Nitrogen isotope chemostratigraphy of the Ediacaran and Early Cambrian platform sequence at Three Gorges,South China

The appearance of multicellular animals and subsequent radiation during the Ediacaran/Cambrian transition may have significantly changed the oceanic ecosystem. Nitrogen cycling is essential for primary productivity and thus its connection to animal evolution is important for understanding the co-evolution of the Earth's environment and life. Here, we first report on coupled organic carbon and nitrogen isotope chemostratigraphy from the entire Ediacaran to Early Cambrian period by using drill core samples from the Yangtze Platform, South China. The results show that δ¹⁵N_TN values were high (~ + 6‰) until middle Ediacaran, gradually dropping down to − 1‰ at the earliest Cambrian, then rising back to + 4‰ in the end of the Early Cambrian. Organic carbon and nitrogen contents widely varied with a relatively constant C/N ratio in each stratigraphic unit, and do not apparently control the carbon and nitrogen isotopic trends. These observations suggest that the δ¹⁵N_TN and C/N trends mainly reflect secular changes in nitrogen cycling in the Yangtze Platform. Onset of the observed negative N isotope excursion coincided with a global carbon isotope excursion event (Shuram excursion). Before the Shuram event, the high δ¹⁵N probably reflects denitrification in a nitrate-limited oceanic condition. Also, degradation of dissolved and particulate organic matter could be an additional mechanism for the ¹⁵N-enrichment, and may have been significant when the ocean was rich in organic matter. At the time of the Shuram event, both δ¹³C_carb and δ¹⁵N_TN values were dropped probably due to massive re-mineralization of organic matter. This scenario is supported by an anomalously low C/N ratio, implying that enhanced respiration resulted in selective loss of carbon as CO₂ with recycled organic nitrogen. After the Shuram event, the δ¹⁵N value continued to decrease despite that δ¹³C_carb rose back to + 4‰. The continued δ¹⁵N drop appears to have coincided with a decreasing phosphorus content in carbonate. This suggests that ocean oxygenation may have generated a more nitrate-rich condition with respect to phosphorus as a limiting nutrient. Similar to the Shuram event, another negative δ¹³C_carb event in the Canglanpuan stage of the Early Cambrian is also characterized by carbon isotopic decoupling as well as the low C/N ratio. The results strongly support that the two stages of the decoupled negative δ¹³C_carb excursions reflect a disappearance of a large organic carbon pool in the ocean. The two events appear to relate with the appearance of new metazoan taxa with novel feeding strategies, suggesting a link between ocean oxygenation, nutrient cycling and the appearance and adaptation of metazoans. The nitrogen isotope geochemistry is very useful to understand the link between the environmental, ecological and biological evolutions.     

The South Um Mongul Cu-Mo-Au prospect in the Eastern Desert of Egypt: From a mid-Cryogenian continental arc to Ediacaran post-collisional appinite-high Ba-Sr monzogranite

The South Um Mongul prospect is a Cu-Mo-Au porphyry system. It is covered by porphyritic dacite and hornblende gabbro. Both units are intruded by monzogranite, which encloses xenoliths of both units. Using LA-ICP-MS U-Pb zircon method, the dacite is dated at ca. 773 ± 6.9 Ma, while the gabbro and the monzogranite are dated at 603 ± 3.5 and 558 ± 4.6 Ma, respectively. The dacite age is consistent with the mid-Cryogenian subduction-related magmatic stage and the gabbro-monzogranite age is comparable to the Ediacaran post-collisional magmatic stage during the evolution of the Arabian-Nubian Shield. The dacite is akin to high-K I-type granitoids and its primitive mantle-normalized trace element patterns show negative Nb anomalies and enrichment in LILE (large ion lithophile elements), Th and U over HFSE. These geochemical characteristics are similar to those of felsic magma formed in a subduction-related tectonic setting. The high La/Yb_cn (7.2–30.9), Nb/Yb (2.63–4.41) and Th/Yb (2.07–3.04) ratios of the dacite are comparable to continental rather than oceanic arc systems. Its low Sm/Yb ratios (1.84–3.13) support the primitive nature of the crust beneath the continental arc and derivation from a garnet-free lower crustal source. The dacite has low Sr/Y ratios (5–9) and its Eu/Eu^⁎ ratios range from 0.66 to 0.83. Similar to dacite, the primitive mantle-normalized trace element patterns of the post-collisional suite show a subduction-related geochemical signature. However, the gabbro is characterized by Th/Ta ratios (3.4–14.8), which are comparable with the within-plate tectonic setting. The subduction-related geochemical signature is inherited from long subduction history beneath the Arabian-Nubian Shield. Both the gabbro and monzogranite are characterized by high Ba (404–590 ppm and 936–1590 ppm, respectively) and Sr (611–708 ppm and 624–793 ppm, respectively) contents, which make them analogous to the Caledonian appinite-high Ba-Sr granite assemblage. The formation of these rocks is related to the Ediacaran lithospheric erosion accompanying slab break-off. This process induced asthenospheric upwelling, which led to partial melting of the lithosphere previously metasomatised by subducted sediments involving carbonates impregnated by hydrothermal barite. Melting of this lithosphere led to the formation of the hornblende gabbro. Underplating by the mafic magma led to melting of the lower crust and the formation of high Ba-Sr monzogranite in the area. The high Sm/Yb (2.94–4.19) and Sr/Y (52–74) ratios of the monzogranite may indicate the presence of garnet in the melted amphibolitic lower crust. The higher Sr/Y ratios, lower HFSE (high field strength elements) contents and the absence of pronounced Eu anomalies in monzogranite relative to dacite suggest the productive nature of the post-collisional magma relative to the continental arc magma in this prospect.     

Chemostratigraphy of the Vendian–Cambrian carbonate sedimentary cover of the Tuva-Mongolian microcontinent

The carbonate sediments from the Vendian–Cambrian shelf of the Tuva-Mongolian microcontinent were dated by Sr and C isotope chemostratigraphy. Analysis of the Sr-isotopic characteristics (0.70725–0.70873) and δ¹³C variations (+ 10.5 to –3.5‰), as well as their comparison with the data on the key sections of Siberia, Africa, Central Asia, Australia, South America, and Spitsbergen, showed that the carbonate sedimentary cover of the Tuva-Mongolian microcontinent accumulated at 600–520 Ma and the carbonate sediments of the Muren Formation and the basal beds of the Bokson Group near the Ukha-Gol River are the oldest. Their sedimentation followed the Marinoan global glaciation.     

The possible synglaciogenic Ediacaran hematitic banded iron salt formation (BISF) at Hormuz Island,southern Iran: Implications for a new style of exhalative hydrothermal iron-salt system

The Ediacaran BISF at Hormuz Island is a newly identified glaciogenic iron-salt deposit in the Tethyan margin of Gondwana. The BISF was formed by synchronous riftogenic A-type submarine felsic volcanism and evaporate deposition. The mineralization occurs in a proximal felsic tuff cone and jaspilitic distal zones and contains 1 million tonne of hematite-rich ore with an average grade of 58% Fe. The ore structure shows cyclicity of macrobandings, mesobandings and microbandings of anhydrite, halite, hematite and chert, which marks a new record in BIFs geohistory. The alteration minerals in the proximal and distal zones are actinolite, ripidolite, epidote, sericite, tourmaline, clinochlore, anhydrite and clay minerals. The occurrence of metamorphosed polygenetic bullet-shape dropstones in BISF attests that there was probably a continuous process of ice melting, episodic submarine volcanism and exhalative hydrothermal banded iron salt formation during the Late Ediacaran time. The non-metamorphosed Neoproterozoic stratigraphy, the presence of genus Collenia, U-Pb dating (558 ± 7 Ma) and the marked negative δ¹³C excursion in cap carbonates are representative of Late Ediacaran glaciation, which has been identified worldwide. The REE+Y display light REE enrichment, unusually strong Tb-Tm anomaly, a weak positive Y anomaly, but no distinguished Eu and Ce anomalies, reflecting the glaciogenic nature of the BISF. The contents of Zr, Hf, Nb, Ta, Th, La, Ce and Y in BISF, dropstones, halite and cap carbonates are similar to those of the Neoproterozoic glaciogenic BIFs. Also, the Ni/Fe, P/Fe ratios and Fe/Ti – Al/Al + Fe + Mn + Ca + Na + K diagram suggest an exhalative hydrothermal Ediacaran-type BISF. The absence of brecciated magnetite in the ore association and the low contents of copper (9–493 ppm) and gold (<5–8 ppb) are not in favor of the IOCG – Kiruna-type iron oxide ores. The co-paragenesis of hematite with several alteration minerals, in particular actinolite, tourmaline and anhydrite, indicates that the exhalative hydrothermal fluids were generated by the interaction of seawater with the felsic rocks and sediments at about 200–500 °C. The interaction of seawater with felsic magma and sediments led to the formation of Mg-rich alteration minerals, leaching Si, Fe, Mn and other elements and forming the potential ore fluids. It is highlighted that the A-type alkaline submarine felsic volcanism could be considered as an exploration target for BISF.     

The Ediacaran radiogenic Sr isotope excursion in the Doushantuo Formation in the Three Gorges area,South China

The Ediacaran period was one of the most important times for the evolution of life. However, the scarcity of well-preserved outcrops of Ediacaran rocks still leaves ambiguity in decoding ambient surface environmental changes and biological evolution.The Ediacaran strata in South China are almost continuously exposed, comprise mainly carbonate rocks with subordinate black shales and sandstones, and they contain many fossils, suitable for study of environmental and biological changes in the Ediacaran. We conducted drilling through the Doushantuo Fm at four sites in the Three Gorges area to obtain continuous, fresh samples without surface alteration and oxidation. We analyzed ⁸⁷Sr/⁸⁶Sr and ⁸⁸Sr/⁸⁶Sr ratios of the fresh carbonate rocks, selected on the basis of microscopic observations and the geochemical signatures of Sr contents, Mn/Sr and Rb/Sr ratios, and δ¹⁸O values, with a multiple collector-inductively coupled plasma-mass spectrometer (MC-ICP-MS).The chemostratigraphy of the ⁸⁷Sr/⁸⁶Sr ratios of the drilled samples displays a smooth curve and two large positive shifts during Ediacaran time. The combination of the detailed chemostratigraphies of δ¹³C, δ¹⁸O and ⁸⁷Sr/⁸⁶Sr values and Mn and Fe contents enables us to decode the surface environmental changes and their causes in the Ediacaran. The first large positive excursion of ⁸⁷Sr/⁸⁶Sr occurred together with negative δ¹³C and positive δ¹⁸O excursions. The higher ⁸⁷Sr/⁸⁶Sr values indicate an enhancement of continental weathering, whereas the positive δ¹⁸O excursion suggests global cooling. Global regression due to global cooling enhanced the oxidative decay of exposed marine organic sediments and continental weathering. Accelerated influx of nutrients promoted primary productivity, resulting in oxidation of dissolved organic carbon (DOC), whereas active sulfate reduction due to a higher sulfate influx from the continents caused remineralization of the large DOC, both of which caused a negative δ¹³C anomaly. The 580 Ma Gaskiers glaciation accounts for the close correlation among the positive ⁸⁷Sr/⁸⁶Sr, negative δ¹³C and positive δ¹⁸O excursions.The second large positive shift of ⁸⁷Sr/⁸⁶Sr firstly accompanied a positive δ¹³C excursion, and continued through the Shuram δ¹³C negative excursion. The positive correlation of δ¹³C and ⁸⁷Sr/⁸⁶Sr values is consistent with an enhanced continental weathering rate due to continental collisions that built Trans-Gondwana mountain chains, and with a higher primary activity due to the enhancement of continental weathering and consequent higher nutrient contents in seawater. The accompanied increase in Mn and Fe contents implies a gradual decline of the seawater oxygen content due to more active aerobic respiration and oxidation of reductive materials flowing in the oceans. In the Shuram excursion, higher ⁸⁷Sr/⁸⁶Sr values and a transition from increase to decrease in Mn and Fe contents were accompanied by the large negative δ¹³C excursion. The higher ⁸⁷Sr/⁸⁶Sr values are the first compelling evidence for enhanced continental weathering, which was responsible for the large δ¹³C anomaly through the remineralization of the DOC by more active sulfate reduction due to a higher sulfate influx. Higher Mn and Fe contents in the early and middle stages of the excursion suggest a decline in the oxygen content of seawater due to oxidative decay of the DOC, whereas in the late stages the decrease in Mn and Fe contents is consistent with oceanic oxygenation.The emergence of Ediacara biota after the Gaskiers glaciation and the prosperity of the latest Ediacaran is concomitant with the formation of more radiogenic seawater with high ⁸⁷Sr/⁸⁶Sr values, suggesting that enhanced continental weathering, and the consequent higher influx of nutrients, played an important role in biological evolution.     

Chemostratigraphy and detrital zircon geochronology of the Neoproterozoic Khorbusuonka Group,Olenek Uplift,Northeastern Siberian platform

This study provides ⁸⁷Sr/⁸⁶Sr, δ¹³C and δ¹⁸O data from the best-preserved limestone and dolomite of the Ediacaran carbonate-dominated Khorbusuonka Group of the Olenek Uplift, NE Siberian Craton, as well as detrital zircon geochronological data from both underlying and overlying sandstones. The Maastakh Formation is characterized by ⁸⁷Sr/⁸⁶Sr ratios of ca. 0.70822 and δ¹³C values between + 4.8 and + 6.0‰. ⁸⁷Sr/⁸⁶Sr ratios in limestones of the Khatyspyt Formation are fairly uniform, ranging from 0.70783 to 0.70806. The carbon isotopic composition slowly decreases from bottom (+ 3.7‰) to top (− 0.2‰) of section. The Sr isotopic composition of the Turkut Formation varies from 0.70824 to 0.70914, value of δ¹³C is about zero: − 0.7…+0.7 ‰. The youngest population of detrital zircons from Maastakh Formation indicates that these rocks were formed not later than 630 Ma. U–Pb detrital zircons data of Kessyusa Group has a single peak at about 543 Ma, which is almost identical to the earlier dating. Based on biostratigraphy and isotopic data, the Sr isotopic compositions from the Khatyspyt Formation (⁸⁷Sr/⁸⁶Sr = 0.70783–0.70806) represent the composition of seawater at 560–550 Ma. Such low values of ⁸⁷Sr/⁸⁶Sr ratio in Ediacaran water were probably caused by the quick opening of Iapetus Ocean.     

The augen gneisses of the Peloritani Mountains (NE Sicily): Granitoid magma production during rapid evolution of the northern Gondwana margin at the end of the Precambrian

The medium- to high-grade polymetamorphic basement rocks of the Peloritani Mountains, northern Sicily, include large volumes of augen gneiss of controversial age and origin. By means of a geochemical and SHRIMP zircon study of representative samples, the emplacement age of the original granitoid protoliths of the augen gneisses and the most likely processes and sources involved in that granitoid magmatism have been determined. U–Pb dating of three samples from widely spaced localities in the Peloritani Mountains yielded igneous protolith ages of 565 ± 5, 545 ± 4 and 545 ± 4 Ma, respectively. These late Ediacaran/early Cambrian ages are much older than was previously assumed on geological grounds, and are typical of the peri-Gondwanan terranes involved in the geodynamic evolution of the northern Gondwana margin at the end of the Avalonian–Cadomian orogeny. Major and trace element compositions and Sr–Nd isotopic data, in combination with zircon inheritance age patterns, suggest that the granitoid protoliths of the Sicilian and coeval Calabrian augen gneisses were generated by different degrees of mixing between sediment- and mantle-derived magmas. The magmas forming the ca. 545 Ma inheritance-rich granitoids appear to have had a significant contribution from partial melting of paragneiss that is the dominant rock type in the medium- to high-grade Peloritanian basement. The closeness of the inferred deposition age of the greywacke protoliths of the paragneisses with the intrusion age of the granitoids indicates rapid latest Precambrian crustal recycling involving erosion, burial, metamorphism to partial melting conditions, and extensive granitoid magmatism in less than ca. 10 Ma.     

Provenance of Neoproterozoic and early Paleozoic siliciclastic rocks of the Teplá-Barrandian unit (Bohemian Massif): Evidence from U–Pb detrital zircon ages

New LA-ICP-MS U–Pb detrital zircon ages from Ediacaran and Paleozoic siliciclastic rocks are used to constrain provenance and paleogeographic affinities of the Teplá-Barrandian unit (TBU) in the centre of the Bohemian Massif (Central Europe, Czech Republic). The samples taken span the period from ≤ 635 Ma to ～ 385 Ma and permit recognition of provenance changes that reflect changes in geotectonic regime. Detrital zircon age spectra of two Ediacaran, one Lower Cambrian and three Upper Ordovician samples resemble the ages known from the NW African proportion of Gondwana, particularly the Trans-Saharan belt, while three rocks from higher Lower Cambrian to Lowermost Ordovician strata contain detritus that may have been derived exclusively from local sources. The age spectrum of the Devonian rock is a combination of the NW Gondwanan and local features. These new findings in combination with a wide range of published data are in agreement with a Neoproterozoic subduction-related setting at the margin of Gondwana followed by a Cambrian/Early Ordovician rifting stage and an Ordovician passive margin setting. Furthermore the data are in favour of a position of the TBU at the Gondwanan margin throughout pre-Variscan times.     

Rare earth elements in phoscorites and carbonatites of the Devonian Kola Alkaline Province,Russia: Examples from Kovdor,Khibina, Vuoriyarvi and Turiy Mys complexes

The Devonian (ca. 385–360 Ma) Kola Alkaline Province includes 22 plutonic ultrabasic–alkaline complexes, some of which also contain carbonatites and rarely phoscorites. The latter are composite silicate–oxide–phosphate–carbonate rocks, occurring in close space-time genetic relations with various carbonatites. Several carbonatites types are recognized at Kola, including abundant calcite carbonatites (early- and late-stage), with subordinate amounts of late-stage dolomite carbonatites, and rarely magnesite, siderite and rhodochrosite carbonatites. In phoscorites and early-stage carbonatites the rare earth elements (REE) are distributed among the major minerals including calcite (up to 490 ppm), apatite (up to 4400 ppm in Kovdor and 3.5 wt.% REE₂O₃ in Khibina), and dolomite (up to 77 ppm), as well as accessory pyrochlore (up to 9.1 wt.% REE₂O₃) and zirconolite (up to 17.8 wt.% REE₂O₃). Late-stage carbonatites, at some localities, are strongly enriched in REE (up to 5.2 wt.% REE₂O₃ in Khibina) and the REE are major components in diverse major and minor minerals such as burbankite, carbocernaite, Ca- and Ba-fluocarbonates, ancylite and others. The rare earth minerals form two distinct mineral assemblages: primary (crystallized from a melt or carbohydrothermal fluid) and secondary (formed during metasomatic replacement). Stable (C–O) and radiogenic (Sr–Nd) isotopes data indicate that the REE minerals and their host calcite and/or dolomite have crystallized from a melt derived from the same mantle source and are co-genetic.     

Delineation of the ca. 2.7 Ga TTG gneisses in the Zanhuang Complex,North China Craton and its geological implications

Through detailed studies we have delineated a suite of banded TTG gneisses from the Zanhuang Complex. The protolith of the gneisses, predominantly tonalite, has undergone intensive metamorphism, deformation and anatexis and in a banded structure is intimately associated with melanocratic dioritic gneiss and leucocratic trondhjemitic veins. SHRIMP Zircon U–Pb data show that the tonalite was formed ca. 2692 ± 12 Ma ago. The tonalitic gneiss has the features of high SiO₂ (67.76–73.31%), high Al₂O₃ (14.38–15.83%), rich in Na₂O (4.48–5.07%) and poor in K₂O (0.77–1.93%). The gneiss is strongly fractioned in REE ((La/Yb)_N = 12.02–24.65) and shows a weak positive Eu anomaly (Eu/Eu^* = 1.05–1.64). It has high contents of Ba (199–588 ppm) and Sr (200–408 ppm), low contents of Yb (0.32–1.00 ppm) and Y (3.41–10.3 ppm) with high Sr/Y ratios (21.77–96.77) and depletion in HFSE Nb, Ta and Ti. These characteristics are similar to those of the high-Si adakitic rocks. The melanocratic dioritic gneiss has low SiO₂ (59.81%), high MgO (6.34%), high Al₂O₃ (14.02%) contents, rich in Na₂O (3.7%) and poor in K₂O (1.79%), with high Mg index (Mg^# = 67). REE and trace elements are on the whole similar to that of the tonalitic gneiss, but compatible element abundances V (116 ppm), Cr (249 ppm), Co (37 ppm) and Ni (179 ppm) are higher. The leucocratic felsic bands (approximating trondhjemite in composition) have major oxides similar to that of the TTG gneisses but the REE and compatible elements are extremely low, which are indicative of the products of anatexis. The tonalitic gneiss has positive ε_Nd(t) (2.37–3.29) and low initial Sr (0.69719–0.70068) values with depleted mantle Nd model age of ca. 2.8 Ga, suggesting its generation from partial melting of mantle-derived juvenile crust. The dioritic gneiss was also derived from subduction environment, but has undergone significant metasomatism of mantle wedge. The delineation of the ca. 2.7 Ga TTG gneisses in the Zanhuang Complex further proves that the North China Craton experienced large-scale continental crustal accretion in early Neoarchean, and gives new constraints on the subdivision of the early blocks and greenstone belts of the craton.     

Tracking connection and restriction of West Gondwana São Francisco Basin through isotope chemostratigraphy

C and Sr isotope compositions of carbonate rocks from the intracontinental São Francisco basin can track ocean connections and restriction. The lower three formations of the Bambuí Group can be grouped into three chemostratigraphic intervals (CI), recording different evolution stages of the basin. Lowermost CI-1 comprises the basal cap carbonates of the Sete Lagoas Formation displaying an initial C negative excursion, followed by a coeval C and Sr positive excursions (δ¹³C values from − 5 to 0‰ and ⁸⁷Sr/⁸⁶Sr ratios from 0.7074 to 0.7082) in 10 m of stratigraphic record. It marks a change from a restricted shallow basin influenced by freshwater to a basin connected to external seawaters due to marine transgression. CI-2 comprises carbonates of the middle portion of the Sete Lagoas Formation with δ¹³C values around 0‰ and ⁸⁷Sr/⁸⁶Sr ratios around 0.7082 that matches those observed worldwide for the Late Ediacaran. It records the onset of a Gondwana sea pathway connecting several epicontinental basins, allowing migration of index-fossil Cloudina sp. Uppermost CI-3 starts after a major positive excursion in the δ¹³C values reaching + 16‰ and a steepened decrease of ⁸⁷Sr/⁸⁶Sr ratios to 0.7075 which are lower than those expected for the Ediacaran-Cambrian boundary. This interval comprises the upper Sete Lagoas, Serra de Santa Helena and Lagoa do Jacaré formations and records the end of the connection of the São Francisco basin to the Gondwana sea pathway setting a restricted epeiric sea. Restriction was probably caused by Late Ediacaran uplifting of orogenic belts surrounding the basin. Other West Gondwana Cloudina bearing units also display the same mismatch in the Sr isotope ratios, suggesting that the establishment of intracontinental basins inside large continental masses may challenge the use of isotope chemostratigraphy for interbasinal correlations.     

Evolution of the composition of seawater through geologic time, and its influence on the evolution of life

The redox state of the surface environment of the early Earth is still controversial, and a detailed and quantitative estimate is still lacking. We carried out in-situ analyses of major, trace, and rare-earth elements of carbonate minerals in rocks with primary sedimentary structures in shallow and deep sea-deposits, in order to eliminate secondary carbonate and contamination of detrital materials, and to estimate the redox condition of seawater through time. Based on the Ce content and anomalies of the carbonate minerals at given parameters of atmospheric CO₂ content (pCO₂) and Ca content of seawater, we calculated the oxygen contents of shallow and deep seawater, respectively. The results show that the oxygen content of the deep sea was low and constant until at least 1.9 Ga. The oxygen content of shallow seawater increased after 2.7 Ga, but fluctuated. It became quite high at 2.5 and 2.3 Ga, but eventually increased after the Phanerozoic. In addition, the calculation of a high pCO₂ condition shows that seawater was more oxic even in the Archean than at present, suggesting a relatively low pCO₂ through geologic time.Our detailed calculations from compositions of carbonate minerals in Three Gorge area, south China show a low oxygen content of seawater after the Snowball Earth until the late Ediacaran, an increase in the late Ediacaran, and a significant decrease around the Precambrian–Cambrian and Nemakit/Daldynian–Tommotian boundaries. These variations were possibly caused by global regression and dissolution of methane hydrates.     

The geochemistry of trace elements in geothermal fluids,Iceland

Trace element geochemistry was studied in geothermal fluids in Iceland. The major and trace element compositions of hot springs, sub-boiling, and two-phase (liquid and vapor) wells from 10 geothermal areas were used to reconstruct the fluid composition in the aquifers at depth. Aquifer fluid temperatures ranged from 4 to 300 °C, pH values between 4.5 and 9.3, and fluids typically contained total dissolved solids <1000 ppm, except in geothermal areas that have seawater and seawater-meteoric water mixtures. Trace alkali elements Li, Rb and Cs are among the most mobile elements in aquifer fluids, with concentrations in the range of <1 ppb to 3.49 ppm Li, <0.01 to 57 ppb Cs, and <1 ppb to 3.77 ppm Rb. Their chemistry is thought to be dominated by rock leaching and partitioning into Na- and K-containing major alteration minerals. Arsenic, Sb, Mo and W are typically present in concentrations in the range of 1–100 ppb. They are relatively mobile, yet Mo may be limited by molybdenite solubility. The alkaline earth elements Ba and Sr are quite immobile with concentrations in the range of <0.1–10 ppb Ba and <1–100 ppb Sr in the dilute fluids, but up to 5.9 ppm Ba and 8.2 ppm Sr in saline fluids. These elements show a systematic relationship with Ca, possibly due to substitution for Ca in Ca-containing major alteration minerals like calcite, epidote and anhydrite. Incorporation into major Ca-minerals may also be important for Mn. Many metals including Fe, Cr, Ni, Zn, Cu, Co, Pb and Ag have low mobility and concentrations, typically <1 ppb for Ag, Cd, Co, Cr, Cu, Ni, and Pb, <10 ppb for Zn and < 100 ppb for Fe, although for some metals higher concentrations are associated with saline fluids. Based on the metals assessed, saturation is approached with respect to many sulfide minerals and in some cases oxide minerals but Cu, Ni and Pb minerals are slightly but systematically undersaturated, and Ag phases significantly undersaturated. Evaluation of mineral-fluid equilibria for these metals is problematic due to their low concentrations, problems associated with assessing the aqueous species distribution by thermodynamic calculations, and uncertainties concerning the exact minerals possibly involved in such reactions. Reaction path calculations, poor comparison of concentrations measured in the samples collected at the wellhead and published downhole data as well as boiling, cooling and mass precipitation calculations suggest removal of many metals due to changes upon depressurization boiling and conductive cooling of the aquifer fluids as they ascend in wells. These results imply that processes such as mass precipitation upon fluid ascent may be highly important and emphasize the importance of considering mass movement in geothermal systems.     

Detrital provenance evolution of the Ediacaran–Silurian Nanhua foreland basin,South China

We report here in-situ U–Pb and Hf isotopic results of detrital zircons from sixteen Cambrian–Silurian siliciclastic samples across the Nanhua foreland basin, South China. Together with published data from Ediacaran–Silurian sandstones in the region, we establish the temporal and spatial provenance evolution across the basin. Except for samples from northeast Yangtze, all other Ediacaran–Silurian samples exhibit a prominent population of 1100–900 Ma, moderate populations of 850–700 Ma and 650–490 Ma, and minor populations of 2500 Ma and 2000–1300 Ma, grossly matching that of crystalline and sedimentary rocks in northern India. Zircon Hf isotopes further reveal four episodes of juvenile crustal growth at 2.5 Ga, 1.8 Ga, 1.4 Ga and 1.0 Ga in the source regions. Utilizing the basin history and late Neoproterozoic to early Paleozoic paleogeography of South China, we conclude that the Ediacaran–Cambrian sediments in the Nanhua foreland basin were mainly sourced from northern India and adjacent orogens, and the Ordovician–Silurian sediments were derived from both locally recycled Ediacaran–Cambrian rocks and eroded Cathaysian basement. The Wuyi–Yunkai late-orogenic magmatic rocks also contributed to the Silurian sediments in the basin. The upper-Ordovician to Silurian samples in northeast Yangtze received higher proportions of local Cryogenian (850–700 Ma) magmatic rocks which were uplifted during late-Ordovician to Silurian time. We speculate that there was an Ediacaran–Cambrian collisional orogen between South China and northern India, shedding sediments to the early Nanhua foreland basin. Far-field stress during the late stage of this collisional orogeny triggered the Ordovician–Silurian intraplate Wuyi–Yunkai orogeny in South China, and erosion of the local Wuyi–Yunkai orogen further provided detritus to the late Nanhua foreland basin.     

Ediacaran seawater temperature: Evidence from inclusions of Sinian halite

Seawater temperatures throughout Earth's history have been suggested to illustrate a long-term cooling trend from nearly 70 °C at ～3500 Ma to around 20 °C at ～800 Ma. The terminal Neoproterozoic prior to the “Cambrian Explosion” is a key interval in evolutionary history, as complex multicellularity appeared with the advent of the Ediacara fauna. These organisms were likely the first that required higher levels of atmospheric and dissolved marine oxygen for their sustainability. It is known that most modern macroinvertebrates are intolerant of temperatures in excess of 45 °C. Perhaps more importantly, these high seawater temperatures limit the potential of dissolved oxygen, and therefore become an integral part of this evolutionary story. Previously, our understanding of seawater temperature during the terminal Neoproterozoic comes only from ¹⁸O/¹⁶O and ³⁰Si/²⁸Si ratios ascertained from a limited number of cherts. Isotopic ratio methods for assessing seawater temperatures are inherently indirect and have a wide range of oscillation. However, maximum homogenization temperatures (Th_max) of primary fluid inclusions in halite provide a direct means of assessing brine temperature, and have been shown to correlate well with average maximum air temperatures. The oldest halites date to the Neoproterozoic–lower Paleozoic (～700–500 Ma), and Ediacaran representatives can be found in Sichuan Province, China, which do preserve primary fluid inclusions for analysis via cooling nucleation methods. We utilized halite samples from the Changning-2 well, correlative to the Dengying Formation (551–542 Ma), to provide a direct assessment of terminal Neoproterozoic seawater temperature. Our measurements indicate that seawater temperatures where these halites formed are highly similar to tropical Phanerozoic seawater temperature estimates. From compiled paleotemperature data, the decline in seawater temperatures over the course of the Proterozoic, accompanied by the reduction of seawater salinity with the sequestration of salt in massive halite deposits in the Neoproterozoic, allowed the ocean system to accumulate more dissolved oxygen, and potentially paved the way for the evolutionary innovation of complex multicellularity.     

Post-collisional carbonatite-hosted rare earth element mineralization in the Hongcheon area,central Gyeonggi massif,Korea: Ion microprobe monazite U‐Th‐Pb geochronology and Nd‐Sr isotope geochemistry

The Hongcheon area in the central Gyeonggi massif is a unique carbonatite locality in South Korea. The age and petrogenesis of this uncommon rock type and associated rare earth element (REE) mineralization still remain uncertain. The NNE trending, 20–50 m wide and ~ 2 km long Fe-REE ore bodies are hosted within a swarm of carbonatite dykes intruding Precambrian basement gneisses. The intrusive nature of the dykes, fenite alteration halos, exsolution intergrowths of constituent minerals and stable isotope data in the literature collectively attest to the ore formation by crystallization of carbonatite magma. The carbonatites are composed primarily of dolomite, ankerite, siderite, magnetite, monazite, apatite, strontianite and pyrite with subordinate quartz, barite, columbite, fergusonite and calcite. The principal carrier phase of REEs is monazite. The REE contents of monazite vary narrowly (TREO = 66.1–69.4 wt.%) irrespective of the textural occurrence. Although the monazite shows a sample-to-sample variation in La/Nd ratio, the textural varieties from each rock sample are similar with respect to this ratio. Thorium contents in monazite are consistently low (average = ca. 2500 ppm) with unusually high (average = ca. 2200) Th/U ratios. Sensitive high-resolution ion microprobe (SHRIMP) dating of monazite yielded a weighted mean ²⁰⁸Pb/²³²Th age of 232.9 ± 1.6 Ma, which agrees with a weighted mean ²⁰⁶Pb/²³⁸U age of 227.2 ± 8.3 Ma within uncertainties. This age, coupled with comparable intrusion ages documented for kimberlites and monzonite-syenite-gabbro-mangerite suite from central Korea, demonstrates the occurrence of mantle-derived alkaline igneous activities and associated REE mineralization following the North and South China collision. The intrusion of the Hongcheon carbonatite and potassic or ultrapotassic suite in central Korea may have resulted from the post-collisional detachment of the subducted slab and consequent upwelling of hot asthenosphere and melting of the overriding lithospheric mantle. Initial Nd‐Sr isotopic ranges of the Hongcheon carbonatite (ε_Nd = ca. − 26, ⁸⁷Sr/⁸⁶Sr = 0.703–0.706) and previous trace element data deny a petrogenetic linkage with the coeval silicate magmas. The metasomatism in the lithospheric mantle source of the Hongcheon carbonatite must have occurred in the distant past (> 1.7 Ga) to generate significantly negative ε_Nd values.     

Neoproterozoic mafic-ultramafic layered intrusion in Quruqtagh of northeastern Tarim Block,NW China: Two phases of mafic igneous activity with different mantle sources

In this paper we report zircon U–Pb age, chemical compositions of rock-forming minerals, and whole-rock elemental and Sr–Nd isotopic data for the No. II mafic-ultramafic intrusive complex (N2MC) in the Quruqtagh area at the northeastern margin of the Tarim Block, northwestern China to evaluate its petrogenesis and tectonic significance. The N2MC with an exposure area of ca. 12 km² has a funnel-shaped cross-section and intruded the Paleoproterozoic basement. U–Pb zircon dating gives a crystallization age of 760 ± 6 Ma. Rock types of the N2MC include lherzolite, pyroxenite, gabbro and minor diorite. Major elements geochemistry of these rocks exhibits a tholeiitic trend with a wide range of SiO₂ contents (38.8–60 wt.%). On the other hand, they are systematically enriched in LILE, LREE and depleted in HFSE and HREE, thus leading to low HFSE/LREE ratios (e.g., Nb/La ≈ 0.3). Isotopically, the studied rocks are characterized by negative whole-rock εNd(t) values (? 7.6 to ? 2.8) and variable high (⁸⁷Sr/⁸⁶Sr)_i (0.7095–0.7059). These features, together with chemical compositions of the rock-forming minerals and the presence of the primary phlogopite and hornblende, suggest that N2MC was likely formed via crystal fractionation/cumulation (with negligible crustal contamination) of a tholeiitic magma derived from a metasomatized subcontinental lithosphere mantle (SCLM) in an extensional environment. The enrichment of the mantle source could be ascribed to the metasomatism by subducted-slab-released fluids before partial melting. Overall, reported Neoproterozoic igneous rocks throughout the Tarim Block constitute two major phases of Neoproterozoic igneous activities, i.e., ca. 825–800 Ma and ca. 780–745 Ma, respectively. Similar to that of many other Rodinian continents, this feature is interpreted to be related to the two phases of Neoproterozoic mantle plume activity under the Rodinia. Furthermore, there exist two types of mafic-ultramafic complex at Quruqtagh, i.e., the ca. 820 Ma carbonatite-bearing and the ca. 760 Ma tholeiitic, which could reflect the presence of two different mantle sources.     

REE fractionation,mineral speciation,and supergene enrichment of the Bear Lodge carbonatites,Wyoming, USA

The Eocene (ca. 55–38 Ma) Bear Lodge alkaline complex in the northern Black Hills region of northeastern Wyoming (USA) is host to stockwork-style carbonatite dikes and veins with high concentrations of rare earth elements (e.g., La: 4140–21000 ppm, Ce: 9220–35800 ppm, Nd: 4800–13900 ppm). The central carbonatite dike swarm is characterized by zones of variable REE content, with peripheral zones enriched in HREE including yttrium. The principle REE-bearing phases in unoxidized carbonatite are ancylite and carbocernaite, with subordinate monazite, fluorapatite, burbankite, and Ca-REE fluorocarbonates. In oxidized carbonatite, REE are hosted primarily by Ca-REE fluorocarbonates (bastnäsite, parisite, synchysite, and mixed varieties), with lesser REE phosphates (rhabdophane and monazite), fluorapatite, and cerianite. REE abundances were substantially upgraded (e.g., La: 54500–66800 ppm, Ce: 11500–92100 ppm, Nd: 4740–31200 ppm) in carbonatite that was altered by oxidizing hydrothermal and supergene processes. Vertical, near surface increases in REE concentrations correlate with replacement of REE(±Sr,Ca,Na,Ba) carbonate minerals by Ca-REE fluorocarbonate minerals, dissolution of matrix calcite, development of Fe- and Mn-rich gossan, crystallization of cerianite and accompanying negative Ce anomalies in secondary fluorocarbonates and phosphates, and increasing δ¹⁸O values. These vertical changes demonstrate the importance of oxidizing meteoric water during the most recent modifications to the carbonatite stockwork. Scanning electron microscopy, energy dispersive spectroscopy, and electron probe microanalysis were used to investigate variations in mineral chemistry controlling the lateral complex-wide geochemical heterogeneity. HREE-enrichment in some peripheral zones can be attributed to an increase in the abundance of secondary REE phosphates (rhabdophane group, monazite, and fluorapatite), while HREE-enrichment in other zones is a result of HREE substitution in the otherwise LREE-selective fluorocarbonate minerals. Microprobe analyses show that HREE substitution is most pronounced in Ca-rich fluorocarbonates (parisite, synchysite, and mixed syntaxial varieties). Peripheral, late-stage HREE-enrichment is attributed to: 1) fractionation during early crystallization of LREE selective minerals, such as ancylite, carbocernaite, and Ca-REE fluorocarbonates in the central Bull Hill dike swarm, 2) REE liberated during breakdown of primary calcite and apatite with higher HREE/LREE ratios, and 3) differential transport of REE in fluids with higher PO₄³⁻/CO₃²⁻ and F⁻/CO₃²⁻ ratios, leading to phosphate and pseudomorphic fluorocarbonate mineralization. Supergene weathering processes were important at the stratigraphically highest peripheral REE occurrence, which consists of fine, acicular monazite, jarosite, rutile/pseudorutile, barite, and plumbopyrochlore, an assemblage mineralogically similar to carbonatite laterites in tropical regions.     

Holocene climate variation determined from rubidium and strontium contents and ratios of sediments collected from the BadainJaran Desert,Inner Mongolia,China

Rubidium (Rb) and strontium (Sr) contents and ratios were analyzed in 197 sediment samples collected from the CGS1 segment of the Chagelebulu Section in the Badain Jaran Desert of China to study millennial scale climate change during the Holocene. The results showed that the Rb and Sr contents and Rb/Sr ratios were low in the samples of dune sands and loess (Mz < 5.64Φ), and those values were high in the samples of loess (Mz > 5.64Φ) and paleosols, these data displayed 11 changing cycles in alternation of peaks and valleys in the chart. In addition, the Rb contents were positively correlated with Mz (mean particle diameter) and clay contents. While the correlations were weaker, Sr contents also showed a tendency to increase with increases in the Mz and clay contents. Based on a comprehensive analysis of the distribution of Rb and Sr within the CGS1 segment, it appears that the observed Rb and Sr contents and ratios varied in accordance with fluctuations of the East Asian winter and summer monsoons. In terms of timing and climate, low values (C1–C11) resulting from winter monsoons had a strong correlation with cold events in the North Atlantic: the period C1 corresponded to times ranging from 400 a to 1400 a and the periods C2, C3, C4, C7, C9, C10, and C11 corresponded to times of 3000 a, 4000 a, 5900 a, 8200 a, 9400 a, 10,300 a, and 11,000 a, respectively. The cold event C5 (6200 a) was also discovered in the North Atlantic in recent; and C6 (7100 a), C8 (8700 a) were discovered in some other places of China. These cold events indicated by Rb and Sr contents and ratios in the Chagelebulu Section of the Badain Jaran Desert recorded the regional response of global climate change during the Holocene.     

The origins of the Mengye potash deposit in the Lanping–Simao Basin,Yunnan Province,Western China

The Lanping–Simao Basin (LSB) is a Mesozoic–Cenozoic continental margin rift basin in Western China. It formed during the opening and closing of the Tethys Ocean. This basin is also known as a “metal belt” as it hosts several metal deposits, besides, the Mengye potash deposit. However, the exact dates of the formation either in the Paleocene or the Cretaceous, and thus the origins of the marine, continental or mixed origins of the Mengye deposits, remain disputed. Based on the basin's evolution, materials of marine origin and/or remnant seawater should be present, but instead the salt layers of the Mengye potash deposit present typically continental lithological features. This study examines and reviews evaporative minerals, Br/Cl and I/Cl molar ratios, and isotopes of S, B, and Sr·I and I/Cl data for this area has not been previously reported. The basin's evaporative minerals are dominated by halite and sylvite. The amounts of anhydrite, chlorocalcite, langbeinite, glaserite, tachyhydrite and glauberite are small. All of these form in both marine and continental environments. The values of I and the I/Cl molar ratios of halite and sylvite are from 0.07 to 0.27 ppm, and from 0.03 to 0.11 × 10^− 6, respectively, dependent on organic substances. Br and molar Br/Cl values are from 89.08 to 555.45 ppm and from 0.06 × 10^− 3 to 0.38 × 10^− 3, respectively. All of the Br/Cl molar ratios are lower than those of seawater, and most of them are < 0.1, suggesting continental or mixed origin. Previously published δ³⁴S, δ¹¹B and ⁸⁷Sr/⁸⁶Sr values for evaporative minerals indicate a continental origin for the Mengye potash deposit. However, materials of hydrothermal origin are widely distributed in the basin and may have played an active role for the formation of the potash deposit. Thus the Mengye potash deposit could be of continental origin, with a remnant seawater trace.