Lithological and Si–O–S isotope geochemistry:constraints on the origin and genetic environment of the selenium(Se)-rich siliceous rocks in Enshi,Hubei Province,China

Se-rich black rock series of the Middle and Late Permian system is widely distributed in Enshi Prefecture with an exposed area of 850 km~2,among which the unique Yutangba black rock series independent selenium deposit with industrial mining significance in the world is produced.However,the source and metallogenic mechanisms of Se are still controversial.In general,terrestrial weathering and submarine hydrothermal processes are the main source end members of Si and Se,and the related siliceous rocks record the deposition process of Si and Se from different sources.The study of lithofacies and paleogeography shows that western Hubei belongs to the near eastwest turn of the Yangzi platform in the Middle and Late Permian and becomes an inter-platform basin with nearly north-south direction.Therefore,the comparative study of the Yutangba deposit and the selenium-rich black rock series in the northern Shadi with high selenium content is expected to reveal the provenance evolution of the two sections in space,and further restrict the Se mineralization mechanism in the Enshi basin.From the element geochemistry study,the black rock series in two study areas may have formed in a transitional position of either the continental margin or continental slope,in the process of sedimentary,more terrigenous clastic materials entered.They are rich in lithophile elements V and Cr.δU>1.0,U/Th and V/(V+Ni)ratio indicate that the Se-rich strata of black rock series in the Enshi areas occurred in an anoxic reducing environment and formed in an environment between the ocean basin and the continental margin.From Si-O isotope geochemistry,the original Si source of the study area is thought to relate to a volcanic eruption,which leads to the enrichment of Si in the seawater.The determined values of S isotope in the black rock series of the two study areas both show the characteristics related to organic reduction/biogenic.

Germanium/silica ratio and trace element composition of Early Cambrian siliceous rocks in Keping:implications for the siliceous rocks'formation and paleoenvironment interpretations

This study used the germanium/silica(Ge/Si)ratios,together with rare earth elements and other trace elements to infer the siliceous source and sedimentary environment of the siliceous rocks located at the bottom of Yuertusi Formation in Northwestern Tarim Basin,Keping,China.Previous studies have shown that this siliceous rock stratum formed at the edge of the carbonate platform on the continental shelf.Researchers suggest that these siliceous rocks were formed by hydrothermal activity,but some still draw different conclusions.Understanding the silicon source and depositional environment of these siliceous rocks would help us learn the processes of environmental changes and the causes of biological explosions during this period.The value of germanium/silica ratios of these siliceous rocks is from 0.15 to 0.37 pmol/mol and much lower than above 10|imol/mol values in siliceous rocks that are known formed by hydrothermal activity.All samples are rich in HREE,which differ from hydrothermal siliceous rocks that are rich in LREE.Most samples lack hydrothermal related elements.All these features show that the source of these siliceous rocks'siliceous is not hydrothermal flu ids.The samples'Ce/Ce*range from 0.88 to 1,and Th/U ratios range from 0.01 to 0.36.These features suggest these siliceous rocks were formed in an anoxic environment.Considering all the evidence,we conclude that the siliceous rock stratum at the bottom of the Lower Cambrian Yuertusi Formation in northwest Tarim Basin.Keping,was formed in anoxic seawater at the edge of the carbonate platform on the continental shelf.Its silicon source is seawater instead of hydrothermal fluid.

Geochemical Indication of Sinian Bedded Siliceous Rocks in the Hunan-Guizhou-Guangxi Area and Their Environmental Significance

: In the Hunan-Guizhou-Guangxi area there have developed very thick bedded siliceous rocks of the late Sinian. The rocks have a fairly pure composition, with an average content of siliceous minerals exceeding 95%. They are relatively rich in Fe and Mn, and poor in Al, Ti and Mg. The Fe/Ti, (Fe+Mn)/Ti, Al/(Al+Fe+Mn) and U/Th ratios and the Al-Fe-Mn and Fe-Mn-(Ni+Co+Cu)×10 triangle diagrams all show that they are hydrothermal sedimentary siliceous rocks. In the rocks the total amount of REEs is low, the δCe shows an obvious negative anomaly and the δEu a weak anomaly, and LREE>HREE, all indicating that they are products of hydrothermal processes. The δ30Si and δ18O values, as well as the formation temperature of the rocks all clearly show that the silica forming the rocks comes from hot water. Besides, analyses of the depositional environment of the rocks using the MnO/TiO2 ratio and the δCe and δ30Si values yield the same conclusion that they are formed in environments from continental marginal slopes of a bathyal environment to oceanic basins of a deep-sea environment.

Geochemical Characteristics of Wuyang Siliceous Rocks in the Southern Margin of North China Craton and its Constraint on the Formation Environment of BIF of Tieshanmiao Formation

Precambrian banded iron formation(BIF)is one of the most important mineral resources in China,mostly abundant in the North China Craton(NCC)with relatively less common in South China.Since the BIF and siliceous rocks both originated from chemical deposition,the syngenetic BIF and Siliceous rocks can help evaluate their environment of formation.We examine here the mineralogy and geochemistry of siliceous rocks associated with the Tieshanmiao Formation BIF,aiming to decipher the conditions of formation of both BIF and Siliceous rocks in the Wuyang area in the NCC.Analysis of the geochemical characteristics of whole rock shows that the Si O2 content of the siliceous rock ranges from 90.11%to 94.85%and is relatively high overall.Trace element contents of Ba and U are also high,the Ba/Sr ratio ranges from 3.89 to 25.28 and the U/Th ratio ranges from 0.09 to 0.20.Finally,theΣREE value of rare earth elements ranges from 57.03 ppm to 152.59 ppm,and these indexes all indicate that siliceous rock resulted from hydrothermal deposition.Plots of Al2 O3-Si O2,Si O2/(K2 O+Na2 O)-Mn O2/Ti O2 and Mn-10×(Cu+Co+Ni)-Fe in discrimination diagrams also verify this interpretation.However,both the Mg O content,ranging from 0.16 to 0.32,and the Fe/Ti ratio,ranging from 2.50 to 9.72,suggest that terrigenous material was added during the depositional process.Major and trace element parameters of siliceous rock,such as the Al/(A1+Fe+Mn)ratio(from 0.81 to 0.93),Mn O/Ti O2(from 0.00 to 0.17),Al/(Al+Fe)(from 0.82 to 0.93),Sc/Th ratio(from 0.21 to 0.50),U/Th(from 0.09 to 0.20),(La/Yb)N(from 0.83 to 3.04),and the(La/Ce)N(from 0.01 to 0.02)all imply that the siliceous rock formed in a continental margin.In addition,the Sr/Ba ratio from 0.08 to 0.26,theδCe value from 0.31 to 0.90,and theδEu value from 0.14 to 0.58,all indicate that the siliceous rock was formed at a relatively deeper water depth and under weak hydrodynamic conditions.Siliceous rock and BIF formed in the same geological setting,with the Si O2/(K2 O+Na2 O)ratio of siliceous rock ranging from 28.61 to 47.43,the Si O2/Al2 O3 ratio from 16.53 to 32.37,and the Si O2/Mg O ratio from 287.28 to 592.81,which are all in agreement with chemical deposition associated with volcanic eruptions.The Al2 O3/Ti O2 ratio from 37.82 to 50.30 indicates that the magma source of siliceous rock was of slightly intermediate composition.During the Late Archean in the Wuyang area,the high concentration and high purity Si O2 quickly precipitated from hydrothermal fluids to finally result in the accumulation of siliceous rock in a marginal sea,while the input corresponding to iron formation components was deposited to form iron formation layers,and limestone was only the product formed during the deposition intervals of siliceous rock and iron formations.In this study,the synsedimentary siliceous rocks of BIF act as a new way to provide direct evidence to understand the formation environment of BIF due to its high geochemical stability.

Paleoproterozoic Underwater Volcanism and Microfossil-Like Structures in the Metasedimentary Siliceous Rocks,Hogland Island,Russia

Geological surveys showed that rhyolite and basalt strata with pillow structures typical for underwater volcanism form sheets over the Svecofennian basement. Original geochemical and isotope-geochemical data confirmed that the rhyolites were formed contemporaneously with the rapakivi granites of the Wiborg Massif（1 640 Ma）, and the basalts are similar to gabbro-anorthosites. Abnormally high content of K2O and relatively low content of Na2O in rhyolites and basalts are interpreted as a result of hydrothermal interaction of eruptive magmas with K-enriched hot seawater. The strata of siliceous metasedimentary rocks（microquartzites） within basaltic and rhyolitic lavas were formed in processes of chemogenic sedimentation and subsequent contact metamorphism during underwater volcanism. Microquartzites showed carbon vastly depleted of heavy isotope 13С. This is typical for rocks formed with participation of living substance. The Raman spectra of the remaining carbon-containing substance have graphite bands. In the microquartzites among basalts and rhyolites we found a community of structures with external and internal morphology similar to modern or fossilized marine microorganisms： spiral cyanobacterias, amoebas, diatoms, foraminifers, virus capsids, flagellates and multicellular organisms. It is assumed that these silificated and ferruginizated microfossils represent the Paleoproterozoic community of marine microorganisms.

Geochemistry of Triassic Siliceous Rocks of the Muyinhe Formation in the Changning-Menglian Belt of Southwest China

The Changning-Menglian belt, distributed over southwestern Yunnan Province in Southwest China, contains oceanic rocks that are considered to be remnants of the Paleotethys. This study observed Triassic siliceous rocks of the Muyinhe Formation in the Changning-Menglian belt and analyzed their geochemistry. The samples have high concentrations of SiO2（81.65 wt.%–88.38 wt.%; average： 84.99 wt.%±2.14 wt.%）. Most of the samples were plotted in the non-hydrothermal field on the Al-Fe-Mn diagram. Most of the samples were plotted in the continental margin field on the Fe2O3/TiO2-Al2O3/（Al2O3＋Fe2O3） and（La/Ce）N-Al2O3/（Al2O3＋Fe2O3） diagrams. Moreover, the samples show a flat REE（rare earth element） pattern normalized to NASC（North America shale composite）. These geochemical results, in addition to the lack of rhythmical bedding of the siliceous rocks, strongly suggest that the siliceous rocks are unlikely to represent pelagic deposits. Although previous studies have suggested that the siliceous rocks are pelagic deposits, the present results indicate that the extent of the pelagic ocean basins in the Paleotethys during the Triassic is probably less than previously believed. These non-pelagic deposits may represent the closure stage of the Paleotethys.

Early Triassic Silicic Volcanics of South China:Petrogenesis and Constraints on the Geodynamic Evolution of the Paleo-Tethys Ocean Region

The only occurrence of Lower Triassic silicic volcanic rocks within the South China Block is in the Qinzhou Bay area of Guangxi Province.LA-ICP-MS zircon U-Pb dating reveals that volcanic rocks of the Beisi and Banba formations formed between 248.8±1.6 and 246.5±1.3 Ma,coeval with peraluminous granites of the Qinzhou Bay Granitic Complex.The studied rhyolites and dacites are characterized by high SiO_(2),K_(2)O,and Al_(2)O_(3),and low MgO,CaO,and P_(2)O_(5) contents and are classified as high-K calc-alkaline S-type rocks,with A/CNK=0.98-1.19.The volcanic rocks are depleted in high field strength elements,e.g.,Nb,Ta,Ti,and P,and enriched in large ion lithophile elements,e.g.,Rb,K,Sr,and Ba.Although the analyzed volcanic rocks have extremely enriched zircon Hf isotopic compositions(ε_(Hf)(t)=-29.1 to-6.9),source discrimination indicators and high calculated Ti-in-zircon temperatures(798-835℃)reveal that magma derived from enriched lithospheric mantle not only provided a heat source for anatectic melting of the metasedimentary protoliths but was also an endmember component of the S-type silicic magma.The studied early Triassic volcanics are inferred to have formed immediately before closure of the Paleo-Tethys Ocean in this region,as the associated subduction would have generated an extensional setting in which the mantle-derived upwelling and volcanic activity occurred.

Ore petrography of low-grade siliceous manganese ores from the Bonai-Keonjhar belt, Orissa, India: The influence of mineral-fabric on their beneficiation

Low grade siliceous manganese ores from the iron ore group of the Bonai-Keonjhar belt, Orissa, India are found mostly in shear zones. The ore characteristics of siliceous manganese ore samples from three differ- ent mines, viz. the Shankar (Barbil OMC lease hold area), the Sone-Patuli (Patmunda, OMM lease hold area), and the Musaghar (Roida, OMDC lease hold area), were studied. These siliceous manganese ores are of three types, respectively: (i) spongy-granular; (ii) massive-mosaic; and (iii) hard-mylonitized. The spongy-gran- ular type contains granular, saccharoidal quartz and the major manganese mineral present is pyrolusite. The second type contains well crystallized quartz and cryptomelane, while the third has cherty, fine grained quartz (mylonite) along with romanechite. All three ores were subjected to physical beneficiation under similar conditions. Both gravity and magnetic separation techniques were employed. The mineral-fabric of the ores has been correlated to the extent of their beneficiation using these physical techniques. Of these three ores only the spongy-granular type responded well to upgrading. The feed with 22% Mn content could be upgraded to 44% with a 28% yield and a 49% recovery. The good response to beneficiation of the spongy- granular sample could be due to the large euhedral crystals of pyrolusite and the friable nature of the sac- charoidal quartz. This study reveals the influence of mineral-fabric on beneficiation of low grade ore, siliceous Mn ore in particular.

Geochemical Characterization of Intermediate to Silicic Rocks in the Global Ophiolite Record

Ophiolites consist predominantly of mafic-ultramafic rocks but also contain in subordinate amounts intermediate to silicic intrusive–extrusive rocks in them.These rocks,although not in large volumes in comparison to mafic–ultramafic units,reveal significant clues about melt evolution,magmatic accretion processes,and partial melting of pre-existing oceanic crust during ophiolite evolution.They also yield ample accessory minerals,such as zircon and monazite,which are widely used to date the timing of oceanic crust generation.We present a global synthesis of the occurrence of such leucocratic,intrusive and volcanic rocks from 150 Phanerozoic to Archean ophiolites,and evaluate models for their genesis during the development of oceanic crust in different tectonic environments.In the ophiolite complexes we have investigated,intrusive and extrusive rocks show a wide range in composition.Intermediate rocks（with Si O2 between 52and 63 wt.%）include andesite and diorite,whereas the silicic rocks（with Si O2 more than 63 wt.%）include dacite,trondhjemite,tonalite and granite.For subduction-relatedandsubduction-unrelated MORB-type ophiolites in the Phanerozoic orogenic belts,the most commonly reported intermediate to silicic intrusive rocks,independent of their original tectonic setting,are trondhjemite,plagiogranite and tonalite,and less commonly quartz-diorite and diorite.These rock types have been documented from 80 percent of the 104ophiolites included in this study.Intermediate to silicic lavas and/or pyroclastic rocks（basaltic andesite,andesite,dacite and rhyolite）are less abundant,and have been reported from only 35 percent of the 104 ophiolites.Trachyte occurs in some of the Rift/Continental Margintype,subduction-unrelated ophiolitesEvolvedrocksinsubduction-unrelated,Rift/Continental Margin ophiolites are predominantly basaltic andesite and andesite,whereas MOR type（mid-ocean ridge）ophiolites exhibit nearly equal proportions of basaltic andesite/andesite and rhyodacite and Plume/MOR type ophiolites are characterized by rhyolites.Intermediate to silicic volcanic uints in the Backarc sub-group of subduction-related ophiolites are characterized by similar amounts of basaltic andesite/andesite and rhyodacite,whereas in the Backarc to Forearc,Forearc,and Volcanic Arc sub-groups they are mainly basaltic andesite/andesite.Intermediate to silicic rocks in Rift/Continental Margin and Plume/MOR type ophiolites are generally LREE-enriched,whereas those in the MOR type vary from LREE-depleted to LREE-enriched.The Backarc and Backarc to Forearc types are similar to the MOR type;silicic rocks of the Forearc and Volcanic Arc types are generally LREE-enriched.The main process in the formation of the majority of the intermediate to silicic rocks in both subduction-unrelated and subduction-related ophiolites is partial melting of basaltic and/or gabbroic rocks beneath the spreading centers,whereas a minor volume in subduction-related ophiolites are adakites that were produced from partial melting of a subducting slab.Silcic to intermediate rocks in Plume/MOR type ophiolites are generated by fractional crystallization of basaltic melt.The incompatible,non-conservative elements,such as Ba and Th,are weakly to strongly enriched in subduction-related ophiolites as a result of shallow to deep enrichment associated with subduction zone processes.The field occurrence and the geochemical character of leucocratic rocks in ophiolites show considerable variations,providing additional constraints on the petrogenesis of ophiolites in different tectonic settings.Fractional crystallization appears to have been an important process in the formation of the intermediate to silicic rocks in Rift/CM and P/MOR ophiolites in the subduction-unrelated class,as well as VA ophiolites in the subduction-related class.In these types of ophiolites magma chambers might have operated as closed-systems for a sufficient amount of time for fractionation and compositional zoning of the magma to take place（Fig.1C1）.Fractional crystallization was of subordinate importance during the igneous construction of the MOR,BA,FA,and BA-FA ophiolites.Instead,partial melting of hydrothermally altered crust was the most common process resulting in the majority of the intermediate to felsic rocks of the Rift/CM（estimated to 60%）,MOR（estimated to 95%）,and the BA,FA and BA-FA（estimated to 75%）ophiolites,as well as a high proportion of the VA ophiolites（;0%）(Fig.1C2).Slab-generated melts that result in the production of intermediate to silicic rocks of adakitic character represent a relatively small fraction（;5%in Phanerozoic ophiolites）of subduction-related ophiolites（Fig.1C3）.Some adakites are very low in incompatible elements（e.g.,La）,suggesting that these melts were generated from highly depleted MORB.Precambrian ophiolites contain a higher percentage of adakites（ca.35%）,indicating that physical conditions were more favorable for slab melting during the Precambrian than in the Phanerozoic.This phenomenon may have resulted from higher geothermal gradient along relatively shallow-dippingsubductionzonesduringthe Precambrian.

Relationships between Basic and Silicic Magmatism in Continental Rift Settings:A Petrogeochemical Study of Carboniferous Post-collisional Rift Silicic Volcanics in Tianshan,NW China

Petrogeochemical data are reported for silicic volcanic rocks from the Tianshan Carboniferous rift, with the aim of discussing the petrogenesis of silicic magmas. Incompatible element vs. incompatible element diagrams display smooth positive trends for the Tianshan Carboniferous rift-related volcanic rocks; the isotope ratios of the silicic lavas [^87Sr/^86S（t）=0.699880.70532; eNd（t）=4.76-8.00; ^206pb/^204pb（t）=17.435-18.017; ^207Pb/^204Pb（t）=15.438-15.509; ^208Pb/^204Pb（t） = 37.075-37.723] encompass those of the basic lavas. These data suggest a genetic link between rhyolites and basalts, but are not definitive in establishing whether silicic rocks are related to basalts through fractional crystallization or partial melting. Geochemical modeling of incompatible vs. compatible elements excludes the possibility that silicic melts are generated by the melting of basaltic rocks, and indicates a derivation by fractional crystallization plus moderate assimilation of wall rocks （AFC） starting from intermediate rocks to silicic rocks. Continuous AFC from basalt to rhyolite, with small rates of crustal assimilation, best explains the geochemical data. The presence or absence of bimodal volcanism （the ＂Daly Gap＂） might be related to cooling rates of magma chambers. In central and eastern Tianshan, the crust was thinner and the cooling rates of the magma chamber within the crust were greater. These conditions resulted in a rapid fall in temperature within the magma reservoir and caused a narrow temperature interval over which intermediate melts formed, effectively reducing the volume of the intermediate melts.

Rhyolites in continental mafic Large Igneous Provinces: Petrology,geochemistry and petrogenesis

We present a detailed review of the petrological and geochemical aspects of rhyolite and associated silicic volcanic rocks(up to 20 vol%of all rocks)reported to date from twelve well known Phanerozoic continental mafic Large Igneous Provinces(LIPs).These typically spread over<104 km^2(rarely 105 km^2 for Parana-Etendeka)area and comprise<10~4 km^3 of extrusive silicic rocks,erupted either during or after the main basaltic eruption within<5 Myr,with some eruption(s)continuing for≤30 Myr.These rhyolites and associated silicic volcanic rocks(60-81 wt.%of SiO2)are mostly metaluminous to peraluminous and are formed via(ⅰ)fractional crystallization of parental mafic magma with negligible crustal contamination,and(ⅱ)melting of continental crust or assimilation and fractional crystallization(AFC)of mafic magma with significant crustal contribution.Rhyolites formed by extensive fractional crystallization are characterized by the presence of clinopyroxene phenocrysts,exhibit steep negative slopes in bivariate major oxides plots and weak to no Nb-Ta anomaly;these typically have temperature>900℃.Rhyolites formed by significant crustal contribution are characterized by strong negative Nb-Ta anomalies,absence of clinopyroxene phenocrysts,and are likely to have a magma temperature<900℃.Geochemical signatures suggest rhyolite melt generation in the plagioclase stability field with a minor fraction originating from lower crustal depths.A large part of the compositional variability in rhyolites,particularly the SrNd-Pb-O isotope ratios,suggests a significant role of continental crust(upper crustal melting or AFC)in the evolution of these silicic rocks in the continental mafic LIPs.

Characteristics of “Guangyuan-Wangcang” trough during Late Middle Permian and its petroleum geological significance in northern Sichuan Basin, SW China

Based on outcrop characteristics, combined with regional tectonic background, drilling and geophysical data, the sedimentary characteristics of the Middle Permian Maokou Formation in the northern Sichuan Basin was studied by means of macroscopic and microscopic observation, geochemical element test, total organic carbon content and vitrinite reflectance measurement. There is a set of deep-water sediments rich in organic matter in the Guangyuan-Wangcang area of northern Sichuan during the late depositional period of the Middle Permian Maokou Formation. The strata are distributed from northwest to southeast, with thickness of 10–30 m, mainly composed of siliceous rocks and siliceous mudstones, intercalated with gravity flow deposits. Siliceous rocks and siliceous mudstones are characterized by thin single layer, flat bedding and rich siliceous radiolarians, calthrop and brachiopod with small body and thin shell, belonging to the typical sedimentary characteristics of deep-water trough facies. The contents of Cu, Co, Mo, Ni and the ratio of Ni to Co in the geochemical tests all indicate that the siliceous rocks are products of deep-water reducing environment. The TOC value ranges from 3.21% to 8.19%, with an average of 5.53%, indicating that the siliceous rocks have good hydrocarbon generation ability. The south side of the trough is in platform margin facies with high energy, and the sediments are mainly thick massive micritic-calcsparite biogenic(clastic) limestone, which is conducive to the formation and evolution of the reservoir. During the late sedimentary period of the Maokou Formation, the northward subduction and extension of the oceanic crust at the northwestern margin of the Yangtze Plate provided the internal dynamic conditions for the formation of the "Guangyuan-Wangcang" trough. According to the location, sedimentary characteristics and formation dynamics of the trough, it is similar to the "Kaijiang-Liangping" trough during Late Permian proposed by previous researchers. It is believed that the "Kaijiang-Liangping" trough already had its embryonic form during the Late Middle Permian.

Deciphering the upper ordovician Wufeng siliceous shale depositional environments(Wuxi,NE Chongqing)based on multi-proxy record

Based on stratigraphic variations of petrology,geochemistry(major,trace elements),and pyrite framboids,we study the sedimentary environment of siliceous rocks of the Wufeng Formation in Wuxi,Northeastern Chongqing,China.Coupled Al2O3/(Al2O3þFe2O3),SiO2/Al2O3,with AleFeeMn values indicate that Wufeng Formation are deposited in a continental margin and influenced by detrital input.UEF-MoEF and V/CreU/Th cross-plots suggest that the siliceous shale was formed in dysoxic to anoxic conditions.Redox proxies imply that the lower,the middle to upper,and the top part of the Wufeng sediments were deposited in an anoxic,dysoxic and oxic environment,respectively.Accordingly,the average size of pyrite framboids are gradually increased from bottom to top,showing that increased oxidisability.A complete vibratory third-order cycle of sea level fluctuations during the Wufeng deposition can be identified.During Wufeng to Longmaxi transition,the sedimentary environment exhibits a short-scale oscillatory pattern and was probably transformed from an outer shelf to inner shelf.Coupled multi-proxies are considered more reliable proxies for deciphering redox conditions in fine-grained sediment.