。锰结核显微构造区域可划分为Type-Ⅰ型和Type-Ⅱ型,其中Type-Ⅰ型为结构致密高反射率的层纹状、柱状、叠层状构造的显微构造区域,Type-Ⅱ型为结构疏松低反射率的掌状、混杂状、环状构造的显微构造区域;Type-Ⅰ型区域的Mn/Fe比值和Ni、Ni + Cu、Co含量均高于Type-Ⅱ型区域。构造致密的Type-Ⅰ型区域代表沉积环境变化较小,生长速率较小;构造疏松的Type-Ⅱ型区域代表沉积环境剧烈变化、结核生长速率较大。西盘古海盆锰结核具有典型的水成型成因特征,通过常微量元素测试数据估算得出西盘古海盆锰结核样品的形成时间为1.48 Ma。据微区分析数据估算得出其生长年龄为2.44 Ma。     

Behavior of rare earth elements in coexisting manganese macronodules,micronodules, and sediments from the central Indian basin

Distribution characteristics of cobalt‐rich manganese deposits were evaluated from stereo photographs and video data on a seamount in the central Pacific Ocean by image analysis, photogrammetric technique, and visual observations. The results show that many locations have high crust coverages with highly undulating micro‐topography. High nodule coverages occur on relatively flat seafloor, and the nodule size distribution varies from uniform to inhomogeneous among different locations. Distribution of these deposits along detailed topographic sections show that the seafloor can be divided into nodule dominant zones between 0° and 3° slopes, with sediment patches up to 4° slopes; and crust dominant zones, which occur on slopes higher than 15°. The transition zone, between 4° and 15° slopes, has many locations, where nodules and crusts co‐occur in varying percentages. The observation of crust outcrops among sediments and nodules, as well as in the gravity core samples, indicates the presence of shallow buried crusts as well, which can substantially enhance resource evaluation of the deposits.     

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。     

A comparative analysis of compositional variations in and between marine ferromanganese nodules and crusts in the South Pacific and their environmental controls

Regional variation of Mn, Fe, Co, Ni and Cu in ferromanganese oxides (nodules and crusts) in the central south Pacific is related to primary productivity, oxygen minimum layer, and calcium carbonate compensation depth. The largely latitudinal influence of these environmental parameters on nodule and crust composition reflects their predominantly latitudinal variation. Primary productivity is the principal regional environmental control, influencing diagenetic enrichment of these elements in nodules through its effect, mediated by the CCD, on supply and concentration of labile organic matter vs. carbonate remains to the sediments. It influences hydrogenetic enrichment of these elements in nodules and crusts through its effect, mediated by the oxygen minimum layer (mainly in the case of crusts), on their export from surface waters.The elements’ varying susceptibility to being scavenged or organically bound influences the contrasting composition of diagenetic vs. hydrogenetic ferromanganese oxides, which is further influenced by depth. Hydrogenesis is the fundamental process governing nodule and crust formation, superimposed on which is diagenesis under specific circumstances; both are subject to intermittent interruption, diminution and augmentation by changes in environmental parameters. Application of regionally operative environmental controls locally explains local compositional variations and helps refine exploration criteria for economically viable nodules and crusts.     

楚科奇海及其邻近海域表层沉积物的元素地球化学特征

北极地区不仅具有丰富的矿产资源,而且在全球变化研究中具有极为重要的地位[1],同时由于其极端环境下的物理、化学作用与中低纬度有较大的差别,导致了这里的海洋地球化学过程的特殊性,因此在基础理论研究中也扮演着十分重要的角色.1999年中国首次北极科学考察对位于北冰洋的楚科奇海及其邻近海域进行了沉积物取样,开展了地球化学研究,并已取得了部分成果[2～4].     

A comparison between manganese nodules and cobalt crust economics in a scenario of mutual exclusivity

The past 20 years have been characterised by limited interest in the economic viability of deep seabed mining with the exception of those mineral ores rich in precious metals such as polymetallic sulphides. This paper goes against the tide. After reviewing the most significant literature, it compares the economic feasibility of mining polymetallic manganese nodules and cobalt-rich ferromanganese crusts in a scenario of mutual exclusivity. It uses a new indicator, the cobalt-nickel price ratio, whose aim is to verify at what metal prices the net present value of the two mining projects equalises. Previous research has shown that the turning margin between manganese nodules and cobalt crusts is a cobalt price of $50/kg. The present paper revises this by showing that the choice between mining crust and nodules depends on fluctuations in the price of nickel. A Monte Carlo simulation proves that cobalt crust mining could be reasonably preferred to manganese nodules at cobalt prices of $40-60/kg if the price of nickel fell below $11/kg. Within this condition, investors would receive the minimum acceptable internal rate of return of 15%, which is at a level of risk closer to the land-based mining. However, when the price of nickel passes the $11/kg threshold, the equilibrium between the two ventures can be reached only at a cobalt price greater than $100/kg, causing cobalt crust to become uncompetitive. Finally, the paper, recognising that prices are not unique drivers, introduces legal, political, technological and environmental concerns to show that the final choice between the two mining ventures cannot be merely driven by economic issues.     

Matrix bound phosphine in sediments of the Changjiang Estuary and its adjacent shelf areas

Matrix bound phosphine (MBP) is commonly considered an important phosphorus form in the natural environment. This paper presents an investigation of the spatial distribution of MBP and its relationship with the environmental factors in the Changjiang Estuary and its adjacent shelf areas (29.5–32°N, 122–124°E). A total of 32 surface sediment samples were collected from April 24 to 30, 2008. MBP was detected in all samples from the Changjiang Estuary and its adjacent shelf surface sediments (0.1–29.7 ng kg⁻¹). The concentration of MBP decreased from the Changjiang Estuary to the East China Sea shelf. Environmental factors such as organic matter, type of sediments, and redox conditions were found to affect the concentration and distribution of MBP in the marine sediments. Although the MBP levels were low in the marine sediments, the marine biogeochemical cycles of MBP in sediments were established and the information presented here will contribute to the understanding of the biogeochemical cycle of phosphorus.     

西太平洋采薇海山群富钴结壳铂族元素地球化学特征与来源

为探讨富钴结壳铂族元素的来源,以西太平洋采薇海山群富钴结壳样品为研究对象,利用X射线衍射法、等离子体发射光谱法和质谱法,对富钴结壳样品进行了矿物组成、主量元素和铂族元素含量分析。研究表明,富钴结壳的主要结晶矿物为水羟锰矿,次要矿物有石英、斜长石、钾长石和碳氟磷灰石,同时含有大量非晶态铁氧/氢氧化物。富钴结壳中Mn和Fe含量最高,且明显富集铂族元素,铂族总量为142～1 352 ng/g,其中Pt为114～1 268 ng/g,占铂族总量的80%以上。老壳层的铂族元素含量高于新壳层,老壳层发生了磷酸盐化作用。富钴结壳的铂族元素之间发生了分异作用,Pd组（PPGE）含量高于Ir组（IPGE）。铂族元素配分模式显示Pt正异常和Pd负异常,具有Pt富集而Pd亏损特征,推测富钴结壳的铂族元素来源于洋壳蚀变过程中海山玄武岩和海水之间的水−岩反应。富钴结壳的铂族元素与CaO、P₂O₅、Ba和Cu正相关,推测铂族元素赋存于磷酸盐矿物相中。富钴结壳生长剖面从上到下,由新到老,铂族元素含量呈逐渐增加趋势,海水氧化性环境和高海洋生产力可增进磷酸盐化作用,从而进一步促进了铂族元素的富集。该研究对于揭示富钴结壳铂族元素的来源具有一定的参考价值。     

广东近岸海湾表层沉积物的稀土元素特征及其物源示踪

本文对广东省近岸10个典型海湾的表层沉积物进行了系统的稀土元素(rare earth elements,REE)测试和分析,以期发现沉积物的物源组成特征及其控制因素。研究结果表明,同一海湾内沉积物的稀土丰度差异不明显,但不同海湾之间具有一定的差别(133.58—251.77mg.kg 1)。球粒陨石标准化配分曲线表现出轻稀土(La到Eu)富集、重稀土(Gd到Lu)亏损、δEu负异常等典型的陆源沉积物特征;PAAS(Post-Archean Australian Shale)标准化配分模式显示出明显的中稀土(Sm到Ho)富集特征,与已报道的国内河流沉积物REE特征相似。海湾沉积物与入海河流沉积物及流域内的原岩组成特征的比较说明,后者对海湾沉积物的控制作用明显。REE配分曲线的一致性和中稀土富集特征表明海湾沉积物主要来自汇入海湾的山溪及河流输入的沉积物。     

庙岛群岛西部海域表层沉积物常量和稀土元素的分布特征及其物源指示意义

通过对庙岛群岛西部海域表层沉积物常量、稀土元素的系统研究,探讨了表层沉积物元素地球化学特征、控制因素及其物质来源。结果表明,庙岛群岛西部海域表层沉积物常量元素以SiO₂和A1₂O₃为主,SiO₂含量随着沉积物粒径变粗逐渐增大,Al₂O₃含量随着沉积物粒径变细逐渐增大。稀土元素(Rare Earth Element,REE)呈现轻稀土元素(Light Rare Earth Element,LREE)富集、重稀土元素(Heavy Rare Earth Element,HREE)平坦以及中等程度的Eu负异常等特征,轻重稀土分异明显,稀土元素球粒陨石配分曲线与黄河沉积物类似。通过因子分析和相关性分析发现研究区沉积物的元素含量主要取决于陆源碎屑,海洋生物沉积和化学作用对沉积物元素含量有一定的影响,元素含量基本服从粒度控制规律。物源判别结果显示,庙岛群岛西部海域沉积物主要来源于黄河物质和辽河物质,并且从南到北辽河物质的混合比例逐渐升高,黄河物质的混合比例逐渐降低。     

长江口及毗邻海区沉积物中磷的分布特征长江口及毗邻海区沉积物中磷的分布特征

于2006年6月和2007年4月在长江口及毗邻海区采集了表层沉积物样品,利用水淘选法对沉积物进行了粒径分级,并采用改进后的SEDEX方法对沉积物样品及分粒级沉积物样品进行了磷形态分析。结果表明,2006年6月和2007年4月长江口及毗邻海区沉积物总磷变化分别为1256~1964 μmol/g和899~1991 μmol/g,其中碎屑磷是磷的主要存在形态。可交换态磷、铁结合态磷、有机磷、自生磷灰石磷及难分解有机磷在长江口外的平面分布比较一致,均在紧邻长江口门外、杭州湾外的条状带出现了含量的高值,而在口门内及口门外河口靠海一侧碎屑磷含量较高。不同形态磷在不同粒径沉积物中的含量不尽相同：有机磷、自生磷灰石磷以及难分解有机磷是小于8 μm粒级沉积物中磷的主要组成部分,而且其在总磷中所占比例随沉积物粒径的增加而下降;碎屑磷则主要集中在粗沉积物中,为32~63 μm及大于63 μm粒级沉积物中磷的主要贡献者。沉积物的粒度分异以及各形态磷在不同粒径沉积物中含量的差异,共同影响着河口沉积物中磷的分布     

长江口及毗邻海区沉积物中磷的分布特征

于2006年6月和2007年4月在长江口及毗邻海区采集了表层沉积物样品,利用水淘选法对沉积物进行了粒径分级,并采用改进后的SEDEX方法对沉积物样品及分粒级沉积物样品进行了磷形态分析。结果表明,2006年6月和2007年4月长江口及毗邻海区沉积物总磷变化分别为12.56~19.64μmol/g和8.99~19.91μmol/g,其中碎屑磷是磷的主要存在形态。可交换态磷、铁结合态磷、有机磷、自生磷灰石磷及难分解有机磷在长江口外的平面分布比较一致,均在紧邻长江口门外、杭州湾外的条状带出现了含量的高值,而在口门内及口门外河口靠海一侧碎屑磷含量较高。不同形态磷在不同粒径沉积物中的含量不尽相同:有机磷、自生磷灰石磷以及难分解有机磷是小于8μm粒级沉积物中磷的主要组成部分,而且其在总磷中所占比例随沉积物粒径的增加而下降;碎屑磷则主要集中在粗沉积物中,为32~63μm及大于63μm粒级沉积物中磷的主要贡献者。沉积物的粒度分异以及各形态磷在不同粒径沉积物中含量的差异,共同影响着河口沉积物中磷的分布。     

黄河口及近海表层沉积物中烃类化合物的组成和分布

为探讨黄河口近海表层沉积物有机质中烃类化合物的分布特征及输运过程,2003年9月采集了南北两个断面表层沉积物样品,对沉积物中正构烷烃和多环芳烃进行了分析,结果表明,黄河口表层沉积物中正构烷烃和多环芳烃的含量分别为0.38~2.55和0.371~0.650μg/g。在南北断面两种烃类化合物的分布明显不同:北断面受石油平台影响,烃类化合物在口门含量较高;南断面受黄河输入影响,由于大颗粒易于沉降,而吸附烃类化合物的能力较强的小颗粒易长距离输运,使这两种烃类化合物的含量从河口到近海整体呈上升的趋势。与北断面相比,南断面受水生源影响相对较弱,而且水生源的贡献随着离岸距离的增加而加强,在最大浑浊带后水生源急剧增强;在南断面多环芳烃主要来源为热解源,北断面多环芳烃受热解源和石油污染的共同影响。     

菲律宾海及其邻近海域表层沉积物中放射虫的分布对不同区域环境的响应

为了解菲律宾海放射虫的区域分布特色,利用同样的样品处理方法,对菲律宾海及其邻近海域的44个表层沉积样中的放射虫进行对比分析,鉴定统计了500个属种,物种多样性较高.菲律宾海表层沉积物中放射虫的群落结构和丰度变化幅度较大,反映了菲律宾海更为复杂的区域生态环境或沉积环境;南海北部放射虫丰度非常高且罩笼虫目占据较大优势,表明...     

东太平洋多金属结核的叠层石包壳及其沉积环境意义

对东太平洋C-C区深海多金属结核的叠层石包壳、多金属结核的表面类型及其分布规律进行了详细研究和合理解释,认为叠层石的形态学特征既是建造叠层石的微生物种类差异的表现,也是环境水动力条件和溶解氧含量不同的反映,这些因素共同决定了多金属结核的表面类型,而南极底流是造成海底水体能量环境、氧化还原电位和微生物种类变化的根本原因.为多金属结核的分布规律和成矿预测提供科学依据.