Do Archean chemical sediments record ancient seawater rare earth element patterns?

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.     

Geochemistry and Si–O–Fe isotope constraints on the origin of banded iron formations of the Yuanjiacun Formation,Lvliang Group,Shanxi, China

Banded iron formations (BIFs) within the Lvliang region of Shanxi Province, China, are hosted by sediments of the Yuanjiacun Formation, part of the Paleoproterozoic Lvliang Group. These BIFs are located in a zone where sedimentation changed from clastic to chemical deposition, indicating that these are Superior-type BIFs. Here, we present new major, trace, and rare earth element (REE) data, along with Fe, Si, and O isotope data for the BIFs in the Yuanjiacun within the Fe deposits at Yuanjiacun, Jianshan, and Hugushan. When compared with Post Archean Australian Shale (PAAS), these BIFs are dominated by iron oxides and quartz, contain low concentrations of Al₂O₃, TiO₂, trace elements, and the REE, and are light rare earth element (LREE) depleted and heavy rare earth element (HREE) enriched. The BIFs also display positive La, Y, and Eu anomalies, high Y/Ho ratios, and contain ³⁰Si depleted quartz, with high δ¹⁸O values that are similar to quartz within siliceous units formed during hydrothermal activity. These data indicate that the BIFs within the Yuanjiacun Formation were precipitated from submarine hydrothermal fluids, with only negligible detrital contribution. None of the BIF samples analyzed during this study have negative Ce anomalies, although a few have a positive Ce anomaly that may indicate that the BIFs within the Yuanjiacun Formation formed during the Great Oxidation Event (GOE) within a redox stratified ocean. The positive Ce anomalies associated with some of these BIFs are a consequence of oxidization and the formation of surficial manganese oxide that have preferentially adsorbed Ho, LREE, and Ce^4 +; these deposits formed during reductive dissolution at the oxidation–reduction transition zone or in deeper-level reducing seawater. The loss of Ce, LREE, and Ho to seawater and the deposition of these elements with iron hydroxides caused the positive Ce anomalies observed in some of the BIF samples, although the limited oxidizing ability of surface seawater at this time meant that Y/Ho and LREE/HREE ratios were not substantially modified, unlike similar situations within stratified ocean water during the Late Paleoproterozoic. Magnetite and hematite within the BIFs in the study area contain heavy Fe isotopes (⁵⁶Fe values of 0.24–1.27‰) resulting from the partial oxidation and precipitation of Fe^2 + to Fe^3 + in seawater. In addition, mass-independent fractionation of sulfur isotopes within pyrite indicates that these BIFs were deposited within an oxygen-deficient ocean associated with a similarly oxygen-deficient atmosphere, even though the BIFs within the Yuanjiacun Formation formed after initiation of the GOE.     

Continentally-derived solutes in shallow Archean seawater: Rare earth element and Nd isotope evidence in iron formation from the 2.9 Ga Pongola Supergroup, South Africa

The chemical composition of surface water in the photic zone of the Precambrian ocean is almost exclusively known from studies of stromatolitic carbonates, while banded iron formations (IFs) have provided information on the composition of deeper waters. Here we discuss the trace element and Nd isotope geochemistry of very shallow-water IF from the Pongola Supergroup, South Africa, to gain a better understanding of solute sources to Mesoarchean shallow coastal seawater. The Pongola Supergroup formed on the stable margin of the Kaapvaal craton ∼2.9 Ga ago and contains banded iron formations (IFs) that represent the oldest documented Superior-type iron formations. The IFs are near-shore, pure chemical sediments, and shale-normalized rare earth and yttrium distributions (REY_SN) exhibit positive La_SN, Gd_SN, and Y_SN anomalies, which are typical features of marine waters throughout the Archean and Proterozoic. The marine origin of these samples is further supported by super-chondritic Y/Ho ratios (average Y/Ho = 42). Relative to older Isua IFs (3.7 Ga) from Greenland, and younger Kuruman IFs (2.5 Ga) also from South Africa, the Pongola IFs are depleted in heavy rare earth elements (HREE), and appear to record variations in solute fluxes related to sea level rise and fall. Sm-Nd isotopes were used to identify potential sediment and solute sources within pongola shales and IFs. The ?_Nd(t) for Pongola shales ranges from −2.7 to −4.2, and ?_Nd(t) values for the coeval iron-formation samples (range −1.9 to −4.3) are generally indistinguishable from those of the shales, although two IF samples display ?_Nd(t) as low as −8.1 and −10.9. The similarity in Nd isotope signatures between the shale and iron-formation suggests that mantle-derived REY were not a significant Nd source within the Pongola depositional environment, though the presence of positive Eu anomalies in the IF samples indicates that high-T hydrothermal input did contribute to their REY signature. Isotopic mass balance calculations indicate that most (?72%) of the Nd in these seawater precipitates was derived from continental sources. If previous models of Fe-Nd distributions in Archean IFs are applied, then the Pongola IFs suggest that continental fluxes of Fe to Archean seawater were significantly greater than are generally considered.     

Stable isotope and Rare Earth Element evidence for recent ironstone pods within the Archean Barberton greenstone belt, South Africa

There is considerable debate about the mode and age of formation of large (up to ∼200 m long) hematite and goethite ironstone bodies within the 3.2 to 3.5 Ga Barberton greenstone belt. We examined oxygen and hydrogen isotopes and Rare Earth Element (REE) concentrations of goethite and hematite components of the ironstones to determine whether these deposits reflect formation from sea-floor vents in the Archean ocean or from recent surface and shallow subsurface spring systems. Goethite δ¹⁸O values range from −0.7 to +1.0‰ and δD from −125 to −146‰, which is consistent with formation from modern meteoric waters at 20 to 25 °C. Hematite δ¹⁸O values range from −0.7 to −2.0‰, which is consistent with formation at low to moderate temperatures (40-55 °C) from modern meteoric water. REE in the goethite and hematite are derived from the weathering of local sideritic ironstones, silicified ultramafic rocks, sideritic black cherts, and local felsic volcanic rocks, falling along a mixing line between the Eu/Eu* and shale-normalized HREE_Avg/LREE_Avg values for the associated silicified ultramafic rocks and felsic volcanic rocks. Contrasting positive Ce/Ce* of 1.3 to 3.5 in hematite and negative Ce/Ce* of 0.2 to 0.9 in goethite provides evidence of oxidative scavenging of Ce on hematite surfaces during mineral precipitation. These isotopic and REE data, taken together, suggest that hematite and goethite ironstone pods formed from relatively recent meteoric waters in shallow springs and/or subsurface warm springs.     

Rare earth elements (REE) and yttrium in stream waters, stream sediments, and Fe-Mn oxyhydroxides: Fractionation, speciation, and controls over REE + Y patterns in the surface environment

We have collected ∼500 stream waters and associated bed-load sediments over an ∼400 km² region of Eastern Canada and analyzed these samples for Fe, Mn, and the rare earth elements (REE + Y). In addition to analyzing the stream sediments by total digestion (multi-acid dissolution with metaborate fusion), we also leached the sediments with 0.25 M hydroxylamine hydrochloride (in 0.05 M HCl), to determine the REE + Y associated with amorphous Fe- and Mn-oxyhydroxide phases. We are thus able to partition the REE into “dissolved” (<0.45 μm), labile (hydroxylamine) and detrital sediment fractions to investigate REE fractionation, and in particular, with respect to the development of Ce and Eu anomalies in oxygenated surface environments. Surface waters are typically LREE depleted ([La/Sm]_NASC ranges from 0.16 to 5.84, average = 0.604, n = 410; where the REE are normalized to the North America Shale Composite), have strongly negative Ce anomalies ([Ce/Ce^∗]_NASC ranges from 0.02 to 1.25, average = 0.277, n = 354), and commonly have positive Eu anomalies ([Eu/Eu^∗]_NASC ranges from 0.295 to 1.77, average = 0.764, n = 84). In contrast, the total sediment have flatter REE + Y patterns relative to NASC ([La/Sm]_NASC ranges from 0.352 to 1.12, average = 0.778, n = 451) and are slightly middle REE enriched ([Gd/Yb]_NASC ranges from 0.55 to 3.75, average = 1.42). Most total sediments have negative Ce and Eu anomalies ([Ce/Ce^∗]_NASC ranges from 0.097 to 2.12, average = 0.799 and [Eu/Eu^∗]_NASC ranges from 0.39 to 1.43, average = 0.802). The partial extraction sediments are commonly less LREE depleted than the total sediments ([La/Sm]_NASC ranges from 0.24 to 3.31, average = 0.901, n = 4537), more MREE enriched ([Gd/Yb]_NASC ranges from 0.765 to 6.28, average = 1.97) and Ce and Eu anomalies (negative and positive) are more pronounced.The partial extraction recovered, on average ∼20% of the Fe in the total sediment, ∼80% of the Mn, and 21-29% of the REEs (Ce = 19% and Y = 32%). Comparison between REEs in water, partial extraction and total sediment analyses indicates that REEs + Y in the stream sediments have two primary sources, the host lithologies (i.e., mechanical dispersion) and hydromorphically transported (the labile fraction). Furthermore, Eu appears to be more mobile than the other REE, whereas Ce is preferentially removed from solution and accumulates in the stream sediments in a less labile form than the other REEs + Y. Despite poor statistical correlations between the REEs + Y and Mn in either the total sediment or partial extractions, based on apparent distribution coefficients and the pH of the stream waters, we suggest that either sediment organic matter and/or possibly δ-MnO₂/FeOOH are likely the predominant sinks for Ce, and to a lesser extent the other REE, in the stream sediments.     

冀东、五台和吕梁地区条带状铁矿的稀土元素特征及其地质意义

详细报道了冀东、五台和吕梁地区条带状铁矿全岩样品的稀土元素分析结果。结果表明,研究区BIF具有非常相似的特征：稀土总量均较低;经页岩标准化的稀土元素配分模式均呈现轻稀土亏损、重稀土富集的特征;Y/Ho比值较高;具有明显的Eu、Y、La的正异常,且这些特征表明研究区BIF的稀土元素来源于火山热液和海水的混合溶液。虽然BIF均显示Eu正异常,但不同类型、不同沉积年龄BIF的铕异常程度不同：与吕梁地区Superior型铁矿相比,冀东和五台地区的Algoma型铁矿显示了更大的Eu正异常;并且自中太古代-新太古代-古元古代,BIF的铕正异常逐渐减小,这可能反映了随着BIF沉积年龄的减小,进入到该地区海水中的高温热液流体逐渐减少;同时,研究区BIF缺乏明显的Ce负异常,可能暗示在BIF沉积时海水的氧化还原状态为缺氧环境。     

Extreme positive Ce-anomalies in a 3.0 Ga submarine volcanic sequence,Murchison Province: Oxygenated marine bottom waters

Systematic positive anomalies of Ce, where Ce/Ce* spans 2.1 to 11.4, are present in basalts and rhyolites of a 2.96 Ga submarine volcanic sequence of the Murchison Province, Western Australia. This volcanic sequence is host to a stratabound Cu–Zn deposit that formed on the seafloor from a seawater hydrothermal system. These are true Ce anomalies as Pr/Pr* < 1. In modern oxygenated marine water Ce is sequestered by Mn-oxides and hydroxides, which coprecipitate with Fe-oxides and hydroxides as nodules and crusts on the ocean floor, as well as Fe–Mn chemical sediments from hydrothermal systems at ocean spreading centers. Fe–Mn sediments have positive Ce anomalies and marine water complementary negative anomalies. Such Ce anomalies have not formerly been reported for Archean hydrothermally altered volcanic rocks. These extreme anomalies are attributed to Mn-transport in shallow-circulating oxygenated marine bottom waters peripheral to the deeper, hotter, hydrothermal system from which the Cu–Zn deposit formed, and record an oxygenated marine environment ~ 500 Ma before the so-called great oxidation event at ~ 2.4 Ga. Results for positive Ce anomalies in the Golden Grove volcanic sequence are complementary to negative anomalies in Archean BIF, collectively stemming from particulate scavenging of Ce^+ 3 in an oxic water column.     

Petrology and geochemistry of the banded iron-formations from Ntem complex greenstones belt,Elom area,Southern Cameroon: Implications for the origin and depositional environment

Banded iron-formations (BIFs) form an important part of the Archaean to Proterozoic greenstone belts in the Southern Cameroon. In this study, major, trace and REE chemistry of the banded iron-formation are utilized to explore the source of metals and to constraint the origin and depositional environment of these BIFs. The studied BIF belongs to the oxide facies iron formations composed mainly of iron oxide (mainly magnetite) mesobands alternating with quartz mesobands. The mineralogy of the BIF sample consists of magnetite and quartz with lesser amount of secondary martite, goethite and trace of gibbsite and smectite. The major element chemistry of these iron-formations is remarkably simple with the main constituents being SiO₂ and Fe₂O₃ which constitute 95.6–99.5% of the bulk rock. Low Al₂O₃, TiO₂, and HFSE concentrations show that they are relatively detritus-free chemical sediments. The Pearson’s correlation matrix of major element reveals that there is a strong positive correlation (r = 0.99) of Al with Ti and no to weak negative correlation of Ti with Mn, Ca and weak positive correlation of Si with Ca, suggesting the null to very minor contribution of detrital material to chemical sediment. The trace elements with minor enrichments are transition metals such as Zn, Cr, Sr, V and Pb. This is an indicator of direct volcanogenic hydrothermal input in chemical precipitates. The studied BIF have a low ΣREE content, ranging between 0.41 and 3.22 ppm with an average of 0.87 ppm, similar to that of pure chemical sediments. The shale-normalized patterns show depletion in light REE, slightly enrichment in heavy REE and exhibit weak positive europium anomalies. These geochemical characteristics indicate that the source of Fe and Si was the result of deep ocean hydrothermal activity admixed with sea water. The absence of a large positive Eu anomaly in the studied BIF indicates an important role of low-temperature hydrothermal solutions. The chondrite-normalized REE patterns are characterized by LREE-enriched (Mean La_CN/Yb_CN = 8.01) and HREE depletion (Mean Tb_CN/Yb_CN = 1.61) patterns and show positive Ce anomalies. With the exception of one sample (LBR133), all of the BIF samples analyzed during this study have positive Ce anomalies on both chondrite- and PASS-normalized plots. This may indicate that the BIFs within the Elom area were formed within a redox stratified ocean. The positive Ce anomalies in the studied samples likely suggest that the basin in which Fe formations were deposited was reducing with respect to Ce, probably in the suboxic or anoxic seawaters.     

Negative Ce Anomaly in the Indian Banded Iron Formations: Evidence for the Emergence of Oxygenated Deep-Sea at 2.9-2.7 Ga

Abstract: Major and rare earth element contents are reported for Late Archean banded iron formations (BIFs) in the Bababudan Group of the Dharwar Craton, South India. The BIFs are mostly composed of SiO₂ (average1ρ = 54.88.1 wt%) and Fe₂O₃* (44.38.2 wt%). The Al₂O₃ and TiO₂ contents are remarkably low, suggesting that detrital components were starved during the BIF deposition. The BIFs have a LREE-enriched pattern with a relatively high (La/Yb)_N (6.644.07). Total REE concentrations (RE) vary from 5.2 to 65.3 ppm. The REE patterns are characterized by the presence of a very large negative Ce anomaly (Ce/Ce*: 0.13-0.83) and a positive Eu anomaly (Eu/Eu*: 0.96-2.45). The Eu/Eu* decreases and (La/Yb)_N increases with a increase of RE. These correlations of REE indices are similar to those of modern hydrothermal iron-rich sediments near a mid-ocean ridge (MOR). Greenstones associated with the BIFs have MORB-like geochemical features. These geochemical and geological lines of evidence indicate that the depositional site of the BIFs was remote from a continent and/or island arc and that the BIFs were in situ hydrothermal sediments near a MOR. A striking negative Ce anomaly in the BIFs indicates that oxygenated deep-sea environments emerged at 2.9-2.7 Ga. The existence of contemporaneous Mn deposits in the Dharwar Craton supports this assertion. Our scenario of oxygen in the Earth's surface of the Late Archean is different from long-held notion that the atmosphere and ocean were persistently anoxic throughout the Archean.     

Changes of oceanic environment before and after the Paleoproterozoic Great Oxidation Event(GOE): Evidence from petrography and geochemistry of banded iron formation(BIF)from the North China Craton

Banded iron formation(BIF)belongs to sedimentary rocks formed in Precambrian marine,which can directly reflect the redox state of the ancient oceans. Mineral composition and geochemistry of BIF can reveal the relative changes of oxygen contents of ancient atmosphere-ocean. The Neoarchean and Paleoproterozoic BIFs widely distributed in the North China Craton(NCC),are the ideal research objects for understanding the changes of the ancient ocean redox environment before and after the Paleoproterozoic Great Oxidation Event(GOE). Our previous studies indicated that the sedimentary facies of the Neoarchean BIF in the NCC are mainly magnetite-type oxide and silicate,with minor carbonate. The sedimentary facies of the Paleoproterozoic BIF are hematite- and magnetite-type oxide,silicate and carbonate,of which the hematite-oxide facies is unique to the Paleoproterozoic BIF. The above mineralogical features suggest that the redox conditions of the Neoarchean and Paleoproterozoic seawater are different. The rare earth element composition of the Neoarchean BIF in the NCC lacks a strong negative Ce anomaly,reflecting that the oxygen content of contemporary seawater is very low and the marine is anoxic. However,a small amount of BIFs in the NCC also present the negative Ce anomalies and a wide range of Th/U ratios,indicating that the local water of the Neoarchean ocean had relatively high oxygen content and was at a weak oxidation state. Compared with the Neoarchean BIFs,the Paleoproterozoic BIFs present a wide range of Ce anomalies(i.e.,no Ce anomalies,positive Ce anomalies and negative Ce anomalies). The hematite-bearing BIF has an obvious negative Ce anomalies,implying that the oxygen content and redox state of Paleoproterozoic seawater changed significantly. Combined with the ratios of Ni/Co,V/(V+Ni)and Th/U of the BIFs in the NCC,the Paleoproterozoic oceans exhibited a suboxidation to oxidation environment. Besides,Neoarchean BIF is strongly enriched in heavy iron isotopes and the non-mass fractionation of S isotope is obvious,whereas the Paleoproterozoic BIF is relatively enriched in light iron isotopes and the non-mass fractionation of S isotope is not obvious. It is summarized that the Neoarchean marine is anoxic,but the oxygen‘oasis' may exist locally,implying that photosynthetic oxygen production already existed in the Late Neoarchean. The ancient ocean presented a layered characteristics during and after the GOE,indicating that the shallow water was generally oxidized and the deep water was reduced.     

古元古代大氧化事件(GOE)前后海洋环境的变化: 来自华北条带状铁建造(BIF)岩相学和地球化学的证据*

条带状铁建造(BIF)是形成于前寒武纪海洋中的化学沉积岩,记录了古海洋氧化还原状态的重要信息。华北克拉通广泛分布的新太古代和古元古代BIF,是了解古元古代大氧化事件(GOE)前后古海洋氧化还原环境变化的理想对象。初步研究表明,华北克拉通新太古代BIF主要为磁铁矿型氧化物相和硅酸盐相,极少数出现碳酸盐相;古元古代BIF包括赤铁矿型和磁铁矿型氧化物相、硅酸盐相和碳酸盐相,其中赤铁矿相是古元古代BIF独有的。以上矿物学特征表明,新太古代和古元古代水体的氧化还原条件是不同的。华北克拉通新太古代BIF的稀土元素组成缺乏强烈的负Ce异常,反映同期海水氧含量非常低,为缺氧状态; 但少量BIF也包含有负Ce异常,同时具有较大变化范围的Th/U值,指示新太古代海洋的局部水体氧含量相对较高,呈弱氧化状态。与新太古代BIF相比,古元古代BIF的Ce异常变化较大,包括无异常、正异常和负异常,尤其是赤铁矿相BIF具明显的负Ce异常,表明古元古代水体的氧含量和氧化还原结构已发生了明显变化; 结合华北克拉通BIF的Ni/Co、V/(V+Ni)和Th/U等比值特征,认为古元古代海洋呈次氧化—氧化环境。新太古代BIF 强烈富集重铁同位素,S同位素非质量分馏效应较为明显;而古元古代BIF相对富集轻铁同位素,S同位素非质量分馏效应不明显。综上,新太古代海洋环境整体缺氧,但局部可能存在氧气“绿洲”,暗示光合产氧作用在太古代晚期已经存在;大氧化事件期间及之后的古海洋总体具上部氧化、下部还原的分层特征。     

黑海西北部冷泉碳酸盐岩的沉积岩石学特征及氧化还原条件的稀土元素地球化学示踪

黑海西北部罗马尼亚大陆架(水深120m)和乌克兰陆坡(水深190m)发育冷泉碳酸盐岩结壳。XRD测试表明此结壳主要由高镁方解石和文石组成。结壳中与渗漏系统微生物活动有关的凝块和葡萄状文石等特殊的沉积组构非常发育。冷泉碳酸盐岩酸可溶部分(碳酸盐岩相矿物)的稀土元素含量很低(0.068×10-6~2.817×10-6),稀土元素页岩标准化配分模式显示罗马尼亚大陆架冷泉碳酸盐岩具有明显的Ce负异常,乌克兰陆坡冷泉碳酸盐岩具Ce的正异常,表明它们是分别在氧化和还原环境中沉积的。稀土元素和V、Cd和U等微量元素的含量在泥晶中最高,亮晶中最低,可能反映成岩过程对元素含量有控制作用。     

辽冀地区条带状铁建造地球化学特征：Ⅱ.稀土元素特征

辽冀地区(鞍山-本溪地区和冀东地区)位于华北克拉通北东部,是我国早前寒武纪条带状铁建造(BIFs)最重要的分布区,主要为新太古代Algoma型。本文系统对比了辽冀地区28个铁矿床200件铁矿石样品的稀土元素特征。结果表明:(1)所有样品的稀土元素特征比较相似:稀土元素总量较低,Y/Ho比值较高;经太古宙后平均澳大利亚页岩(PAAS)标准化后呈现重稀土相对富集、轻稀土相对亏损的配分模式,La异常不明显,强烈的Eu正异常和明显的Y正异常,暗示研究区铁矿石成矿物质主要来源于海底高温热液和海水的混合溶液;与冀东地区BIFs相比,鞍本地区Eu异常更为明显,说明鞍本地区BIFs显示更多的热液特征;(2)铁矿石的Ce/Ce*变化范围为0.77~1.09,缺乏明显的Ce负异常,说明其沉积于还原的海水环境;(3)辽冀地区BIFs的稀土元素总量、Eu异常、Y异常和Y/Ho比值变化范围均比较大,可能与BIFs沉积过程中碎屑物质的加入有关;与鞍本地区相比,冀东地区BIFs的Eu正异常、Y正异常程度均小于鞍本地区,热液和海水特征均不明显,Y/Ho比值更接近球粒陨石(26~28),可能暗示冀东地区有更多的碎屑物质的加入。     

Geochemistry and SHRIMP U‐Pb Zircon Dating of Mafic Rocks North of Zunhua City,Eastern Hebei,North China Craton: Paleoproterozoic Gabbro rather than Neoarchean Ophiolite

Abundant mafic-ultramafic blocks and dikes occur in the area north of Zunhua City, eastern Hebei Province, and were previously suggested to be part of a late Archean ophiolitic assemblage. We employed SHRIMP zircon dating and a geochemical study on these mafic and surrounding rocks to test the ophiolite hypothesis. The SHRIMP data suggest that three metagabbro samples were metamorphosed at ～1.8 Ga. Numerous ～2.5 Ga zircons display strong oscillatory zoning, characteristic of zircons from granitoid rocks but not from gabbro, so we suggest that these are xenocrystic grains. The age of these xenocrystic zircons and their metamorpbic rims suggests that these mafic blocks formed in Paleoproterozoic. The surrounding gneiss of intermediate composition also contains 2.5 Ga zircons with oscillatory zoning and 1.8 Ga metamorphic rims. Fractionated REE patterns and Nb, Ta, Zr, Hf negative anomalies to variable extent were observed in the mafic blocks and surrounding rocks, also supporting a significant difference in the chemistry of ophiolitic rocks. Our data suggest that many mafic blocks in northern Zunhua are not part of a late Archean ophiolite complex but part of a tectonically dismembered Paleoproterozoic intrusive gabbro complex. This study shows that late Paleoproterozoic metamorphism occurred in the western part of eastern Hebei Province.     

Rare earth element distribution in >400 °C hot hydrothermal fluids from 5°S, MAR: The role of anhydrite in controlling highly variable distribution patterns

Two submarine hydrothermal vent fields at 5°S, Mid-Atlantic Ridge (MAR) - Turtle Pits and Comfortless Cove - emanate vapor-phase fluids at conditions close to the critical point of seawater (407 °C, 298 bars). In this study, the concentration and distribution of rare earth element (REE) and yttrium (Y) has been investigated. Independent of the major element composition, the fluids display a strong temporal variability of their REE + Y concentrations and relative distributions at different time scales of minutes to years. Chondrite-normalized distributions range from common fluid patterns with light REE enrichment relative to the heavy REE, accompanied by positive Eu anomalies (type I), to strongly REE + Y enriched patterns with a concave-downward distribution with a maximum enrichment of Sm and weakly positive or even negative Eu anomalies (type II). The larger the sum of REE, the smaller Ce_CN/Yb_CN and Eu/Eu∗. We also observed a strong variability in fluid flow and changing fluid temperatures, correlating with the compositional variability.As evident by the positive correlation of total REE, Ca, and Sr concentrations in Turtle Pits and Comfortless Cove fluids, precipitation/dissolution of hydrothermal anhydrite controls the variability in REE concentrations and distributions in these fluids and the transformation of one fluid type to the other. The variable distribution of REE can be explained by the accumulation of particulate anhydrite (with concave-downward REE distribution and negative Eu anomaly) into a fluid with common REE distribution (type I), followed by the modification of the REE fluid signature due to dissolution of incorporated anhydrite. A second model, in which the type II fluids represent a primary REE reaction zone fluid pattern, which is variably modified by precipitation of anhydrite, can also explain the observed correlations of total REE, fractionation of LREE/HREE and size of Eu anomaly as well as Ca, Sr. The emanation of such a fluid may be favored in a young hydrothermal system in its high-activity phase with short migration paths and limited exchange with secondary minerals. However, this model is not as well constrained as the other and requires further investigations.The strongly variable REE fluid signature is restricted to the very hot, actively phase-separating hydrothermal systems Turtle Pits and Comfortless Cove at 5°S and has not been observed at the neighboring Red Lion vent field, which continuously emanates 350 °C hot fluid and displays a stable REE distribution (type I).     

General relations in the trace-element composition of zircons from eclogites with implications for the age of eclogites in the belomorian mobile belt

Analysis of currently available data (877 individual high-precision zircon analyses) on the composition of zircons from eclogite complexes worldwide reveals general relations in the zircon composition: an anomalous decrease in the Th concentration (no higher than 3 ppm on average) and the Th/U ratio (0.33 on average), a significant decrease in the concentrations of all REE (to 22 ppm) and particularly LREE (<2 ppm), and relatively low concentrations of Y (34 ppm), U (100 ppm), and P (41 ppm) at an elevated Hf concentration (11 400 ppm on average). The REE patterns of eclogitic zircons are noted for pronounced flat HREE patterns, poorly pronounced (if any) negative Eu anomalies, strongly reduced positive Ce anomalies (Ce/Ce* = 11 on average), and U-shaped configurations of LREE patterns up to the development of negative Nd anomalies. The relations detected in the distribution of trace elements and REE in eclogitic zircons are of universal nature and occur irrespective of the rock type (metabasites, metaultrabasites, or gneisses) and the metamorphic pressure (eclogites of high and ultrahigh pressure). The application of the aforementioned criteria makes it possible to reliable distinguish eclogitic zircons from those of magmatic or metamorphic genesis (not related to high-pressure metamorphism). Eclogites in the Belomorian Mobile Belt (in the Salma and Gridino areas) were determined to contain zircons in metagabbro eclogites; the cores of these zircons have an age of 2.8?C2.9 Ga and are of magmatic genesis, whereas their outer metamorphic zones have an age of 1.9 Ga and a trace-element composition typical of eclogitic zircons. Hence, the Belomorian Mobile Belt was affected only by single (Svecofennian, at ??1.9 Ga) episode of eclogite metamorphism of Archean rocks.     

辽宁弓长岭铁矿二矿区条带状铁建造地球化学特征及成因探讨

本文以弓长岭铁矿二矿区磁铁石英岩、磁铁富矿和蚀变围岩样品为研究对象,进行了主量元素、微量元素、稀土元素和Fe同位素的测试。结果表明:磁铁石英岩主要由TFe2O3和SiO2组成,Al2O3和TiO2质量分数较低,微量元素质量分数和稀土元素质量分数均较低;经澳大利亚后太古界平均页岩(PAAS)标准化的稀土配分模式呈现出轻稀土亏损和重稀土富集,La、Eu和Y的正异常明显,Ce的异常不明显,Y/Ho值较高;富集Fe的重同位素,且与海底喷发热液经过氧化沉淀后的Fe同位素特征一致。磁铁富矿与磁铁石英岩的地球化学特征有很好的一致性和继承性,但磁铁富矿的REE和Eu质量分数较高,且较磁铁石英岩富集Fe的轻同位素,范围更大,与蚀变岩的Fe同位素组成相近。弓长岭铁矿的磁铁石英岩是陆源物质加入很少的古海洋化学沉积岩,为喷出的海底热液与海水的混合条件下氧化沉淀形成的。磁铁富矿推测为富Fe的轻同位素热液对磁铁石英岩进行改造,经过去硅富铁作用形成的。     

≥3700 Ma pre-metamorphic dolomite formed by microbial mediation in the Isua supracrustal belt (W. Greenland): Simple evidence for early life?

Chemical (meta)sedimentary rocks in the amphibolite facies ≥3700 Ma Isua supracrustal belt (W. Greenland) are mostly strongly deformed, so there is only a small chance of the survival of features such as stromatolites or microfossils that would be direct proof of a ≥3700 Ma biosphere. Therefore the search for evidence of ≥3700 Ma life in Isua rocks has focused on chemical signatures, particularly C-isotopes. The new approach presented here is based on whole rock chemistry rather than isotopic signatures. Isua chemical sedimentary rocks have Ca–Mg–Fe bulk compositions that coincide with ferroan dolomite – siderite/Fe-oxide mixtures. Most have low Al₂O₃, TiO₂ contents (<0.5 and <0.05 wt% respectively) showing minimal contamination from terriginous materials. Identical seawater-like REE + Y shale-normalised trace element signatures with La, Ce, Eu and Y positive anomalies are found in magnetite-rich banded iron formation (BIF – such as the geochemical standard IF-G), dolomite-rich rocks and quartz–carbonate–calc-silicate rocks. Additionally from a rare, small area of low deformation in Isua, there are ∼3700 Ma pillow lava interstices consisting of quartz + tremolite + calcite derived from pre-metamorphic dolomite + silica. Thus the dolomite in the chemical sediments and the pillow interstice was part of the pre-metamorphic assemblage, and was deposited from seawater and/or low-temperature groundwater (as shown by the REE + Y chemistry). Therefore, at least some Isua carbonate rocks are sedimentary or diagenetic in origin rather than being formed by metasomatism at 600–500 °C as proposed by Rose et al. (1996. American Journal of Science 296, 1004–1044).     

碳酸盐(岩)的稀土元素特征及其古环境指示意义

稀土元素主要通过交代碳酸盐矿物的Ca^{2+0进入碳酸盐格架,所以沉积碳酸盐(岩}的稀土元素特征能够很好的指示沉积流体来源和古环境。常用的稀土元素指标包括稀土元素总量(ΣREE)、稀土元素配分型式、以及La、Ce、Eu、Gd和Y等元素的异常指数。碳酸盐(岩)的稀土元素含量可能受到硅酸盐矿物、Fe-Mn氧化物/氢氧化物和磷酸盐等非碳酸盐组分以及成岩蚀变作用的影响。因此,在分析过程中,我们只有排除这些影响因素,才能用碳酸盐(岩)的稀土元素指标来探讨流体来源和古环境。这要求我们采集新鲜剖面上的样品,并用适当浓度的弱酸进行分步溶样,提取适当的组分,避免样品中的非碳酸盐组分干扰原始沉积组分的稀土元素特征。不同的沉积水体和沉积相下形成的碳酸盐(岩)具有不同的稀土元素特征:从太古宙到全新世的海相碳酸盐(岩)记录了LREE亏损、La正异常和高Y/Ho值的稀土元素特征;海底孔隙水的稀土元素特征则受氧化-还原条件、离子络合形式、孔隙流体来源的制约;热液流体具有LREE富集、Eu正异常的稀土元素特征;河水和湖泊有相对平坦的稀土元素特征。因此,碳酸盐(岩)的稀土元素特征具有重要的古环境指示意义。     

辽宁弓长岭铁矿床磁铁矿稀土元素特征及其地质意义

辽宁弓长岭铁矿床是我国著名的沉积变质型铁矿床,其二矿区的磁铁富矿达大型规模,属国内之最.为探讨弓长岭铁矿床铁矿的物质来源、形成环境和富矿成因,本文以二矿区六个铁矿体的贫铁矿石和富铁矿石中磁铁矿单矿物为研究对象,利用电感耦合等离子体质谱进行了系统的稀土元素测试.结果表明,所有样品中磁铁矿的稀土元素总量(∑REEs)和Y具有非常一致的特征:稀土元素总量较低,Y/Ho比值较高;经太古界后平均澳大利亚页岩( PAAS)标准化呈现重稀土相对富集、轻稀土相对亏损的分馏模式,大部分呈现La正异常,所有样品都有明显的Eu和Y正异常,这些特征表明研究区的磁铁矿成矿物质主要来源于海底高温热液和海水;虽然磁铁矿的Ce/Ce*为0.69～ 0.97,但大多数样品缺乏真正意义的Ce负异常,这暗示其沉积于还原的海水环境;富铁矿石磁铁矿的稀土元素总量和Eu含量明显高于贫铁矿石的磁铁矿,而且含富矿的上含铁带Eu异常明显较高,表明富铁矿石磁铁矿具有更明显的热液特征,是在贫铁矿石的基础上受热液活动形成的.