Light Rare Earth Element Depletion Research Articles

Unravelling the processes controlling apatite formation in the Phalaborwa Complex (South Africa) based on combined cathodoluminescence, LA-ICPMS and in-situ O and Sr isotope analyses

The Phalaborwa world-class phosphate deposit (South Africa) is hosted by a Paleoproterozoic alkaline complex mainly composed of phoscorite, carbonatite, pyroxenitic rocks, and subordinate fenite. In addition, syenite and trachyte occur in numerous satellite bodies. New petrological and in-situ geochemical data along with O and Sr isotope data obtained on apatite demonstrate that apatite is in the principal host rocks (pyroxenitic rocks, phoscorite and carbonatite) formed primarily by igneous processes from mantle-derived carbonatitic magmas. Early-formed magmatic apatite is particularly enriched in light rare earth elements (LREE), with a decrease in the REE content ascribed to magma differentiation and early apatite fractionation in isolated interstitial melt pockets. Rayleigh fractionation favored a slight increase in δ18O (below 1%) at a constant Sr isotopic composition. Intrusion of fresh carbonatitic magma into earlier-formed carbonatite bodies locally induced re-equilibration of early apatite with REE enrichment but at constant O and Sr isotopic compositions. In fenite, syenite and trachyte, apatite displays alteration textures and LREE depletion, reflecting interaction with fluids. A marked decrease in δ18O in apatite from syenite and trachyte indicates a contribution from δ18O-depleted meteoric fluids. This is consistent with the epizonal emplacement of the satellite bodies. The general increase of the Sr isotope ratios in apatite in these rocks reflects progressive interaction with the country rocks over time. This study made it possible to decipher, with unmatched precision, the succession of geological processes that led to one of the most important phosphate deposits worldwide.

Zircon geochemistry of Edong granitoids in the Middle-Lower Yangtze Metallogenic Belt (Eastern China): Constraints on W-Cu-Fe skarn mineralization

It has long been established that skarn deposits of different metals are associated with intrusions of different compositions. Intermediate-felsic granitoids in the Edong district of the Middle-Lower Yangtze Metallogenic Belt host skarn deposits with varying W-Cu-Fe proportions, yet previous whole-rock geochemical studies could not distinguish between the magmatic suites that formed the different skarn deposits. In this study, LA-ICP-MS zircon geochemical data are presented for the Ruanjiawan W skarn (60300 t WO3), Tongshankou Cu skarn (0.6 Mt Cu), Tonglushan Cu-Fe skarn (1.1 Mt Cu and 56.8 Mt Fe) and Jinshandian Fe skarn (200 Mt Fe) deposits in the Edong district. Zircons from the ore-forming intrusions of these skarn deposits are all characterized by heavy rare earth element (HREE) enrichments and light rare earth element (LREE) depletions, with positive Ce anomalies and slightly negative Eu anomalies. Tungsten contents in zircons from the W ore-forming intrusion (0.02–3.16 ppm W; avg. 1.14 ppm) are generally higher than in zircons from the Cu ore-forming intrusion (0.00–0.24 ppm W; avg. 0.03 ppm). Copper content in zircons from the Cu ore-forming intrusion is higher than in those from the W ore-forming intrusion. Fertile intrusive rocks from the four skarn deposits contain zircons with high calculated Ce4+/Ce3+ ratios (Ruanjiawan: 71.7; Tongshankou: 207.5; Tonglushan: 263.6; Jinshandian: 189.0. Fluorine content of the Ruanjiawan intrusion is higher than the Tonglushan and Jinshandian intrusions, followed by the Tongshankou intrusion. Chlorine contents show the opposite trend. We propose that the different source regions for the ore-fertile intrusions is the critical factor that controls the metal content, oxygen fugacity and volatile components. Our studies suggest that zircon geochemistry is a good indicator to distinguish tungsten causative intrusions from copper- and iron ore related intrusions (i.e. W content ≧ 1.14 ppm and Ce4+/Ce3+ ratios ≦ 207.5).

Petrology and geochemistry of mafic and ultramafic cumulate rocks from the eastern part of the Sabzevar ophiolite (NE Iran): Implications for their petrogenesis and tectonic setting

The Late Cretaceous Sabzevar ophiolite represents one of the largest and most complete fragments of Tethyan oceanic lithosphere in the NE Iran. It is mainly composed of serpentinized mantle peridotites slices; nonetheless, minor tectonic slices of all crustal sequence constituents are observed in this ophiolite. The crustal sequence contains a well-developed ultramafic and mafic cumulates section, comprising plagioclase-bearing wehrlite, olivine clinopyroxenite, olivine gabbronorite, gabbronorite, amphibole gabbronorite and quartz gabbronorite with adcumulate, mesocumulate, heteradcumulate and orthocumulate textures. The crystallization order for these rocks is olivine ​± ​chromian spinel → clinopyroxene → plagioclase → orthopyroxene → amphibole. The presence of primary magmatic amphiboles in the cumulate rocks shows that the parent magma evolved under hydrous conditions. Geochemically, the studied rock units are characterized by low TiO2 (0.18–0.57 ​wt.%), P2O5 (<0.05 ​wt.%), K2O (0.01–0.51 ​wt.%) and total alkali contents (0.12–3.04 ​wt.%). They indicate fractionated trends in the chondrite-normalized rare earth element (REE) plots and multi-element diagrams (spider diagrams). The general trend of the spider diagrams exhibit slight enrichment in large ion lithophile elements (LILEs) relative to high field strength elements (HFSEs) and positive anomalies in Sr, Pb and Eu and negative anomalies in Zr and Nb relative to the adjacent elements. The REE plots of these rocks display increasing trend from La to Sm, positive Eu anomaly (Eu/Eu∗ ​= ​1.06–1.54) and an almost flat pattern from medium REE (MREE) to heavy REE (HREE) region [(Gd/Yb)N ​= ​1–1.17]. Moreover, clinopyroxenes from the cumulate rocks have low REE contents and show marked depletion in light REE (LREE) compared to MREE and HREE [(La/Sm)N ​= ​0.10–0.27 and (La/Yb)N ​= ​0.08–0.22]. The composition of calculated melts in equilibrium with the clinopyroxenes from less evolved cumulate samples are closely similar to island arc tholeiitic (IAT) magmas. Modal mineralogy, geochemical features and REE modeling indicate that Sabzevar cumulate rocks were formed by crystal accumulation from a hydrous depleted basaltic melt with IAT affinity. This melt has been produced by moderate to high degree (~15%) of partial melting a depleted mantle source, which partially underwent metasomatic enrichment from subducted slab components in an intra-oceanic arc setting.

Sulphur-rich mantle metasomatism of Kaapvaal craton eclogites and its role in redox-controlled platinum group element mobility

Eclogite mantle xenoliths from various kimberlite occurrences on the Kaapvaal craton show evidence for depth- and redox-dependent metasomatic events that led to variable base metal sulphide and incompatible element enrichments. Eclogite xenoliths from the Roberts Victor, Jagersfontein, Kimberley (Kamfersdam) and Premier kimberlites were investigated for their silicate and base metal sulphide geochemistry, stable oxygen isotope compositions and oxybarometry. The variably metasomatised eclogites had basaltic, picritic and gabbroic protolith compositions and have garnet δ18O values that range from +3.3 to +7.9‰, which, when coupled with the trace element characteristics, indicate oceanic lithosphere protoliths that had undergone variable degrees of seawater alteration. The deepest equilibrated eclogites (175–220 km depth) from near the base of the Kaapvaal craton lithosphere are the most refractory and feature significant light rare earth element (LREE) depletions. They show the most oxidised redox compositions with ∆logƒO2 values of FMQ-3.9 to FMQ-1.5. Subtle metasomatic overprinting of these eclogites resulted in base metal sulphide formation with relatively depleted and highly fractionated HSE compositions. These deepest eclogites and their included base metal sulphides suggest interaction with relatively oxidised melts or fluids, which, based on their HSE characteristics, could be related to precursor kimberlite metasomatism that was widespread within the Kaapvaal craton mantle lithosphere. In contrast, eclogites that reside at shallower, “mid-lithospheric” depths (140–180 km) have been enriched in LREE and secondary diopside/phlogopite. Importantly, they host abundant metasomatic base metal sulphides, which have higher HSE contents than those in the deeper eclogites at the lithosphere base. The mid-lithospheric eclogites have more reducing redox compositions (∆logfO2 = FMQ-5.3 − FMQ-3.3) than the eclogites from the lowermost Kaapvaal lithosphere. The compositional overprint of the shallower mantle eclogites resembles basaltic rather than kimberlitic/carbonatitic metasomatism, which is also supported by their relatively reducing redox state. Base metal sulphides from the mid-lithospheric eclogites have HSE abundances and distributions that are similar to Karoo flood basalts from southern Africa, suggesting a link between the identified shallow mantle metasomatism of the Kaapvaal cratonic lithosphere and the Karoo large igneous event during the Mesozoic. The sulphide-hosted platinum group element abundances of the mid-lithospheric eclogites are higher compared with their analogues from the deeper lithospheric eclogites, which in combination with their contrasting oxidation states, may imply redox-controlled HSE mobility during sulphur-rich metasomatism of continental mantle lithosphere.

Genetic Characterisation of Ironstone Deposits from the Agbaja Formation Southern Bida Basin Central Nigeria: Evidence From Rare Earth Elements

The oolithic and pisolithic Agbaja ironstone deposit of the Campano- Maastrichtian southern Bida Basin around Lokoja districts is one of the most studied ironstone formations within the Nigerian Inland basins where controversies still surrounds the origin of the ironstone deposits. Though analyses of Rare Earth Element (REE+Y) distributions in chemical sedimentary rocks has been proved to offer an opportunity to gain new insights into likely ancient palaeo-environmental conditions based on the distinct differences in the rare earth element geochemistry between different types of water and their respective precipitates, but this has not been properly utilized in unraveling the mystery surrounding the origin of this deposit. The present study therefore, is an attempt to provide clues to further understand the genetic characterization of these ores from geochemical data based on the rare earth elements. Geological field mapping was carried out in the study area and representative samples from different rock exposures and outcrops were collected. Seventeen (17) representative samples of the various rock types collected from the field were selected for geochemical analysis. The results reveal a total REE contents of the oolithic and pisolithic ironstone samples range from 189.2 to 471.3ppm with an average of 332.56ppm, with all of the samples having positive Gd anomalies and characterized by the unique absence of Ce anomaly (Ce/Ce*=0.95–1.01), a slight positive Eu anomaly (Eu/Eu*=0.99–1.12) with slight enrichment in Light Rare Earth Element (LREEs) and depletion in Heavy Rare Earth Element HREEs except in sample BH1 which shows gradual increase from LREE to HREE (La-Lu). Absence of negative Ce anomaly and the slight positive Ce anomaly in the oolithic and pisolithic ironstone samples is attributed to enrichment of Ce relative to other REE3+ through mobilization of Ce as Ce3+ under reducing condition during early diagenesis and re-precipitation at the oxidized front while the LREE may be attributed to contribution of enriched particulate during chemical precipitation and recrystallization of iron and during kaolinitization. Also, the absence of Ce fractionation suggests that detrital sedimentation dominates over a hydrothermal contribution. Similarity, the positive Eu anomaly suggests that the samples are sourced from continental source. The absence of significant correlations or weak correlations between the Ce/Ce* and REE, and between Ce/Ce* and Eu/Eu*, suggests a slight effect of diagenetic processes on the REE concentrations. The lower Y/Ho ratios rules out marine input and points towards the influence of terrigenous materials. Thus, the combinations of LREE depletion along with low Y/Ho ratios below those of seawater suggest records of continental signatures which are significantly masked by detrital components. With all the above inferences, Fe oxides and oxyhydroxides and phosphates minerals which have a high affinity for REE in diagenetic fluid along with kaolinite are the possible sources of the REE contamination. Thus, the change in REE abundance results from changes in various diagenetic or progressive alterations of REE contents with increasing geological time, scavenging of REE on iron oxides and oxyhroxides and affinity of the REE to Kaolinite. It also reflects the existence of REE-rich minerals such as monazite and apatite. Thus, the above evidence from the REE studies have refuted marine or hydrothermal sources for these deposits and points towards detrital sources from fluvial input into the basin as material for the formation of the precursor for the ironstone.

Integrated major and trace element study of clinopyroxene in basic, intermediate and acidic volcanic rocks from the middle Okinawa Trough: Insights into petrogenesis and the influence of subduction component

Magmatism is very common in the Okinawa Trough. However, the influence of magmatic processes, including fractional crystallization and magma mixing, on the petrogenesis of volcanic rocks is poorly understood. The in situ major and trace element compositions of clinopyroxene in co-genetic basalts, andesites, trachyandesites and rhyolites from the Iheya Ridge in the middle Okinawa Trough are examined to determine their petrogenesis and the influence of slab subduction. Regarding the types of mineral zoning, in basalt and andesite, clinopyroxene phenocrysts are unzoned. In trachyandesite, the clinopyroxene phenocrysts can be classified into three groups: normal zoned, oscillatory zoned and unzoned. Similarly, unzoned and reverse zoned clinopyroxene phenocrysts are the two main structures in rhyolites. According to the major element contents and distinct distribution patterns of rare earth elements (REEs), we identify various clinopyroxene domains in their host volcanic rocks. Type 1 clinopyroxene domains in basalts and trachyandesites are dark, have high Mg# values and are strongly depleted in light REEs (LREEs) with no significant Eu anomalies. The Type 2 clinopyroxene domains in basalts and trachyandesites and all clinopyroxene phenocrysts in andesites are bright, have low Mg# values and are strongly depleted in LREEs and have significant negative Eu anomalies. Clinopyroxene domains in rhyolites have significant negative Eu anomalies and can be divided into two types: Type 1 clinopyroxene domains are characterized by strong depletion in LREEs, Sr, P and high field strength elements (HFSEs), while Type 2 clinopyroxene domains are slightly depleted in LREEs and have small negative P anomalies. The continuously changing major element composition and parallel distribution of trace element spider diagrams suggest that all these clinopyroxene phenocrysts in the studied volcanic rocks were derived from co-genetic magmas and the compositional transition of clinopyroxene from basalts to rhyolites attributed to different extents of fractional crystallization of various minerals (e.g., clinopyroxene, orthopyroxene, plagioclase and apatite). The oscillatory zoned and reversed zoned clinopyroxene phenocrysts show that magma mixing and recharge events with co-genetic magmas are common in the middle Okinawa Trough magma system. The origin of clinopyroxene phenocrysts involves contributions from subducted sedimentary components of 2.5% sediment melts and 1.5% sediment fluids and is deduced based on the equilibrium melts of clinopyroxene phenocrysts in basalts. The geochemical study of clinopyroxene provides evidence for the contributions of magmatic processes and slab subduction to the petrogenesis of Okinawa Trough volcanic rocks.

Formation of the Vergenoeg F–Fe–REE Deposit (South Africa) by Accumulation from a Ferroan Silicic Magma

AbstractSituated in the centre of the Paleoproterozoic Bushveld Large Igneous Province (LIP) of South Africa the Vergenoeg F–Fe–REE deposit is one of the largest, but at the same time most unusual, fluorite deposits on Earth. In situ major and trace element analyses of fayalite, magnetite, ilmenite, fluorapatite, fluorite and allanite from fayalite-rich rocks are combined with oxygen isotope data for fayalite, magnetite and ilmenite to unravel the complex evolution of the deposit. Textural and compositional characterization of the fayalite-rich rocks supports a magmatic formation as cumulates and an intense late hydrothermal overprint. Fayalite accumulated together with minor Ti-rich magnetite, ilmenite, fluorapatite and allanite from a highly evolved, H2O-poor felsic melt at low oxygen fugacity. Chondrite-normalized rare earth element (REE) patterns of fayalite and the recalculated parental melts, using fayalite–rhyolite partition coefficients, exhibit positive trends with strong enrichment of the heavy REE (HREE) relative to the light REE (LREE). Apart from the LREE depletion the patterns are similar to those of highly fractionated high-silica REE rhyolites that often occur in siliceous LIPs. We attribute the LREE depletion to crystallization of accessory allanite, the main host of the LREE in the cumulates. Chondrite-normalized REE patterns of the parental melt prior to fayalite accumulation, recalculated using allanite–rhyolite partition coefficients, resemble the composition of the rhyolites of the Rooiberg Group and therefore document a petrogenetic link to the Bushveld LIP. High δ18O values of fayalite (up to ≈7·4 ‰) are consistent with its crystallization in a rhyolitic melt that has formed by extensive fractionation from basic melts of the Rustenburg Layer Suite, the mafic member of the Bushveld LIP. Primary fluorite crystallized together with rare quartz, and a second generation of fayalite, magnetite and ilmenite from rare intercumulus melt in interstices between cumulate fayalite. Textural and mineral compositional data, as well as the generally negative δ18O values of magnetite (–2·9 to 0 ‰), are in agreement with the main magnetite–fluorite ore formation in Vergenoeg being related to a hydrothermal overprint, which was responsible for further F and Fe enrichments of the rocks. Fluorine-rich fluids, released from the crystallizing granites of the felsic member of the Bushveld LIP (Lebowa Granite Suite), caused the extensive alteration of fayalite to bowlingite and its replacement by Ti-poor magnetite and quartz. The hydrothermal overprint was associated with the widespread formation of secondary fluorite and minor fluorapatite. Our new petrogenetic model for the Vergenoeg deposit, as constrained from the primary fayalite cumulates, implies that the formation of the Vergenoeg deposit was directly linked to the evolution of the Bushveld LIP.

Geochemistry of mafic volcanics in the Bayingou ophiolitic mélange, Western Tianshan, NW China: Implications for magma genesis and tectonic setting

This paper reports on the occurrence of mid-ocean-ridge basalts (MORB), boninites, and mafic volcanics with affinities to ocean island basalts (OIB) in the Bayingou Palaeozoic ophiolites, Western Tianshan, NW China, which is one of the best preserved ophiolitic sequences, and are the youngest ophiolites reported in the Western Tianshan during the Late Palaeozoic. The MORB samples have comparatively low TiO2 concentrations (0.84–1.20 wt%) and total rare earth element (REE) contents (25.30–55.97 ppm). The ISr values and εNd(t) values of MORBs range from 0.70480 to 0.70540 and + 3.58 to +6.90, respectively. The boninite sample has high SiO2 (53.79 wt%), very low TiO2 (0.22 wt%), high MgO (14.71 wt%), and a Mg# (100 × Mg2+/(Mg2++Fe2+)) value of 75. The boninite sample also has higher Cr (983 ppm) and Ni (230 ppm) contents and lower high field strength element content (e.g. Zr, Y, V, and heavy REEs) in comparison to the MORBs. The light REE (LREE) content of the boninite is slightly enriched, whereas most MORB samples display a depletion of LREEs ((La/Yb)N = 0.63–0.86), thus indicating that there are normal-type MORBs in this area. The OIB samples are characterized by a high concentration of TiO2 (1.89–3.15 wt%) and total REE content (100.68–151.07 ppm) with enriched LREEs ((La/Yb)N = 5.62–6.80). The ISr values and εNd(t) values of OIBs range from 0.70520 to 0.70541 and − 0.24 to +2.21, respectively. The whole rock Sr, Nd, and Pb isotopic compositions of OIB samples are plotted in the field between enriched mantle II (EMII) and PREMA. Such geochemical variation implies two mantle sources at the spreading zone: possibly, one source from the MORB and several sources from EMII-type mantle (mantle plum) in combination with characteristics of trace elements (Zr, Hf, Nb, Ta, Pb, and Ce).Petrogenetic modelling suggests that MORB may have derived from partial melting (ca. 10–20%) of a mantle peridotite that had previously experienced MORB extraction. For boninites, petrogenetic modelling suggests that these rocks are a product of about 20% partial melting of a source that previously experienced about 12% melt extraction from the source that formed the normal-type MORB. A hot plume may have been the thermal factor influencing the generation of the boninites. Volcanic rocks with OIB affinities in the Bayingou ophiolites are generated by 4.4–5.4% partial melting of the deeper mantle (EMII) and has a garnet lherzolite composition. The source of OIBs is affected by contamination of ancient oceanic lithosphere and terrigenous sediments, and is the same as other OIBs that occur in Palaeozoic ophiolites in Western Tianshan, indicating that these ophiolites may have formed in the same subduction event during the Palaeozoic. Our findings indicate that basaltic rocks in the Bayingou ophiolites formed in the supra-subduction zone (SSZ) environment in response to the subduction of Southern Tianshan Ocean during the late Early Carboniferous. The northward subduction of Southern Tianshan Ocean occurred until at least the late Early Carboniferous. In addition, the Northern Tianshan Ocean developed into a relatively mature ocean basin at the same time as the occurrence of MORB in the Bayingou ophiolites.

Geochemical and 13C trends in sedimentary deposits of coastal Pondicherry region, East coast of India – Insights from a borehole study

Major, trace, rare earth elements and 13C isotope results of sediments collected up to the depth of 150 m below ground level (m bgl) have been interpreted in relation to the provenance, weathering and deposition conditions of a multi layered sedimentary formation of Pondicherry region located in East Coast of India. The samples fall in the coarse to medium grain size range (mean Mz: 0.29–1.32) and the sorting values (mean SD: 0.29–1.04) mostly infer very well sorted nature of sediments. Skewness (mean Ski: 0.09-0.99) shows the domination of very fine skew while the kurtosis (mean KG: 0.76–7.73) shows sediments from extremely lepto kurtic to platy kurtic nature. Micro-structural studies infer that sediments are derived from multiple sources and transported towards the littoral zone through the fluvial processes. Relatively depleted elemental concentrations with respect to upper continental crust (UCC) (elemental ratios < 1) are noticed in most of the sediments suggesting contribution of the weathered source rocks. Chondrite normalized distributions of the selected rare earth elements show uniform trends characterized by light rare earth element enrichment and heavy rare earth element depletion, which is a typical pattern of UCC exposed to weathering and erosion. Elemental ratios such as La/Sc (2.06–6.64), Th/Sc (0.66–4.13), Th/Cr (0.06-0.26) and Th/Co (0.46–1.54) and ternary plots (La-Th-Sc, Th-Hf-Co) indicate the contribution of felsic rocks that are inherently heterogeneous in nature. Observed positive Eu anomaly in Post Archean Australian Shale (PAAS) normalized patterns indicates contribution of plagioclase minerals. Th/U ratio (2.12–9.57) of the sediments reflects deposition under oxic condition (shallow marine) whereas deeper sediments reveal anoxic condition (deep marine), which is further confirmed by δ13CTIC variations (−11.4 to +5.12‰ vs. VPDB) and Eu analmoly. Cr/Th ratio and total REE content indicate that there is no/negligible input of volcanic ash to these sediments.

In-site mineral geochemistry and whole-rock Fe isotopes of the quartz-magnetite-pyroxene rocks in the Wuyang area, North China Craton: Constraints on the genesis of the pyroxene-rich BIF

Quartz-magnetite-pyroxene (QMP) rocks with high Fe contents are of greatly economic and petrological importance and generally occur within the oldest and largest exposures of supracrustal rocks preserved on Earth. However, the chemical composition and genesis of QMP rocks remain unclear. To constrain the protolith and genesis, we present new whole-rock geochemistry and Fe isotopic data, mineral EPMA and LA-ICP-MS analysis and X-ray mapping for the QMP rocks in the Wuyang area, North China Craton. The Wuyang QMP rocks have undergone high-temperature metamorphism and have special mineral assemblages with coexisting magnetite, quartz, clinopyroxene and variable orthopyroxene. Pyroxenes of the Wuyang QMP rocks show very distinct major, trace and rare earth element (REE) compositions from those of the nearby pyroxene-marbles and pyroxenite intrusions. Such difference excludes a contact metamorphic origin for pyroxenes of the QMP rocks. X-ray elemental mapping suggests that Fe-poor carbonate minerals (dolomite and calcite) and quartz inclusions are well preserved in these pyroxene grains and no reaction phenomenon can be observed between them, indicating that these pyroxenes are not the product of metamorphic decarbonation reactions of pre-existing sedimentary silica and Fe-rich carbonate phase. Shale-normalized REE + Y patterns of the whole-rock samples and pyroxenes display geochemical features consistent with classic banded iron formations (BIFs), which show light REE depletion, positive LaSN, EuSN and YSN anomalies. This indicates that the geochemical features are compositionally inherited from their original pure chemical sediments. The Wuyang QMP rocks are therefore considered as pyroxene-rich BIF. Neotocite and hisingerite inclusions in pyroxene grains from the QMP rocks could be metamorphic products of some early Fe- and Mn-rich silicates before pyroxene. Moreover, the Wuyang QMP rocks are enriched in light iron isotopes similar to other Fe- and Ca-rich minerals in Archean BIFs. Therefore, we inferred that pyroxene from the QMP rocks could result from dehydration of initial sedimentary hydrous Ca-, Mg- and Mn-containing Fe(II)-silicate gel during diagenesis and re-crystallization in later metamorphism, providing a new interpretation for the origin of pyroxene-rich BIF.

Rare Earth Elements and Yttrium (REY) Geochemistry of Reefal Limestones in the Ordovician, Tarim Basin, NW China and their Paleoenvironment Implications

This study examines the rare earth elements and yttrium (REY) concentrations of twenty‐five samples from the reef outcrop exposed along the Lianglitage Mountain in the Ordovician, Tarim Basin in China. The concentration analysis provides constraints on the paleoenvironment during reef deposition. Based on the detailed sedimentology and petrographic work, we divide the reef facies into four sub‐facies: the base facies, reef‐core facies, reef‐flank facies, and sealing facies. The geochemical data (such as major and trace elements, carbon and oxygen isotopes, and REYs) are further used to study the coeval seawater characteristics as well as potential diagenesis overprints. The result indicated that the diagenesis has little effect on the REY patterns of the reefal limestones. The REY concentrations of the reefal limestones are overall low (ranging from 3.69 to 19.60 ppm, arithmetic mean=10.22 ppm, SD=5.4). The PAAS‐normalized REY patterns are consistently flat compared to the typical well‐oxidized, shallow marine water patterns. However, the light REE (LREE) depletions, positive La anomalies, negative Ce anomalies and positive Y anomalies, suggest that these reefal limestones are likely an indicative of contemporaneous seawater REY signals. The seawater‐like Y/Ho ratios (average at 37.51) further support that REY signals in these limestones are likely a reflection of seawater with little diagenetic modifications. The low Y/Ho ratios presented only in the reef‐flank facies and sealing facies are likely a suggestion of detrital contamination. Hence, this study confirms that REY patterns of the limestones at the base facies and reef‐core facies can record ancient seawater information, and reefs can be used as a potential geochemical proxy for paleoenvironment studies throughout the Earth's history.

Redox-sensitive trace element distribution in the Loma Negra Formation in Argentina: The record of an Ediacaran oxygenation event

The limestones of the Loma Negra Formation provide an excellent opportunity to examine the behaviour of rare earth elements plus yttrium (REY) due to the near-zero diagenetic alteration of the carbonate system. The terrigenous supply to this unit was minimal or scarce in relation to the depth of seawater in which the limestones accumulated. The interpreted palaeoenvironment suggests that limestones could have originated by suspension fall-out in a shallow, open marine ramp. The diagenetic features, composition, and original microtextures are considered good criteria for investigating their REY composition. Burial diagenesis products were limited and limestones largely preserved their original texture and organic matter, as well as their isotope and trace element composition. The study of REY distribution in the Loma Negra Formation in different settings of the Tandilia System revealed systematic chemostratigraphic patterns related to uniform palaeo-redox conditions. The general light rare-earth element depletion, marked positive La, Y, and Gd anomalies, as well as the clear negative Ce anomalies, are further features typically ascribed to oxidizing seawater conditions. From these results, it can be concluded that the Loma Negra Formation documents an oxygenation event that stands out in the overall anoxic Ediacaran ocean. This record may be correlated with the mid-Ediacaran oxygenation event (ca. 580 Ma). This may support the hypothesis that the Clymene Ocean was well oxygenated and connected during the Ediacaran, at least in the southwestern border of Gondwana.

Nature and evolution of the lithospheric mantle revealed by water contents and He-Ar isotopes of peridotite xenoliths from Changbaishan and Longgang basalts in Northeast China

The nature and evolution of the lithospheric mantle underlying Northeast (NE) China were investigated by assessing the mineral chemistry, water contents, and noble gas (He-Ar) isotopes of peridotite xenoliths captured by Cenozoic basalts from the Changbaishan and Longgang regions. The xenoliths, which have 863–1141 °C equilibration temperatures, primarily comprise spinel lherzolites and rare spinel harzburgites. The Mg# (Fo) values of olivine in the peridotite xenoliths vary from 86.9 to 91.3. The clinopyroxenes have high Ti/Eu and low (La/Yb)N, and their chondrite-normalized rare earth elements (REEs) exhibit light REE-depletion to -enrichment patterns, indicating that the mantle underneath the investigated region was predominantly subjected to partial melting (1%–10%) and was metasomatized by silicate melts. The measured 3He/4He ratios of the Changbaishan xenoliths have a narrow range from 5.8 Ra to 8.4 Ra with an average of 7.4 Ra. The 3He/4He isotopic ratios of the Longgang xenoliths varied from 4.7 Ra to 8.1 Ra with an average of 5.9 Ra; slightly lower than the Changbaishan xenoliths. The whole-rock H2O contents of the studied peridotite ranged from 9 to 132 ppm. The high H2O contents in excess of 50 ppm (up to 132 ppm) might represent newly accreted and cooled asthenospheric materials, while those with H2O contents lower than 50 ppm (as little as 9 ppm) may represent thinned, relic, ancient lithospheric mantle. These geochemical evidences, in combination with published data, indicated that the lithospheric mantle beneath the Changbaishan and Longgang in NE China is dominated by the younger and more fertile lithospheric mantle with a minor ancient and refractory keel. In addition, the lithospheric mantle of this area was metasomatized by melts related to the recent subduction event (e.g., Pacific oceanic plate). Therefore, the westward-dipping Pacific oceanic plate subduction had an important contribution to the transformation of the lithospheric mantle beneath NE China.

Neoproterozoic magmatism in the northern margin of the Yangtze Block, China: Implications for slab rollback in a subduction-related setting

The South Qinling Belt was located in the northern part of the Yangtze Block during the Neoproterozoic. Here we investigate two major magmatic intrusions in the northern and southern part of the belt, the Douling plutons (DLP) and the Fenghuangshan plutons (FHSP), to gain insights into the Neoproterozoic tectonic processes along the northern segment of the Yangtze Block. Zircon grains in the DLP yield weighted mean 206Pb/238U ages of 750–709 Ma, whereas those from the FHSP show ages of 749–728 Ma. The new results, together with the published data, reveal that these plutons were emplaced at ca. 759–685 Ma and ca. 802–704 Ma, respectively. Geochemically, the intermediate-felsic rocks from the DLP and FHSP show enrichment of light rare earth elements (LREE) and large-ion lithophile elements (LILE) (Rb, Ba and K), depletion of high field strength elements (HFSE) (Nb, Ta, P and Ti), and low Sr/Y and (La/Yb)N values, which are typical features of arc magmatic rocks. The gabbros from the FHSP have high Mg#, and display LREE and LILE (Rb, Ba, K, and Sr) enrichment and depletion of HFSE (Th, U, Nb, Ta, and Ti), suggesting that they were probably formed in a mantle wedge setting. Both DLP and FHSP show arc-related geochemistry modified by slab-derived fluids, and were formed at relatively high-temperature and low-pressure conditions. However, they display distinct Sr-Nd-Hf isotopic compositions. Zircon grains of two samples from the DLP respectively show mean εHf(t) values of −2.6 ± 0.3 and 0.9 ± 0.3, whereas zircon grains of four samples from the FHSP show mean εHf(t) values ranging from 7.5 ± 0.5 to 8.7 ± 0.4. The DLP shows dominantly negative εNd(t) values and inconsistent initial 87Sr/86Sr ratios, whereas FHSP shows relatively constant and positive εNd(t) values (3.69–3.74) but variable initial 87Sr/86Sr ratios. The Sr-Nd-Hf isotopic and geochemical features suggest that the enriched mantle and crustal materials were involved in the magma evolution of the DLP, whereas the FHSP is characterized by significant juvenile components with a rising asthenospheric mantle source playing a key role. We propose a subduction-related setting for these intrusions, and envisage slab rollback during the Neoproterozoic.

Archaean phosphates: a case study of transformation processes in apatite from the Barberton greenstone belt

Multiple tools have been used to determine the sensitivity of phosphates from the early Archaean Barberton greenstone belt to transformation. The assessment of the degree of transformation is crucial for verifying data about the parameters of the paleo-environment. From the obtained results, three generations of phosphates can be distinguished. Group A is observed in cherts and banded iron formation BIF early-generation fluor-hydroxyapatite that precipitated from seawater. It is characterized by flat rare earth element (REE) patterns with a positive Eu anomaly and high Y/Ho ratio in the range of 54–70. Apatites in this group lack any visible indicators of secondary alterations at the micro- and nanoscales. Fourier transform infrared spectra indicate that these apatites are relatively rich in water, and, due to cationic substitution, their OH-stretching regions exhibit complex ordering and numerous component bands. The characteristics observed in the cherts and silicified felsic volcaniclastics of group B imply advanced metasomatic alteration. They exhibit light and heavy REE depletion and an absence of water in the halogen site. Nanoscale investigations reveal cracks, pores, nanofluid inclusions and nanochannel-like structures, as well as inclusions. Group C is represented by igneous-derived apatites that partially reflect their igneous origin. The phosphates are predominantly fluorapatite with typical magmatic apatite REE distribution patterns. Imaging at the micro- and nanoscales indicates that they partially preserve the signature of igneous origin. It seems that some of the analyzed apatite partially preserved their primordial features; therefore, they might be used for the reconstruction of Archaean abiotic systems.

Geochronology, geochemistry and tectonic implications of a new ophiolitic mélange in the northern West Junggar, NW China

The West Junggar, located in the southernmost part of the Central Asian Orogenic Belt (CAOB), is a key region for understanding the Paleozoic evolution of the CAOB. Issues of the timing of initial subduction and tectonic unit connections in northern West Junggar still remain controversial. In this study, we report a new ophiolitic mélange named the E'min ophiolitic mélange in northern West Junggar. The tectonic blocks in the E'min ophiolitic mélange are mainly composed of serpentinized peridotite, serpentinite, gabbros, pillow basalts, and cherts, with a matrix consisting of highly deformed serpentinites. A gabbro exhibits a zircon SHRIMP U-Pb age of 476 ± 2 Ma, and the zircon grains have δ18O values similar to those of mantle zircons. Those basalt samples display depletions of light rare earth element (REE) relative to heavy REEs. They exhibit weak enrichment of Ba and Th, and moderate depletion of Nb and Ta. The basalts display similar geochemical characteristics to that of fore–arc basalts in the present-day fore–arc setting. The gabbros exhibit high MgO and compatible element contents, but low TiO2, total REE and high field strength element (HFSE) contents. They exhibit light REE depletion, enrichment in large-ion lithophile elements, and depletion of HFSEs. The boninite-like geochemical patterns of the gabbros indicate that they were formed in a subduction-related environment, and were derived from an extremely depleted mantle source infiltrated by subduction-derived fluids and/or melts. The E'min ophiolitic mélange has a geochemical make-up similar to those of suprasubduction-zone (SSZ)-type ophiolites formed in a forearc setting. Hence, we propose that the E'min ophiolitic mélange formed in a forearc setting and may represent the initial subduction in northern West Junggar. Based on geochronological data, we propose that the E'min ophiolite, together with the Kujibai, Hoboksar and Hongguleleng ophiolites, formed during a similar period and comprise a huge E–W trending ophiolitic belt.

Modern carbonate ooids preserve ambient aqueous REE signatures

Skeletal and non-skeletal components of marine sedimentary rocks have been analyzed for the purpose of reconstructing the rare earth element (REE) and yttrium (Y) compositions of paleo-seawater, but skeletal carbonates frequently have proven to be unreliable recorders of seawater chemistry. Here, we present a systematic multi-technique assessment of rare earth and other trace elements in ooid sands from the modern Great Bahama Bank (GBB–marine) and Great Salt Lake (GSL–continental) based on strong-acid (hydrofluoric and nitric) and weak-acid (acetic) digestions, as well as laser ablation (LA) of ooid cortices and nuclei. The results show that Bahamian ooid cortices possess shale-normalized REE + Y features nearly identical to those of shallow seawater, including limited contamination from siliciclastic REEs. An admixture of even 0.2% of detritally sourced material can modify the primary marine REE + Y patterns by, for example, increasing the light REE (LREE) content. Mean values of LA data for Bahamian ooid cortices exhibit similar REE + Y signatures to those produced by acetic acid digestion, but LA data are generally noisier, primarily as a result of low REE concentrations and the small volume of carbonate ablated in analysis. Screening out samples with ΣREE <0.9 ppm reveals more uniform, seawater-like REE + Y patterns in individual ooid cortices as well as high, uniform REE distribution coefficients (116 ± 21, from La to Lu) with respect to ambient seawater. Ooid laminae show no distinct alternation between oxic and anoxic pore fluid characteristics, suggesting that growing ooids primarily formed under oxic conditions in carbonate shoal settings, even when buried during their resting phase. Unlike Bahamian ooids, shale-normalized REE + Y patterns of GSL ooids digested in weak acid show slightly depleted LREE compositions that may deviate from ambient fluids owing to release of REEs from an included clay fraction based on comparison between digestion and LA methods. Multiple ablation spots within the same cortex allowed direct comparison of more and less contaminated portions of a single ooid. Nearly uniform positive Ce anomalies may be related to strongly alkaline water conditions. Individual ablation spots that are partially overprinted by siliciclastic-derived REEs contain variable Zr contents (from 0.096 to ~4 ppm) and flattened shale-normalized LREE patterns. The least-contaminated GSL ooid cortex yields an LREE-depleted REE + Y distribution. Normalization of the REE + Y distributions of least-contaminated GSL ooids using reliable GBB ooid distributions (i.e., with ΣREE > 0.9 ppm) returns a flat pattern, suggesting similar degrees of LREE depletion controlled by carbonate complexation under similar aqueous alkalinity conditions in Great Salt Lake and Bahamian waters. In summary, ooids can be a reliable proxy for REE + Y characteristics of ambient surficial waters when adopting suitable analytical methods, including laser ablation, that allow the identification and isolation of a contamination signal from siliciclastic detritus.

Geology, Apatite Geochronology, and Geochemistry of the Ernest Henry Inter-lens: Implications for a Re-Examined Deposit Model

The Ernest Henry Iron-Oxide-Copper-Gold deposit is the largest known Cu-Au deposit in the Eastern Succession of the Proterozoic Mount Isa Inlier, NW Queensland. Cu-Au mineralization is hosted in a K-feldspar altered breccia, bounded by two major pre-mineralization shear zones. Previous research suggests that Cu-Au mineralization and the ore-bearing breccia formed simultaneously through an eruption style explosive/implosive event, facilitated by the mixing of fluids at ~1530 Ma. However, the preservation of a highly deformed, weakly mineralized, pre-mineralization feature (termed the Inter-lens) within the orebody indicates that this model must be re-examined. The paragenesis of the Inter-lens is broadly consistent with previous studies on the deposit, and consists of albitization; an apatite-calcite-quartz-garnet assemblage; biotite-magnetite ± garnet alteration; K-feldspar ± hornblende alteration; Cu-Au mineralization and post-mineralization alteration and veining. Apatite from the paragenetically early apatite-calcite-quartz-garnet assemblage produce U–Pb ages of 1584 ± 22 Ma and 1587 ± 22 Ma, suggesting that the formation of apatite, and the maximum age of the Inter-lens is synchronous with D2 deformation of the Isan Orogeny and regional peak-metamorphic conditions. Apatite rare earth element-depletion trends display: (1) a depletion in rare earth elements evenly, corresponding with an enrichment in arsenic and (2) a selective light rare earth element depletion. Exposure to an acidic NaCl and/or CaCl2-rich sedimentary-derived fluid is responsible for the selective light rare earth element-depletion trend, while the exposure to a neutral to alkaline S, Na-, and/or Ca-rich magmatic fluid resulted in the depletion of rare earth elements in apatite evenly, while producing an enrichment in arsenic. We suggest the deposit experienced at least two hydrothermal events, with the first event related to peak-metamorphism (~1585 Ma) and a subsequent event related to the emplacement of the nearby (~1530 Ma) Williams–Naraku Batholiths. Brecciation resulted from competency contrasts between ductile metasedimentary rocks of the Inter-lens and surrounding shear zones against the brittle metavolcanic rocks that comprise the ore-bearing breccia, providing permeable pathways for the subsequent ore-bearing fluids.

Origin of facies zonation in microbial carbonate platform slopes: Clues from trace element and stable isotope geochemistry (Middle Triassic, Dolomites, Italy)

AbstractLimestones containing radiaxial fibrous cements were sampled along the southern slope of the late Anisian (Middle Triassic) Latemar carbonate platform in the Dolomites, northern Italy. The Latemar upper slopes comprise massive microbial boundstone, whereas lower slopes are made of clinostratified grainstone, rudstone and breccia. Samples are representative of a seawater column from near sea‐level to an aphotic zone at about 500 m water depth. Radiaxial fibrous cements were analyzed for carbon (δ13C) and oxygen (δ18O) stable isotopic composition, as well as major and trace element content, to shed light on the origin of the slope facies zonation. The δ13C vary between 1·7‰ and 2·3‰ (Vienna Pee‐Dee Belemnite), with lowest values at palaeo‐water depths between 70 m and 300 m. Radiaxial fibrous cements yielded seawater‐like rare earth element patterns with light rare earth element depletion (NdSN/YbSN ≈ 0·4), superchondritic yttrium/holmium ratios (≈55) and negative cerium anomalies. Cadmium reaches maximum values of ca 0·5 to 0·7 μg/g at palaeo‐water depths between 70 m and 300 m; barium contents (0·8 to 1·8 μg/g) increase linearly with depth. The downslope patterns of δ13C and cadmium suggest increased nutrient and organic matter contents at depths between ca 70 m and 300 m and point to an active biological pump. The peak in cadmium and the minimum of δ13C mark a zone of maximum organic matter respiration and high nutrient and organic matter availability. The base of this zone at ca 300 m depth corresponds with the transition from massive microbial boundstone to clinostratified grainstone, rudstone and breccia. The microbial boundstone facies apparently formed only in seawater enriched in organic matter, possibly because this organic matter sustained benthic microbial communities at Latemar. The base of slope microbialites on high‐relief microbial carbonate platforms may be a proxy for the depth to maximum respiration zones of Palaeozoic and Mesozoic periplatform basins.

An Integrated Apatite Geochronology and Geochemistry Tool for Sedimentary Provenance Analysis

AbstractSediment provenance studies utilizing detrital geochronology are often limited by source‐rock non‐uniqueness with respect to mineral age. Thus, the development of integrated techniques which permit identification of source rock age and lithology are highly desirable. In this case study from the southern Massif Central, France, we target modern‐river sediment from the river Tarn to assess the utility of combined U‐Pb and multiple trace‐element geochemical analysis of detrital apatite as a provenance tool. The study area was chosen because the sediment source areas chiefly comprise a relatively simple mix of medium‐ to low‐grade Variscan metasediments and late Variscan granitoids, which should yield detrital apatite readily distinguishable by age, trace‐element chemistry, or both. Based on comparison with previously published apatite trace‐element data from metasedimentary rocks and granitoids, pelitic apatite in the river Tarn detritus is primarily distinguished by high Sr/Mn, light rare‐earth element depletion (LREE) and low actinide contents, whereas granitic apatite is characterized by much lower Sr/Mn, and high LREE and actinide abundances. These source rock determinations are highly consistent with apatite trace‐element data from Tarn tributaries that drain either predominantly metapelitic or granitoid catchments. U‐Pb analysis of detrital rutile was also undertaken on those catchments for comparative purposes. As pelitic and granitic apatite can be readily distinguished, samples that have experienced downstream sediment mixing can then be comprehensively characterized. Using this method we identify a source lithology for nearly every analyzed apatite grain in the river sediment, even though 59% of the analyzed grains do not yield reliable U‐Pb ages.