Depletion Of Heavy Rare Earth Elements Research Articles

Geochemical Characteristics of Soil Rare Earth Elements within Spontaneous Combustion Coalfields of Rujigou Coal Mine

(1) Background: The spontaneous combustion of coal (SCC) not only consumes huge amounts of coal resources but also causes environmental degradation. Rare earth elements (REE) can be taken as an effective indicator to evaluate the environmental effects of SCC. Coal in the Rujigou Mine has been spontaneously combusting for hundreds of years. (2) Methods: The geochemical properties of REE and major elements in the soil of the Rujigou coal mine are methodically examined to reveal the environmental effects of SCC. (3) Results: Soil REE concentration in the Rujigou mine is 216.09 mg/kg, and there is an enrichment of light rare earth elements (LREE) and a depletion of heavy rare earth elements (HREE), LREE/HREE in Rujigou mine was 5.52. The spontaneous combustion of coal could change the vertical distribution of REE, which is conducive to the enrichment of LREE. According to the Eu anomaly and δCe/δEu, the source of material in this mine may be derived from the terrigenous clastic rock controlled by weak reduction. Aluminum and titanium have similar geochemical behavior to REE, especially LREE. The concentration of sulfur is negatively correlated with REE, especially HREE. Calcium, sodium, and magnesium all had a negative correlation with LREE. (4) Conclusions: The spontaneous combustion of coal can lead to the fractionation of light and heavy rare earth elements, resulting in the enrichment of LREE and depletion of HREE.

Discovery of Late Permian Adakite in Eastern Central Asian Orogenic Belt: Implications for Tectonic Evolution of Paleo-Asian Ocean

The Permian to Triassic period represents a pivotal phase in the evolution of the Paleo-Asian Ocean, marked by significant tectonic transitions from subduction, collision, and post-orogenic extension. The timing of closure of the Paleo-Asian Ocean in northeastern China has always been controversial. In this contribution, the petrology, zircon U-Pb geochronology and geochemistry are conducted on granite found in well HFD1, Songliao Basin, eastern part of Central Asian orogenic belt. Zircon U-Pb dating indicates that granite crystallized at 258.9 ± 2.2 Ma, as the product of magmatism occurred in the early Late Permian. The rocks have high SiO2, Al2O3, Na2O content, negative Eu anomaly, light enrichment of rare-earth elements, depletion of heavy rare-earth elements, high Sr (448.29–533.11 ppm, average 499.68 ppm), low Yb (0.49–0.59 ppm, average 0.54 ppm), Y (4.23–5.19 ppm, average 4.49 ppm), and high Sr/Y ratios (98–125, average 112) and can be classified as O-type adakite. This is the first discovery of late Paleozoic adakite in the Songliao Basin and the neighboring areas. The geochemistry of adakite indicates derivation by partial melting of MORB-type subducted oceanic crust, indicating that the subduction of the Paleo-Asian Oceanic lithosphere lasted until at least 258.9 Ma.

Mineralogy and element geochemistry of the Bayan Obo (China) carbonatite dykes: Implications for REE mineralization

The Bayan Obo deposit in China is the world's largest rare earth element (REE) deposit. However, its genesis remains highly debated. It is considered to have a close genetic association with carbonatites because of the presence of nearby carbonatite dykes and the geochemical similarities between these dykes and the orebody. However, the evolution of these dykes and associated REE mineralization remain poorly understood, hindering the origin interpretation of the deposit. This study provides new insights into the petrography, mineralogy, and major- and trace-element geochemistry of these carbonatite dykes and rock-forming minerals to reconstruct the magmatic evolution and REE enrichment of the deposit. The dykes evolved from dolomite- to calcite-dominated (i.e., calcite and fenitized calcite) carbonatites, and their REE content remarkably increased, with the latter developing strong REE mineralization. The dolomites and minor calcites within the dolomite carbonatites exhibit a steep negative slope with high light REE (LREE) enrichment and heavy REE (HREE) depletion, similar to the whole rock. In contrast, the calcites from the calcite-dominated carbonatites exhibit flat REE patterns with HREE enrichment. Combined with previous isotopic data and our petrology, mineralogy, and geochemistry study, we propose that these rocks are derived directly from the low-degree melting of the underlying mantle source. REE mineralization may be related to the progressive crystallization of rock-forming calcites of calcite-dominated carbonatites. Monazite, bastnäsite, parisite, and huanghoite are the dominant REE minerals and exhibit intimate associations with barite and alkaline silicate minerals such as aegirine, biotite, K-feldspar, and albite. This assemblage indicates that the REE were primarily transported via REE–sulfate and REE–alkali complexes, with the latter favoring HREE, and the precipitation of alkaline silicate minerals destabilized these REE complexes, facilitating REE mineralization.

Concentration, speciation, and fractionation of rare earth elements in alluvial soils in contiguous karst landform, southwestern China

Karst is a unique landform formed by strong chemical weathering of carbonate rocks. This study investigated the concentration and speciation of rare earth elements and yttrium (REY) in alluvial soils and REY fractionation from carbonate rocks and alluvial soils in the world's largest contiguous karst landform in southwestern China. The results showed that the REY of alluvial soils ranged from 73.77 to 1251.56 μg⋅g−1, with a median value of 230.30 μg⋅g−1, which was higher than that of alluvial soils across China (178 μg⋅g−1) and the upper continental crust (168 μg⋅g−1), revealing a high background of REY in these karst areas. Meanwhile, the average REY in alluvial soils (244.96 μg⋅g−1) was close to 14 times that in carbonate rocks (17.61 μg⋅g−1) in the study area, indicating that REY was significantly enriched in the pedogenesis. Correlation analysis showed that the REY concentration was not significantly related to any single factor (i.e., Fe2O3, MnO, Al2O3, TOC, pH, or CIX). BCR speciation analysis revealed a declining trend in the proportion of REY across the residual (F4, 73.21 %), reducible (F2, 19.40 %), oxidizable (F3, 6.89 %), and weakly acid-extracted (F1, 0.50 %) phases. Additionally, significant REY fractionations from carbonate rocks to alluvial soils were observed. The bedrock-normalized REY pattern revealed an enrichment of light rare-earth elements (LREE) and middle rare-earth elements (MREE), a depletion of heavy rare-earth elements and yttrium (HREY), and positive Ce and Gd anomalies. Secondary mineral phases that formed during weathering—such as clay minerals, oxyhydroxides, phosphates, and organic matter—played an important role in the retention and fractionation of the REY in the soils. Besides these natural factors, anthropogenic inputs also contributed to the REY fractionation, as indicated by the slight positive Gd anomaly in the karst alluvial soils. Furthermore, the differences of δCe and δEu in the soils developed from three types of pedogenic rocks—including carbonate, basalt, and granite—were discussed. The different δEu anomalies could help to identify the parent rocks of alluvial soils.

Melting processes, cooling rates, and tectonic settings of the Neo-Tethyan mantle: the in-situ mineral chemical record

Peridotites in the Yarlung Zangbo ophiolite (YZO) have the potential to elaborate the mantle dynamics that operated below the Neo-Tethyan oceanic crust. Here, we measured major and trace element concentrations of minerals (e.g., clinopyroxene, orthopyroxene, olivine, and spinel) in YZO harzburgites and lherzolites to trace the origin and evolution of the YZO. The rare earth element (REE) patterns of clinopyroxenes in lherzolites and harzburgites plot within the field of abyssal and forearc peridotites, respectively, indicating that the latter experienced a higher degree of partial melting. Based on the relative extents of light (LREE) and heavy (HREE) REE depletions in clinopyroxene, we classified the lherzolites into two groups (I and II). The group I clinopyroxenes are depleted in HREEs and enriched in LREEs and MREEs compared to those of group II. Meanwhile, the REE patterns of harzburgite clinopyroxenes are identical to that of group II, although they display lower REE concentrations. Models based on REE abundances in clinopyroxene suggest that group I lherzolites experienced ~8–11% partial melting in the spinel domain, whereas group II lherzolites formed after 5% melting in the garnet domain followed by 6–9% and 9–16% partial melting in the spinel domain, respectively. These high degrees of melting may suggest that the harzburgites formed in a supra-subduction zone (SSZ) setting. Surprisingly, the REE-in-two-pyroxenes thermometer (TREE) shows that the YZO peridotites record high-temperature cooling at 991–1218 °C which is lower than the conditions below mid-oceanic ridges (MORs), but compatible with recent reports of high closure temperatures in forearc environments. Furthermore, our TREE results constrain the cooling rate of the YZO peridotites to ~0.01–0.5 °C/yr, overlapping with rates reported for SSZ, MOR, and abyssal peridotites. By integrating the petrological, geochemical, and thermal features, we tentatively interpret the group I lherzolites accreted in an Early Cretaceous forearc during subduction initiation, whereas the group II lherzolites and the harzburgites formed by further melting of the earlier lherzolites in a SSZ setting.

An early Paleozoic accumulation-foundering cycle of ultramafic cumulates in the Harlik arc and its implications for continental crustal growth in the Altaids

Lower crustal ultramafic cumulates that are normally denser than the ambient mantle peridotites are prone to founder back into the convecting mantle, prompting the formation of continental Moho and andesitic crust at subduction zones. However, foundering events of ultramafic cumulates have not been widely reported in island arcs, including the Altaids, one of the largest accretionary orogens. The Altaids involved prominent continental crustal growth by the development of an archipelago in the Phanerozoic. But the scarcity of foundering events of ultramafic cumulates hinders a better understanding of the formation mechanism of andesitic crust in the Altaids. In this study, we report two dioritic plutons in the Harlik arc, southern Altaids, trying to identify the accumulation-foundering cycles of dense ultramafic cumulates. LA-ICP-MS dating revealed that the Miaoergou and Banfanggou plutons in the Harlik arc were intruded at ca. 445 ± 6 Ma and 423 ± 4 Ma, respectively. The homogeneous Miaoergou pluton is mainly composed of quartz diorites, they have a high- to medium-K calc-alkaline composition, and show enrichments in light rare earth elements (LREE) and large ion lithophile elements (LILE), but depletions in high field strength elements (HFSE, especially Nb and Ta) and heavy rare earth elements (HREE). They also have juvenile isotopic signatures (εNd(t) = +3.3 − +3.7, initial 87Sr/86Sr = 0.70399–0.70452), which together suggest that they were derived from fractional crystallization of the coeval hydrous basaltic magmas in an arc setting. The heterogenous Banfanggou pluton comprises a spectrum of lithologies from hornblende gabbro to diorite. The hornblende gabbros and diorites have a high- to medium-K calc-alkaline composition, and show enrichments in LREE and LILE, but depletions in HREE and HFSE. They all have juvenile isotopic compositions with εNd(t) ranging from +3.5 to +4.2, and (87Sr/86Sr)i from 0.70384 to 0.7047, respectively, indicating that their parental magmas were intruded in a subduction-related setting, and underwent fractional crystallization of clinopyroxene, plagioclase, amphibole and quartz. Both pulses of hydrous basaltic magmatism involved open-system conditions, with the development of mafic microgranular enclaves (MMEs) in the diorites and their mingling. In a synthesis of the published data, we found that the Harlik arc was continuously affected by subduction in the early Paleozoic, through extensive arc magmatism from ca. 452 to 440 Ma, the Harlik arc matured with the accumulation of thick ultramafic cumulates in its lower crust. The foundering of these ultramafic cumulates occurred later, which led to strong extension and related A-type granitic magmatism at ca. 436 Ma. This accumulation-foundering cycle of ultramafic cumulates facilitated the formation of andesitic composition and continental Moho in the Harlik arc, and contributed to the significant continental crustal growth in the Altaids.

Tonian Continental Arc Magmatism of the Porongos Complex, Dom Feliciano Belt, Southern Brazil

This study provides new information on the deformation, metamorphism, and tectonic setting of the metavolcanic rocks of the southern portion of the Porongos Complex, southern Brazil. The structural analysis enabled the identification of three deformational phases, formed under ductile to semi-ductile conditions. D1 progressed through deformation partitioning, comprising closed to isoclinal folds and an axial plane foliation. Then, simple shear prevailed, resulting in isoclinal folds, sigma-type porphyroclasts, foliation transposition, and mylonitic rocks. D2 comprises open to gentle folds and an axial plane cleavage. The formation of shear bands is ascribed to the semi-ductile D3. The mineral assemblage represented by phengite + chlorite + clinozoisite-epidote + actinolite + albite + quartz associated with the temperatures obtained through the chlorite geothermometer (316°C) indicates greenschist facies conditions. The protoliths of these metavolcanic rocks are geochemically discriminated as calc-alkaline, dacite-to-rhyodacite, with peraluminous compositions. The bulk trace element compositions show enrichment in large-ion lithophile elements and light rare-earth elements and depletion in heavy rare-earth elements. Also, negative Nb, P, Ti, and Ta anomalies are observed in the multielement diagram. All these geochemical features are typical of rocks formed in continental magmatic arcs. Geochemical comparison with other pre-collisional Tonian orthometamorphic rocks from the Dom Feliciano Belt demonstrates strong similarities, which corroborates the prior interpretation of a continental arc setting for the origin of these Tonian rocks.

Late Paleozoic Tectonic Evolution of the Northern Great Xing’an Range, Northeast China: Constraints from Carboniferous Magmatic Rocks in the Wunuer Area

Northeast China composes the main part of the Central Asian Orogenic Belt. Traditionally, Northeast China has been considered a collage of several microcontinental blocks. However, the tectonic evolution of these blocks remains uncertain. Igneous rocks can be used to infer the magmatic histories of the blocks and thus help reconstruct their evolution. In this study, we present new zircon U–Pb and whole-rock geochemical data for Carboniferous igneous rocks from the Wunuer area, northern Great Xing’an Range, Northeast China, to constrain the Carboniferous amalgamation of the united Xing’an–Erguna and Songnen–Zhangguangcai Range massifs. On the basis of zircon U–Pb dating results, we identify two main stages of magmatism, i.e., early Carboniferous (332–329 Ma) and late Carboniferous (312–310 Ma). The early Carboniferous igneous rocks include diorites and granodiorites, with the former being classified as calc-alkaline to tholeiitic and the latter as tholeiitic. Both rock types are enriched in Th and U and depleted in Nb and Ti. The rocks display slightly fractionated rare earth element (REE) patterns, with an enrichment in light REEs and a depletion in heavy (H)REEs. The geochemical characteristics of the early Carboniferous rocks indicate that they formed in a subduction-related continental-arc setting. The late Carboniferous igneous rocks include monzogranites and syenogranites, both of which are classified as high-K calc-alkaline rocks and show enrichment in Th, U, and Rb and depletion in Nb and Ti. The rocks display strongly fractionated REE patterns, with an enrichment in light REEs and a depletion in HREEs. The geochemical characteristics of the late Carboniferous rocks indicate that they formed in a syn-collisional tectonic setting. Combining the new geochronological and geochemical results and inferred tectonic settings with regional magmatic data, we propose a new three-stage model to interpret the late Paleozoic tectonic evolution of the united Xing’an–Erguna and Songnen–Zhangguangcai Range massifs of Northeast China: (1) early Carboniferous (360–340 Ma) subduction of the Paleo-Asian oceanic plate beneath the united Xing’an–Erguna Massif and formation of the Wunuer oceanic basin in the Yakeshi area; (2) early to late Carboniferous (340–310 Ma) sustained subduction of the Paleo-Asian oceanic plate beneath the united Xing’an–Erguna Massif and initiation of subduction of the Wunuer oceanic basin; and (3) late Carboniferous–early Permian (310–275 Ma) syn-collisional to post-collisional tectonic transition between the united Xing’an–Erguna Massif and the Songnen–Zhangguangcai Range Massif.

Petrogenesis and tectonic setting of Early Cretaceous mafic dykes in the North Qinling Orogenic Belt, central China: constraints on the lithospheric lower crust delamination

Late Mesozoic mafic dykes, which are widely developed in the North Qinling Orogenic Belt (NQOB), include abundant geodynamic information. This paper describes the mafic dykes that intrude the Late Jurassic granite in the Dayu and Kuyu areas, and reports important petrological constraints for the late Mesozoic tectonic transition from compression to extension in the NQOB. Three zircon U–Pb results show that the minimum ages of the mafic dykes are 139.8 ± 1.4 Ma, 137.4 ± 1.7 Ma and 133.4 ± 0.9 Ma, indicating that the emplacement age of the Dayu and Kuyu mafic dykes is 140–133 Ma. Petrogeochemical analyses suggest that the mafic dykes belong to the high-K calc-alkaline shoshonite series with low SiO2 (46.93–56.73 wt%), MgO (1.88–9.10 wt%) and TiO2 (1.17–1.82 wt%), and high Al2O3 (13.98–17.46 wt%), TFe2O3 (7.81–10.92 wt%) and K2O (1.28–4.78 wt%). The mafic dykes are enriched in large ion lithophile elements (e.g. Rb, Ba, K, La, Sr) and depleted in high-field-strength elements (e.g. Nb, Ta, Zr, Ti). These samples have the right-sloping chondrite-normalised rare earth element patterns, which suggest light rare earth element enrichment and heavy rare earth elements depletion with no obvious Eu anomalies (δEu = 0.94–1.11). The I Sr, ε Nd(t), ε Hf (t) and T DM2(crust) values are 0.7056–0.7060, −10.60 to −5.98, −14.1 to −2.8, and 1382.4 ± 25.1 to 2081.9 ± 47.6 Ma, respectively. Both elemental and isotopic geochemistry show that the formation of Dayu and Kuyu mafic dykes is due to the partial decompression melting of previously enriched lithospheric mantle during a delamination process. The mafic dykes have undergone fractionation crystallisation of Mg–Fe phase minerals during magma ascent, accompanied by some crustal contamination. Combined with the regional tectonic setting, we suggested that the NQOB experienced intra-continental extension during the Early Cretaceous. KEY POINTS Early Cretaceous (140–133 Ma) mafic dykes have been discovered in the middle part of the North Qinling Orogenic Belt. The remote effect of the Paleo-Pacific Plate subduction has reached the middle of the North Qinling Orogenic Belt. The North Qinling Orogenic Belt entered the extensional stage in the Early Cretaceous (140–133 Ma).

The isotopic origin of Lord Howe Island reveals secondary mantle plume twinning in the Tasman Sea

Thermochemical convective instabilities in the mantle, often referred to as mantle plumes, cause mantle melting that give rise to ocean island basalts (OIB) in intraplate settings. The array of radiogenic isotope signatures in global intraplate OIB indicate that although plumes are individual entities, they share enriched components that resemble various parts of subducted crust and a hypothetical mantle matrix termed “focal zone” (FOZO). Each plume is expected to rise with an individual buoyancy flux, thereby producing variable volumes of melting with some OIB forming subaerial islands, whereas others produce submarine volcanoes.Here, we report the first radiogenic isotope data (Sr, Nd, Pb and Hf) for lavas of Lord Howe Island (LHI) in the Tasman Sea, the most prominent subaerial expression of the hypothesised Lord Howe mantle plume. Major element data are consistent with a moderate degree of partial melting, and heavy rare earth element depletion indicates melting occurred in the presence of garnet, consistent with other global plume lavas. Radiogenic SrNd isotopic data are similar to those defining the relatively primitive FOZO component with no clear enriched mantle affinity. The nearby Tasmantid Seamounts are also sourced from a mantle plume, and have similar SrNd character. However, combined 208Pb/204Pb and 207Pb/204Pb vs 206Pb/204Pb ratios of LHI lavas are inconsistent with a FOZO-type source. Instead, Pb isotopes overlap with typical enriched mantle 1 (EM1) lavas (e.g., Pitcairn, Tristan da Cunha), trending slightly higher than the Northern Hemisphere Reference Line (NHRL). Hafnium isotopes follow trends observed in lavas of the archetypal EM1 Pitcairn-Gambier islands, and are partially decoupled from 143Nd/144Nd; this decoupling is rare among OIB. The combined element-isotope data indicate that LHI forms the most recent expression of a mantle plume track in the Tasman Sea. Albeit unique in its 208Pb*/206Pb* isotope code among global mantle plumes, the resemblance of LHI lavas with the spatially related and contemporaneous Taupo seamount of the parallel Tasmantid plume track in the Tasman sea supports a genetic relation of both plumes. The proposed common origin of the two parallel plume tracks requires a larger plume underpinning the Tasman sea with individual plume fingers rising towards the surface, possibly in a triple plume network considering the on-shore Cosgrove track in eastern Australia. The subaerial expression of LHI contrasts the submarine Tasmantid Seamounts; this expression is only possible due to the continental ribbon that forms the island's foundation, suggesting secondary plume fingers display similar low buoyancy fluxes. Plain language summaryLord Howe Island is predominantly composed of basaltic rocks, which are created when mantle underneath the crust melts and the subsequent magma rises to the surface and erupts out of a volcano. The chemical composition of these volcanic rocks can provide us with valuable information about geologic processes. Moreover, we can compare the composition of islands like Lord Howe to better investigate and understand volcanic networks that exist deep within the Earth. The composition of Lord Howe Island basalts was investigated for the first time using specialised instruments that can separate individual elements into different isotopes. The ratios of these different isotopes reflects the composition of the mantle source which can be enriched by the presence of subducted crustal rocks, oceanic rocks and sediments. Our data indicate the distinctive reservoir that Lord Howe Island samples were derived from is the same reservoir as that of the nearby Taupo Seamount volcano. We infer from this that a piece of ancient crust is stuck in the mantle, and the two volcanoes are sampling it. This study supports a theory of a large, linked volcanic network under the Tasman Sea, and adds to the growing body of research investigating ‘double-chain’ volcanism in the Pacific and Atlantic oceans.

Garnet geochemistry of the giant Beiya gold–polymetallic deposit in SW China: Insights into fluid evolution during skarn formation

The Beiya deposit in the central Jinshajiang–Ailaoshan metallogenic belt of SW China is the country’s largest gold skarn and third largest gold deposit. In this study of the Beiya deposit, we use garnet mineralogy and geochemistry to delineate three skarn alteration zones (i.e., contact, proximal and distal skarn). We investigate the possible controls on the rare earth element (REE) incorporation into skarn-type garnet, the ore-fluid evolution, and metasomatic dynamics. Garnet in the Beiya deposit belongs to the grossular–andradite solid solution series, and comprises three types: (1) Grt1 andradite (Adr67–88Grs9–32) in the contact skarn, exhibiting light REE (LREE) enrichments, heavy REE (HREE) depletions, and positive Eu anomalies; (2) Oscillatory-zoned Grt2 andradite (Adr55–98Grs1–44) in proximal skarn, which has moderate to low LREE/HREE enrichments and varying Eu anomalies; (3) Grt3 andradite (Adr29–76Grs22–69) in distal skarn with low LREE/HREE enrichments and minor negative Eu anomalies. Grt1, Grt2 and Grt3 yielded lower intercept U–Pb ages of 36.4 ± 1.8 Ma (MSWD = 0.87, n = 67), 34.8 ± 0.7 Ma (MSWD = 1.8, n = 31) and 33.4 ± 1.0 Ma (MSWD = 1.2, n = 25). Garnet shows compositional changes from Grt1 to Grt3 due to the fluid-wallrock reactions. With decreasing andradite and increasing grossular contents, the (La/Yb)N ratio decreases. Ore-forming fluids changed from diffusive metasomatism to infiltration metasomatism, and then again to diffusive metasomatism. Meanwhile, the ore-fluid physicochemical conditions changed from acidic to near-neutral (both oxidised), whilst the water/rock ratio first increased and then decreased. The proximal skarn recorded high water/rock ratio with intermittent boiling events, leading to fluctuating oxygen fugacity, which is conducive to ore deposition. Therefore, the skarn-type garnet composition from the various alteration zones can reveal the fluid activity and physicochemical fluid evolution path, preserving rich information about the mineralisation process.

Petrogenesis of the Alubaogeshan intrusion in the Maodeng–Xiaogushan area, southern great xing'an range, NE China: Implications for magma evolution and tin–polymetallic mineralization

• The Alubaogeshan intrusion formed at ca. 134 Ma and belongs to transitional I–A 2 -type granite . • The Alubaogeshan intrusion was formed by partial melting of a Neoproterozoic juvenile crust. • The syenogranite porphyry evolved from the porphyritic monzogranite. • Fluid–melt interaction is crucial for W mineralization. • The magma evolutionary degree influences the size of the Sn–polymetallic deposits in the SGXR. The Alubaogeshan intrusion, consisting of porphyritic monzogranite in the central part and syenogranite porphyry in the edge, is genetically related to the Maodeng–Xiaogushan Sn–polymetallic deposit. This paper aims to investigate the genetic link between these two granite phases and the relationship between magma evolution and Sn mineralization. LA-ICP-MS zircon U–Pb dating of the porphyritic monzogranite and syenogranite porphyry yielded ages of 134 ± 1.0 Ma and 133 ± 0.5 Ma, respectively. The Alubaogeshan intrusion has high SiO 2 and total alkali (Na 2 O + K 2 O) contents, with low Al 2 O 3 , Fe 2 O 3 , FeO, and MgO contents, belonging to high-K calc-alkaline metaluminous–weakly peraluminous granites. Chondrite-normalized rare earth element (REE) patterns are characterized by light REE enrichment and heavy REE depletion, with extremely negative Eu anomalies. In addition, the intrusion was also enriched in Rb, Th, U, K, Zr, Hf, and light REE and strongly depleted in Ba, Sr, P, and Ti. Mineralogical and geochemical characteristics, together with high zircon saturation temperature, indicate that the Alubaogeshan intrusion belongs to transitional I–A 2 -type granites. Compared with the porphyritic monzogranite, the syenogranite porphyry reveals higher SiO 2 content and lower TiO 2 , Al 2 O 3 , Fe 2 O 3 , FeO, CaO, MgO, and P 2 O 5 contents, with more obvious negative anomalies of Eu, Ba, Sr, P, and Ti. The temporal and spatial relationship and geochemical characteristics of the two rocks indicate that the syenogranite porphyry evolved from the porphyritic monzogranite. The modeling results show that the fractional crystallization of amphibole, plagioclase, K-feldspar, biotite, apatite, monazite, and allanite occurred during the magma evolution. The granitic magma differentiation plays a key role in the formation of the Maodeng–Xiaogushan Sn–polymetallic deposit. The ε Hf ( t ) values of zircon range from 2.58 to 7.08, and the two-stage Hf model ages range from 619 Ma to 850 Ma, implying that the Alubaogeshan intrusion was predominantly derived from partial melting of a Neoproterozoic juvenile crust. The TE 1,3 values of the ore-related granites from W–(Sn) deposits are generally higher than 1.1, suggesting that fluid–melt interaction is crucial for W mineralization. The degree of magmatic evolution is one of the controlling factors for the size of Sn–polymetallic deposits in the southern Great Xing′an Range.

Origin of microbial–hydrothermal bedded dolomites in the Permian Lucaogou Formation lacustrine shales, Junggar Basin, NW China

Dolomite is widely developed in the shale sequences of saline lakes and has significance in paleoenvironmental, paleoclimatic, and petroleum geology research. In this study, a new end-member type of dolomite is discovered from the Permian Lucaogou Formation in the Junggar Basin, northwest China, along with its geological significance. The microbial–hydrothermal origin of the bedded dolomite is evident from the development of hydrothermal minerals (including barite and cubic pyrite) and methanogenic micro-organisms. In terms of geochemistry, the bedded dolomite has high (Ba/La)N ratios (~2.8) and Sr contents (~594.9 ppm) and positive Sr anomalies (Sr/Sr* ~3.8). Chondrite-normalized rare earth element (REE) patterns exhibit light REE enrichment, heavy REE depletion, slightly positive Ce anomalies, and negative Eu anomalies. The bedded dolomite has relatively low 87Sr/86Sr ratios (~0.705283), high δ13C values (~6.63‰ ), and low δ18O values (~−9.92‰ ). All these indicate that the dolomitizing fluid is a mixed source of hydrothermal fluids and lake waters, and the hydrothermal fluids and microbial methanogenesis provided the Mg2+ and C, respectively. The combination of microbial and hydrothermal activity overcame the limitation of dolomitization hydration shells around Mg2+. In terms of geological significance, the studied Lucaogou Formation was deposited in an extensional tectonic setting under hot–arid climatic conditions, which controlled the high-frequency interbedding and meter-scale cyclicity of sediment deposition of dolomites and shales. The combined effects of tectonism and paleoclimate may be important factors for the formation of bedded dolomite, enrichment of organic matter and hydrocarbons in saline lacustrine shales.

Petrogenesis and Tectonic Implication of the Hongtaiping High-Mg Diorite in the Wangqing Area, NE China: Constraints from Geochronology, Geochemistry and Hf Isotopes

This study presents new data from zircon U–Pb dating and Hf isotope analysis, as well as whole-rock major- and trace-element compositions of the Hongtaiping high-Mg diorite in the Wangqing area of Yanbian, NE China. Laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) zircon U–Pb dating gives an eruption age of ca. 267 Ma for the high-Mg diorite. These samples have MgO contents of 13.30% to 16.58% and high transition metal element concentrations, classified as sanukite. Their rare earth element (REE) contents range from 45.2 to 68.4 ppm and are characterized by slightly positive Eu anomalies (Eu/Eu* = 1.08–1.17). They show enrichment in light REEs (LREEs) and depletion in heavy REEs (HREEs), with LREE/HREE ratios = 6.54–6.97 and (La/Yb)N values = 7.24–8.08. The Hongtaiping high-Mg diorite is enriched in Rb, U, K, and Sr, but depleted in Th, Nb, and Ta. High MgO contents, Mg# values, and transition metal element concentrations imply that the magma experienced insignificant crystallization fractionation and crustal contamination. Relatively homogenous positive Hf isotopic values indicate that the original magma was generated by the partial melting of a depleted mantle wedge that was metasomatized by subducting slab fluids. The magma was generated by the moderate degree partial melting (20%–30%) of a garnet lherzolite source. Combined with previous studies, this shows that the high-Mg diorite was formed by the northward subduction of the Paleo-Asian oceanic plate during the Middle Permian.

Crust–mantle interaction recorded by Early Cretaceous volcanic rocks within the southern margin of the North China Craton

This study presents new geochronological and geochemical data for Early Cretaceous volcanic rocks in the southern margin of the North China Craton (NCC), to discuss the crust–mantle interaction. The studied rocks include pyroxene andesites from Daying Formation, hornblende andesites and andesites from Jiudian Formation, and rhyolites from a hitherto unnamed Formation. These rocks formed in Early Cretaceous (138–120 Ma), with enrichment in light rare earth elements (REE), depletion in heavy REE and arc-like trace elements characteristics. Pyroxene andesites show low SiO2 contents and enriched Sr–Nd–Pb–Hf isotopic compositions, with orthopyroxene phenocryst and Paleoproterozoic (2320–1829 Ma) inherited zircons, suggesting that they originated from lithospheric mantle after metasomatism with NCC lower crustal materials. Hornblende andesites have low SiO2 contents and high Mg# (Mg# = 100 Mg/(Mg + Fe2+)) values, indicating a lithospheric-mantle origin. Considering the distinct whole-rock Sr isotopic compositions we divide them into two groups. Among them, the low (87Sr/86Sr)i andesites possess amount inherited Neoarchean to Neoproterozoic (2548–845 Ma) zircons, indicating the origin of lithospheric mantle with addition of Yangtze Craton (YC) and NCC materials. In comparison, the high (87Sr/86Sr)i andesites, with abundant Neoarchean–Paleozoic inherited zircons (3499–261 Ma), are formed by partial melting of lithospheric mantle with incorporation of NCC supracrustal rocks and YC materials. Rhyolites have extremely high SiO2 (77.63–82.52 wt.%) and low total Fe2O3, Cr, Ni contents and Mg# values, combined with ancient inherited zircon ages (2316 and 2251 Ma), suggesting an origin of NCC lower continental crust. Considering the presence of resorption texture of quartz phenocryst, we propose a petrogenetic model of ‘crystal mushes’ for rhyolites prior to their eruption. These constraints record the intense crust–mantle interaction in the southern margin of the NCC. Given the regional data and spatial distribution of Early Cretaceous rocks within NCC, we believe that the formation of these rocks is related to the contemporaneous far-field effect of the Paleo-Pacific Plate.

Petrographic and geochemical characteristics of nodular carbonate-bearing fluorapatite in the lacustrine shale of the Shahejie Formation, Dongying Depression, Bohai Bay Basin

A varying abundance of carbonate-bearing fluorapatite (CFA) nodules in Eocene lacustrine shale in the Bohai Bay Basin was observed; however, mineralogical and geochemical awareness is lacking, which limits the specific understanding of CFA formation mechanisms and paleoenvironmental proxies. We specified the petrology, trace elements (TE), rare earth elements and yttrium (REY) of the CFA nodules by using an integrated approach of cathodoluminescence, micro-Fourier transform infrared spectroscopy, electron microprobe analysis and laser ablation–inductively coupled plasma–mass spectrometry. The results suggest that CaO (25.85 to 39.95 wt%), P2O5 (17.19 to 29.35 wt%) and F (0.71 to 2.99 wt%) are the dominant components of the CFA nodules, with low Mn/Fe ratios and few incorporations of CO32−. They show selective concentrations of Sr (avg. 14,963.3 ppm), Ba (avg. 1831.6 ppm), U (avg. 314.2 ppm), Zr (avg. 263.5 ppm), and Th (avg. 185.4 ppm) and apparent negative Y anomalies with low Y/Ho ratios (18.40 to 28.90). These CFA nodules were classified into three types according to REY patterns normalized to the Post-Archean Australian Shale (PAAS). Type A nodules enclosed by micritic calcite laminae are middle rare earth elements (MREE) enriched which yield a typical “bell-shaped” REY pattern, nonanomalies of Ce and a good correlation of ΣREY with Ce/Ce* (R2 = 0.90) and Ba (R2 = 0.95). Type B nodules in the clay and organic-rich laminae were better phosphatized and display more heavy rare earth elements (HREE) depletion, minimal Ce anomalies and a good correlation between CaO and P2O5 (R2 = 0.84) than type A nodules. Type C nodules are rare but show light rare earth elements (LREE) enrichment relative to type A and B nodules. The adsorption of P, TE and REY by Fe-(oxyhydr)oxide and organic matter is significant for CFA formation through the “dissolution-recapture-reprecipitation” process in the ambient pore water of the Fe reduction zone during early diagenesis. The retention of HREE as HREE(CO3)2− in more reducing bottom water is critical to the HREE depletion for type B and C nodules, while the release of LREE from bacterial-mediated degradation of organic matter into ambient pore water enhances the concentration of LREE on type C nodules. Deviation of the REY patterns is probably related to the differential suboxic redoxclines for the deposition of calcite-rich and clay- and organic-rich laminae of shale, which are considered the depositional environment proxies of lacustrine shale.

Geochemical Characteristics and Fluid Properties of the Qixia Formation Dolomites of the Middle Permian in the Shuangyushi Block, NW Sichuan Basin, China

On the basis of petrology, in combination with analysis of the geochemical characteristics of major and trace elements, REE (rare earth elements), carbon isotopes, oxygen isotopes, strontium isotopes and fluid inclusions, the geochemical characteristics and fluid properties of the Qixia Formation dolomites of the Middle Permian Qixiain the Shuangyushi block in the NW Sichuan Basin were systematically studied. The analysis results of the samples show that the Qixia dolomites are mainly composed of medium, coarse, medium-coarse crystalline and dolomites with polymodal crystal size distribution, and cloudy centers and clear rims. They generally show dark purple cathodoluminescence (CL) colors in the centers and orange red CL colors in the rims. The Qixia dolomites are relatively highly ordered (0.79–0.95, averaging 0.90). The CaO and MgO contents show a negative correlation. They are characterized by higher Mg/Ca ratio (0.89–0.92, averaging 0.91), high Fe (94–2,991 ppm, averaging 622 ppm), high Mn (26–185 ppm, averaging 102 ppm), high Na (210–374 ppm, averaging 277 ppm) contents, low Sr (53–218 ppm, averaging 93 ppm) content and lower ∑REE (1.10–5.56 ppm, averaging 2.08 ppm) concentrations. The REE patterns of the dolomites are similar to those of the calcites (C1), and are characterized by light REE (LREE) enrichment, heavy REE (HREE) depletion (LREE/HREE = 5.38–9.58, averaging 7.10), and Eu (0.65–4.19, averaging 1.70) and Ce (0.99–9.52, averaging 2.61) positive anomalies. They have consistent δ13C (1.98–4.27‰ VPDB, averaging 3.01‰ VPDB) and δ18O (−9.54‰–−4.65‰ VPDB, averaging −7.09‰ VPDB) values with the coeval seawater. The salinity index Z is larger than 120, with diagenetic temperature higher than normal temperature. The average value of 87Sr/86Sr is positive (0.707150–0.712273, averaging 0.708669), while some samples are consistent to those of the coeval seawater. Their homogenization temperatures of fluid inclusions (96.3°C–105.0°C, averaging 101.1°C) exceed 100°C, which is equivalent to the buried paleogeothermal temperature, and their salinity (12.3%–14.3%, averaging 13.5%) is 3–5 times that of normal seawater. Based on the regional geological setting and previous research achievements, the dolomitized fluids in the Qixia Formation are probably derived from seawater or marine fluids sealed in pores under shallow-burial environment. The dolomites experienced late alternation by deep high-salinity hydrothermal fluids, and were formed before the Middle-Late Triassic Period.

Late Summer Water Sources in Rivers and Lakes of the Upper Yana River Basin, Northern Eurasia, Inferred from Hydrological Tracer Data

Major ions, stable isotopes, and trace elements, including rare earth elements (REEs), are used as natural tracers in the qualitative assessment of potential water sources in lakes and rivers of the upper Yana River basin, between Verkhoyansk and Chersky Ranges, during the late summer period. Three distinct regions were sampled, and a dominant water source in each region was qualitatively inferred from water chemistry data. The REE distribution pattern was found to be highly regional and controlled by pH and carbonate contents. Mountain headwater stream at the Verkhoyansk Range north slope, the Dulgalakh River, shows an input from a mixture of shallow groundwater and icing meltwater, with a depleted isotopic signature (δ18O below –21‰), d-excess (dex = δ2H − 8·δ18O) above 18, enrichment in Mg and Sr, and depletion in heavy REEs. The Derbeke Depression lakes and streams are fed by rainfall having ultra-low total dissolved solids (TDS) content, below 25 mg/L, and a convex-up REE pattern. In a medium mountainous river at the Chersky Range flank, the Dogdo River, leaching through fissured Jurassic carbonates is a dominant runoff pathway. Riverine water is heavily depleted in light REEs, but enriched in Mo, Rb, Sb, W and U. In the Dulgalakh River water, high positive Sm and Gd anomalies were observed, attributed either to local geology (greenshists), historical mining legacy, or contemporary winter road operations.

Origin of hematite in the Middle Cretaceous red chalks on the eastern coast of England

Chalks are generally believed to have formed in shallow marine environments. However, the consensus on sources of Fe and origin of hematite in red chalks remains elusive. To better understand the origin of hematite in the Middle Cretaceous red chalks on the eastern coast of England, the evidence has been gathered through diffuse reflection, trace element and iron isotope analysis and combining with the lithologic and stratigraphic characteristics. Rare earth element (REE) patterns exhibit upper-continental-crust-like signatures such as enrichment in light REEs and depletion in heavy REEs. The Fe isotopic composition of the red chalk is typically heavier than that of igneous rocks (except for one sample) and shows negative Eu anomalies (Eu/Eu* = 0.58–0.73), which indicates that the hematite in the red chalk is not of microbial or hydrothermal, but of sedimentary origin. At the same time, the analysis of trace elements suggests that the felsic rocks and sedimentary derivatives are the source of non-carbonate components in the red chalks. The pedogenic features such as mudcracks, secondary white chalks, and calcareous nodules appear in the red chalks, as documented through the field stratigraphic observations. Based on the above evidence and the sedimentary environment of the overlying and underlying layers, it is inferred that the red chalk was deposited in the supratidal environment that had undergone some degree of desiccation and pedogenic modification.

Late Jurassic Paleotethyan oceanic slab break-off revealed by Sr-Nd-Hf isotopes of Na-rich adakitic granites from northwestern Turkey

The Mesozoic geodynamic evolution of the Paleotethys Ocean is critical but a poorly known piece of the geological history of the Sakarya Zone, north Turkey. Here, we describe new integrated research of zircon U-Pb geochronology, bulk-rock major-trace element and Sr–Nd isotopes as well as Hf isotope of zircons from the granitic rocks of the Demirköy and Kızıldamlar plutons located in Bilecik area along the western Sakarya Zone, northwestern Turkey. Zircon U–Pb ages obtained by LA-ICP-MS reveal that the granitic magma intruded into the basement rocks during the Late Jurassic (ca. 162–157 Ma). The granites are tholeiitic and show slightly metaluminous to peraluminous geochemical affinities. The granite samples are adakitic, having relatively high Na2O (6.35–7.58 wt%) and Sr (172–580 ppm), and low K2O (0.39–1.13 wt%) and Y (3.2–5.3 ppm), and thus have high Sr/Y (70–250). The samples exhibit enrichment of light rare earth elements (REE) and large ion lithophile elements (LILE) and depletion in heavy REE and the high field strength elements (HFSE; e.g., Nb, Ti, Ta). The samples possess low 87Sr/86Sr(t) values of 0.70313 to 0.70372, and εNd(t) of −0.66 to +9.24. Zircon grains exhibit positive εHf (t) values of 5.0 to 12.8 and depleted mantle model ages of Hf (TDM1 = 0.24 to 0.68 Ga). These geochemical features and Sr–Nd–Hf radiogenic isotope systematics reveal that the adakitic rocks were likely formed by low degree melting (<10%) of the eclogitic part of an oceanic slab and subsequent melt fractionation and crustal contamination. An ongoing subduction scenario cannot explain the formation of the investigated adakitic rocks. We suggest that the adakitic plutons were generated through slab break-off after the final closure of the Paleotethys Ocean throughout the Late Jurassic (ca. 162–157 Ma). Considering the previous data, the continental back-arc basin system, leading to the opening of Neotethys Ocean at the southern margin of the continent, has been put forward to decipher the Late Jurassic tectonic evolution of the Paleotethys Ocean and the western Sakarya Zone.