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1.
H Elderfield C.J Hawkesworth M.J Greaves S.E Calvert 《Geochimica et cosmochimica acta》1981,45(4):513-528
Analyses have been made of REE contents of a well-characterized suite of deep-sea (> 4000 m.) principally todorokite-bearing ferromanganese nodules and associated sediments from the Pacific Ocean. REE in nodules and their sediments are closely related: nodules with the largest positive Ce anomalies are found on sediments with the smallest negative Ce anomalies; in contrast, nodules with the highest contents of other rare earths (3 + REE) are found on sediments with the lowest 3 + REE contents and vice versa. ratios in the nodules (～0.51244) point to an original seawater source but an identical ratio for sediments in combination with the REE patterns suggests that diagenetic reactions may transfer elements into the nodules. Analysis of biogenic phases shows that the direct contribution of plankton and carbonate and siliceous skeletal materials to REE contents of nodules and sediments is negligible. Inter-element relationships and leaching tests suggest that REE contents are controlled by a P-rich phase with a REE pattern similar to that for biogenous apatite and an Fe-rich phase with a pattern the mirror image of that for sea water. It is proposed that 3 + REE concentrations are controlled by the surface chemistry of these phases during diagenetic reactions which vary with sediment accumulation rate. Processes which favour the enrichment of transition metals in equatorial Pacific nodules favour the depletion of 3 + REE in nodules and enrichment of 3 + REE in associated sediments. In contrast, Ce appears to be added both to nodules and sediments directly from seawater and is not involved in diagenetic reactions. 相似文献
2.
Geochemistry of Rare Earth Elements in the Ocean 总被引：4，自引：0，他引：4
This work briefly outlines modern ideas on geochemistry of rare earth elements (REE) in the ocean. Sources of REE and chemical properties of these elements, which govern their migration ability in natural processes, are considered. The REE behavior in the river water–seawater mixing zone is analyzed. The fractionation of dissolved and suspended REE in oceanic water in both aerobic and anaerobic conditions is also considered. It is shown that the variability of REE composition in pelagic sediments reflects the fractionation of these elements in the oceanic water as a consequence of material differentiation in the ocean. The REE distribution in terrigenous, authigenic, hydrothermal, and biogenic constituents of sediments, such as clay, bone debris, barite, phillipsite, Fe–Mn oxyhydroxides (ferromanganese nodules and micronodules), Fe–Ca hydroxo-phosphate, diatoms, and foraminifers, is considered. 相似文献
3.
4.
Upper Triassic-Jurassic black shale at Marvast, Iran, contains grey to green-grey ellipsoidal nodules of monazite ranging from 0.1 to 2?mm across. The presence of host-rock mineral inclusions within the monazite grains, low Th content in the monazite, lack of relict yellow cores (characteristic of igneous monazite), and the absence of monazite in the other sedimentary sequences in the Marvast area rule out a detrital origin for the monazite nodules and suggest authigenic crystallization during sediment compaction. Enrichment of the cores of the monazite grains in mid-range to heavy rare-earth elements (REE) and their rims in La + Ce point to variations in the degree of REE mobility and/or evolving composition of the diagenetic mineralizing fluid during nodule growth. The phosphorus and REE required for monazite crystallization were probably derived from seawater and adsorbed on clays and Fe-Mn hydroxides. The interstitial fluids expelled from the sediments during burial compaction and diagenesis became enriched in P and REE through complexing. The association of the Marvast monazite nodules with the black shale may indicate that organic complexes aided in the mobilization and transport of the REE into the pore fluids. Detailed field investigations in the study area and vicinity show that authigenic monazite in the upper Triassic-Jurassic shale sections is spatially associated with quartz lenses. It is likely that these lenses are surface expressions of shallow intrusive magmas, which provided the heat that promoted the mobilization and redistribution of the REE and P, and initiated precipitation of monazite in the overlying sediments. 相似文献
5.
Rare earth elements (REE) concentrations of Archean and Proterozoic chemical sediments are commonly used as proxies to study secular trends in the geochemistry of Precambrian seawater. In addition, similarities in the REE signatures of Archean chemical sediments and modern seawater have led researchers to argue that some Archean rocks originated as biochemical precipitates (i.e., microbial carbonates) in shallow marine (e.g., peritidal) environments. However, terrestrial waters, including river water and groundwater, also commonly exhibit REE fractionation patterns that resemble modern seawater. Here, we present the seawater-like REE data for groundwaters from central México as additional evidence that these patterns are not unique to the marine environment. The shale-normalized REE patterns of the groundwaters are compared to those of modern seawater (open ocean and nearshore), Holocene reefal microbial carbonates and corals, and Archean chemical sediments using statistical means (i.e., ANOVA and Wilcoxon analyses) in order to quantify the similarities and/or differences in the REE patterns. Shale-normalized (SN) Ce anomalies and measures of REE fractionation [i.e., (La/Yb)SN, (Pr/Yb)SN, (Nd/Yb)SN, and (Gd/Yb)SN] of the central México groundwater samples are statistically indistinguishable from those of modern seawater. Moreover, except for differences in the Ce anomalies, which are lacking in Archean chemical sediments, the REE patterns of the central México groundwaters are also statistically similar to REE patterns of Archean chemical sediments, especially those of the 3.45 Ga Strelley Pool Chert. Consequently, we suggest that without additional information, it may be premature to unequivocally conclude that Archean chemical sediments record REE signatures of an Archean ocean. 相似文献
6.
为了探讨富钴结壳的稀土和铂族元素是否有相似的形成机制,对西太平洋海山富钴结壳稀土和铂族元素进行了类比研究.结果表明:富钴结壳的∑REY范围为1 433.7×10-6~2 888.0×10-6,其中Ce占到近50%,北美页岩标准化后显示较平坦的稀土模式和显著的Ce正异常特征.根据稀土配分模式及已有的Nd同位素结果,富钴结壳具有亲陆壳属性.富钴结壳具有极高的Pt (115.5×10-9~1 132.0×10-9)、(Pt/Pd)N和 (Pt/Os)N值,Ir与Pt及Rh与Pt显示良好相关性.经球粒陨石标准化后显示较一致PGE (platinum-group elements) 配分模式,从Os到Pt逐渐富集,Pd元素强烈亏损.已有的Os同位素研究结果显示物源在地质历史时期从幔源属性向陆源属性变化,但富钴结壳PGE元素内部相对含量仍在一定程度上保持稳定.研究认为:富钴结壳对海水中的稀土清扫具有选择性,Ce的正异常恰恰是结壳对海水稀土中Ce的优先选择造成的,从而导致海水亏损Ce.然而海水中Ce的亏损并未改变新形成富钴结壳的稀土模式,原因是在海洋中存在适量的具有亏损Ce特征的磷酸盐等组分,理论上只需要氧化物类稀土与磷酸盐类稀土消耗的稀土与海水中的补给平衡即可.只是在相关过程中,海洋中氧化物类对稀土的选择更具有主动性,而磷酸盐类表现更多的继承关系.尽管Os同位素显示物源供给发生变化,然而富钴结壳PGE模式相对稳定.因此富钴结壳PGE模式同样可以用富钴结壳对PGE的选择性吸收解释,因富钴结壳优先选择Pt与Ir以及相对排斥Pd和Os,形成了现有独特的PGE模式. 相似文献
7.
ＲＥＥ是了解和研究地球表生过程的一个重要手段。通过ＲＥＥ的化学性质、物源和在表生水中的迁移和分配，综述了ＲＥＥ在表生过程水中的独特行为和再分配的全过程，同时利用表生水作用的代表产物——页岩，讨论了ＲＥＥ在水与古沉积物中的作用和指示意义。由于ＲＥＥ测试方法中存在的问题，指出了过去研究中可能错误的结论和当前重新评估ＲＥＥ在水和岩石圈演化中分配及其地质意义的重要性 相似文献
8.
贵州瓮安陡山沱组磷块岩稀土元素地球化学特征与沉积期后变化 总被引：4，自引：0，他引：4
贵州瓮安陡山沱组磷块岩保存了可能是全球最早的后生动物化石 (瓮安动物群 ),对于瓮安动物群出现过程中的古海洋环境重建具有重要科学意义。但必须对成岩后生作用对磷块岩中的稀土元素改造进行评估。通过对贵州瓮安陡山沱组磷块岩的磷质碎屑、磷质和白云质胶结物、磷条带和泥条带等的稀土元素地球化学特征研究,确定沉积期后变化对稀土元素的改造影响不大。上矿层磷块岩沉积期形成的磷质碎屑、成岩期形成的白云质和磷质胶结物具相同的稀土元素配分模式,暗示了沉积期后的改造作用对瓮安陡山沱组磷块岩保存的原生沉积信息影响不大。瓮安陡山沱组磷块岩具有显著的重稀土亏损特征。磷块岩的磷质和白云质胶结物、伴生磷质碎屑、强风化磷块岩相近的ErN/LuN 比值,表明沉积期后的改造作用不是重稀土元素亏损的主要原因。磷块岩的ErN/LuN、LaN/NdN 与Ce/Ce 间的相关性,表明越氧化的沉积环境中,轻和重稀土元素亏损越强。 相似文献
9.
The aquatic chemistry of rare earth elements in rivers and estuaries 总被引：17，自引：0，他引：17
Edward R. Sholkovitz 《Aquatic Geochemistry》1995,1(1):1-34
Laboratory experiments were carried out to determine how pH, colloids and salinity control the fractionation of rare earth elements (REEs) in river and estuarine waters. By using natural waters as the reaction media (river water from the Connecticut, Hudson and Mississippi Rivers) geochemical reactions can be studied in isolation from the large temporal and spatial variability inherent in river and estuarine chemistry. Experiments, field studies and chemical models form a consistent picture whereby REE fractionation is controlled by surface/solution reactions. The concentration and fractionation of REEs dissolved in river waters are highly pH dependent. Higher pH results in lower concentrations and more fractionated composition relative to the crustal abundance. With increasing pH the order of REE adsorption onto river particle surfaces is LREEs > MREEs > HREEs. With decreasing pH, REEs are released from surfaces in the same order. Within the dissolved (<0.22 µm) pool of river waters, Fe-organic colloids are major carriers of REEs. Filtration through filters and ultrafilters with progressively finer pore sizes results in filtrates which are lower in absolute concentrations and more fractionated. The order of fractionation with respect to shale, HREEs > MREEs > LREEs, is most pronounced in the solution pool, defined here as <5K and <50K ultrafiltrates. Colloidal particles have shale-like REE compositions and are highly LREE enriched relative to the REE composition of the dissolved and solution pools. The addition of sea water to river water causes the coagulation of colloidal REEs within the dissolved pool. Fractionation accompanies coagulation with the order of sea water-induced removal being LREEs > MREEs > HREEs. While the large scale removal of dissolved river REEs in estuaries is well established, the release of dissolved REEs off river particles is a less studied process. Laboratory experiments show that there is both release and fractionation of REEs when river particles are leached with seawater. The order of sea water-induced release of dissolved REE(III) (LREEs > MREEs > HREEs) from Connecticut River particles is the same as that associated with lowering the pH and the same as that associated with colloidal particles. River waters, stripped of their colloidal particles by coagulation in estuaries, have highly evolved REE composition. That is, the solution pool of REEs in river waters are strongly HREE-enriched and are fractionated to the same extent as that of Atlantic surface seawater. This strengthens the conclusions of previous studies that the evolved REE composition of sea water is coupled to chemical weathering on the continents and reactions in estuaries. Moreover, the release of dissolved Nd from river particles to sea water may help to reconcile the incompatibility between the long oceanic residence times of Nd (7100 yr) and the inter-ocean variations of the Nd isotopic composition of sea water. Using new data on dissolved and particle phases of the Amazon and Mississippi Rivers, a comparison of field and laboratory experiments highlights key features of REE fractionation in major river systems. The dissolved pool of both rivers is highly fractionated (HREE enriched) with respect to the REE composition of their suspended particles. In addition, the dissolved pool of the Mississippi River has a large negative Ce-anomaly suggesting in-situ oxidation of Ce(III). One intriguing feature is the well developed maximum in the middle REE sector of the shale normalized patterns for the dissolved pool of Amazon River water. This feature might reflect competition between surface adsorption and solution complexation with carbonate and phosphate anions. 相似文献
10.
菱铁矿很好地记录了过去地质流体的信息,能够用于示踪生物地球化学反应相关的成岩作用带。台湾国姓地区中新世海相泥页岩中发育自生的菱铁矿结核,其成因尚未厘清。野外观察发现菱铁矿以不连续透镜体平行散布于泥页岩中,主要由自生碳酸盐菱铁矿（78.63%）等矿物组成。菱铁矿的稀土元素配分模式为轻稀土亏损、中稀土富集,无Ce异常,指示菱铁矿形成于弱氧化的沉积环境,弱氧化的环境促进了菱铁矿在次氧化带的沉淀。菱铁矿的δ13CVPDB和δ18OVPDB值分别为-3.69‰~+0.08‰和-1.09‰~+0.25‰,指示菱铁矿形成于次氧化带,碳源很可能是海水和有机质降解混合产生。研究表明自生菱铁矿能够被用于识别沉积物中的生物地球化学过程和指示成岩作用带。 相似文献
11.
David Z. Piper 《Geochimica et cosmochimica acta》1974,38(7):1007-1022
The concentrations of rare-earth elements (REE) have been measured in 31 ferromanganese nodules from the Pacific and Indian Oceans and vary by almost a factor of 5. Too few nodules have been analyzed to define possible regional trends. The shale-normalized patterns, however, permit division of nodules into two groups: those from depth greater than 3000–3500 m and those from less depth. The factors that determine this change in the relative concentration of REE may be related to the mineralogy of manganese phases and/or the transport of REE to the deep ocean by particulate matter.Comparison of the REE patterns of nodules with those of phillipsite, phosphorite, clays, CaCO3 and seawater suggests that the patterns of these phases reflect fractionation from an initial pattern closely resembling that of shale. By assuming that the accumulation rate of REE in clays, CaCO3 and nodules is represented by that for surface sediments, it has been possible to estimate an accumulation rate of phillipsite in pelagic sediments of the Pacific of 0.02 mg/cm2/yr. 相似文献
12.
Sunit Kumar Addy 《Geochimica et cosmochimica acta》1979,43(7):1105-1115
The shale-normalized REE patterns of manganese nodules from the northwest Atlantic show enrichment in Sm and Eu relative to the heavier and lighter REE, excluding Ce, and are similar to the patterns previously observed in deep water (> 3000m) nodules from the Pacific. The inverse relation of this pattern to that of sea water and the high Ce anomaly (average 5.5) indicate that probably the REE in the nodules originate from sea water and the nodules are possibly hydrogenous. The patterns for micronodules are similar to those of the nodules but the concentrations of REE were substantially higher in two of them.The red clay occurring on abyssal hills where nodules and micronodules are found also shows higher REE concentrations over terrigenous gray clay. The latter is devoid of nodules and micronodules and occurs in abyssal plains. The excess REE in the red clay also show a pattern similar to those of the nodules and micronodules. Most of the micronodule samples show a lower Ce anomaly (1.7) and lower Co concentration compared to the nodules, so it is inferred that at least some micronodules were formed during post-depositional periods when the conditions were less oxidizing than average. 相似文献
13.
The behavior of rare earth elements (REE) and Th is studied along the west–east transect at 22°N across the Atlantic Ocean. It is shown that both REE and Th contents, relative to Al (the most lithogenic element), increase toward the pelagic region. The increasing trend becomes more complicated due to variations in the content of biogenic carbonate that serves as a diluting component in sediments. The REE composition varies symmetrically relative to the Mid-Atlantic Ridge (MAR) emphasizing a weak hydrothermal influence on sediments of the ridge axis, although the well-known criteria for hydrothermal contribution, such as Al/(Al + Mn + Fe) and (Fe + Mn)/Ti, do not reach critical values. Variations in the REE content and composition allowed us to distinguish the following five sediment zones in the transect: (I) terrigenous sediments of the Nares abyssal plain; (II) pelagic sediments of the North American Basin; (III) carbonate ooze of the MAR axis; (IV) pelagic sediments of the Canary Basin; and (V) terrigenous clay and calcareous mud of the African continental slope and slope base. Ferromanganese nodules of the hydrogenetic type with extremely high Ce (up to 1801 ppm) and Th (up to 138 ppm) contents occur in pelagic sediments. It is ascertained that P, REE, and Th concentrations depend on Fe content in Atlantic sediments. Therefore, one can suggest that only a minor amount of phosphorus is bound in bone debris. The low concentration of bone debris phosphorus is a result of relatively high sedimentation rates in the Atlantic, as compared with those in pelagic regions of the Pacific. 相似文献
14.
The sedimentation and ore formation were studied in sediments from nine stations located in the 24°W profile in the Brazil
Basin of the Atlantic Ocean. The sediments are represented by mio- and hemipelagic muds, which are variably enriched in hydrothermal
iron and manganese oxyhydroxides. As compared to the sediments from other basins of the Atlantic Ocean, these rocks are marked
by extremely high manganese contents (up to 1.33%) and maximal enrichment in Ce. It was shown that the positive Ce anomaly
is related to the REE accumulation on iron oxyhydroxides. Influence of hydrothermal source leads to the decrease of Ce anomaly
and LREE/HREE ratio. In the reduced sediments, preservation of positive Ce anomaly and/or its disappearance was observed after
iron and manganese reduction. The REE contents were determined for the first time in the Ethmodiscus oozes of the Brazil Basin. Ore deposits of the Brazil Basin are represented by ferromanganese crust and ferromanganese nodules.
Judging from the contents of iron, manganese, rare, and trace elements, these formations are ascribed to the sedimentation
(hydrogenic) deposits. They are characterized by a notable positive Ce anomaly in the REE pattern. The extremely high Ce content
(up to 96% of total REE) was discovered for the first time in the buried nodules (Mn/Fe = 0.88). 相似文献
15.
Ellen E. Martin Susanna W. Blair George D. Kamenov Howie D. Scher Elodie Bourbon Chandranath Basak Derrick N. Newkirk 《Chemical Geology》2010,269(3-4):414-431
Nd isotopes preserved in fossil fish teeth and ferromanganese crusts have become a common tool for tracking variations in water mass composition and circulation through time. Studies of Nd isotopes extracted from Pleistocene to Holocene bulk sediments using hydroxylamine hydrochloride (HH) solution yield high resolution records of Nd isotopes that can be interpreted in terms of deep water circulation, but concerns about diagenesis and potential contamination of the seawater signal limit application of this technique to geologically young samples.In this study we demonstrate that Nd extracted from the > 63 μm, decarbonated fraction of older Ocean Drilling Program (ODP) sediments using a 0.02 M HH solution produces Nd isotopic ratios that are within error of values from cleaned fossil fish teeth collected from the same samples, indicating that the HH-extractions are robust recorders of deep sea Nd isotopes. This excellent correlation was achieved for 94 paired fish teeth and HH-extraction samples ranging in age from the Miocene to Cretaceous, distributed throughout the north, tropical and south Atlantic, and composed of a range of lithologies including carbonate-rich oozes/chalks and black shales. The strong Nd signal recovered from Cretaceous anoxic black shale sequences is unlikely to be associated with ferromanganese oxide coatings, but may be derived from abundant phosphatic fish teeth and debris or organic matter in these samples.In contrast to the deep water Nd isotopic signal, Sr isotopes from HH-extractions are often offset from seawater values, suggesting that evaluation of Sr isotopes is a conservative test for the integrity of Nd isotopes in the HH fraction. However, rare earth elements (REE) from the HH-extractions and fish teeth produce distinctive middle REE bulge patterns that may prove useful for evaluating whether the Nd isotopic signal represents uncontaminated seawater. Alternatively, a few paired HH-extraction and cleaned fish teeth samples from each site of interest can be used to verify the seawater composition of the HH-extractions. The similarity between isotopic values for the HH-extraction and fish teeth illustrates that the extensive cleaning protocol applied to fish teeth samples is not necessary in typical, carbonate-rich, deep sea sediments. 相似文献
16.
Rare Earth Element Patterns in the Karst Terrains of Guizhou Province, China: Implication for Water/Particle Interaction 总被引：1，自引：0，他引：1
The authors determine the concentrations of dissolved (<0.22 μm) rare earth elements (REE) and suspended particulate matter
(SPM) of typical karst rivers in Guizhou Province, China during the high-flow period. The concentrations of acid-soluble REE
extracted from SPM using diluted hydrochloric acid are also obtained to investigate water/particle interaction in the river
water. The dissolved REE contents in the river water are extremely low in the rivers of the study. The dissolved REE distribution
patterns normalized by the Post Archean Australia Shale (PAAS) in the karst rivers are not flat, show slight enrichment of
heavy REE to light REE, and also have significant negative Ce and Eu anomalies. The acid-soluble REE appears to have similar
distribution patterns as characterized by MREE enrichment and slight LREE depletion, with unremarkable Ce and Eu anomalies.
The PAAS-normalized REE distribution patterns of SPM are flat with negative Eu anomalies. The contents and distribution patterns
of REE in the SPM are closely related to the lithological character of the source rocks. The SPM contains almost all the REE
produced in the process of surficial weathering. This demonstrates that particle-hosted REE are the most important form of
REE occurrence. REE fractionation, which takes place during weathering and transport, leads to an obvious HREE enrichment
in the dissolved loads relative to the SPM. Y/Ho ratio can be used to shed light on REE behaviors during water/particle interaction. 相似文献
17.
Six graywackes from the Archean greenstone belt in the Wind River of Wyoming and 11 graywackes and three shales from the Archean Fig Tree Group, South Africa, were analyzed for the rare earth elements (REE). There are real deviations beyond analytical uncertainty among sediments from the same formation. The absolute abundance of the REE (∑REE) is somewhat lower than that of the North American shale composite (NASC) which is representative of younger sedimentary rocks. Still, the results confirm previous suggestions that the RE pattern in Precambrian sediments is the same as the NASC but that, relative to the heavy REE, graywackes are slightly enriched in the light REE, shales are depleted, and there is a slight enrichment in Eu relative to the NASC. The average abundance of Eu relative to the other REE for all the Precambrian sediments is the same as that in chondritic meteorites. Attesting to the complexity of graywacke genesis, there is no correlation between the variations in the REE parameters and the variations in major or minor element concentrations. In particular, there is no obvious correlation between the excess Eu and Sr abundance. The total amount of REE, the ratio, and the Eu enrichment factor, however, all increase in the graywackes with the amount granite-gneiss detritus in the rocks. In general, the REE distributions in Archean graywackes and shales appear to be related to the relative amounts of clastic feldspar, mica, and minor phases which concentrate the REE. 相似文献
18.
藏南沙拉岗锑矿稀土和微量元素地球化学示踪及成矿物质来源 总被引：7，自引：1，他引：6
藏南沙拉岗锑矿赋存于下白垩统甲不拉组碳质板岩、泥质粉砂岩、硅质岩及燕山期辉绿岩和喜山期辉长岩中,受近东西向层间破碎带和近南北向构造破碎带控制。围岩蚀变较弱,围绕矿体呈对称性的面状、带状分布。稀土和微量元素测试结果表明碳质板岩和硅质岩具有与上地壳和太古宙后页岩非常相似的稀土配分模式。喜山期辉长岩以轻稀土相对亏损、重稀土相对富集和Eu轻度亏损的平坦型稀土配分模式有别于以轻稀土轻度富集、Eu无异常的稀土配分模式为特征的藏南燕山期辉绿岩。锑矿石具有轻稀土强烈富集、分馏程度高、Eu中度亏损、Ce强烈亏损的配分模式,与洋中脊黑烟囱-白烟囱中热液流体和喷流沉积物的Eu强正异常、海水的Ce中等负异常和重稀土富集的稀土配分模式及沃西Sedex型W-Sb-Au矿的稀土配分模式明显不同,但与喜山期辉长岩的稀土配分模式具有明显的互补关系。此外,锑矿石以其强Nb负异常及Ce和Ba正异常的微量元素特征,展示出与喜山期辉长岩的弱Nb负异常和强Rb正异常及碳质板岩-硅质岩的Nb、Ba负异常和轻度Ce、Rb、Th正异常的异同点,矿石δ34S除个别样品为10.3‰和-41.6‰外,均分布在-2.6‰~-4.1‰区间,反映成矿物质主要来源于岩浆的特点。前人测定的流体包裹体氢、氧同位素值分别为δD=-151‰~-166‰,δ18O=9.4‰~12.3‰,显示岩浆水和地下水的混合性质。因此沙拉岗锑矿是形成于中新世、与藏南拆离系有关的浅成低温热液型矿床,成矿物质主要来源于喜山期辉长岩岩浆,少量来源于围岩,成矿流体部分来源于岩浆期后热液,部分来源于地下水。 相似文献
19.
Rare earth element and yttrium (REE+Y) concentrations were determined in 49 Late Devonian reefal carbonates from the Lennard Shelf, Canning Basin, Western Australia. Shale-normalized (SN) REE+Y patterns of the Late Devonian samples display features consistent with the geochemistry of well-oxygenated, shallow seawater. A variety of different ancient limestone components, including microbialites, some skeletal carbonates (stromatoporoids), and cements, record seawater-like REE+Y signatures. Contamination associated with phosphate, Fe-oxides and shale was tested quantitatively, and can be discounted as the source of the REE+Y patterns. Co-occurring carbonate components that presumably precipitated from the same seawater have different relative REE concentrations, but consistent REE+Y patterns. Clean Devonian early marine cements (n = 3) display REE+Y signatures most like that of modern open ocean seawater and the highest Y/Ho ratios (e.g., 59) and greatest light REE (LREE) depletion (average NdSN/YbSN = 0.413, SD = 0.076). However, synsedimentary cements have the lowest REE concentrations (e.g., 405 ppb). Non-contaminated Devonian microbialite samples containing a mixture of the calcimicrobe Renalcis and micritic thrombolite aggregates in early marine cement (n = 11) have the highest relative REE concentrations of tested carbonates (average total REE = 11.3 ppm). Stromatoporoid skeletons, unlike modern corals, algae and molluscs, also contain well-developed, seawater-like REE patterns. Samples from an estuarine fringing reef have very different REE+Y patterns with LREE enrichment (NdSN/YbSN > 1), possibly reflecting inclusion of estuarine colloidal material that contained preferentially scavenged LREE from a nearby riverine input source. Hence, Devonian limestones provide a proxy for marine REE geochemistry and allow the differentiation of co-occurring water masses on the ancient Lennard Shelf. Although appropriate partition coefficients for quantification of Devonian seawater REE concentrations from out data are unknown, hypothetical Devonian Canning Basin seawater REE patterns were obtained with coefficients derived from modern natural proxies and experimental values. Resulting Devonian seawater patterns are slightly enriched in LREE compared to most modern seawaters and suggest higher overall REE concentrations, but are very similar to seawaters from regions with high terrigenous inputs. Our results suggest that most limestones should record important aspects of the REE geochemistry of the waters in which they precipitated, provided they are relatively free of terrigenous contamination and major diagenetic alteration from fluids with high, non-seawater-like REE contents. Hence, we expect that many other ancient limestones will serve as seawater REE proxies, and thereby provide information on paleoceanography, paleogeography and geochemical evolution of the oceans. 相似文献
20.
珠江三角洲地区上更新统与全新统之间广泛发育1层杂色黏土,其成因多认为主要是由上更新统沉积物在末次冰盛期暴露于地表风化而成。对取自珠江三角洲3条钻孔（PRD09、PRD16和PRD17）的岩心样品分析表明,受风化作用的影响,其稀土元素含量和分异特征发生了较明显的变化。杂色黏土层的稀土总量大大低于下伏沉积物,而在邻近风化层的下伏沉积物中稀土元素却表现为明显富集,尤其是重稀土元素的富集。风化作用强度较大的PRD09孔和PRD17孔下伏沉积物中的稀土富集程度高于风化作用强度相对较小的PRD16孔。珠江三角洲在末次冰盛期时普遍发育的酸性介质条件,促进了风化层的稀土元素发生溶解和迁移。在风化过程中,由于轻、重稀土元素具有不同的溶解迁移能力和吸附能力,导致杂色黏土层的REE指标值（LREE/HREE、(La/Gd)N和(La/Yb)N）高于下伏沉积物。风化过程对Ce、Eu异常有一定的影响,但不十分明显,杂色黏土层的Ce、Eu异常值仅略低于下伏沉积物。 相似文献