S, C, O, H Isotope Data and Noble Gas Studies of the Maoniuping LREE Deposit, Sichuan Province, China: A Mantle Connection for Mineralization

The Maoniuping REE deposit, located about 22 km to the southwest of Mianning, Sichuan Province, is the second largest light REE deposit in China, subsequent to the Bayan Obo Fe-Nb-REE deposit in the Inner Mongolia Autonomous Region. Tectonically, it is located in the transitional zone between the Panxi rift and the Longmenshan-Jinpingshan orogenic zone. It is a carbonatite vein-type deposit hosted in alkaline complex rocks. The bastnaesite-barite, bastnaesite-calcite, and bastnaesite- microcline lodes are the main three types of REE ore lodes. Among these, the first lode is distributed most extensively and its REE mineralization is the strongest. The δ^34Sv.cDT values of the barites in the ore of the deposit vary in a narrow range of ＋5.0 to ＋5.1‰ in the bastnaesite-calcite lode and ＋3.3 to ＋5.9‰ in the bastnaesite-barite lode, showing the isotopic characteristics of magma-derived sulfur. The δ^13Cv-PDB values and the δ^Ov.SMOW values in the bastnaesite-calcite lode range from -3.9 to -6.9‰ and from ＋7.3 to ＋9.7 ‰, respectively, which fall into the range of ＂primary carbonatltes＂, showing that carbon and oxygen in the ores of the Maoniuping deposit were derived mainly from a deep source. The δ^13Cv.PDB values of fluid inclusions vary from -3.0 to -5.6‰, with -3.0 to -4.0‰ in the bastnaesitecalcite lode and -3.0 to -5.6‰ in the bastnaesite-barite lode, which show characteristics of mantle- derived carbon. The δDv-SMOW values of fluid inclusions range from -57 to -88‰, with -63 to -86‰ in the bastnaesite-calcite lode and -57 to -88‰ in the bastnaesite-barite lode, which show characteristics of mantle-derived hydrogen. The δ^18OH2OV.SMOW values vary from ＋7.4 to ＋8.6‰ in the bastnaesitecalcite lode, and ＋6.7 to ＋7.8‰ in the bastnaesite-barite lode, almost overlapping the range of ＋5.5 to ＋9.5‰ for magmatic water. The 4He content, R/Ra ratios are （13.95 to 119.58）×10^-6 （cm^3/g）STP and 0.02 to 0.11, respectively, and ^40Ar/^36Ar is 313± 1 to 437 ± 2. Considering the 4He increase caused by high contents of radioactive elements, a mantle-derived fluid probably exists in the inclusions in the fluorite, calcite and bastnaesite samples. The Maoniuping deposit and its associated carbonatite-alkaline complex were formed in 40.3 to 12.2 Ma according to K-Ar and U-Pb data. All these data suggest that large quantities of mantle fluids were involved in the metallogenic process of the Maoniuping REE deposit through a fault system.

Attribution of the Langshan Tectonic Belt: Evidence from zircon U-Pb ages and Hf isotope compositions

This study describes a previously unidentified Neoproterozoic mafic dyke emplaced in the northern flank of the Langshan Tectonic Belt. This dyke intruded into the micaquartz schist of the Zhaertaishan Group, and yielded an age of 908 ± 8 Ma. The youngest U-Pb ages of micaquartz schist from the Zhaertaishan Group in the Langshan area were 1118 ± 33 Ma,1187 ± 3 Ma and 1189 ± 39 Ma,suggesting that the depositional age of the protolith of the schist was between 908 ± 8 Ma and 1118 ± 33 Ma. In addition, 436 U-Pb age data and 155 Lu-Hf isotopic data from six samples in the Langshan Tectonic Belt and one Permian greywacke from the Wuhai area show distinct differences between the northern and southern flanks of the Main Langshan area. The U-Pb ages of the northern flank are primarily Meso-Neoproterozoic; similar ages have not been identified in the southern flank to date.Moreover, two-stage Hf model ages of the northern flank feature three age peaks at ～900 Ma,～1700 Ma and ～2600 Ma; this differs from Hf model ages of the southern flank, which feature one strong age peak at ～2700 Ma. These results suggest that the northern and southern flanks of the Main Langshan area have different geochronologic characteristics and should be divided further. Based on the U-Pb ages and Hf model ages, the northern and southern flanks of the Main Langshan area are named the North and South Langshan Tectonic Belts. Comparison of the U-Pb age and two-stage Hf model age distributions from the North Langshan Tectonic Belt, South Langshan Tectonic Belt, Alxa Block and the North China Craton(NCC) reveal that the North Langshan Tectonic Belt is similar to the Alxa Block and that the South Langshan Tectonic Belt is similar to the NCC. In addition, the zircon U-Pb age of 860 ±7 Ma commonly observed in the Alxa Block was detected in the Permian greywacke from the Wuhai area of the NCC, which suggests that the amalgamation of the North and South Langshan Tectonic belts(i.e.,the amalgamation of the Alxa Block and the NCC), occurred between Devonian and late Permian.

Archean Mass-independent Fractionation of Sulfur Isotope:New Evidence of Bedded Sulfide Deposits in the Yanlingguan-Shihezhuang area of Xintai,Shandong Province

Multiple sulfur isotope ratios （^34S/^33S/^32S） of Archean bedded sulfides deposits were measured in the Yanlingguan Formation of the Taishan Group in Xintai, Shandong Province, East of China; 633S = -0.7%o to 3.8‰,δ^34S = 0.1‰-8.8‰, △^33S = -2.3‰ to -0.7‰. The sulfur isotope compositions show obvious mass-independent fractionation （MIF） signatures. The presence of MIF of sulfur isotope in Archean sulfides indicates that the sulfur was from products of photochemical reactions of volcanic SO2 induced by solar UV radiation, implying that the ozone shield was not formed in atmosphere at that time, and the oxygen level was less than 10-5 PAL （the present atmosphere level）. The sulfate produced by photolysis of SO2 with negative △^33S precipitated near the volcanic activity center; and the product of element S with positive △^33S precipitated far away from the volcanic activity center. The lower △^33S values of sulfide （-2.30‰ to --0.25‰） show that Shihezhuang was near the volcanic center, and sulfur was mostly from sulfate produced by photolysis. The higher △^33S values （-0.5‰ to -‰） indicate that Yanlingguan was far away from the volcanic center and that some of sulfur were from sulfate, another from element S produced by photolysis. The data points of sulfur isotope from Yanlingguan are in a line parallel to MFL （mass dependent fractionation line） on the plot of δ^34S--δ^33S, showing that the volcanic sulfur species went through the atmospheric cycle into the ocean, and then mass dependent fractionation occurred during deposition of sulfide. The data points of sulfur isotope from Shihezhuang represent a mix of different sulfur source.

Petrological and geochemical characteristics of mafic rocks from the Neoproterozoic Sugetbrak Formation in the northwestern Tarim Block,China

The Neoproterozoic Sugetbrak Formation in the Aksu area,which is located at the northwest margin of Tarim Block,comprises mafic rocks and provides key records of the evolution of the Rodinia supercontinent.However,the genetic relationship among these mafic rocks exposed in different geographical sections are still unclear.In this study,the petrology,geochemistry,and Sr-Nd-Pb isotope geochemistry of the mafic rocks exposed in the Aksu-Wushi and Yuermeinark areas have been studied in some detail along three sections.The authors found that the mafic rocks in these three typical sections were mainly composed of pyroxene and plagioclase,containing a small amount of Fe-Ti oxides and with typical diabasic textures.All the mafic rocks in this region also showed similar geochemical compositions.They were characterised by high TiO_(2)contents(1.47%–3.59%)and low MgO(3.52%–7.88%),K_(2)O(0.12%–1.21%).Large ionic lithophile elements(LILEs)(Rb,Sr,and Cs)were significantly depleted.Meanwhile,high field strength elements(HFSEs)were relatively enriched.In the samples,light rare earth elements(LREEs)were enriched,while heavy rare earth elements(HREEs)were depleted.Based on the Zr/Nb,Nb/Y,and Zr/TiO_(2)ratios,the Aksu mafic rocks belong to a series of sub-alkaline and alkaline transitional rocks.The mafic rocks along the three typical sections showed similar initial values of^(87)Sr/^(86)Sr(I_(Sr))(0.7052–0.7097)and ε_(Nd)(t)(–0.70 to–5.35),while the Pb isotopic compositions with^(206)Pb/^(204)Pb,^(207)Pb/^(204)Pb and^(208)Pb/^(204)Pb values of 16.908–17.982,15.487–15.721,37.276–38.603,respectively.Most of the samples plot into the area near EM-Ⅰ,indicating that the magma of the mafic rocks might have derived from a relatively enriched mantle with some crustal materials involved.The geochemical element characteristics of most samples showed typical OIB-type geochemical characteristics indicating that the source region had received metasomatism of recycled materials.Combining with the regional geological background and geochemical data,we inferred that the mafic rocks of the Sugetbrak Formation in the Aksu area were formed in an intraplate rift environment.Summarily,based on our study,the mafic rocks of the Sugetbrak Formation in the Aksu area were derived from a common enriched mantle source,and they were product of a magmatic event during the rift development period caused by the breakup of the Rodinia supercontinent.

Titanium Isotope Analysis of Igneous Reference Materials using a Double-spike MC-ICP-MS Method

Ti separation was achieved by ion-exchange chromatography using Bio-Rad AG 1-X8 anion-exchange and DGA resins.For high-Fe/Ti and high-Mg/Ti igneous samples,a three-column procedure was required,whereas a two-column procedure was used for low-Fe/Ti and low-Mg/Ti igneous samples.The Ti isotopes were analysed by MC-ICP-MS,and instrumental mass bias was corrected using a ^(47)Ti-^(49)Ti double-spike technique.The ^(47)Ti-^(49)Ti double-spike and SRM 3162a were calibrated using SRM 979-Cr,certificated value ^(53)Cr/^(52)Crt rue=0.11339.Isobaric interference was evaluated by analysing Alfa-Ti doped with Na,Mg,Ca,and Mo,and results indicate that high concentrations of Na and Mg have no significant effect on Ti isotope analyses;however,Ca and Mo interferences lead to erroneousδ^(49/47)Ti values when Ca/Ti and Mo/Ti ratios exceed 0.01 and 0.1,respectively.Titanium isotopic compositions were determined for 12 igneous reference materials,BCR-2,BHVO-2,GBW07105,AGV-1,AGV-2,W-2,GBW07123,GBW07126,GBW07127,GBW07101,JP-1,and DTS-2b.Samples yieldδ^(49/47)Ti(‰)of−0.035±0.022,−0.038±0.031,0.031±0.022,0.059±0.038,0.044±0.037,0.000±0.015,0.154±0.044,−0.044±0.018,0.010±0.022,0.064±0.043,0.169±0.034,and−0.047±0.025(relative to OL-Ti,±2SD),respectively;of which isotopic compositions of DTS-2b,JP-1,GBW07101,GBW07105,GBW07123,GBW07126,and GBW07127 are reported for the first time.Standard Alfa-Ti was analysed repeatedly over a ten-month period,indicating a reproducibility of±0.047(2SD)forδ^(49/47)Ti,similar to the precisions obtained for geochemical reference materials.

Iron Isotope Compositions of Podiform Chromitites from Dazhuqu and Luobusha Ophiolites, Southern Tibet

Podiform chromitites crop out in ophiolitic harzburgites as pod-like bodies associated with dunite envelopes with various thickness. It is widely accepted that the change of melt compositions caused by melt-rock reaction, especially an increase in silica content, plays a crucial role in the generation of podiform chromitite(e.g., Arai and Yurimoto, 1994;Zhou et al., 1994). Due to the presence of ultrahigh pressure and highly reduced minerals, the genesis of some podiform chromitites was attributed to some deep processes(e.g., Arai, 2013;Yang et al., 2007). Although much progress has been achieved, the formation mechanism of podiform chromitites are still in dispute. Iron isotope may be a potential tool to give further insight to the issue, given that some high temperature processes, such as partial melting, metasomatism, magma differentiation and redox change, can result in measurable iron isotopic fractionation to different extent(e.g. Chen et al., 2014;Weyer and Ionov, 2007;Zhao et al., 2009). This study investigates the Fe isotope compositions of chromitites and chromite dunites from Dazhuqu and Luobusha ophiolites. For Dazhuqu chromite dunites, δ56 Fe(relative to the standard, IRMM-014) values range from-0.02‰ to 0.11‰ in olivines and from 0.03‰ to 0.08‰ in chromites. Chromites in Dazhuqu chromitites show δ56 Fe values varying from-0.03‰ to 0.02‰. In nodular and densely disseminated chromitites from Luobusha, olivines have δ56 Fe values of olivines and chromites are 0.09–0.35‰ and-0.15–0.08 ‰, respectively. Chromites from Luobusha massive chromitites have δ56 Fe values of 0.07–0.12 ‰. Based on theorical calculations, chromites should be heavier than olivines in Fe isotope compositions ?56 FeOl-Chr ≈-0.08‰ at 1300 ℃ according to the ionic model(e.g., Macris et al., 2015;Sossi and O’Neill, 2017). However, most of our samples, except for two samples, have ?56 FeOl-Chr values that are greater than zero, indicating a disequilibrium inter-mineral Fe isotopic fractionation. There is a positive correlation between Fo and δ56 Fe(or ?56 FeOl-Chr) of olivines but no positive correlation between Mg# and δ56 Fe(or ?56 FeOl-Chr) of chromites. This phenomenon suggests that the Fe isotopic dis-equilibration may be caused by migrating melts in dunitic channels rather than by the sub-solidus Fe-Mg exchange(Xiao et al., 2016;Zhang et al., 2019). Additionally, the wide δ56 Fe range of chromites is similar to those of the subduction-related basalts and boninites, inferring that their parental magmas form in the suprasubduction zone.

Iron isotope fractionation during fenitization:a case study of carbonatite dykes from Bayan Obo,Inner Mongolia,China

As a powerful tracer in high-temperature geochemistry,Fe isotopes have been studied for their behaviour during fl uid exsolution and evolution related to felsic magma system,but that for carbonatite magma system remains unknown.Here we study the Fe isotope fractionation behaviour during fenitization–processes that widely occur associated with carbonatite or alkaline intrusions.Nine fenite/carbonatite samples from carbonatite dykes at Bayan Obo area are analyzed for their Fe isotope compositions as well as elemental compositions.Combined with previous reported carbonatite δ^(56)Fe data,the results show that carbonatites range from-0.35‰to 0.28‰,with an average of-0.10‰in δ^(56)Fe values,while fenites range from-0.17‰to 0.30‰,with an average of 0.11‰in δ^(56)Fe values.This indicates that fenitizing fl uids exsolved from carbonatite melts are enriched in heavier Fe isotopes.Such a Fe isotope fractionation trend is diff erent from that for fl uid exsolution from felsic magmatism.δ^(56)Fe values in fenites are negatively correlated with indicators of fenitization intensity such as(Na+K),Ti,Ba,Th,Nb,U or Pb abundances,likely refl ecting that Fe isotopes fractionate during the evolution of the fenitizing fl uids.Thus,Fe isotopes are a valuable tool for tracing fl uid exsolution and evolution relevant to carbonatite magmatism and related metal mineralization.

Fe Isotope Geochemistry of Hydrothermal Fe Exhalites

The sediments atop the sequence of ophiolite usually contain Fe(-Mn-Si)exhalites,chemical sediments that aremainlycomposedofamorphousFe-Mn oxy-hydroxides and chert/jasper.They were precipitated from hydrothermal fluids produced by deep leaching of basalt particularly during volcano activity or seafloor spreading.These hydrothermal Fe exhalites provide a good record for the depositional environment and the ocean environment as well.A well-preserved Phanerozoic Fe deposit,Motuosala Fe-Mn deposit,resulted from hydrothermal exhalation,was investigated for its trace element and Fe isotope geochemistry.The deposit is located in Xinjiang province,China and is hosted in a suit of Carboniferous volcano-sedimentary clastic rocks.The Fe deposit is mainly composed of massive hematite Fe oreand banded hematite-jasper ore.The hematite ore/band and jasper band were subjected to be analyzed.They are both composed mainly of Fe2O3 and Si O2,with very low contents of Al2O3 and Ti O2(<1%),indicating they werechemical precipitates with little detrital contamination.They both show slightly LREE depleted or near flat PAAS-normalised REE patterns,with positive Eu anomalies and Y anomolies,indicating that they were sourced from a mixture of high-temperature fluids and seawater.Compared to the hematite Fe ore/band,the jasper band shows higher EuSN/EuSN*but lower Y/Ho values.δ56Fe values for the hematite Fe ores are clustered around-0.3‰,similar to those for high-temperature fluids.The jasper samples show heavier Fe isotope compositions varying from-0.1‰to0.5‰,indicating that they were resulted from partial Fe precipitation.For all samples,δ56Fe values are related to Y/Ho and EuSN/EuSN*values.The results indicate that the hematite Fe ore and jasper were deposited in different environments.The jasper was deposited in a more anoxic condition with higher hydrothermal fluids/seawater ratio,probably when the hydrothermal activity was more intense;while the hematite Fe ore was deposited in a more oxic condition with lower hydrothermal fluids/seawater ratio,probably when the hydrothermal activity was weaker.

Chemical and Isotopic Characteristics of the Water and Suspended Particulate Materials in the Yangtze River and Their Geological and Environmental Implications

The chemical and isotopic characteristics of the water and suspended particulate materials（SPM） in the Yangtze River were investigated on the samples collected from 25 hydrological monitoring stations in the mainsteam and 13 hydrological monitoring stations in the major tributaries during 2003 to 2007. The water samples show a large variation in both δD（ 30‰ to 112‰） and δ18O（ 3.8‰ to 15.4‰） values. Both δD and δ18O values show a decrease from the river head to the Jinsha Jiang section and then increase downstream to the river mouth. It is found that the oxygen and hydrogen isotopic compositions of the Yangtze water are controlled by meteoric precipitation, evaporation, ice（and snow） melting and dam building. The Yangtze SPM concentrations show a large variation and are well corresponded to the spatial and temporal changes of flow speed, runoff and SPM supply, which are affected by the slope of the river bed, local precipitation rate, weathering intensity, erosion condition and anthropogenic activity. The Yangtze SPM consists of clay minerals, clastic silicate and carbonate minerals, heavy minerals, iron hydroxide and organic compounds. From the upper to lower reaches, the clay and clastic silicate components in SPM increase gradually, but the carbonate components decrease gradually, which may reflect changes of climate and weathering intensity in the drainage area. Compared to those of the upper crust rocks, the Yangtze SPM has lower contents of SiO2, CaO, K2 O and Na2 O and higher contents of TFe2 O3 and trace metals of Co, Ni, Cu, Zn, Pb and Cd. The ΣREE in the Yangtze SPM is also slightly higher than that of the upper crust. From the upper to lower reaches, the CaO and MgO contents in SPM decrease gradually, but the SiO2 content increases gradually, corresponding to the increase of clay minerals and decrease of the carbonates. The δ30SiSPM values（ 1.1‰ to 0.3‰） of the Yangtze SPM are similar to those of the average shale, but lower than those of the granite rocks（ 0.3‰ to 0.3‰）, reflecting the effect of silicon isotope fractionation in silicate weathering process. The δ30SiSPM values of the Yangtze SPM show a decreasing trend from the upper to the middle and lower reaches, responding to the variation of the clay content. The major anions of the river water are HCO 3, SO 4 2, Cl, NO 3, SiO 4 4 and F and the major cations include Ca2＋, Na＋, Mg2＋, K＋ and Sr2＋. The good correlation between HCO3-content and the content of Ca2＋may suggest that carbonate dissolution is the dominate contributor to the total dissolved solid（TDS） of the Yangtze River. Very good correlations are also found among contents of Cl, SO4 2, Na＋, Mg2＋, K＋and Sr2＋, indicating the important contribution of evaporite dissolution to the TDS of the Yangtze River. High TDS contents are generally found in the head water, reflecting a strong effect of evaporation in the Qinghai-Tibet Plateau. A small increase of the TDS is generally observed in the river mouth, indicating the influence of tidal intrusion. The F and NO3 contents show a clear increase trend from the upstream to downstream, reflecting the contribution of pesticides and fertilizers in the Chuan Jiang section and the middle and lower reaches. The DSi shows a decrease trend from the upstream to downstream, reflecting the effect of rice and grass growth along the Chuan Jiang section and the middle and lower reaches. The dissolved Cu, Zn and Cd in the Yangtze water are all higher than those in world large rivers, reflecting the effect of intensive mining activity along the Yangtze drainage area. The Yangtze water generally shows similar REE distribution pattern to the global shale. The δ30SiDiss values of the dissolved silicon vary from 0.5‰ to 3.7‰, which is the highest among those of the rivers studied. The δ30SiDiss values of the water in the Yangtze mainsteam show an increase trend from the upper stream to downstream. Its DSi and δ30SiDiss are influenced by multiple processes, such as weathering process, phytolith growth in plants, evaporation, phytolith dissolution, growth of fresh water diatom, adsorption and desorption of aqueous monosilicic acid on iron oxide, precipitation of silcretes and formation of clays coatings in aquifers, and human activity. The δ34SSO4 values of the Yangtze water range from 1.7‰ to 9.0‰. The SO4 in the Yangtze water are mainly from the SO4 in meteoric water, the dissolved sulfate from evaporite, and oxidation of sulfide in rocks, coal and ore deposits. The sulfate reduction and precipitation process can also affect the sulfur isotope composition of the Yangtze water. The87Sr/86Sr ratios of the Yangtze water range from 0.70823 to 0.71590, with an average value of 0.71084. The87Sr/86Sr ratio and Sr concentration are primary controlled by mixing of various sources with different87Sr/86Sr ratios and Sr contents, including the limestone, evaporite and the silicate rocks. The atmospheric precipitation and anthropogenic inputs can also contribute some Sr to the river. The δ11B values of the dissolved B in the Yangtze water range from 2.0‰ to 18.3‰, which is affected by multifactors, such as silicate weathering, carbonate weathering, evaporite dissolution, atmospheric deposition, and anthropogenic inputs.

Investigation of matrix effects in the MC-ICP-MS induced by Nb, W, and Cu: Isotopic case studies of iron and copper

Some elements normally occur at trace levels while the majority of natural geological materials may be exceedingly enriched in some special cases, such as the Bayan Obo ore deposit where REE and Nb are extremely enriched. These elements may not be removed completely during purification. Therefore, matrix effects will be caused during stable isotope ratio measurement in the MC-ICP-MS. Experiments have shown that the established methods of chromatographic separation of Cu, Fe, and Zn using AG MP-1 Anion Exchange Resin cannot make ef-fective separation of Nb, W, and Cu from Fe using 20 mL 6 M HCl. It is also observed that the elution curves of W and Cu overlap at working conditions and thus W is present in measurable amounts in some sample solutions. Matrix effects in the MC-ICP-MS induced by Nb, W, and Cu during Fe isotope ratio measurements and by W during Cu isotope ratio measurements were thus investigated by examining their changes in delta values between doped and undoped standards. The results show that the effects of the matrix elements Nb, W, or Cu on Fe isotope ratio measurements are minimal in the case of m(Nb)/m(Fe)<0.005, m(W)/m(Fe)<0.01, or m(Cu)/m(Fe)<0.6. This finding, combined with the extremely low levels of W and Cu, and the fact that nearly 90% of Nb can be removed during purification, demonstrates that the methods of chromatographic separation of Fe established before are suitable for Bayan Obo ore samples and that the methods can be simplified when Cu elution is unnecessary. The effects of the matrix element W on Cu isotope determinations are minimal in the case of m(W)/m(Cu)<0.7. Therefore, W exerts no significant effect on the measurements of Cu isotopes for the majority of natural geological materials.

Chemical and Isotopic Characters of the Water and Suspended Particulate Materials in the Yellow River and Their Geological and Environmental Implications

The chemical and isotopic characteristics of the water and suspended particulate materials （SPM） in the Yellow River were investigated on the samples collected from 29 hydrological monitoring stations in the mainstem and several major tributaries during 2004 to 2007. The JD and δ^18O values of the Yellow River water vary in large ranges from -32%0 to -91‰ and from -3.1‰ to -12.5‰, respectively. The characters of H and O isotope variations indicate that the major sources of the Yellow River water are meteoric water and snow melting water, and water cycle in the Yellow River basin is affected strongly by evaporation process and human activity. The average SPM content （9.635 g/L） of the Yellow River is the highest among the world large rivers. Compared with the Yangtze River, the Yellow River SPM has much lower clay content and significantly higher contents of clastic silicates and carbonates. In comparison to the upper crust rocks, the Yellow River SPM contains less SiO2, CaO, K2O and Na2O, but more TFe203, Co, Ni, Cu, Zn, Pb and Cd. The abnormal high Cd contents found in some sample may be related to local industrial activity. The REE contents and distribution pattern of the Yellow River SPM are very close to the average value of the global shale. The average δ^30Sisp in the Yellow River （-0.11‰） is slightly higher than the average value （-0.22‰） of the Yangtze River SPM. The major factors controlling the δ^30Si SPM of the Yellow River are the soil supply, the isotopic composition of the soil and the climate conditions. The TDS in the Yellow River are the highest among those of world large rivers. Fair correlations are observed among Cl, Na^＋, K^＋, and Mg^2＋ contents of the Yellow River water, indicating the effect of evaporation. The Ca^2＋ and Sr^2＋ concentrations show good correlation to the SO42 concentration rather than HCO3-concentration, reflecting its origin from evaporates. The NO3-contents are affected by farmland fertilization. The Cu, Zn and Cd contents in dissolved load of the Yellow River water are all higher than those of average world large rivers, reflecting the effect of human activity. The dissolved load in the Yellow River water generally shows a REE distribution pattern parallel to those for the Yangtze River and the Xijiang River. The δ^30Si values of the dissolved silicon vary in a range from 0.4%0 to 2.9%0, averaging 1.34%o. The major processes controlling the Dsi weathering process of silicate rocks, growth of and δ^30SiDiss of the Yellow River water are the phytolith in plants, evaporation, dissolution of phytolith in soil, growth of fresh water diatom, adsorption and desorption of aqueous monosilicic acid on iron oxide and human activities. The average δ^30^SiDiss value of the Yellow River is significantly lower than that of the Nile River, Yangtze River and Siberia rivers, but higher than those of other rivers, reflecting their differences in chemical weathering and biological activity. The δ^34SSO4 values of the Yellow River water range from -3.8%0 to 14.1%o, averaging 7.97%0. There is some correlation between SO4^2- content and δ^34SSO4. The factors controlling the δ^34SSO4 of the Yellow River water are the SO4 in the meteoric water, the SO4 from gypsum or anhydrite in evaporite rocks, oxidation and dissolution of sulfides in the mineral deposits, magmatic rocks and sedimentary rocks, the sulfate reduction and precipitation process and the sulfate from fertilizer. The ^87Sr/^86Sr ratios of all samples range from 0.71041 to 0.71237, averaging 0.71128. The variations in the ^87Sr/^86Sr ratio and Sr concentration of river water are primarily caused by mixing of waters of various origins with different 87Sr/S6Sr ratios and Sr contents resulting from water-rock interaction with different rock types.

Discovery of Mass Independent Oxygen Isotopic Compositions in Superscale Nitrate Mineral Deposits from Turpan-Hami Basin,Xinjiang,China and Its Significance

The Turpan-Hami Basin in eastern Xinjiang is one of the driest regions on Earth and a premier environment to form and preserve nitrate.A large nitrate ore field in this basin was found recently.It is estimated there are about 2.5 billion tons of resources of nitrate,and the amount is as much as the Atacama Desert super-scale nitrate deposit in Chile.Nitrate is one of a few minerals with mass-independent fractionation（MIF）,and the oxygen isotope MIF is an effective method to determine the source of nitrate.Theδ^（17）O,δ^（18）O of nitrate were measured by fluorination and thermal decomposition method.The date indicated that this is the first time that oxygen isotope MIF has been located in inland nitrate minerals.The results obtained by two methods are similar,⊿^（17）=δ^（17）O-0.52×δ^（18）O=12‰-17‰.The experiment and observation data proved that oxygen isotope MIF of nitrate are the result of photochemical reactions in the troposphere and stratosphere.Thus, evidence from MIF oxygen isotopic compositions indicate that long term atmospheric deposition of nitrate aerosol particles produced by photochemical reactions is the source of the deposits.

Extreme Enrichment of Tellurium in Deep-Sea Sediments

Tellurium is a sort of scattered rare element on the earth. Its concentration is very low in earth＇s crust, only 1.0 ng/g. However, it has extremely high abundance in Co-rich crusts, marine polymetallic nodules, deep-sea sediments and aerolites. To find out the origin of tellurium enrichment in deep-sea sediments, we analyzed and compared tellurium concentrations and helium isotope compositions in the magnetic parts and those in the bulk parts of deep-sea sediments. The result indicates that the helium content, 3He/4He ratio and tellurium concentration are obviously higher in the magnetic parts than those in the bulk parts. The 3He abundance varies synchronously with the tellurium concentration. 3He and Te have a distinct positive correlation with each other. It is the first time that the paper brings forward that the extreme enrichment of tellurium in deep-sea sediments, like helium isotope anomalies, probably results from the input of interplanetary dust particles （IDPs）. Similarly, the extreme enrichment of tellurium in marine polymetallic nodules and Co-rich crusts is possibly related to IDPs.

Comparison of Redox States between the Ultramafic Bodies of Xigaze and Luobusha Ophiolites, Tibet, China

The tectonic setting of podiform chromitite formation still remains highly debated. There is a close correlation between tectonic settings and oxygen fugacity(fO2)(e.g., Ballhaus, 1993;Dare et al., 2009;Parkinson and Arculus, 1999). Here we present results of fO2 of chromites determined by M?ssbauer spectroscopy from both the Luobusha and Dazhuqu areas along Yarlung Zangbo suture zone, Southern Tibet. The fO2 values(-1.02~0.04 log units against the FMQ buffer) and Cr#(22~54%) in chromites from lherzolites and harzburgites of both areas are similar to those of abyssal peridotites, indicating that they may be residues after partial melting at spreading centers. However, both dunite envelopes and chromitites from Luobusha have high fO2 values(0.04~2.25 log units) and Cr#(73~84%), showing an affinity to boninitic melts, and thus form in a suprasubduction zone. Dazhuqu dunites show diverse fO2 values(-0.22~2.19 log units) and Cr#(22~82%), indicating that they form in distinct settings. Chromitites and chromite dunites from Dazhuqu have low fO2 values(-0.3~0.71 log units) and Cr#(16~63%), both of which are similar to those of MORB-like basalts, inferring that they form in an extensional setting. Both high-Cr and high-Al chromitites from other typical podiform chromite ore deposits, such as Kempirsai, Oman, and Albania ophiolites, also show high fO2 values(e.g., Chashchukhin and Votyakov, 2009;Melcher et al., 1997;Quintiliani et al., 2006;Rollinson and Adetunji, 2015), while the distribution-limited small chromitites and chromite dunites from Dazhuqu exhibit low fO2 values. The phenomenon infers that the suprasubduction zone is more beneficial to the formation of podiform chromitites.

Comparison of Different-sized Chromite Mineralizations in the Yarlung-Zangbo Ophiolite Belt, Southern Tibet

Podiform chromitites are characteristically occurred in ophiolites(e.g.,Thayer,1964;Dickey,1975).However,the metallogenic processes for podiform chromitites are still unclear.Early models involved fractional crystallization and crystal settling from picritic or basaltic melts in magma chambers(Dickey,1975;Boudier and Coleman,1981),but it was also proposed that podiform chromitites formed from partial melting and melt extraction in host mantle peridotites(Dick,1977;Dick and Bullen,1984).Recent studies by the majority of authors have suggested that melt-rock interaction at the Moho transition zone may have played a key role in the formation of podiform chromitites(Zhou and Robinson,1994;Zhou et al.,1996,2005,2014;Robinson,2008;Page and Barnes,2009;Uysal et al.,2009,2012;González-Jiménez et al.,2011,2015).Based on the occurrence of some ultrahigh pressure minerals(e.g.diamond and coesite)in chromitites,it has been proposed recently that the formation of podiform chromitite is likely related to multiple processes inclusing mantle recycling(Yang et al.,2007;Yamamoto et al.,2013).Although geat progresses have been made towards understanding the genesis of podiform chromitites,some fundamental issues in remain unanswered.For examples,what are the major controls on the size of chromitites?And why some ophiolites contain large podiform chromitite bodies,whereas most ophiolitic massifs are essentially chromitite-barren? The Yarlung-Zangbo Ophiolite belt is one of the most famous ophiolite zone in the world.It contains fresh peridotites as well as different-sided podiform chromitites.The Luobusha ophiolite in the eastern segment of the belt hosts the largest chromite deposit in China.In the central and western segments of belt the Dazhuqu and Dongbo ophiolitic massifs contain some small-scale chromitite bodies.Such characteristics make the Yarlung-Zangbo Ophiolites an ideal subject to investigate the major controls on the metallogenesis of podiform chromitites. The Luobusha chromitites are large lens and enclosed in dunite.In contrast,the Dazhuqu and Dongbo chromitites display generally as narrow dykes or irregular seams with dunite envelopes.The closely spatial association of the chromitites and dunite envelopes,together with their textural features,support a petrogenetic model that the chromitites from the Luobusha,Dazhuqu and Dongbo massifs form from reaction of melt with host peridotite.In terms of chemical composition of chromite,there are distinctive differences between those from the Luobusha and the Dazhuqu or the Dongbo.Chromite from the Luobusha chromitites has high Cr#(71-82),whereas Chromite in the Dazhuqu chromitites show relatively low Cr#(16-63),and chromite in the Dongbo chromitites includes low Cr#(11-47)and high Cr#(70-81)types.For the Dongbo and Dazhuqu massifs,linear trends of Cr#with Mg O,Fe Ot,Ni,Ga,V and Sc in chromite from the chromitites and dunites of are similar to those of the host peridotites,suggesting that the melt-rock reaction may provide major budget of Cr for the chromitites.The similar compositions at a given Cr#in chromite from these rocks also demonstrate that the chromitites may have been formed by in-situ crystallization of chromite under low melt/rock ratio.In contrast,the Luobusha chromitites have different trends of compositions in chromite from that of the host peridotites,implying that the formation of the chromitite bodies requires a continual replenishment of Cr-rich melts from deeper mantle.Fractionation and accumulation of chromite from a large volume of Cr-rich melt may play an important role on the formation of the Luobusha chromitites.MORB-normalized trace element patterns of chromite from the Luobusha chromitites suggest that it has been formed from Cr-rich boninitic melt at surpra-subduction zone(SSZ)setting.However,the Dongbo and Dazhuqu chromitites have formed originally from a MORB-affinity melt at a mid-ocean ridge(MOR)environment. In summary,the Luobusha chromitites crystallized from a Cr-rich melt in a dynamic conduit,where fractional crystallization and crystal settling play a key role in formation of the large chromitites.In contrast,the small-scale mineralizations of the Dongbo and Dazhuqu chromitite pods are formed from in situ produced melts.Podiform chromitites can be formed in MOR environment,whereas the higher Cr content in boninitic melt and assimilation of subducted slab materials at SSZ setting may benefit the formation of large chromite deposit.

Isotopic Composition of Waters in the Dem?novská dolina Valley and Its Underground Hydrologic System During Winter and Spring of 2010/2011

In the Dem?novská dolina Cave system（Slovakia） and its vicinity,32 sampling places for regular observation（in 2-months interval） of δ18O and δ2H in water were established.This monitoring included precipitation waters,waters in the surface streams,waters of the underground hydrological system as well as the dripping seepage waters of the cave system.Altitudinal extent of the area was from 800 m a.s.l.（lowermost cave entrance） to 2024 m a.s.l.（Chopok Mt.on the top of the crystalline range）.Initial results show some similarities but also differences within the analyzed water types.For precipitation,a high variability of isotopic composition was confirmed,from quite depleted up to more enriched waters(δ18O from-16.8‰ up to-5.7‰;δ2H from-121.6‰ to-32.7‰).During the recharge process and groundwater/surface water formation,precipitation water is homogenized,what is reflected in much more stable isotope content.The most depleted(δ18O ≈-11.7‰ to-10.8‰;δ2H ≈-78.9‰ to-73.4‰) were the waters of surface streams,running from the northern slopes of the Nízke Tatry Mts.,formed by crystalline rocks,alochtonous to the underground hydrological system.Smaller autochtonous surface water streams（formed in the side valleys of the main karstic canyon） are slightly enriched(heavier,as δ18O ≈-11.4‰ to-10.6‰;δ2H ≈-78.3‰ to-71.5‰),what reflects lower altitudes of their watersheds.Interesting is the distribution of the isotope content of the underground streams in the cave system.The most depleted are the underground streams directly（visibly） communicating with surface waters(δ18O≈-11.33±0.13‰;δ2H≈-76.88±1.68‰).Extent of the relationship of underground streams to the autochtonous seepage waters（slow circulation through the fissures） is manifested by respective portion of isotopically enriched waters–as the underground streams show different isotope composition.The combination of the alochtonous water components（from surface streams reaching the karstic area from the adjacent crystalline via swallow holes） and autochtonous water components（recharged directly in karstified limestones） is visible especially on the subsurface stream of Dem?novka.The most isotopically enriched（heaviest） of all water types are dripping seepage waters(δ18O ≈-10.4‰ to-9.4‰;δ2H ≈-71.6‰ to-65.0‰).

Occurrence of Mafic Rocks within Ediacaran Strata in the Aksu Region,NW Tarim Craton,and its Geological Implications

The Tarim Craton is an ancient Precambrian continental block,and detailed knowledge of its thermo-tectonic history is crucial for understanding the early history of continental evolution.Abundant layered mafic rocks,which have commonly been regarded as basalts,occur within the Ediacaran Sugetbrak Formation(Fm.)in the Aksu region of the northwestern Tarim Craton.Clear intrusive features have now been discovered,including mafic rocks truncating Ediacaran sedimentary layers,exhibiting an intrusion-baked margin where they interact with both the overlying and bottom wall rocks,and displaying a fine-grained transition zone from their interior to their margins.The new findings demonstrate that these mafic rocks within the Aksu Ediacaran strata were not erupted basalts but instead are intrusive diabase dykes.Therefore,these mafic rocks cannot be used to constrain the timing of the Sugetbrak Fm.in the Aksu area,nor as marker layers for regional stratigraphic correlation.Furthermore,the Ediacaran thermo-tectonic evolution in this region,deduced from the assumption that the mafic rocks are lavas,needs to be revised.

The Marine Redox Change and Nitrogen Cycle in the Early Cryogenian Interglacial Time: Evidence from Nitrogen Isotopes and Mo Contents of the Basal Datangpo Formation, Northeastern Guizhou, South China

Cryogenian Datangpo Formation was deposited during the interglacial time between the Sturtian and Marinoan ice ages. We studied nitrogen isotope compositions and contents of Mo of the black shales from the basal Datangpo Formation in northeastern Guizhou, South China, for an attempt to reconstruct the marine redox change and nitrogen cycle during the interglacial time. Based on lithostratigraphy as well as geochemical profiles, the basal black shales can be divided into four intervals： Interval 1 has the lowest δ^（15）N value（＋5.0‰）; in interval 2, δ^（15）N values vary between ＋6.4‰ and ＋7.4‰（the first peak）; interval 3 records stable values of δ^（15）N around ＋6‰; and interval 4 is characterized by its higher δ^（15）N values, between ＋6.7‰ and ＋7.8‰（the second peak）. The values of enrichment factor of Mo decrease from 56.8 to 2.6 with the ascending stratigraphic trend. It indicated that immediately after the Sturtian glaciations, the marine seawater above the transitional zone between the shelf to slope of the southern margin of the Yangtze Platform was stratified, with shallow seawater being oxic but deep water being sulfidic. Subsequently, high denitrification rates prevailed in expanded suboxic areas in spite of a short emergence of an oxic condition in the surface seawater, and the deep seawaters were still anoxic or even euxinic.

Assessment of Different Digestion Procedures for Mo Isotope Measurements of Black and Grey Shales Using the Double Spike Technique

This study investigates the behavior of Mo and Mo isotopes (δ^(98)Mo) in shales following leaching with HCl and HNO_(3) with the aim of simplifying the shale dissolution procedure.Up to 6%of the Mo was lost and the Mo isotopes were unaffected when shales were leached using 9 M HCl after ashing.Bulk sample digestion or leaching by 4 M or more concentrated HCl after ashing were all found to be acceptable and reliable approaches to the analysis of Mo isotopes in shales.After black shale (CAGS-BS) was leached with 2 M HCl,1 M HCl,and 9 M HNO_(3),the Mo concentration ([Mo]) in the leachate was lower and δ^(98)Mo was heavier than that obtained from bulk digestion.A Mo isotope mass-balance model showed that the δ^(98)Mo in the residues was lighter than the δ^(98)Mo from the bulk digestion of CAGS-BS and of crustal igneous rocks.No more Mo was lost,nor did Mo isotope fractionation,if the double spike was added before rather than after ashing and followed by bulk digestion or leaching with 9 M HCl.For efficiency,leaching using 4 M or more concentrated HCl after ashing is preferred for Mo isotope measurements.

Advances in Isotope Geochronology and Isotope Geochemistry:A Preface

Isotope geochronology and isotope geochemistry are important branches of geochemistry. They are based on variations in radiogenic or stable isotope ratios of elements and provide key chemical fingerprints to understand dynamic evolution of the Earth and other planetary bodies from the past to the present, and from their interior to exterior systems.