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1366 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。     

南海铁锰结核(壳)的稀土元素地球化学

于1987年5—6月间,中、西德在南海进行地球科学调查,获得5个铁锰结壳、6个铁锰结核样品。本文在利用X荧光法测定15个稀土元素的基础上,对南海铁锰结核(壳)的稀土丰度、配分模式与伴生元素的关系以及稀土的来源作了较为详细的探讨。研究表明,南海铁锰结核(壳)的平均丰度为1625×10~(-6),铁锰结核为2167×10~(-6),分别要比太平洋结核高1—2倍,比太平洋北部沉积物高3—4倍,比南海沉积物高10—20倍;结核和结壳的稀土经球粒陨石标准化后的配分模式基本相同,Ce正异常,Eu亏损不明显;与伴生元素、沉积物及岩石稀土对比研究表明,结核(壳)中稀土主要来自南海中酸性岩类风化、淋漓后缓慢沉积。     

印度洋钙质软泥和硅质软泥稀土元素组成和富集机制

本文针对采自印度洋深海中最常见的两类生物成因沉积物——钙质软泥和硅质软泥，开展了全岩样和不同粒级组分中常微量元素、稀土元素和Y（REY）含量的系统分析，探讨了两类沉积物中REY的组成特征、物质来源和富集机制。研究表明，钙质软泥以富含CaO和Sr为主要特征，硅质软泥则富集SiO₂、Al₂O₃、Fe₂O₃等。钙质软泥中∑REY平均含量为40.56×10-6，轻稀土元素（LREE）略有富集，REY有向细粒沉积物中富集的特征，PAAS标准化后全岩样和不同粒级组分均表现为Ce负异常、Eu和Y正异常；REY以自生来源为主，继承了海水的组成特征，同时也受到了热液流体物质和洋底玄武岩风化产物的影响。硅质软泥中∑REY的含量为248.54×10-6，LREE相对富集，REY在4φ以细的沉积物中富集；研究站位沉积物中∑REY含量处于边界品位附近，但在细粒级沉积物中重稀土元素（HREY）含量则达到了工业品位；该类沉积物细粒组分中REY主要来自陆源或火山碎屑组分中黏土矿物和铁锰氧化物吸附作用，粗粒组分中REY来源则主要与生物作用相关；硅质软泥中REY的富集与沉积物中磷灰石等矿物相关，部分不同来源的REY可能是在沉积之后的成岩过程中再次分配向磷灰石、钙十字沸石等矿物中富集。     

Ferromanganese Nodules and their Associated Sediments from the Central Indian Ocean Basin: Rare Earth Element Geochemistry

Abstract

The rare earth element (REE) distribution in nine deep-sea ferromanganese nodules and their associated siliceous sediments from the Central Indian Ocean Basin (CIOB) have been studied to elucidate the REE relationship among them. Total REE concentration varies from 398–928 ppm in the nodules and 137–235 ppm in the associated sediments, suggesting two- to four-fold enrichment in the nodules compared to associated sediments. REE of nodules and their associated sediments show a positive correlation, suggesting REE are supplied from a common source such as seawater. The positive correlation between REE of nodules and sediments from the CIOB is contrary to the competitive scavenging of REE between nodules and sediment in the equatorial Pacific Ocean. REEs in the nodules are carried by Fe, P, and Ti, whereas in the sediment they are carried by P and Mn phases. A similar REE fractionation pattern with middle REE enrichment over heavy and light REE in both the nodules and their associated sediment suggest fractionation is independent of REE abundance and their carrier phases.     

Arsenic in sediments of the North Atlantic Ocean and the Eastern Mediterranean Sea

Chemical extraction techniques show that the majority of the arsenic in North Atlantic deep-sea sediments is associated with an iron phase compositionally similar to that found in deep-sea ferromanganese nodules (As/Fe ～ 11 · 10^?4) and is probably of seawater origin. Some sediments also contain As associated with Fe oxides produced by continental weathering. A minority (～8%) of the arsenic is of detrital origin but is not associated with Fe or Mn oxides; it has a content (1.7 ppm) similar to the average crustal abundance. In the Eastern Mediterranean Sea, near-shore sediments contain As associated with land-derived Fe oxides (As/Fe ～ 2 · 10^?4), but As/Fe ratios increase to ～ 13 · 10^?4 in deep-sea sediments as the contribution of seawater derived arsenic becomes dominant. Arsenic is enriched in metalliferous sediments (As/Fe ～ 20?50 · 10^?4) but As/P ratios of metalliferous sediments, deep-sea ferromanganese nodules and deep-ocean water are all similar. Although a hydrothermal contribution cannot be discounted, it is likely that the arsenic is also of seawater origin, suggesting that hydrothermal iron oxyhydroxides remove As more efficiently from seawater than do iron phases (goethite) in deep-sea sediments and nodules. Arsenic accumulates in deep-sea sediments (～ 6 μg cm^?2 10^?3 yr^?1) at sediments (～ 120 μg cm^?2 10^?3 yr^?1) at rate sufficient to balance river input input (～3 · 10¹⁰ g yr^?1). These estimates give an oceanic residence time for arsenic of 1–2 · 10⁵ yr.     

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.     

Trace elements in ferromanganese nodules from the central indian ocean basin

Thirty-three bulk ferromanganese nodules from the sediment–water interface of siliceous sediment domain from the Central Indian Ocean Basin were analyzed for 50 elements including 6 new (Be, As, Se, Sn, Sb, and Bi) using inductively coupled plasma–mass spectrometer. The Mn/Fe ratio and triangular plot (Fe-Mn-{Cu+Ni+Co?×?10}) suggest that ferromanganese nodules are of hydrogenetic, early diagenetic, and diagenetic origin. In the ferromanganese nodules, Mo, Sb, Bi, and As are highly enriched ～320, 160, 90, and 50 times compared with upper continental crust, respectively. A majority of the elements such as Be, Sc, Ti, V, Co, As, Se, Sr, Y, Zr, Nb, Sn, rare earth elements (REEs), Pb, Bi, P, Th, U, Hf, and Ta are associated with Fe, whereas, Cu, Ni, Zn, Mo, Li, Ga, Sb, Mg, and Cs are associated with Mn in the ferromanganese nodules. Redox proxies such as U/Th (0.14) and Mo/Mn (0.0019) ratio in the ferromanganese nodules suggest their formation under oxic conditions.     

Ferromanganese Nodules and their Associated Sediments from the Central Indian Ocean Basin: Rare Earth Element Geochemistry

The rare earth element (REE) distribution in nine deep-sea ferromanganese nodules and their associated siliceous sediments from the Central Indian Ocean Basin (CIOB) have been studied to elucidate the REE relationship among them. Total REE concentration varies from 398-928 ppm in the nodules and 137-235 ppm in the associated sediments, suggesting two- to four-fold enrichment in the nodules compared to associated sediments. REE of nodules and their associated sediments show a positive correlation, suggesting REE are supplied from a common source such as seawater. The positive correlation between REE of nodules and sediments from the CIOB is contrary to the competitive scavenging of REE between nodules and sediment in the equatorial Pacific Ocean. REEs in the nodules are carried by Fe, P, and Ti, whereas in the sediment they are carried by P and Mn phases. A similar REE fractionation pattern with middle REE enrichment over heavy and light REE in both the nodules and their associated sediment suggest fractionation is independent of REE abundance and their carrier phases.     

中国海域固体矿产资源分布及其区划——砂矿资源和铁锰(微)结核-结壳

综述和研究了我国海域砂矿资源和(微)结核—结壳的分布及其区划。我国的滨海砂矿广泛分布于渤海、黄海、东海和南海,但各省区的砂矿资源分布不同。近年来在我国海域新发现和圈定了多处砂矿品位异常区和矿物高含量区,可分为3个成矿带和24个成矿远景区,资源储量可观。在黄海、东海仅分布铁锰结核,没有发现铁锰结壳,但它们的金属元素含量低,没有潜在资源意义。南海东北陆坡、中央海盆西部和中部是(微)结核、结壳分布较多的区域。南海东北陆坡、海山及其周缘坡脚处的(微)结核、结壳其稀土元素含量较高,可能具有一定的潜在经济价值,今后调查中应引起重视。     

全球三大洋海山钴结壳资源量估算

钴结壳具有Co、Ni、Cu和Mn及其他金属的潜在矿产资源和储存在结壳层中古环境信息的双重意义。与深海多金属结核和热液硫化物矿床相比,具有较高Co、Ni和Pt含量的海山钴结壳有可能成为商业勘探的潜在目标。为合理地估算出全球三大洋海山钴结壳资源量,基于我国西太平洋海山钴结壳拖网采样调查资料和对太平洋海山钴结壳资源分布规律和钴结壳矿区圈定参数指标的深入研究,按海山不同高度、不同洋壳年龄赋予不同结壳厚度,进而计算出全球三大洋海山钴结壳分布面积为3 039 452.14km2和干结壳资源量为(1 081.166 1~2 162.332 2)×108 t。太平洋海山钴结壳分布面积为2 123 087.12km2和干结壳资源量为(513.244~1 026.488)×108 t,大西洋海山钴结壳分布面积为512 509.74km2和干结壳资源量为(116.503 2~233.006 4)×108 t,印度洋海山钴结壳分布面积为403 855.28km2和干结壳资源量为(81.484 9~162.969 8)×108 t。三大洋海山钴结壳的Mn、Co、Ni和Cu金属量分别为(138.848 0~277.696 0)×108 t,(3.967 6~7.935 2)×108 t、(2.793 6~5.587 2)×108 t和(0.825 1~1.650 2)×108 t。根据钴结壳的Co含量、Co通量和厚度相关分析,所赋予的钴结壳厚度占理论推测厚度的6.10%~12.20%,这与Ku等得出"钴结壳生长时间约占其整个生命史4%"的认识非常相近。三大洋海山钴结壳实测厚度与赋值厚度对比分析表明,太平洋海山钴结壳赋值厚度平均值为1.87cm,实测厚度平均值为1.77cm,相对误差为5.35%,大西洋和印度洋相对误差分别为18.18%和23.23%。研究数据表明按海山高度和洋壳年龄所赋的钴结壳厚度基本合理,估算出的钴结壳资源量基本可靠。本文首次估算出三大洋海山钴结壳资源量,为整个海盆和三大洋海山钴结壳资源量估算提供了新方法。     

东菲律宾海表层沉积物中元素的赋存状态

为了解东菲律宾海不同类型表层沉积物中元素的赋存状态,采用化学提取方法对有无新型铁锰结壳发育站位表层沉积物样品进行了分级提取及测试,不同类型表层沉积物中成矿和稀土元素的赋存状态总体一致,表明研究区表层沉积物形成于相似的地质和海洋环境中。成矿元素中Fe绝大部分赋存在残渣态中,Mn、Cu、Co和Ni则主要赋存在铁锰氧化物结合态中,稀土元素也主要赋存在这两个相态中,碳酸盐结合态、铁锰氧化物结合态和有机结合态对重稀土元素优先吸附或具络合作用,引起重稀土元素的相对富集和铈的负异常,残渣态优先吸附轻稀土元素,导致轻稀土元素的富集和铈的正异常,火山物质则使表层沉积物残渣态表现出铕的正异常特征。同时,不同表层沉积物样品间也存在一定的差异,这与其局部形成条件——铁锰结壳发育与否有关。     

西太平洋卡罗琳洋脊CM4海山铁锰结壳矿物学和地球化学特征

2017年8月中国科学院海洋研究所在西太平洋低纬度海区的卡罗琳洋脊CM4海山开展了多学科综合调查,发现该海山山体表面分布着大量的铁锰结壳。本文对该海山的5个铁锰结壳样品进行了矿物学和地球化学研究,利用X射线衍射(XRD)、电感耦合等离子光谱及质谱(ICP-OES、ICP-MS)等测试技术分析了铁锰结壳的矿物组成、主微量元素和稀土元素含量,并进一步探讨了铁锰结壳的成因类型。结果表明,该海山铁锰结壳的矿物组成以水羟锰矿为主,含有少量钡镁锰矿、水钠锰矿、针铁矿、纤铁矿、石英和方解石。该海山铁锰结壳的Mn、Fe、Co、Ni、Cu元素平均含量分别为24.24%、15.14%、0.16%、0.34%、0.01%。与全球各大洋海山区铁锰结壳相比,该海山样品的Cu含量很低。该海山铁锰结壳的稀土元素(REY)含量相对偏低,总体为轻稀土(LREE)富集;稀土(REY)配分模式显示相对平坦的特征,呈明显的Ce正异常,轻微的Y负异常和Ho正异常。样品的矿物组成、元素比值、元素组合等都表明该海山铁锰结壳属于水成成因,未受明显的成岩作用影响。     

麦哲伦海山群富钴结壳元素地球化学特征及赋存状态

为探究大洋富钴结壳的元素地球化学特征和赋存状态,以西太平洋麦哲伦海山群5个富钴结壳样品为研究对象,通过X射线衍射法、等离子体发射光谱法、等离子体质谱法及相态分析手段,分析了富钴结壳的矿物组成、主量元素和稀土元素含量。结果表明,富钴结壳样品主要结晶矿物为水羟锰矿,次要矿物包括石英、斜长石和钾长石,同时含有大量非晶态铁氧/氢氧化物。富钴结壳样品中Mn和Fe含量最高, Mn为16.87%～26.55%, Fe为14.34%～18.08%。富钴结壳明显富集稀土元素,其稀土总量为1 287～2 000μg/g,Ce含量为632～946μg/g,约占稀土总量的50%;轻稀土含量为1 037～1 604μg/g,重稀土含量为249～395μg/g,轻稀土元素明显高于重稀土元素。稀土元素配分模式呈现Ce正异常而Eu无异常,具有Ce富集特征。麦哲伦海山群富钴结壳是水成沉积成因,基本没有受到海底热液活动和成岩作用的影响。元素赋存状态与其矿物相密切相关, Na、K、Ca、Mg和Sr主要赋存于碳酸盐相, Mn、Ba、Co和Ni主要赋存于锰氧化物相, Fe、Al、P、Ti、Cu、Pb、V、Zn、Zr和REE主要...     

Minor and rare elements in manganese crusts and nodules and sediments from the Manihiki plateau and adjacent areas: Results of HMNZS Tui cruises

Six manganese crusts, 13 manganese nodules, and 16 sediments were analyzed by instrumental neutron activation analysis. Data were generated on selected major and minor elements but geochemical evaluations are based only on Fe, Sc, U, Th, and the rare earth elements (REE). Manganese crusts and manganese nodules have comparable trivalent REE contents and show a shale‐like distribution pattern. Both crusts and nodules are characterized by a positive Ce anomaly but the anomaly is higher in nodules. REE contents in manganese nodules show a linear dependence on the Fe content, and it is concluded that these elements are incorporated in the Fe‐rich (δ‐MnO₂) phase. In the crusts, the REE correlate with Sc and are therefore assumed to be associated with the clay minerals. Uranium contents are significantly higher in the crusts than in nodules whereas Th is slightly higher in the nodules. There is a clear positive correlation between U and Th in nodules but there are too few data to make a similar conclusion for crusts. Compositional data suggest a division of the sediments into two groups. The carbonate sediments have much lower REE contents and a more pronounced negative Ce anomaly than the clays, while both show a lithogenous component as indicated by a slight negative Eu anomaly.     

Rare earth element geochemistry of hydrothermal deposits from Southwest Indian Ridge

The REE compositions of hydrothermal deposits and basalt samples from the Southwest Indian Ridge (SWIR) were determined with ICP-MS.The results show that there are significant differences between different types of samples although all samples show relative LREE enrichment.The contents of REE in hydrothermal sulfides and alterated rocks samples are lower (from 7.036 × 10 6 to 23.660 × 10 6),while those in the white chimney deposits are relatively higher (ranging from 84.496 × 10 6 to 103.511 × 10 6).Both of them are lower than basalts.Chondrite-normalized REE distribution patterns show that sulfides and alterated rocks samples are characterized by significant positive Eu anomalies.On the contrary,white chimney deposits have obvious negative Eu anomalies,which may be caused by abundant calcite existing in the white chimney samples.Both the content and distribution pattern of REE in sulfides suggest that REE most possibly is originally derived from hydrothermal fluids,but influenced by the submarine reducing ore-forming environment,seawater convection,mineral compositions as well as the constraint of mineral crystallizations.     

The Role of Primary-Producer-Mediated Organic Complexation in Regional Variation in the Supply of Mn,Fe, Co,Cu, Ni and Zn to Oceanic,Non-Hydrothermal Ferromanganese Crusts and Nodules

Oceanic, non-hydrothermal ferromanganese crusts and nodules are variably enriched in Mn, Fe, Co, Cu, Ni and Zn. Comparison of the content of these elements in crusts and nodules with the level of primary productivity in the South Pacific Ocean suggests that primary-producer-mediated complexation of several of these elements by organic ligands in solution may contribute to explaining a pattern of distinctive associations observed between compositional variations for these elements in these deposits and variations in the level of primary productivity.     

Uptake of selenium and other oxyanionic elements in marine ferromanganese concretions of different origins

The concentration of selenium in marine ferromanganese concretions varies between 0.02 and 1.2 mg kg⁻¹, with an average of 0.6 mg kg⁻¹. This is about two orders of magnitude lower than previously reported. In contrast to minor cationic elements, the concentrations of selenium are relatively uniform between ferromanganese concretions of different origins, except for hydrothermal crusts. It shows the same trends of element enrichment as other oxyanionic elements. The incorporation of selenium into ferromanganese concretions is attributed to adsorption of selenate on iron and manganese oxides.     

帕里西维拉海盆西缘中段铁锰结核的地球化学特征和成因类型

深海铁锰结核能有效记录海域内重大地质事件和气候环境信息,且富含多种金属物质极具资源潜力,因而广受关注。通过对帕里西维拉海盆西侧边缘中段海域内新发现的12个站位铁锰结核的地球化学特征研究,发现与全球主要成矿区内的铁锰结核相比,Mn及主要赋存在锰氧化物中的Ni、Cu、Mo的含量较低(分别为8.20%~25.24%、0.11%~0.54%、0.08%~0.31%和0.01%~0.03%),主要由铁的羟基氧化物吸附的Ti,以及还会与钙磷酸盐发生耦合置换反应的REY的含量较高(分别为0.45%~1.88%、0.04%~0.19%),含量中等的Co(0.06%~0.27%)在铁锰相物质和硅酸盐相内核中分散分布。样品REY的标准化配分模式显示出明显一致的Ce正异常和Y负异常。铁锰结核从海水中捕获的Ce^3+容易被氧化成难溶且不具有活性的Ce^4+,Y则在结核内存在形式不稳定,容易发生解吸,致使Ce和Y分别呈现出相对于其他REY逐步富集和亏损的特征。研究区形成时间较晚,铁锰结核生长发育的时间不足,且四周地形较高,缺乏与外界连通的水道,阻碍了诸如来自南极的富氧底层流的大规模进入。区域内结核样品主要为水成型,成岩成因组分的供给太低,降低了主要有用组分的含量。以上诸多因素可能会导致区域内的铁锰结核难以富集成矿。     

Comparative mineralogy and geochemistry of hydrothermal iron‐rich crusts from the Pitcairn,Teahitia‐mehetia,and Macdonald hot spot areas of the S. W. pacific

Abstract

Hydrothermal iron‐rich crusts have been recovered from a number of hot spot volcanos including Crough Seamount, Pitcairn Volcanos 2 and 1, Cyana Seamount, Teahitia, Moua Pihaa, and Macdonald Seamount in the S. W. Pacific. Mineralogically, the crusts consists of ferrihydrite with traces of the weathering products of volcanic ash (feldspar, nontronite, pyroxene, and serpentinite). The iron oxyhydroxide phase has a mean particle size of 3–4 nm indicating rapid deposition. Electron microprobe studies have revealed the presence of filamentous iron‐silica deposits within the crusts reflecting the possible bacterial oxidation of iron from the hydrothermal fluids. The crusts display wide variability in composition both between individual sampling stations and between seamounts. Endmember analysis shows that the compositional data can be resolved into three endmembers: a Fe‐rich endmember, a light and heavy rare earth element endmember, and a Ba (barite)‐rich endmember. The Fe‐rich endmember appears to contain very low concentrations of most trace elements. For bulk samples, the composition of the iron‐rich crusts reflects dilution of the iron oxyhydroxide phase by volcanic ash and, to a lesser extent, a hydrogenous component. This is illustrated by the wide variability in SiO₂ (11.1–71.3%) and Mn (0.01–1.21%) contents of the crusts. For iron‐rich crusts containing greater than 40% Fe, the Pitcairn crusts display lower contents of Pb, Ba, Mo, U, Th, As, and rare earth elements (REE) and lower cerium anomalies than those from Teahitia. REE profiles of crusts from each of the hot spot volcanoes are characterized by small negative cerium anomalies but pronounced positive europium anomalies. The low average La/Fe ratios of the crusts from the various seamounts (47–572 X 10^‐6) and positive Eu anomalies of the crusts suggest rapid deposition of the iron oxyhydroxide near the hydrothermal vent. The high Fe/Mn ratio of vent fluids at hot spot volcanoes (8.5–5.6) may account for the formation of these iron‐rich crusts. The present data indicate that there may be differences in the nature of the iron‐rich crusts based on the depth of occurrence. This influences the temperature of the venting hydrothermal fluids and the possibility of occurrence of submarine phreatomagmatic eruptions.     

深海富REY泥中稀土元素赋存载体及其富集机制研究进展

综合前人发表的关于太平洋、大西洋以及印度洋等深海沉积物中稀土元素含量的数据,本文较为系统地阐述了全球深海富REY泥(REY-rich mud)的分布,分析了不同沉积环境下富REY泥中稀土元素的赋存载体及其控制因素,并进一步探讨了赋存载体中稀土元素的富集机制。研究发现深海富REY泥主要分布在太平洋和印度洋的深海盆地中,其中西北太平洋南鸟岛附近海域沉积物中稀土元素最为富集,是较为有利的稀土资源勘探潜力区。邻近热液区,深海沉积物中稀土元素含量受热液活动影响较大,稀土元素的主要赋存相是Fe-Mn水合(氢)氧化物,可能是热液流体扩散过程中,颗粒物中的Fe-Mn水合(氢)氧化物等吸附(scavenge)海水中的稀土元素所致。而在远离热液区的正常深海富REY泥中,高磷含量以及低沉积速率是导致其稀土含量相对较高的主要因素,赋存载体主要是生物成因磷灰石(鱼牙骨碎屑)。在磷灰石早期成岩阶段,海水和孔隙水中的REY进入磷灰石,在羟基磷灰石晶格中REE~(3+)与磷灰石中的Ca~(2+)发生类质同象替代:REE~(3+)+Na~+?2Ca~(2+)和REE~(3+)+Si~(4+)?Ca~(2+)+P~(5+),使其不断地富集稀土元素,但这还需要进一步研究。