Pub Date : 2024-05-07DOI: 10.1016/j.sesci.2024.100178
Guy Bertin Takam Tchoupe , Ekah Nzume Ndime , Donald Hermann Fossi , Arlette Soh Djoukouo , Milan Stafford Tchouatcha , Steven Arnold Mbita Motto , Sylvestre Ganno , Jean Paul Nzenti
The increasing importance of rare earth elements (REE) and critical metals in contemporary society has led us to investigate the mineral potential of the Ngaoumbol area, located within Cameroon's Central African Fold Belt (CAFB). In this study, we have conducted a comprehensive analysis that includes petrography, whole rock geochemistry, and mineral chemistry, along with the application of an outlook coefficient known as Koult, with the aim to evaluate the prospectivity of the Ngaoumbol iron formations as a potential source of REE-Y resources. This coefficient is defined as the ratio of the relative abundance of critical Rare Earth Elements to the relative abundance of excess REE. The iron formations in the Ngaoumbol area are fine-to medium-grained foliated rocks with alternating magnetite and actinolite bands and quartz bands, suggesting a sedimentary parentage. These rocks have an average REE-Y content of 1438.43 ppm and a Koult of 0.77, indicating their potential as raw sources for REE. Furthermore, the investigated samples exhibit high average Zr content (7748 ppm), suggesting that the rocks may host potentially economic Zr ore. The Zr-REE-Y mineralization in the Ngaoumbol area is hosted in detrital zircon, monazite and xenotime, probably deriving from the weathering of alkaline/subalkaline rocks surrounding the deposits. Our findings suggest that the Ngaoumbol area has promising REE and Zr resources. However, further exploration and evaluation are necessary to determine the extent and economic viability of these resources.
{"title":"Mineralization of Zr-REE-Y in the Ngaoumbol iron formations, central Cameroon: Insights from petrography, mineral chemistry and whole rock geochemistry","authors":"Guy Bertin Takam Tchoupe , Ekah Nzume Ndime , Donald Hermann Fossi , Arlette Soh Djoukouo , Milan Stafford Tchouatcha , Steven Arnold Mbita Motto , Sylvestre Ganno , Jean Paul Nzenti","doi":"10.1016/j.sesci.2024.100178","DOIUrl":"https://doi.org/10.1016/j.sesci.2024.100178","url":null,"abstract":"<div><p>The increasing importance of rare earth elements (REE) and critical metals in contemporary society has led us to investigate the mineral potential of the Ngaoumbol area, located within Cameroon's Central African Fold Belt (CAFB). In this study, we have conducted a comprehensive analysis that includes petrography, whole rock geochemistry, and mineral chemistry, along with the application of an outlook coefficient known as Koult, with the aim to evaluate the prospectivity of the Ngaoumbol iron formations as a potential source of REE-Y resources. This coefficient is defined as the ratio of the relative abundance of critical Rare Earth Elements to the relative abundance of excess REE. The iron formations in the Ngaoumbol area are fine-to medium-grained foliated rocks with alternating magnetite and actinolite bands and quartz bands, suggesting a sedimentary parentage. These rocks have an average REE-Y content of 1438.43 ppm and a Koult of 0.77, indicating their potential as raw sources for REE. Furthermore, the investigated samples exhibit high average Zr content (7748 ppm), suggesting that the rocks may host potentially economic Zr ore. The Zr-REE-Y mineralization in the Ngaoumbol area is hosted in detrital zircon, monazite and xenotime, probably deriving from the weathering of alkaline/subalkaline rocks surrounding the deposits. Our findings suggest that the Ngaoumbol area has promising REE and Zr resources. However, further exploration and evaluation are necessary to determine the extent and economic viability of these resources.</p></div>","PeriodicalId":54172,"journal":{"name":"Solid Earth Sciences","volume":"9 2","pages":"Article 100178"},"PeriodicalIF":2.0,"publicationDate":"2024-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2451912X24000163/pdfft?md5=2f786786a7f2ca785cf2ff9bfb4a9839&pid=1-s2.0-S2451912X24000163-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140878536","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-17DOI: 10.1016/j.sesci.2024.100176
Dan Wang , Yuanbao Song , Zhiming Sun , Wei Zhang , Wei Liu , Xiaoyong Yang
The Zhuqing vanadium–titanium magnetite is a large deposit recently discovered in the western margin of the Yangtze Block, where the Zhuqing gabbroic intrusion and associated Fe–Ti–V oxide deposits are fund and dated at 1647 ± 39 Ma (MSWD = 0.79) through U–Pb dating of gabbro zircons. The εHf(t) values of zircons are all positive, with an average of 10.7. The average age of the one-stage model age (TDM) is 1661 Ma, which is very close to the diagenetic and metallogenic age 1647 ± 39 Ma (MSWD = 0.79). These new results indicate that the magma source come directly from the mantle. The contents of Al2O3, CaO, and (Na2O + K2O) increases with the increase of SiO2 contents, while, the contents of MgO, TiO2, and Fe2O3 decreases with the increase of SiO2 contents. Mg# is relatively stable with the increase of SiO2 contents. In the primitive mantle-normalized trace element spider diagrams and chondrite-normalized rare earth element patterns, the characteristics of all samples are similar to that of ocean island basalts (OIBs), showing a right inclination curve. Meanwhile the western margin of the Yangtze Block as an essential part of the supercontinent of Colombia, began to extend at 1.7 Ga, lasted to ca. 1.4 Ga, and finally split. These suggest that the Zhuqing gabbroic intrusion and associated Fe–Ti–V oxide deposits with OIB characteristics formed in the Late Paleoproterozoic, which is a response to the breakup of the Colombian supercontinent in the western margin of the Yangtze Block.
{"title":"Petrogenesis, metallogenesis, and geodynamic setting of the Zhuqing gabbroic intrusion and associated Fe–Ti–V oxide deposits in the SW Yangtze Block, South China","authors":"Dan Wang , Yuanbao Song , Zhiming Sun , Wei Zhang , Wei Liu , Xiaoyong Yang","doi":"10.1016/j.sesci.2024.100176","DOIUrl":"https://doi.org/10.1016/j.sesci.2024.100176","url":null,"abstract":"<div><p>Th<strong>e</strong> Zhuqing vanadium–titanium magnetite is a large deposit recently discovered in the western margin of the Yangtze Block, where the Zhuqing gabbroic intrusion and associated Fe–Ti–V oxide deposits are fund and dated at 1647 ± 39 Ma (MSWD = 0.79) through U–Pb dating of gabbro zircons. The εHf(t) values of zircons are all positive, with an average of 10.7. The average age of the one-stage model age (T<sub>DM</sub>) is 1661 Ma, which is very close to the diagenetic and metallogenic age 1647 ± 39 Ma (MSWD = 0.79). These new results indicate that the magma source come directly from the mantle. The contents of Al<sub>2</sub>O<sub>3</sub>, CaO, and (Na<sub>2</sub>O + K<sub>2</sub>O) increases with the increase of SiO<sub>2</sub> contents, while, the contents of MgO, TiO<sub>2</sub>, and Fe<sub>2</sub>O<sub>3</sub> decreases with the increase of SiO<sub>2</sub> contents. Mg<sup>#</sup> is relatively stable with the increase of SiO<sub>2</sub> contents. In the primitive mantle-normalized trace element spider diagrams and chondrite-normalized rare earth element patterns, the characteristics of all samples are similar to that of ocean island basalts (OIBs), showing a right inclination curve. Meanwhile the western margin of the Yangtze Block as an essential part of the supercontinent of Colombia, began to extend at 1.7 Ga, lasted to ca. 1.4 Ga, and finally split. These suggest that the Zhuqing gabbroic intrusion and associated Fe–Ti–V oxide deposits with OIB characteristics formed in the Late Paleoproterozoic, which is a response to the breakup of the Colombian supercontinent in the western margin of the Yangtze Block.</p></div>","PeriodicalId":54172,"journal":{"name":"Solid Earth Sciences","volume":"9 2","pages":"Article 100176"},"PeriodicalIF":2.0,"publicationDate":"2024-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2451912X2400014X/pdfft?md5=56b33865de76dfbce3515500924c7155&pid=1-s2.0-S2451912X2400014X-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140605606","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A conceptual model has been proposed based on water samples collected from geothermal springs in the Shyok suture zone of North-West Himalayas, Ladakh geothermal province, India by nurturing hydrogeochemistry, mineralogical insights, and stable isotopic (δD, δ18O) systematics. The reservoir rock is comprised of granitic segment with intrusion of volcano-plutonics and a variety of meta-sedimentaries which becomes more exposed towards western side of the valley in the form of Shyok Ophiolitic melange. Thermal waters, located above 3100 m above msl, with variable genetic classification (Changlung: Na–HCO3; Panamik: both Na–HCO3 and mixed type; Pulthang: purely mixed type), have TDS and temperature lying between 587 and 2278 mg/L and 28−78 °C, respectively. High concentration of trace elements (Li, B, As, Cs, Rb, W) in geothermal fluids points to the magmatic origin regarding their enrichment mechanism. Surface manifestation of hydrothermal/evaporitic minerals like thenardite, trona, sylvite, halite, nahcolite, thermonatrite, etc. establishes a signature of high-temperature at shallow level of reservoir and their dissolution kinetics decipher origin of solutes apart from weathering of alkali/alkaline aluminosilicates. Utilizing empirical chemical geothermometry and Si-Enthalpy mixing modelling, the estimated reservoir temperatures exhibit significant variability ranging from 100 to 210 °C and reservoir silica concentration 382 mg/L with average circulation depth of geothermal waters around 1.8 Km and fluid residence time of 2640 years. The Shyok-Nubra springs liberate substantial amount of CO2-enriched water, with degassing flux of 6.26 × 105 mol of CO2/year. δD and δ18O systematics reveal that geothermal springs are recharged by meteoric water, snow-melt and magmatic fluid with cold-water component of 27.1–62.4% mixed with hot fluids. Thermal springs are recharged from a single reservoir source located a shallow level towards North-West of Changlung having large lateral flow of about 25 Km generating Panamik and Pulthang fluids with subsequent dilution. This study highlights the extent and consequences of water–rock interaction across diverse lithologies (granite and mafic volcanics) in the Himalayas, emphasizing its implications over fluid circulation time and subsurface temperature considerations which rationalizes the evolution of geothermal fluids.
{"title":"Tracing the evolution of shallow geothermal springs in the Shyok−Nubra Valley of North-West Himalayas, India through hydrogeochemistry and stable isotopes (δ18O, δD)","authors":"Parashar Mishra , Archisman Dutta , Ahsan Absar , Vivek Prakash Malviya , Pankaj Saini , Ayodhaya Prasad Thapliyal , Sayandeep Banerjee","doi":"10.1016/j.sesci.2024.100175","DOIUrl":"https://doi.org/10.1016/j.sesci.2024.100175","url":null,"abstract":"<div><p>A conceptual model has been proposed based on water samples collected from geothermal springs in the Shyok suture zone of North-West Himalayas, Ladakh geothermal province, India by nurturing hydrogeochemistry, mineralogical insights, and stable isotopic (δD, δ<sup>18</sup>O) systematics. The reservoir rock is comprised of granitic segment with intrusion of volcano-plutonics and a variety of meta-sedimentaries which becomes more exposed towards western side of the valley in the form of Shyok Ophiolitic melange. Thermal waters, located above 3100 m above msl, with variable genetic classification (Changlung: Na–HCO<sub>3</sub>; Panamik: both Na–HCO<sub>3</sub> and mixed type; Pulthang: purely mixed type), have TDS and temperature lying between 587 and 2278 mg/L and 28−78 °C, respectively. High concentration of trace elements (Li, B, As, Cs, Rb, W) in geothermal fluids points to the magmatic origin regarding their enrichment mechanism. Surface manifestation of hydrothermal/evaporitic minerals like thenardite, trona, sylvite, halite, nahcolite, thermonatrite, etc. establishes a signature of high-temperature at shallow level of reservoir and their dissolution kinetics decipher origin of solutes apart from weathering of alkali/alkaline aluminosilicates. Utilizing empirical chemical geothermometry and Si-Enthalpy mixing modelling, the estimated reservoir temperatures exhibit significant variability ranging from 100 to 210 °C and reservoir silica concentration 382 mg/L with average circulation depth of geothermal waters around 1.8 Km and fluid residence time of 2640 years. The Shyok-Nubra springs liberate substantial amount of CO<sub>2</sub>-enriched water, with degassing flux of 6.26 × 10<sup>5</sup> mol of CO<sub>2</sub>/year. δD and δ<sup>18</sup>O systematics reveal that geothermal springs are recharged by meteoric water, snow-melt and magmatic fluid with cold-water component of 27.1–62.4% mixed with hot fluids. Thermal springs are recharged from a single reservoir source located a shallow level towards North-West of Changlung having large lateral flow of about 25 Km generating Panamik and Pulthang fluids with subsequent dilution. This study highlights the extent and consequences of water–rock interaction across diverse lithologies (granite and mafic volcanics) in the Himalayas, emphasizing its implications over fluid circulation time and subsurface temperature considerations which rationalizes the evolution of geothermal fluids.</p></div>","PeriodicalId":54172,"journal":{"name":"Solid Earth Sciences","volume":"9 2","pages":"Article 100175"},"PeriodicalIF":2.0,"publicationDate":"2024-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2451912X24000138/pdfft?md5=4a81d5bcb869b5acf2b7196b84fd2a96&pid=1-s2.0-S2451912X24000138-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140543358","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-08DOI: 10.1016/j.sesci.2024.100165
Nazir-ur- Rehman , Sajjad Ahmad , Shah Faisal , Shuja Ullah , Mumtaz Ali Khan , Fakhrul Islam
More recently Kohat's fold-thrust belt, including the Karak area has emerged as an important hydrocarbon fertile region of the western Himalayan orogenic system. The Eocene and Paleocene strata, including mechanical weak Eocene units representing a shallow decollement have a noticeable contribution to the deformation style and petroleum system of the area. In the present study, surface mapping is integrated with seismic information to elucidate the structural style of the Karak area, the data reveal that there are two different structural entities, separated by Karak Fault Zone. The northern domain portrays salt diapiric structures representing doubly plunging and complexity overturned, and fault bounded folds' geometries. However, in the subsurface below the Eocene sequence, the deformation is characterized by south-directed imbricate thrust system. In contrast, because of the absence of Eocene salt horizon, the southern domain of the Karak area illustrates a brittle style of deformation, mimicking fault propagation folding. In addition, an array of south-verging imbricate system from a regional basal decollement translates rock as old as Permian along the Surghar range frontal thrust. It can be observed that fault geometry and fold styles in the north and south of Karak Fault Zone are entirely different. Restored cross-sections across the area indicate 35% of shortening has been accommodated in the area. Moreover, from the present study it has been concluded that in the purlieu of Karak Fault Zone, possibly occupy auspicious structural traps at top Paleocene Lockhart level.
{"title":"Structural modeling of the southern Kohat Basin and Frontal Ranges; implications for tectonic evolution and hydrocarbon play","authors":"Nazir-ur- Rehman , Sajjad Ahmad , Shah Faisal , Shuja Ullah , Mumtaz Ali Khan , Fakhrul Islam","doi":"10.1016/j.sesci.2024.100165","DOIUrl":"https://doi.org/10.1016/j.sesci.2024.100165","url":null,"abstract":"<div><p>More recently Kohat's fold-thrust belt, including the Karak area has emerged as an important hydrocarbon fertile region of the western Himalayan orogenic system. The Eocene and Paleocene strata, including mechanical weak Eocene units representing a shallow decollement have a noticeable contribution to the deformation style and petroleum system of the area. In the present study, surface mapping is integrated with seismic information to elucidate the structural style of the Karak area, the data reveal that there are two different structural entities, separated by Karak Fault Zone. The northern domain portrays salt diapiric structures representing doubly plunging and complexity overturned, and fault bounded folds' geometries. However, in the subsurface below the Eocene sequence, the deformation is characterized by south-directed imbricate thrust system. In contrast, because of the absence of Eocene salt horizon, the southern domain of the Karak area illustrates a brittle style of deformation, mimicking fault propagation folding. In addition, an array of south-verging imbricate system from a regional basal decollement translates rock as old as Permian along the Surghar range frontal thrust. It can be observed that fault geometry and fold styles in the north and south of Karak Fault Zone are entirely different. Restored cross-sections across the area indicate 35% of shortening has been accommodated in the area. Moreover, from the present study it has been concluded that in the purlieu of Karak Fault Zone, possibly occupy auspicious structural traps at top Paleocene Lockhart level.</p></div>","PeriodicalId":54172,"journal":{"name":"Solid Earth Sciences","volume":"9 2","pages":"Article 100165"},"PeriodicalIF":2.0,"publicationDate":"2024-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2451912X24000035/pdfft?md5=1a97c8f27a62fdbc251faaac5b2fb37f&pid=1-s2.0-S2451912X24000035-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140063106","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-02-02DOI: 10.1016/j.sesci.2024.01.002
Mokake Esue Fidelis , Mary Ewokolo Moloua Etutu , Bisse Salomon Betrant , Bokanda Ekoko Eric , Florence Njinto Kwankam , Victor L. Wotany , Lemnyuy Prosper Yiika , E. Mengu Emmanuel , Njoh, N. Clevis , N. Nfor Shannon , Patrick Mendi Wajiba , Chin Thiery Berinyuy , Kah Odilia Sih , Christorpher M. Agyingi
The Mundeck and Mungo River Formation sandstones located within the Douala sub basin in Cameroon were subjected to both petrographic and geochemical analyses to unveil their geological characterization such as chemical and mineralogical maturity, litho-tectonic setting, climate and weathering intensity of the source area at the time of their formation. Petrographic studies reveals that the sandstones show variable colours ranging from reddish to brownish, pinkish, grey and white with textures ranging from medium to coarse grained. The studied sandstones consist of various types of angular to sub angular, quartz, rock fragments, mica, feldspar. Modal analysis data and plots of detrital modes of the studied sandstones on Qt–F–RF diagrams suggest that they were derived from a plutonic source rock (igneous origin) with little or no contribution from metamorphic sources. Plot of the Qm–F–L diagram of the studied sandstones reveal a quartzose recycled and transitional continental provenance fields. Mineralogical classification of these sandstones from Qt–F–RF triangular diagram classifies them as arkose, lithic arkose and sub-litherarenite. Bivariate plot of Qp/(F + R) vs (Qm + Qp)/(F + R), SiO2 Vs Al2O3 +K2O + Na2O coupled with values of Chemical index Alteration (CIA = 70–99) and plagioclase index Alteration (PIA>80) reveal a moderate to high intensity of weathering in the source area under a semi-humid to humid paleoclimatic conditions with high lixiviation of feldspars (PIA>80 %) for the studied sandstones. The mineralogical maturity index (MMI = 3–9) coupled with the new index of compositional variation (ICVnew <1) reveal that the sandstones are sub mature to mature. Geochemical binary plots of La/Sc, Th/Co, Th/Sc couple with plots of DF1vs DF2 and K2O/Na2O vs SiO2 points to an igneous felsic source rock formed in a passive margin for the studied sandstones.
对位于喀麦隆杜阿拉次盆地的蒙代克和蒙戈河地层砂岩进行了岩石学和地球化学分析,以揭示其地质特征,如化学和矿物学成熟度、岩石构造环境、气候以及形成时源地的风化强度。岩石学研究显示,这些砂岩呈现出不同的颜色,从淡红色到褐色、粉红色、灰色和白色,纹理从中等到粗粒不等。所研究的砂岩由各种类型的角状至亚角状石英、岩石碎片、云母和长石组成。所研究砂岩的模态分析数据和 Qt-F-RF 图上的碎屑模态图表明,这些砂岩来自柱状源岩(火成岩源),变质源很少或没有。所研究砂岩的 Qm-F-L 图显示了石英质再循环和过渡大陆来源领域。根据 Qt-F-RF 三角图对这些砂岩进行的矿物学分类将其划分为石英质砂岩、石英质砂岩和亚锂辉石岩。Qp/(F + R) vs (Qm + Qp)/(F + R)、SiO2 Vs Al2O3 +K2O + Na2O 的双变量图以及化学蚀变指数(CIA = 70-99)和斜长石蚀变指数(PIA>;80)显示,在半湿润至潮湿的古气候条件下,所研究砂岩的源区风化强度为中度至高度,长石的活化程度较高(PIA>80 %)。矿物学成熟度指数(MMI = 3-9)和新的成分变异指数(ICVnew <1)显示,这些砂岩从亚成熟到成熟。La/Sc、Th/Co、Th/Sc 的地球化学二元图以及 DF1 vs DF2 和 K2O/Na2O vs SiO2 的图表明,所研究的砂岩是在被动边缘形成的火成长岩。
{"title":"Geochemical maturity, litho-tectonic settings and source area paleoweathering characterization of the Cretaceous Mundeck and Mungo River Formation sandstones, North Western, Douala sub basin, West Africa: A petrographic and geochemical approach","authors":"Mokake Esue Fidelis , Mary Ewokolo Moloua Etutu , Bisse Salomon Betrant , Bokanda Ekoko Eric , Florence Njinto Kwankam , Victor L. Wotany , Lemnyuy Prosper Yiika , E. Mengu Emmanuel , Njoh, N. Clevis , N. Nfor Shannon , Patrick Mendi Wajiba , Chin Thiery Berinyuy , Kah Odilia Sih , Christorpher M. Agyingi","doi":"10.1016/j.sesci.2024.01.002","DOIUrl":"https://doi.org/10.1016/j.sesci.2024.01.002","url":null,"abstract":"<div><p>The Mundeck and Mungo River Formation sandstones located within the Douala sub basin in Cameroon were subjected to both petrographic and geochemical analyses to unveil their geological characterization such as chemical and mineralogical maturity, litho-tectonic setting, climate and weathering intensity of the source area at the time of their formation. Petrographic studies reveals that the sandstones show variable colours ranging from reddish to brownish, pinkish, grey and white with textures ranging from medium to coarse grained. The studied sandstones consist of various types of angular to sub angular, quartz, rock fragments, mica, feldspar. Modal analysis data and plots of detrital modes of the studied sandstones on Qt–F–RF diagrams suggest that they were derived from a plutonic source rock (igneous origin) with little or no contribution from metamorphic sources. Plot of the Qm–F–L diagram of the studied sandstones reveal a quartzose recycled and transitional continental provenance fields. Mineralogical classification of these sandstones from Qt–F–RF triangular diagram classifies them as arkose, lithic arkose and sub-litherarenite. Bivariate plot of Qp/(F + R) <em>vs</em> (Qm + Qp)/(F + R), SiO<sub>2</sub> Vs Al<sub>2</sub>O<sub>3</sub> +K<sub>2</sub>O + Na<sub>2</sub>O coupled with values of Chemical index Alteration (CIA = 70–99) and plagioclase index Alteration (PIA>80) reveal a moderate to high intensity of weathering in the source area under a semi-humid to humid paleoclimatic conditions with high lixiviation of feldspars (PIA>80 %) for the studied sandstones. The mineralogical maturity index (MMI = 3–9) coupled with the new index of compositional variation (ICV<sub>new</sub> <1) reveal that the sandstones are sub mature to mature. Geochemical binary plots of La/Sc, Th/Co, Th/Sc couple with plots of DF1vs DF2 and K<sub>2</sub>O/Na<sub>2</sub>O <em>vs</em> SiO<sub>2</sub> points to an igneous felsic source rock formed in a passive margin for the studied sandstones.</p></div>","PeriodicalId":54172,"journal":{"name":"Solid Earth Sciences","volume":"9 1","pages":"Article 100164"},"PeriodicalIF":2.0,"publicationDate":"2024-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2451912X24000023/pdfft?md5=4b08e3cd1639d14ac42c7ddac0f63b6c&pid=1-s2.0-S2451912X24000023-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139674770","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-01-30DOI: 10.1016/j.sesci.2024.01.001
Likai Ge, Qiaoqin Xie, Jun Yan, Shan Huang, Liu Yang, Quanzhong Li, Jiancheng Xie
The origin and evolution of tungsten ore, a key metal resource, have long been controversial. In order to reveal the origin of tungsten mineralization related to weakly fractionated I-type granites, we have carried out detailed in situ element analysis on apatite from gabbro-diorite enclaves and their host rocks (biotite granodiorites) in Zhuxiling deposit, Jiangnan orogenic belt. The groups of apatite samples were identified, respectively from gabbro-diorite enclaves (Group A) representing deep early magma, and biotite granodiorites with weak tungsten mineralization stage (Group B) and strong tungsten mineralization stage (Group C). The three-group apatite samples with high F (2.15–4.74 wt.%) and low Cl (<0.19 wt.%) contents, belong to fluoroapatite, and have LREE enrichment, negative Eu anomalies (Eu/Eu∗ = 0.27–0.52), and low Sr/Y ratios (mainly <1). The Sr content difference between the apatite studied and host rocks, and the gradual increase of Sr contents from Group A to Group B to Group C, indicate that high tungsten content magma mixing is the dominant cause of mineralization in the Zhuxiling region. The studied apatite samples with different internal zonal textures, suggest that more significant oscillatory growth zone is associated with higher tungsten content, more complex internal compositions, and longer crystallization times. Apatite trace elements (e.g., Sr, Y, Eu/Eu∗, REE) characteristics indicate that the Zhuxiling mineralized intrusions mainly experienced shallow feldspar crystalline differentiation. The F- and Li-rich, high evolution degree, and moderate oxygen fugacity of magma may contribute to tungsten mineralization in the Zhuxiling region.
{"title":"Geochemistry of apatite from Zhuxiling tungsten deposit, eastern China: A record of magma evolution and tungsten enrichment","authors":"Likai Ge, Qiaoqin Xie, Jun Yan, Shan Huang, Liu Yang, Quanzhong Li, Jiancheng Xie","doi":"10.1016/j.sesci.2024.01.001","DOIUrl":"https://doi.org/10.1016/j.sesci.2024.01.001","url":null,"abstract":"<div><p>The origin and evolution of tungsten ore, a key metal resource, have long been controversial. In order to reveal the origin of tungsten mineralization related to weakly fractionated I-type granites, we have carried out detailed in situ element analysis on apatite from gabbro-diorite enclaves and their host rocks (biotite granodiorites) in Zhuxiling deposit, Jiangnan orogenic belt. The groups of apatite samples were identified, respectively from gabbro-diorite enclaves (Group A) representing deep early magma, and biotite granodiorites with weak tungsten mineralization stage (Group B) and strong tungsten mineralization stage (Group C). The three-group apatite samples with high F (2.15–4.74 wt.%) and low Cl (<0.19 wt.%) contents, belong to fluoroapatite, and have LREE enrichment, negative Eu anomalies (Eu/Eu∗ = 0.27–0.52), and low Sr/Y ratios (mainly <1). The Sr content difference between the apatite studied and host rocks, and the gradual increase of Sr contents from Group A to Group B to Group C, indicate that high tungsten content magma mixing is the dominant cause of mineralization in the Zhuxiling region. The studied apatite samples with different internal zonal textures, suggest that more significant oscillatory growth zone is associated with higher tungsten content, more complex internal compositions, and longer crystallization times. Apatite trace elements (e.g., Sr, Y, Eu/Eu∗, REE) characteristics indicate that the Zhuxiling mineralized intrusions mainly experienced shallow feldspar crystalline differentiation. The F- and Li-rich, high evolution degree, and moderate oxygen fugacity of magma may contribute to tungsten mineralization in the Zhuxiling region.</p></div>","PeriodicalId":54172,"journal":{"name":"Solid Earth Sciences","volume":"9 1","pages":"Article 100163"},"PeriodicalIF":2.0,"publicationDate":"2024-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2451912X24000011/pdfft?md5=fb144e05328940a25163c1aa32e0fc15&pid=1-s2.0-S2451912X24000011-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139652811","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-01-25DOI: 10.1016/j.sesci.2023.12.001
Haotian Liu , Xing Ding , Haibo Yan , Kaixuan Liu , Junfeng Liu , Xiaolong Huang
Metal dissolution, complexation, and speciation are the key processes that facilitate metal mobilization and transport in fluids. Niobium (Nb), a kind of critical metal, has traditionally been regarded as a fluid-immobile element; however, it sometimes shows apparent hydrothermal mobility and even mineralization. Studying the solubility and complexation of Nb in fluids is thus crucial for understanding its dissolution, transport, enrichment, and mineralization. In this paper, we reviewed the geological observations on Nb mobility related to magmatic-hydrothermal and metamorphic fluid activities, especially compiled and reprocessed the published data on Nb solubility and related thermodynamic calculation to discuss the complexation and speciation of Nb in fluids. Previous solubility experiments demonstrate that Nb has much higher solubility in F-bearing solutions than in other solutions (Cl−, ClO4−, CO32−, HCO3−, OH−, SO42−, etc.), the maximum of which is up to ∼3 wt% in a 2 mol/kg HF solution. It is revealed that Nb solubility is related to the solution's composition, pH, ionic strength, oxygen fugacity, temperature, and pressure. High solubility could be found in neutral and weakly-basic solutions at near ambient temperature and pressure or in F-bearing fluids at high-temperature and high-pressure conditions. Modeling calculations show that Nb could be soluble and stable in fluids as the mononuclear or polynuclear complexes, such as fluoride complexes, hydroxide complexes, chloride complexes, and hexametalate ions, etc. Thereinto, Nb–OH–F complexes should play a dominant role in Nb hydrothermal mobility and be enriched in medium–high temperature, acidic, and F-bearing fluids. Experiments and modeling calculation have also inferred the existence of the species (e.g., , , and ), in which the F coordination number is no more than 3. Considering that it could have higher F contents than the experimental solutions (F < 4 wt%), we believe that natural mineralized F-rich fluids would facilitate the formation of the species with higher F coordination numbers due to the positive relationship between the F coordination number in the species and F content in fluids
金属溶解、络合和分化是促进金属在流体中移动和迁移的关键过程。铌(Nb)是一种临界金属,传统上被认为是一种不流动的流体元素;然而,它有时会表现出明显的热液流动性,甚至矿化。因此,研究铌在流体中的溶解度和络合度对于了解铌的溶解、迁移、富集和矿化至关重要。在本文中,我们回顾了与岩浆-热液和变质流体活动有关的铌流动性地质观察结果,特别是对已发表的铌溶解度数据和相关热力学计算进行了汇编和再处理,以讨论铌在流体中的络合和富集问题。以往的溶解度实验表明,铌在含氟溶液中的溶解度远高于在其他溶液(Cl-、ClO4-、CO32-、HCO3-、OH-、SO42-等)中的溶解度,其中在2 mol/kg HF溶液中的溶解度最大可达∼3 wt%。研究表明,铌的溶解度与溶液的成分、pH 值、离子强度、氧富集度、温度和压力有关。在接近环境温度和压力的中性和弱碱性溶液中,或在高温高压条件下的含氟流体中,铌的溶解度都很高。模型计算表明,铌在流体中可以单核或多核络合物的形式溶解和稳定,如氟化物络合物、氢氧化物络合物、氯化物络合物和六金属酸根离子等。因此,Nb-OH-F 复合物应在铌热液流动性中起主导作用,并在中高温、酸性和含 F 的流体中富集。实验和模型计算还推断出存在 F 配位数不超过 3 的物种(如 Nb(OH)4+yFy-、Nb(OH)3+yF2y- 和 Nb(OH)2+yF3y-)。考虑到其 F 含量可能高于实验溶液(F < 4 wt%),我们认为,由于物种中的 F 配位数与流体中的 F 含量之间存在正相关,富含 F 的天然矿化流体将促进 F 配位数更高的物种的形成。与 Nb-OH-F 复合物相比,Nb-OH 复合物的稳定性和可溶性较差,但在含有低浓度配体阴离子的稀溶液或碱性溶液中占主导地位。此外,还讨论了需要进一步补充的实验和需要解决的问题,这将加深我们对与热液活动有关的铌循环和矿化是如何发生的的理解。
{"title":"The solubility and complexation of Niobium in hydrothermal fluids","authors":"Haotian Liu , Xing Ding , Haibo Yan , Kaixuan Liu , Junfeng Liu , Xiaolong Huang","doi":"10.1016/j.sesci.2023.12.001","DOIUrl":"https://doi.org/10.1016/j.sesci.2023.12.001","url":null,"abstract":"<div><p>Metal dissolution, complexation, and speciation are the key processes that facilitate metal mobilization and transport in fluids. Niobium (Nb), a kind of critical metal, has traditionally been regarded as a fluid-immobile element; however, it sometimes shows apparent hydrothermal mobility and even mineralization. Studying the solubility and complexation of Nb in fluids is thus crucial for understanding its dissolution, transport, enrichment, and mineralization. In this paper, we reviewed the geological observations on Nb mobility related to magmatic-hydrothermal and metamorphic fluid activities, especially compiled and reprocessed the published data on Nb solubility and related thermodynamic calculation to discuss the complexation and speciation of Nb in fluids. Previous solubility experiments demonstrate that Nb has much higher solubility in F-bearing solutions than in other solutions (Cl<sup>−</sup>, ClO<sub>4</sub><sup>−</sup>, CO<sub>3</sub><sup>2−</sup>, HCO<sub>3</sub><sup>−</sup>, OH<sup>−</sup>, SO<sub>4</sub><sup>2−</sup>, etc.), the maximum of which is up to ∼3 wt% in a 2 mol/kg HF solution. It is revealed that Nb solubility is related to the solution's composition, pH, ionic strength, oxygen fugacity, temperature, and pressure. High solubility could be found in neutral and weakly-basic solutions at near ambient temperature and pressure or in F-bearing fluids at high-temperature and high-pressure conditions. Modeling calculations show that Nb could be soluble and stable in fluids as the mononuclear or polynuclear complexes, such as fluoride complexes, hydroxide complexes, chloride complexes, and hexametalate ions, etc. Thereinto, Nb–OH–F complexes should play a dominant role in Nb hydrothermal mobility and be enriched in medium–high temperature, acidic, and F-bearing fluids. Experiments and modeling calculation have also inferred the existence of the species (e.g., <span><math><mrow><mtext>Nb</mtext><msub><mrow><mo>(</mo><mtext>OH</mtext><mo>)</mo></mrow><mrow><mn>4</mn><mo>+</mo><mi>y</mi></mrow></msub><msup><mi>F</mi><mrow><mi>y</mi><mo>−</mo></mrow></msup></mrow></math></span>, <span><math><mrow><mtext>Nb</mtext><msub><mrow><mo>(</mo><mtext>OH</mtext><mo>)</mo></mrow><mrow><mn>3</mn><mo>+</mo><mi>y</mi></mrow></msub><msubsup><mi>F</mi><mn>2</mn><mrow><mi>y</mi><mo>−</mo></mrow></msubsup></mrow></math></span>, and <span><math><mrow><mtext>Nb</mtext><msub><mrow><mo>(</mo><mtext>OH</mtext><mo>)</mo></mrow><mrow><mn>2</mn><mo>+</mo><mi>y</mi></mrow></msub><msubsup><mi>F</mi><mn>3</mn><mrow><mi>y</mi><mo>−</mo></mrow></msubsup></mrow></math></span>), in which the F coordination number is no more than 3. Considering that it could have higher F contents than the experimental solutions (F < 4 wt%), we believe that natural mineralized F-rich fluids would facilitate the formation of the species with higher F coordination numbers due to the positive relationship between the F coordination number in the species and F content in fluids","PeriodicalId":54172,"journal":{"name":"Solid Earth Sciences","volume":"9 1","pages":"Article 100162"},"PeriodicalIF":2.0,"publicationDate":"2024-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2451912X2300048X/pdfft?md5=93401c0a514d356ffb21056ee20d2bfb&pid=1-s2.0-S2451912X2300048X-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139652812","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-12-15DOI: 10.1016/j.sesci.2023.10.002
Mengfei Ruan , Jintuan Wang , Xiaolin Xiong , Li Li
Metasomatic zircons in ultramafic rocks are crucial in tracking orogenic processes. Metasomatic zircons are conceived to form by local zircon saturation resulting from effective Zr transport during metamorphic events and incomplete Zr accommodation in mantle minerals. However, the accommodation capacity of Zr in mantle minerals remains unknown, hampering our understanding of zircon genesis in ultramafic rocks. Here we performed experiments at 2.0−6.0 GPa and 1050−1200 °C and determined Zr content (solubility) in the mantle minerals at zircon saturation (ZCZS). The results show that ZCZS values for the main mantle minerals are olivine (ol, 3.68 ± 0.27 ppm) < orthopyroxene (opx, 4.67 ± 0.23 ppm) < clinopyroxene (cpx, 28−1403 ppm) ≤ garnet (grt, 294−2222 ppm) with ZCZS for amphibole (amp, 189−546 ppm) and magnetite (mag, 263−630 ppm) overlapping that for cpx and grt under the experimental conditions. The significant variations of ZCZS for cpx and grt depends on mineral composition and P−T conditions. In detail, the ZCZS for cpx increases with temperature, Al2O3 content of cpx, and decreases with pressure; that for grt increases with temperature and XAlm (molar fraction of almandine) in garnet. Important implications of this study include: 1) Considering the very low ZCZS for ol and opx, dunite and harzburgite are prone to zircon saturation during the infiltration of Zr-bearing metamorphic agents; 2) Because garnet is the main reservoir of Zr in garnet peridotite, metamorphic decomposition of garnets may produce inter-granular zircons; 3) The ZCZS for garnet excellently correlates with XAlm and T, providing a potential geo-thermometer for garnet-bearing zircon saturated rocks.
{"title":"Zr solubility in mantle minerals at zircon saturation: Implications for zircon genesis in ultramafic rocks","authors":"Mengfei Ruan , Jintuan Wang , Xiaolin Xiong , Li Li","doi":"10.1016/j.sesci.2023.10.002","DOIUrl":"10.1016/j.sesci.2023.10.002","url":null,"abstract":"<div><p>Metasomatic zircons in ultramafic rocks are crucial in tracking orogenic processes. Metasomatic zircons are conceived to form by local zircon saturation resulting from effective Zr transport during metamorphic events and incomplete Zr accommodation in mantle minerals. However, the accommodation capacity of Zr in mantle minerals remains unknown, hampering our understanding of zircon genesis in ultramafic rocks. Here we performed experiments at 2.0−6.0 GPa and 1050−1200 °C and determined Zr content (solubility) in the mantle minerals at zircon saturation (ZCZS). The results show that ZCZS values for the main mantle minerals are olivine (ol, 3.68 ± 0.27 ppm) < orthopyroxene (opx, 4.67 ± 0.23 ppm) < clinopyroxene (cpx, 28−1403 ppm) ≤ garnet (grt, 294−2222 ppm) with ZCZS for amphibole (amp, 189−546 ppm) and magnetite (mag, 263−630 ppm) overlapping that for cpx and grt under the experimental conditions. The significant variations of ZCZS for cpx and grt depends on mineral composition and P−T conditions. In detail, the ZCZS for cpx increases with temperature, Al<sub>2</sub>O<sub>3</sub> content of cpx, and decreases with pressure; that for grt increases with temperature and X<sub>Alm</sub> (molar fraction of almandine) in garnet. Important implications of this study include: 1) Considering the very low ZCZS for ol and opx, dunite and harzburgite are prone to zircon saturation during the infiltration of Zr-bearing metamorphic agents; 2) Because garnet is the main reservoir of Zr in garnet peridotite, metamorphic decomposition of garnets may produce inter-granular zircons; 3) The ZCZS for garnet excellently correlates with X<sub>Alm</sub> and T, providing a potential geo-thermometer for garnet-bearing zircon saturated rocks.</p></div>","PeriodicalId":54172,"journal":{"name":"Solid Earth Sciences","volume":"8 4","pages":"Pages 283-294"},"PeriodicalIF":2.0,"publicationDate":"2023-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2451912X23000387/pdfft?md5=25076f6b44bcdcc240d34580fe6a30aa&pid=1-s2.0-S2451912X23000387-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138620682","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-12-15DOI: 10.1016/j.sesci.2023.09.001
Ying Wei , Ming-Xing Ling , Hong Zhang , Yu-Long Liu , Xiao-Yong Yang
Bayan Obo, located in the north margin of the Yinshan Block, North China Craton (NCC), contains the Archean to Paleoproterozoic basement rocks which may shed light on the early crustal evolution of the NCC. In this paper, to reveal the formation and modification of the basements, we report Hf isotope of zircons from the biotite plagiogneisses in Bayan Obo. Combined with the published U–Pb ages and Hf isotope compositions of the zircons from the Bayan Obo basement rocks, a comprehensive review was employed to provide new insights into the formation and modification of the basement in this area. The oldest formation age of the basement rocks was found to be approximately 2.6 Ga, with positive εHf(t) values indicating the contribution from the depleted mantle to the rocks. The age of ∼2.0 Ga marks the major formation period of the basement rocks. The varied εHf(t) values (−17.2 to +8.9) of the magmatic zircons suggest a mixture origin between the depleted mantle and crustal rocks for the gneiss. The basement went through extensive metamorphism during 1.95–1.9 Ga. In addition, zircon U–Pb–Hf isotope data of the Precambrian units in Guyang and Wuchuan, which are adjacent to Bayan Obo, were compiled for comparison. The comprehensive review on the data of the concordant magmatic zircons indicates the existence of 3.5 Ga crustal fragments in the Yinshan Block. The melting of the depleted mantle and the addition of juvenile materials into the crust at 2.6–2.9 Ga and 2.45–2.55 Ga were confirmed by the high positive εHf(t) values of the magmatic and inherited zircons. An increase in remelting of the crust at 2.0 Ga is deduced from the extremely unradiogenic Hf isotope of the magmatic zircons.
{"title":"Zircon Hf isotopic compositions of the basement gneiss in Bayan Obo: Constraints on crustal evolution of the Yinshan Block in the North China Craton","authors":"Ying Wei , Ming-Xing Ling , Hong Zhang , Yu-Long Liu , Xiao-Yong Yang","doi":"10.1016/j.sesci.2023.09.001","DOIUrl":"10.1016/j.sesci.2023.09.001","url":null,"abstract":"<div><p>Bayan Obo, located in the north margin of the Yinshan Block, North China Craton (NCC), contains the Archean to Paleoproterozoic basement rocks which may shed light on the early crustal evolution of the NCC. In this paper, to reveal the formation and modification of the basements, we report Hf isotope of zircons from the biotite plagiogneisses in Bayan Obo. Combined with the published U–Pb ages and Hf isotope compositions of the zircons from the Bayan Obo basement rocks, a comprehensive review was employed to provide new insights into the formation and modification of the basement in this area. The oldest formation age of the basement rocks was found to be approximately 2.6 Ga, with positive <em>ε</em><sub><em>Hf</em></sub><em>(t)</em> values indicating the contribution from the depleted mantle to the rocks. The age of ∼2.0 Ga marks the major formation period of the basement rocks. The varied <em>ε</em><sub><em>Hf</em></sub><em>(t)</em> values (−17.2 to +8.9) of the magmatic zircons suggest a mixture origin between the depleted mantle and crustal rocks for the gneiss. The basement went through extensive metamorphism during 1.95–1.9 Ga. In addition, zircon U–Pb–Hf isotope data of the Precambrian units in Guyang and Wuchuan, which are adjacent to Bayan Obo, were compiled for comparison. The comprehensive review on the data of the concordant magmatic zircons indicates the existence of 3.5 Ga crustal fragments in the Yinshan Block. The melting of the depleted mantle and the addition of juvenile materials into the crust at 2.6–2.9 Ga and 2.45–2.55 Ga were confirmed by the high positive <em>ε</em><sub><em>Hf</em></sub><em>(t)</em> values of the magmatic and inherited zircons. An increase in remelting of the crust at 2.0 Ga is deduced from the extremely unradiogenic Hf isotope of the magmatic zircons.</p></div>","PeriodicalId":54172,"journal":{"name":"Solid Earth Sciences","volume":"8 4","pages":"Pages 255-266"},"PeriodicalIF":2.0,"publicationDate":"2023-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2451912X23000363/pdfft?md5=d6225c370defe5b72593f73965cd0463&pid=1-s2.0-S2451912X23000363-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"134993811","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}