rare earth element and sr nd isotope geochemistry of phosphatic rocks in neoproterozoic ediacaran doushantuo formation in zhangcunping section from western hubei province south china abstract phosphatic rocks are widely distributed in neoproterozoic ediacaran doushantuo formation in yangtze platform south china in this study we examined samples from the zhangcunping section in western hubei province with major element rare earth element ree and sr nd isotopic analyses on the phosphorites and the host dolostone rocks we employed an acid leaching method to separate the carbonate acetic acid leachable and phosphate hydrochloric acid leachable fractions in all the samples the geochemical differences between the different fractions can be recognized based on the p2o5 ree contents and sr nd isotopic characteristics the carbonate fractions in the rocks display low total ree concentrations with seawater like ree patterns super chondritic y ho ratios moderate negative ce anomalies and positive eu anomalies indicating these carbonates have retained the signatures of paleo seawater on the contrary the phosphate fractions display high total ree concentrations with hat shaped ree patterns generally lower y ho ratios weak negative ce anomalies and positive eu anomalies which may have recorded the features of diagenetic fluids negative ce anomalies and positive eu anomalies displayed in the carbonate fractions of the studied samples may also indicate the anoxic environments of ocean basins in south china during the deposition of the neoproterozoic ediacaran doushantuo formation a geochemical comparison between lower phosphorite layer and upper phosphorite layer indicates a greater degree of diagenesis occurred in the lower phosphorite layer than the upper phosphorite layer the negative end t values of the samples suggest continental crustal sources for the rees and the lower values in the phosphorite samples 6 9 to 6 0 than the dolostone samples 5 5 to 3 8 may suggest different processes for them and it is likely that the rees in the phosphorites have been modified by diagenetic fluids with ree contributions of pore fluids derived from the clastic silicates in the strata which generally have lower end t values whereas the dolostone took the rees from the ambient seawater mainly

rare earth element geochemistry of ferromanganese crusts from the hawaiian archipelago central pacific abstract the rare earth element ree composition of ferromanganese deposits from the hawaiian archipelago was determined as part of a geochemical investigation into the origin and environment of deposition of crusts most samples exhibit shale normalized ree patterns which are typical of hydrogenous ferromanganese deposits patterns of two todorokite and manjiroite rich crusts are significantly different from those of the other samples the range of concentrations in typical hawaiian crusts sum of ree 0 15 0 25 wt is in the uppermost portion of that reported for deep sea fe mn nodules shallow water 2000 m as well as slightly greater ree fractionation large positive ce anomalies attributed to the oxidative scavenging at the mno 2 surface are observed on all samples except one the slight light ree lree depletion in shallow water crusts relative to deeper samples is discussed in terms of variations in the ree concentrations in the water column and the relative complexing behavior of the ree no significant trend in ce concentration with depth is observed partition coefficient calculations suggest that concentrations of trivalent ree in crusts are affected by their availability in seawater to a greater extent than by the composition of the scavenging ferromanganese oxide flocs

uptake of elements from seawater by ferromanganese crusts solid phase associations and seawater speciation marine fe mn oxyhydroxide crusts form by precipitation of dissolved components from seawater three hydrogenetic crust samples one phosphatized and two hydrothermal mn oxide samples were subjected to a sequential leaching procedure in order to determine the host phases of 40 elements those host phase associations are discussed with respect to element speciation in seawater the partitioning of elements between the two major phases mn oxide and fe oxyhydroxide can in a first order approximation be explained by a simple sorption model related to the inorganic speciation of the elements in seawater as has been proposed in earlier models free and weakly complexed cations such as alkali and alkaline earth metals mn co ni zn tl i and partly y are sorbed preferentially on the negatively charged surface of the mno2 in hydrogenetic crusts the driving force is a strong coulombic interaction all neutral or negatively charged chloro cd hg tl carbonate cu y pb and u and hydroxide be sc ti fe zr nb in sn sb te hf ta bi th and tl iii complexes and oxyanions v cr as se mo and w bind to the slightly positively charged surface of the amorphous feooh phase while coulombic interaction can explain the sorption of the negatively charged species the binding of neutral species is based on specific chemical interaction organic complexation of elements in deep ocean water seems to be at most of minor importance surface oxidation can explain some strong metal associations e g of co and tl with the mno2 and te with the feooh sorption reactions initially driven by coulombic forces are often followed by the formation of specific bonds between the adsorbate and the atoms of the oxide surface differences in the associations of some metals between the non phosphatized and phosphatized hydrogenetic crusts and between the hydrogenetic and the hydrothermal samples reflect the different physico chemical environments of formation and speciations in oxic seawater vs less oxic fluids especially for the redox sensitive metals such as mo and v these environmental related differences indicate that the methodology of chemical speciation used here in combination with spectroscopic methods may allow for the detection of changes in paleoceanographic conditions recorded during the several tens of millions of years of crust growth

compositional variations in manganese carbonate micronodules from the lower proterozoic nsuta deposit ghana product of authigenic precipitation or post formational diagenesis abstract detailed petrographic and microprobe studies of micronodules identified in the manganese carbonate orebody and adjacent mn rich rocks at the 2 2 ga nsuta deposit ghana indicate distinct lithologic control on nodule structure and chemical composition nodules in the mn rich rocks adjacent to the manganese carbonate orebody conform with the well banded nature of the rock and are distinctly zoned into alternating bands compositionally dominated by mg kutnahorite and mg ca rhodochrosite individual nodules are partially or completely cemented by thin dark silica and carbonates of ca mg mn solid solution nodules in the orebody on the contrary are generally massive homogeneous consist predominantly of rhodochrosite and are only partially cemented by dark silica based on the stratigraphic relationship of the nodule bearing rocks to the manganese carbonate orebody and the variations in texture and composition observed in the nodules it would appear that the mn carbonate nodules precipitated diagenetically in response to changing pore water chemistry and or metal mn and ca supply the overall mineralogical and geochemical features indicate in addition that the nodules may have preserved original carbonate compositions both metastable and stable during burial diagenesis and low grade regional metamorphism

evaluation of the application of rare earth elements to paleoceanography anomalous departures of rare earth elements ree from similarity of chemical behaviour are most evident in a comparison of ce with its neighbors under reducing conditions ce3 acts like other ree but oxidized ce4 is adsorbed on mn fe oxyhydroxides or organic particulates and consequently the remaining solution will tend to exhibit a negative ce anomaly in addition more subtle fractionations may emphasize the light or the heavy or the middle ree a pattern of ree may be recorded by immediate diagenesis on a suitable chemical substrate such as apatite fish debris conodonts carbonate or chert this record was originally thought to reflect the paleoredox conditions of primary deposition however any such primary record may be overprinted by late diagenetic alteration early analyses of ree in conodonts from a wide range of sediments suggested a prevalence of reducing conditions no ce anomaly in pre carboniferous oceans and more common oxidation negative ce anomaly in the late paleozoic however recent research by other investigators indicates that variations in cean are more diverse in origin and in particular many are distorted to an unknown extent by late diagenesis in any case it is now clear that geological age does not show a consistent relationship to the level of the ce anomaly the ce anomaly apparently does not play any regular role in the isotopic events that accompany prominent mass extinctions further research is required to understand and thus make useful the controls on the ce anomaly

rare earth element and srnd isotope geochemistry of phosphate nodules from the lower cambrian niutitang formation nw hunan province south china abstract phosphate nodules are widely distributed in the early cambrian black shale sequence in yangtze platform south china in this study we carried out x ray diffraction major element rare earth element and sr nd isotopic studies on phosphate nodules from two pc c sections in hunan province south china two different types of phosphate nodules can be recognized based on ree and nd isotopic characteristics type 1 with seawater like ree patterns higher end t values and type 2 with hat shaped ree patterns and more negative end t values we suggest that the difference in ree patterns and nd isotopic compositions between the two types reflects changes in pore water geochemistry from seawater dominated towards diagenetic fluid dominated conditions during early diagenesis positive eu anomalies are displayed in most samples and are likely to record not only the anoxic environments but also the involvement of submarine exhalative hydrothermal fluids which prevailed in south china during early cambrian

geochemistry of ferromanganese nodules from domes site a northern equatorial pacific multiple diagenetic metal sources in the deep sea abstract the major and minor element composition of ferromanganese nodules from domes site a has been determined by x ray fluorescence methods three phases appear to control the bulk compositions mn and fe oxyhydroxides and aluminosilicates relatively wide compositional variations are evident throughout the area nodules with high mn fe ratios high cu mg mo ni and zn concentrations and high todorokite mno 2 ratios have granular surface textures and are confined to an east west trending depression with thin quaternary sediment cover nodules with low mn fe ratios high concentrations of as ca ce co la p sr ti v y and zr and low todorokite mno 2 ratios have smooth surfaces and are confined to shallower areas with relatively thick quaternary sediment to the north and south of the depression all nodules in the area have compositions which are influenced by diagenesis but those with the most marked diagenetic signature high mn fe and cu ni ratios low ce la ratios and more todorokite are found in areas of very slow or non existent sedimentation many of these nodules are actually in contact with outcropping tertiary sediment this paradox may be resolved by postulating by analogy with some shallow water occurrences that the nodules accrete from bottom waters which have enhanced particulate and dissolved metal contents derived from diagenetic reaction in areas remote from the site of nodule formation the metals are supplied in a bottom flow probably antarctic bottom water which also erodes or prevents modern sedimentation in the depression nodules on the flanks of the depression are not evidently affected by this flow and derive at least pan of their constituent metals from diagenetic reaction in the underlying quaternary sediment apparently abyssal diagenetic nodules can have an immediate and a remote diagenetic metal source metal fluxes derived from pore water dissolved metal gradients may not be relevant to particular accreting nodules if a significant fraction of their metals is derived from outside the area in which they form

petrography and high resolution geochemical records of lower jurassic manganese rich deposits from monte mangart julian alps abstract deposits with unusually high mn contents sampled at monte mangart in the julian alps include organic rich marlstone and black shale with interbedded manganoan and siliceous limestone which were deposited during the early toarcian oceanic anoxic event mn enrichment during that period has been related to global sea level change coincident with increasing subsidence rate the formation of fe mn nodules marking a hardground at the base of the monte mangart section seems to be triggered by release of mn from remote hydrothermal vents into a region of relatively elevated submarine topography where oxidizing conditions prevailed however very high mn contents in carbonate phases above the hardground imply an additional diagenetic source of this element in the lower part of this section the whole stratigraphic sequence ca 30 m displays a transition from mn rich up to 8 8 sediments in the lower part to mn poor less than 1 8 sediments in the middle and upper parts the drastic decrease in mn content s up section is accompanied by a clear decrease in the mean size of pyrite framboids indicating more intense anoxia euxinia in the water column in the presence of mn2 conditions of high alkalinity induced precipitation of mn carbonates during early diagenetic processes negative 13ccarb values coincident with high mn contents indicate involvement of organic matter in the mineralization process the striking similarity of ce ce and mn profiles demonstrates that consistent with redox chemistry of mn and ce under anoxic conditions ce3 and mn2 were mobilized and released into pore water where precipitation of mn carbonates occurred

rare earth element geochemistry of laminated diatom mats from tropical west pacific evidence for more reducing bottomwaters and higher primary productivity during the last glacial maximum rare earth elements ree along with selected major and trace elements were measured in laminated ethmodiscus rex diatom mats and associated sediments diatomaceous clay and pelagic clay in two sediment cores collected from the parece vela basin of the eastern philippine sea ree distributions are characterized by strong enrichment of middle ree mree and heavy ree hree over light ree lree and slight enrichment of mree over hree this distribution pattern suggests that ree compositions of the laminated e rex diatom mats were not the product of e rex blooms an inference also supported by the fact that ti normalized ree concentrations are not clearly different from those in the diatomaceous clay and pelagic clay comparison of ree patterns with the vertical distribution of authigenic phases in the sediment indicates that lree were dominantly associated with detrital materials whereas mree and hree were selectively enriched by mn oxyhydroxides and authigenic phosphates in the pelagic clay a weak negative ce anomaly cannot be linked to oxic depositional conditions but instead is attributed to the retention of a negative ce anomaly associated with authigenic phosphates in the laminated e rex diatom mats a weak positive ce anomaly is consistent with depositional sulfidic anoxic conditions and is interpreted to represent enhanced scavenging of reduced aqueous ce3 by barite in a strongly reducing environment moreover variably negative to positive ce anomalies in the diatomaceous clay may reflect the concurrent operation of the two processes controlling ce accumulation in the laminated e rex diatom mats and pelagic clay the study cores show a ubiquitous positive eu anomaly owing to the presence of volcanic materials the smaller eu anomaly in the laminated e rex diatom mats and diatomaceous clay relative to that in the pelagic clay may be attributed to the release of reduced eu2 from mineral phases to the sediment pore water under strongly reducing conditions previous studies have shown that the advection of lower circumpolar water lcpw strengthened during the last glacial maximum lgm which should have resulted in better ventilation of the deep eastern philippine sea evidence presented here for more reducing bottomwater conditions during the laminated e rex diatom mats formation implicates elevated primary productivity and enhanced organic sinking fluxes as primary controls on redox changes in the eastern philippine sea during the lgm enhanced primary productivity and more reducing bottomwaters during the laminated e rex diatom mats deposition resulted in a larger respired carbon pool in the deep eastern philippine sea which may have been part of a larger scale modulation of atmospheric co2 variation during pleistocene glacial interglacial cycles by deep ocean carbon storage c 2011 elsevier b v all rights reserved

shrimp zircon u pb geochronological and whole rock geochemical evidence for an early neoproterozoic sibaoan magmatic arc along the southeastern margin of the yangtze block abstract it has been generally accepted that the south china block was formed through amalgamation of the yangtze and cathaysia blocks during the proterozoic sibaoan orogenesis but the timing and kinematics of the sibao orogeny are still not well constrained we report here shrimp u pb zircon geochronological and geochemical data for the taohong and xiqiu tonalite granodiorite stocks from northeastern zhejiang southeastern margin of the yangtze block our data demonstrate that these rocks dated at 913 15 ma and 905 14 ma are typical amphibole rich calc alkaline granitoids formed in an active continental margin combined with previously reported isotopic dates for the 1 0 ga ophiolites and 0 97 ga adakitic rocks from northeastern jiangxi the timing of the sibao orogenesis is thus believed to be between 1 0 and 0 9 ga in its eastern segment it is noted that the sibao orogeny in south china is in general contemporaneous with some other early neoproterozoic 1 0 0 9 ga orogenic belts such as the eastern ghats belt of india and the rayner province in east antarctica indicating that the assembly of rodinia was not finally completed until 0 9 ga

diagenetic constraints on the use of cerium anomalies as palaeoseawater redox proxies an isotopic and ree study of cambrian phosphorites seawater rare earth element ree distributions show heavy ree enrichment and cerium depletion but these characteristics are only rarely found in ancient marine authigenic minerals such as carbonate fluorapatite and calcite this enigma may be due to changing ree distributions in seawater through time or to post depositional redistribution of ree differentiating between these two factors is however far from straightforward as their relative importance is likely to vary and evidence is often ambiguous in this article we present ree as well as strontium and sulphur isotope data for basal cambrian phosphorites of south china which confirm the emerging rule of thumb that granular phosphorites seldom reveal extreme departures from the seawater norm and tend to undergo therefore less diagenetic alteration of ree spectra than skeletal apatites and other phosphate types this study reveals stratigraphic trends in ce anomalies ce ce that could be taken to imply the preservation of a palaeoenvironmental signal however further investigation of our data shows that such trends in phosphorites can also be caused by post depositional alteration which tends to 1 increase ree contents 2 reverse ce depletion 3 alter eu anomalies and 4 concentrate preferentially the middle ree mree further alteration which may be due to weathering has led to hree depletion and positive la and y anomalies tetrad effect this is the first study where ceanom and phosphate bound sulphate s isotope values could be compared for one particular stratigraphic section which provides us with an additional tool for the interpretation of diagenetic redox conditions least altered phosphorites from meishucun that yield a strongly negative ceanom constrain early cambrian seawater 34s to about 33 we conclude that phosphorite ceanom primarily records variations in the local conditions of diagenesis while outlining some special cases in which diagenetic redox conditions may broadly reflect local bottom water redox conditions

introduction to and classification of manganese deposits of china abstract manganese mn ore deposits are widely distributed in china and can be divided into six types based on origin and subsequent modifications 1 sedimentary 2 volcanic sedimentary 3 metamorphosed 4 hydrothermally modified 5 hydrothermal and 6 supergene sedimentary and supergene mn ore deposits are economically the most important mn ore deposits and ore bearing sequences are distributed temporally from the proterozoic through the quaternary but they principally are middle proterozoic sinian cambrian ordovician devonian carboniferous permian triassic and quaternary ages the largest mn metallogenic periods in china are sinian and devonian in contrast to the widespread proterozoic cretaceous and oligocene mn deposits found elsewhere in the world mn bearing stratigraphic successions in china can be divided into six types of lithologic associations 1 black shale series 2 chert mudstone limestone 3 carbonate 4 mudrock carbonate 5 volcanic sedimentary and 6 epeirogenic clastic rock types the most important mn metallogenic regions in china are 1 yanliao 2 border of hunan sichuan guizhou hubei provinces 3 southern shaanxi and northeastern sichuan 4 middle guizhou and eastern yunnan 5 southwestern guangxi 6 southeast yunnan 7 hunan guangxi guangdong fujian and 8 xinjiang the most striking characteristics of mn ore deposits in china are the wide distribution in geological ages and variety of compositional types of ores such as fe mn b mn p mn co mn ca mn ca mg mn among others the primary mn ores of china are mainly mn carbonates

geochemistry of hydrothermal mn oxide deposits from the s w pacific island arc abstract hydrothermal mn oxide crusts have been removed from the tonga kermadec ridge the first such hydrothermal deposits to be reported in the s w pacific island arc in several respects the deposits are similar to hydrothermal mn crusts from oceanic spreading centre settings they are limited in areal extent comprise well crystalline birnessite and generally display extreme fractionation of mn from fe they are strongly depleted in many elements compared to hydrogenous mn deposits but are comparatively enriched in li zn mo and cd the group ia and group iia metals show strong intercorrelations and the behaviour of mg in the purest samples may indicate the extent to which normal seawater has influenced the composition of the deposits certain aspects of the deposits are not typical of hydrothermal mn deposits in particular at least some of the crusts have developed on a sediment or unconsolidated talus substrate some crusts or specific layers within some crusts display a chemical composition which suggests a significant input from normal seawater

ferromanganese nodules from manop sites h s and r control of mineralogical and chemical composition by multiple accretionary processes abstract the chemical composition of ferromanganese nodules from the three nodule bearing manop sites in the pacific can be accounted for in a qualitative way by variable contributions of distinct accretionary processes these accretionary modes are 1 1 hydrogenous i e direct precipitation or accumulation of colloidal metal oxides in seawater 2 2 oxic diagenesis which refers to a variety of ferromanganese accretion processes occurring in oxic sediments and 3 3 suboxic diagenesis which results from reduction of mn 4 by oxidation of organic matter in the sediments geochemical evidence suggests processes 1 and 2 occur at all three manop nodule bearing sites and process 3 occurs only at the hemipelagic site h which underlies the relatively productive waters of the eastern tropical pacific a normative model quantitatively accounts for the variability observed in nearly all elements zn and na however are not well explained by the three end member model and we suggest that an additional accretionary process results in greater variability in the abundances of these elements variable contributions from the three accretionary processes result in distinct top bottom compositional differences at the three sites nodule tops from h are enriched in ni cu and zn instead of the more typical enrichments of these elements in nodule bottoms in addition elemental correlations typical of most pelagic nodules are reversed at site h the three accretionary processes result in distinct mineralogies hydrogenous precipitation produces mno2 oxic diagenesis however produces cu ni rich todorokite and suboxic diagenesis results in an unstable todorokite which transforms to a 7 a phase birnessite upon dehydration the presence of cu and ni as charge balancing cations influence the stability of the todorokite structure in the bottoms of h nodules which accrete dominantly by suboxic diagenesis na and possibly mn 2 provide much of the charge balance for the todorokite structure limited growth rate data for h nodules suggest suboxic accretion is the fastest of the three processes with rates at least 200 mm 106 yr oxic accretion is probably 10 times slower and hydrogenous 100 times slower since these rates predict more suboxic component in bulk nodules than is calculated by the normative analysis we propose that suboxic accretion is a non steady state process variations in surface water productivity cause pulses of particulate flux to the sea floor which result in transient mn reduction in the surface sediments and reprecipitation on nodule surfaces

formulation of coseismic changes in earth rotation and low degree gravity field based on the spherical earth dislocation theory in this paper we present analytical formulas to compute the coseismic earth rotation change polar motion and length of day and low degree gravity field change based on a spherical dislocation theory using the preliminary reference earth model and our formulas we calculate coseismic changes in earth s rotation and low degree stokes coefficients caused by the four largest earthquakes since 1960 the results verify that the present method is consistent with previous studies but the method cannot be verified by the observations a case study on the 2011 tohoku oki earthquake mw 9 0 indicates that the coseismic earth rotation change depends on the magnitude and source parameters and results show a difference between a point source and finite fault model we also investigate the effect of seawater redistribution on coseismic earth rotation change but the effect is small and can be neglected

geochemistry and geochronology of a hydrothermal ferromanganese deposit from the north fiji basin abstract a study of north fiji basin surface sediment geochemistry has indicated one core to be of predominately hydrothermal origin this core contains a 38 cm thick ferromanganese oxide deposit that conformably overlies foraminiferal ooze uranium series and major rare earth and trace element chemical analyses were performed in order to understand the origin and age of this unusual deposit the onset of hydrothermal deposition at 128 18ka b p has been determined by excess 230 th dating of the oxide ooze contact both 226 ra and 222 rn are supplied to the overlying water column by diffusion from the 230 th rich ferromanganese deposit foraminifera tests within the deposit are replaced by and coated with the ferromanganese rich material calculated metal accumulation rates are comparable to or exceed rates from other known hydrothermal areas such as the east pacific rise bauer basin famous and tag areas rare earth element results indicate a partial hydrogenetic contribution to a predominantly hydrothermal signature in the ferromanganese part of the deposit vertical element distributions reveal variations that are interpreted as changes in the nature of hydrothermal activity at this site r mode factor analysis of the elemental data indicates three major factors low temperature hydrothermal volcanic ash detrital and high temperature hydrothermal that together account for 95 of the sample variability the combined geochemical data reveal a sequence of deposition at this site of initial volcanism ash fall followed by high temperature and then low temperature hydrothermal mineralization lasting for up to 128 ka

effects of phosphatization on the geochemical and mineralogical composition of marine ferromanganese crusts most hydrogenetic ferromanganese crusts in the central pacific consist of two growth generations a phosphatized older growth generation that is impregnated with carbonate fluorapatite cfa and a younger non phosphatized growth generation geochemical and mineralogical investigations of non phosphatized and phosphatized crust layers revealed significant differences that are not simply dilution effects by cfa certain elements are depleted in old crusts compared to young crusts in the order si fe al ti co mn pb others like ni zn cu y and rees rare earth elements are mostly enriched suboxic conditions in the phosphate rich water of the oxygen minimum zone that infiltrated the crusts caused a partial redissolution of crust phases resulting in mobilization of associated elements a partial recrystallization of more stable phases and a secondary input of nutrient type elements the frequent occurrence of todorokite in phosphatized crust layers indicates that mn mobilized from the vernadite crust phase was partially recrystallized as todorokite which is more stable under suboxic conditions incorporating ni cu and zn into the crystal lattice but rejecting co other metals like pb y and rees probably form stable phosphate phases in phosphatized crusts our investigations emphasize that under the influence of phosphatization diagenetic remobilization and reorganization in fe mn crusts took place in contrast to non phosphatized crusts the older phosphatized crust generation no longer represents a complete primary crust precipitate therefore young non phosphatized and old phosphatized crust generations should be considered as two different sample types with respect to geochemical composition mineralogy and evolution we also suggest that most methods for age determination like the 87sr86sr isotopic dating method or co chronometry cannot be used for phosphatized crusts without caution

sedimentary geochemistry of manganese implications for the environment of formation of manganiferous black shales the sedimentary geochemistry of manganese is dominated by the redox control of its speciation higher oxidation states mn super 3 and super 4 occurring as insoluble oxyhydroxides in well oxygenated environments and the lower oxidation state mn super 2 being much more soluble in oxygen deficient settings its geochemical behavior is therefore quite different in oxic and anoxic environments and where oxic and anoxic conditions are juxtaposed mn is recycled between the two environments in modern marine sediments mn is present above its crustal abundance as an oxyhydroxide in all slowly accumulating pelagic sediments of the deep ocean and in surficial deposits of continental margin environments diagenetic recycling of mn in the latter causes surficial deposits to have larger mn enrichments than in many pelagic sediments bottom sediments of permanently anoxic basins show no enrichments and have mn concentrations that are controlled solely by the aluminosilicate fraction manganese carbonates kutnohorite and calcic rhodochrosite are found only in anoxic sediments accumulating beneath surface oxic horizons and therefore under oxygenated bottom waters in many nearshore environments such enrichments are due to delivery of mn by burial of surface oxyhydroxides into the subsurface anoxic environment where they are dissolved pore water mn levels can reach saturation with respect to a mixed mn ca carbonate phase in such sediments the diagenetic origin for these phases is shown by their carbon isotope compositions which typically indicate a carbon source from decomposing organic matter the presence of mn carbonates therefore signifies that the host sediment must have accumulated under oxygenated bottom waters on the basis of this information it is proposed that in contrast to several current explanations for the formation of mn carbonates kutnohorite and rhodochrosite in ancient organic rich shales limestone and marl sequences and in many mn ore deposits the occurrence of these mineral phases indicates that the sediments originally accumulated beneath oxygenated bottom waters by analogy with the present mn carbonates could not have formed in the bottom waters of anoxic basins these diagenetic phases however did form where mn was supplied at a high rate namely by the burial of oxyhydroxide enriched surface sediments to a subsurface anoxic environment this situation could only have occurred under oxygenated bottom waters the presence of mn carbonates in ancient black shales and in some carbonate rich rocks lends strong support to the notion that these rocks did not necessarily form in anoxic basins but owe their carbon richness to a high supply of organic matter to sediments deposited under oxygenated bottom waters probably in continental margin settings

the influence of suboxic diagenesis on the formation of manganese nodules in the clarion clipperton nodule belt of the pacific ocean abstract polymetallic nodules and a single fe mn crust from the clarion and clipperton zone ccz of the equatorial eastern pacific have been analyzed to determine their chemical and mineralogical compositions icp oes analyses of bulk nodules from the ccz indicate that the nodules formed under oxic diagenetic conditions with typical mn fe ratios of 4 6 ni cu values of 2 3 wt co contents of 0 12 0 17 wt however detail analyses of individual growth layers by electron microprobe analyses empa reveal much larger chemical heterogeneity of individual layers with mn fe ratios ranging from 800 two different genetic types of layers can be distinguished layer type 1 dense layer with average mn fe ratios of 1 80 average ni cu of 0 81 wt co contents of 0 30 wt hydrogenetic metal precipitation from oxic waters these layers consist of fe vernadite mno2 epitaxially intergrown with feroxyhyte feooh nanoparticles layer type 2 growth structures dendritic growth structures and dense layers with average mn fe ratios of 96 ni cu of 3 9 wt co contents of 0 08 wt and a distinct ni cu maximum of 6 51 wt at a mn fe ratio of 56 suboxic diagenetic metal precipitation from suboxic pore waters type 2 layers mainly consist of turbostratic phyllomanganates such as 10 a vernadite 7 a vernadite and todorokite are minor compounds mixed layer type 3 these layers can occur as zones of low reflectivity in the transition from layer type 1 to 2 or build up inhomogeneous growth structures of nm thin layers of low or high reflectivity the mn fe ratios of this material range between 3 and 11 ni cu of 1 4 6 wt and co contents are between 0 02 and 0 77 wt in most cases these growth structures represent a mixture of type 1 and 2 layers x ray photoelectron spectroscopy xps of the recent outermost nm layers of nodules top rim and bottom side indicates hydrogenetic accretion processes under recent oxic conditions both from seawater and pore water the mixed type ccz nodules are interpreted to consist of an oxic hydrogenetic and a suboxic diagenetic end member calculations of the proportions of the individual layer end members show that suboxic layers make up about 50 60 of the chemical inventory of the ccz nodules whereas oxic hydrogenetic layers comprise about 35 40 the remaining part 5 10 consists of incorporated sediment particles occurring along cracks and pores these results demonstrate that suboxic conditions alternate with oxic conditions during the growth of nodules in the eastern ccz this is probably due to fluctuating bioproductivity in the equatorial pacific surface waters during glacial interglacial periods which led to changing organic carbon flux to the sediment and changing oxygen consumption in near surface sediments furthermore reduced ventilation of the deep ocean during glacial periods may have led to suboxic conditions in near surface sediments our investigations prove that bulk chemistry data of whole nodules only provides an average of individual layers that build up the nodules and is inappropriate for genetic interpretation

new insight into a subduction related orogen a reappraisal of the geotectonic framework and evolution of the japanese islands abstract the geotectonic framework and the evolutionary history of the japanese islands need revision in accordance with the various geophysical geological evidence gathered by new methodologies in the recent years including seismic tomography vibroseis ground breaking seismic experiments and detrital zircon chronology these investigations have addressed various themes such as 1 seismic profile of the crust and mantle beneath the japanese islands 2 high precision ages of the protoliths of high p t metamorphic rocks and 3 provenance of terrigenous clastics the results have led to a number of important findings including 1 detection of a large mass of slab around the mantle boundary layer suggesting the long term oceanic subduction beneath japan 2 confirmation of the subhorizontal piled nappe structure for the entire crust of japan 3 finding a new high p t metamorphosed accretionary complex unit that represents the youngest blueschist in japan 4 finding of the oldest early cambrian arc batholith and cover sediments and 5 the identification of plural arc batholiths which have already been erased from the surface based on a synthesis of these new data this article presents a re evaluation of the conventional geotectonic subdivision of the subduction related orogen in japan re definition of the elements and their mutual boundaries and re consideration of the geotectonic evolution of the japanese islands in particular the historical change in provenance suggests that proto japan has experienced large scale tectonic erosion in multiple stages and the corresponding large amounts of continental crust materials were subducted for understanding the orogenic growth of japan during the last ca 500 million years the significance of tectonic erosion coupled with continental contraction as well as the oceanward accretionary growth requires further attention

paleoredox variations in ancient oceans recorded by rare earth elements in fossil apatite abstract rare earth element concentrations in biogenic apatite of conodonts fish debris and inarticulate brachiopods were determined in over 200 samples from cambrian to modern sediments tests for experimental bias caused by the chemicals used to separate fossils from the rock matrix and for interlaboratory interexperiment or interspecies related variations clearly show that no resolvable fractionation of ree occurs incorporation of ree in biogenic apatite of recent fish debris occurs near the sediment water interface soon after deposition and reflects characteristics of seawater the original ree signature apparently survives subsequent burial and diagenesis cerium variations in fish debris from modern environments are controlled by redox potential ce is fractionated by co precipitation with metallic oxides under oxidizing conditions this fractionation produces a negative ce anomaly ce anom in seawater that is reflected in the sedimented fish debris conversely no fractionation of ce occurs under reducing conditions resulting in ce concentrations that are normal to enriched in anoxic seawater and fish debris deposited under local or basinwide anoxic conditions extrapolation of observations of the redox control of ce anom in modern oceans to fossil apatite indicates that anoxic conditions were prevalent in lower paleozoic and lower triassic oceans whereas in the upper paleozoic the world ocean was generally oxidizing

genesis of ferromanganese crusts from the tag hydrothermal field the rare earth element ree geochemistry and nd isotopic composition of marine ferromanganese crusts allow insight into their environment of deposition we present ree along with major and trace element data from a suite of samples collected near an active hydrothermal site from the mid atlantic ridge and demonstrate extreme ree variability over short spatial scales both positive and negative ce anomalies are observed along with varied fractionation of the rees some of the fe mn crusts are formed directly from low temperature hydrothermal fluids channelled over 3 km from any high temperature vent site a significant hydrothermal component is observed in one fe mn crust sampled other samples collected from the same area are predominantly hydrogenous and form at a wide range of accumulation rates depending on the hydrothermal plume input the identification of extreme heterogeneity in source and depositional environment within one hydrothermal field suggests that 1 this variability can be resolved both spatially and temporally within a fossil hydrothermal deposit and 2 the integrated record provided by bulk analysis should be interpreted with caution

the whole rock cerium anomaly a potential indicator of eustatic sea level changes in shales of the anoxic facies abstract the whole rock cerium anomaly tested for outer shelf upper slope stratigraphic sections from the middle ordovician through the lower silurian of scotland is proposed as an empirical technique to develop a eustatic 3rd order or finer scale sea level curve this interval was chosen as it straddles the well documented late ordovician glaciation and can be defined by graptolite zones the anomaly is calculated from neutron activation analysis of low carbonate phosphate free fossil free field identified shales of the graptolite facies by comparison of the normalized cerium content with the linearized trend of the normalized composition of other rare earth elements in order of atomic number for sections originally deposited in the main pycnocline below the surface mixed layer values of the anomaly for a given sample would indicate its position on the redox curves developed for the early paleozoic by wilde 1987 changes in the anomaly that are positive with time would indicate a lowering of sea level as the apparent depth on the redox curve would reflect more oxic conditions relative changes negative with time would indicate a rise in sea level as the apparent depth reflects more anoxic conditions depending on the vertical sample spacing and the time interval sampled resolution of the order of 1 m y might be achieved thus the vail et al 1977 curves of the 3rd order 1 to 10 m y or of finer scale could be obtained by this technique with the proper choice of section accordingly for the early through middle paleozoic when the main pycnocline was anoxic this geochemical technique could be used to develop eustatic sea level curves and additionally offer an independent calibration for seismic stratigraphy as well as an indicator of glacial interglacial climatic sequences or eustatic changes due to fluctuations in global ridge crest volumes

yttrium and rare earth elements in fluids from various deep sea hydrothermal systems rare earth element ree and yttrium y concentrations were measured in fluids collected from deep sea hydrothermal systems including the mid atlantic ridge mar i e menez gwen lucky strike tag and snakepit the east pacific rise epr i e 13 n and 17 19 s and the lau vai lili and manus vienna woods pacmanus desmos back arc basins bab in the south west pacific in most fluids y is trivalent and behaves like ho chondrite normalized y ree y reen concentrations of fluids from mar epr and two bab sites i e vai lili and vienna woods showed common patterns with lree enrichment and positive eu anomalies ree analysis of plagioclase collected at lucky strike strengthens the idea that fluid ree contents are controlled by plagioclase phenocrysts other processes however such as ree complexation by ligands cl f so42 secondary phase precipitation and phase separation modify ree distributions in deep sea hydrothermal fluids ree speciation calculations suggest that aqueous ree are mainly complexed by cl ions in hot acidic fluids from deep sea hydrothermal systems ree concentrations in the fluid phases are therefore influenced by temperature ph and duration of rock fluid interaction unusual y reen patterns found in the pacmanus fluids are characterized by depleted lree and a positive eu anomaly the demos fluid sample shows a flat y reen pattern which increases regularly from lree to hree with no eu anomaly these manus basin fluids also have an unusual major element chemistry with relatively high mg so4 h2s and f contents which may be due to the incorporation of magmatic fluids into heated seawater during hydrothermal circulation ree distribution in pacmanus fluids may stem from a subseafloor barite precipitation and the ree in demos fluids are likely influenced by the presence of sulfate ions

formation of ferromanganese crusts on northwest intertropical pacific seamounts electron photomicrography and microprobe chemistry abstract seven ferromanganese crusts from the northwest intertropical pacific seamounts were analyzed for photomicroscopic growth structures microprobe chemistry and ages based on co chronometer growth rate the crusts on the marshall islands seamounts are thick and are divided into phosphatized lower older and nonphosphatized upper younger growth generations the older crust consists of compact laminations and columns impregnated with carbonate fluoapatite cfa whereas the younger crust is characterized by porous botryoids and columns of mno2 and fe oxyhydroxide the crusts on the federated states of micronesia fsm and palau islands seamounts are thin and are often incorporated with inorganic opal a in the uppermost part comprising the younger generation some crusts show scours and fractures although the growth of crusts has been often interrupted by mass failure of slope sediments the crusts on the marshall islands seamounts are estimated to have grown at rate of about 3 mm ma since the middle eocene and to have been phosphatized in the late oligocene during the host seamounts were located beneath the equatorial zone of high productivity prolonged infiltration of the oxygen minimum zone omz water into shallower water older crusts redistributed crust composition by precipitating cfa enriching subsequent amounts of mn and ni and removing some co the younger crust has formed at slower rate about 2 mm ma under the stronger influence of bottom water circulation in the north of the equatorial zone concentrating abundant co in the uppermost part of some crusts siliceous skeletons transform with burial to inorganic opal a and si rich fe oxyhydroxide suggesting that biosilica diagenesis can enhance crust growth

origin of negative ce anomalies in mixed hydrothermal hydrogenetic fe mn crusts from the central indian ridge abstract layered fe mn crusts from the off axis region of the first segment of the central indian ridge north of the rodrigues triple junction were studied geochemically and mineralogically vernadite mno2 is the main mineral oxide phase 230thxs and co concentrations suggest high growth rates of up to 29 mm myr and a maximum age of the basal crust layer of 1 ma whereas most of the major and minor elements show concentrations which are typical of hydrogenetic formation co pb ni and ti concentrations are strikingly lower concentrations and distribution of the strictly trivalent rare earths and yttrium rey are typical of hydrogenetic ferromanganese oxide precipitates but in marked contrast the crusts are characterized by negative cesn shale normalized anomalies and ce pr sn ratios less than unity profiles through the crusts reveal only minor variations of the rey distribution and ce pr sn ratios range from 0 45 to 0 68 compared to ratios of up to 2 for typical hydrogenetic crusts from the central indian basin the apparent bulk partition coefficients between the crusts and seawater suggest that for the strictly trivalent rey the adsorption desorption equilibrium has been reached positive ce anomalies in the partition coefficient patterns reveal preferential uptake of ce but to a lesser extent than in normal hydrogenetic crusts a new parameter excess ce cexs to quantify the degree of decoupling of ce from rey iii is established on the basis of partition coefficients cexs cebulk ratios suggest that the cir crusts formed by precipitation of fe mn oxides from a hydrothermal plume and that in hydrothermal plumes and normal seawater the enrichment of ce results from the same oxidative sorption process the growth rates calculated with 230thxs data as well as with the co formula are inversely related to cexs

sedimentary manganese metallogenesis in response to the evolution of the earth system abstract the concentration of manganese in solution and its precipitation in inorganic systems are primarily redox controlled guided by several earth processes most of which were tectonically induced the early archean atmosphere hydrosphere system was extremely o2 deficient thus the very high mantle heat flux producing superplumes severe outgassing and high temperature hydrothermal activity introduced substantial mn2 in anoxic oceans but prevented its precipitation during the late archean centered at ca 2 75 ga the introduction of photosystem ii and decrease of the oxygen sinks led to a limited buildup of surface o2 content locally initiating modest deposition of manganese in shallow basin margin oxygenated niches e g deposits in india and brazil rapid burial of organic matter decline of reduced gases from a progressively oxygenated mantle and a net increase in photosynthetic oxygen marked the archean proterozoic transition concurrently a massive drawdown of atmospheric co2 owing to increased weathering rates on the tectonically expanded freeboard of the assembled supercontinents caused paleoproterozoic glaciations 2 45 2 22 ga the spectacular sedimentary manganese deposits at ca 2 4 ga of transvaal supergroup south africa were formed by oxidation of hydrothermally derived mn2 transferred from a stratified ocean to the continental shelf by transgression episodes of increased burial rate of organic matter during ca 2 4 and 2 06 ga are correlatable to ocean stratification and further rise of oxygen in the atmosphere black shale hosted mn carbonate deposits in the birimian sequence ca 2 3 2 0 ga west africa its equivalents in south america and those in the francevillian sequence ca 2 2 2 1 ga gabon are correlatable to this period tectonically forced doming up attenuation and substantial increase in freeboard areas prompted increased silicate weathering and atmospheric co2 drawdown causing glaciation on the neoproterozoic rodinia supercontinent tectonic rifting and mantle outgassing led to deglaciation dissolved mn2 and fe2 concentrated earlier in highly saline stagnant seawater below the ice cover were exported to shallow shelves by transgression during deglaciation during the sturtian glacial interglacial event ca 750 700 ma interstratified mn oxide and bif deposits of damara sequence namibia was formed the varangian marinoan ca 600 ma cryogenic event produced mn oxide and bif deposits at urucum jacadigo group brazil the datangpo interglacial sequence south china liantuo nantuo varangian event contains black shale hosted mn carbonate deposits the early paleozoic witnessed several glacioeustatic sea level changes producing small mn carbonate deposits of tiantaishan early cambrian and taojiang mid ordovician in black shale sequences china and the major mn oxide carbonate deposits of karadzhal type central kazakhstan late devonian the mesozoic period of intense plate movements and volcanism produced greenhouse climate and stratified oceans during the early jurassic oae organic rich sediments host many mn carbonate deposits in europe e g urkut hungary in black shale sequences the late jurassic giant mn carbonate deposit at molango mexico was also genetically related to sea level change mn carbonates were always derived from mn oxyhydroxides during early diagenesis large mn oxide deposits of cretaceous age at groote eylandt australia and imini tasdremt morocco were also formed during transgression regression in greenhouse climate the early oligocene giant mn oxide carbonate deposit of chiatura georgia and nikopol ukraine were developed in a similar situation thereafter manganese sedimentation was entirely shifted to the deep seafloor and since ca 15 ma b p was climatically controlled glaciation deglaciation assisted by oxygenated polar bottom currents aabw nadw the changes in climate and the sea level were mainly tectonically forced

comparison between datangpo type manganese ores and modern marine ferromanganese oxyhydroxide precipitates based on rare earth elements abstract datangpo type sedimentary manganese deposits which are located in northeastern guizhou province and its adjacent areas are mn carbonate type deposits hosted in black carbonaceous shale that represent a series of medium to large deposits containing a huge tonnage of reserves paas normalized rare earth element distribution patterns of manganese ores record hat shaped rey ree y plots characterized by pronounced middle rare earth element enrichment evident positive ce anomalies weak to strong positive eu anomalies and negligible negative y anomalies these rey geochemical characteristics are different from those of country rocks and record the processes and features of sedimentation and diagenesis manganese was precipitated as mn oxyhydroxide particles in oxidized water columns with the sorption of a certain amount of rare earth elements subsequently transforming from mn oxyhydroxides to rhodochrosite and redistributing rey in reducing alkaline pore water during early diagenesis a number of similarities can be observed through a comparison of datangpo type manganese ores and modern marine ferromanganese oxyhydroxide precipitates based on their rare earth elements the precipitation of datangpo type manganese ores is similar to that of hydrogenetic crusts and nodules based on their positive ce anomalies and relatively higher total rey concentrations however several differences also exist compared to hydrogenetic crusts and nodules datangpo type manganese ores record smaller positive ce anomalies lower total rey concentrations unobvious fractionation between y and ho and weak to strong positive eu anomalies these were caused by quicker sedimentary rates in the oxic water columns of the shallower basin after which pore water became strongly reducing and alkaline due to the degradation of organic matter in the early diagenetic stage in addition compared to typical deposits in the world datangpo type manganese ores are similar to hydrogenetic deposits and different than hydrothermal deposits all of these characteristics of manganese ores indicate that datangpo type manganese ores the principal metallogenic factors of which include oxidation conditions during deposition and reducing conditions during early diagenetic stages represent hydrogenetic deposits

the distribution of rare earth and minor elements in manganese nodules micronodules and sediments along an east west transect in the southern pacific abstract rare earth and other trace elements in manganese nodules micronodules and surface sediments from a transect in the southwestern pacific basin at 42 s were determined by instrumental neutron activation analysis the data include analyses of 23 manganese nodules 10 micronodules and 15 sediments the ree distributions along the transect suggest that three major processes were involved in the accumulation of these elements these are 1 adsorption from seawater onto highly reactive fe rich particles from hydrothermal particle plumes at the crest of the east pacific rise 2 adsorption from seawater onto the fe rich ferromanganese mineral phase vernadite and 3 supply of terrigenous material only the second process leads to significant ree enrichment in the manganese nodules enrichment is highest in nodules from areas influenced by northward flowing antarctic bottom water

environments and processes of manganese deposition concentration of manganese in solution and its deposition takes place by redox controlled processes in a variety of modern and ancient geologic and geochemical environments modern mn deposition occurs predominantly in deep sea areas rather than shallow water domains although deep sea sedimentary deposits dominate hydrothermal contribution of mn to the ocean system may be substantial mn deposition from hydrothermal solutions at or near sea floor spreading centers and less commonly in island arc areas is known in addition near and far field dispersion of mn from vent sites is also substantial such distributions are controlled by the flow rate and egress temperature of the solution and the residence time of mn in seawater thus even in sedimentary deposit domains at least partial derivation of mn from a hydrothermal source is possible sedimentary fe mn crusts on older volcanic substrates on seamounts form by hydrogenous deposition of metal concentrated from terrigenous sources in the mid water column oxygen minimum zones thus the presence or absence of volcanic rocks is not a clear indication of whether sedimentary mn deposits particularly in the ancient geologic record are the result of a totally terrigenous or a totally volcanogenic source abyssal fe mn nodules are considered to form from a basin water hydrogenous and or pore water early diagenetic supply of metals but in most cases the extent of supply from either of the sources is unknown the metal incorporation mechanisms of free moving nodules is little understood and it is possible that in most cases both sources contribute to the nodule composition therefore no nodule should be considered as totally hydrogenous or totally early diagenetic based only on its bulk composition the determined growth rate giving only an average value cannot by itself reveal the growth history of the nodules biological participation directly or indirectly controls mn deposition the stratified black sea demonstrates the concentration of mn in solution in an anoxic zone its advection toward the redox interface and its precipitation in an oxygenated condition similar stratified basins are contemplated for ancient mn deposition in shallow water basin margin areas geologic and geochemical signatures indicate that during sea level highstands stratified basins formed in which mn was concentrated in solution in the anoxic part corresponding transgression led to the impingement of the redox interface on the continental shelf and precipitation of mn oxides could take place across the interface during transgression regression cycles offshore in anoxic or dysaerobic conditions mn carbonate could form by early diagenetic reaction of mn super 2 with co 2 or hco 3 super produced by organic carbon oxidation critical mn deposits occurring in transgressive glaciogenic and black shale bearing ancient sequences support this paleoenvironmental model for mn deposition

trace and rare earth element geochemistry of black shale and kerogen in the early cambrian niutitang formation in guizhou province south china constraints for redox environments and origin of metal enrichments abstract early cambrian black shales of south china not only host important sponge arthropod and other soft bodied fossils that have helped to trace early metazoan diversification but also show extreme enrichments of a number of trace metals in particular ni mo and v in this study we use a new approach by analyzing rare earth elements in kerogen extracted from the black shales together with a number of redox sensitive trace element compositions and total organic carbon toc concentrations in an early cambrian black shale sequence in zunyi guizhou province south china to place better constraints on the oceanic redox conditions and the origin of the extreme metal enrichment our data show significant negative ce anomalies ce ce as low as 0 4 occurring in kerogen which indicate an oxygenated surface environment of primary productivity in consistent with the concept that the organic matter is mainly derived from organisms in the euphotic zone mass balance calculation suggests that the kerogen associated ree can dominate the measured black shale ree budget while similarity between our measured ree patterns and those of similarly aged phosphorites indicates that the ree content of ancient phosphorites may have also derived initially from organic matter the redox sensitive trace elements such as u v mo and their ratios of u al v al and mo al in black shales show different correlation patterns with toc contents the upper black shales show a good metal toc correlation but such a correlation is absent in the lower part the lower black shales exhibit much higher metal enrichments compared to black sea sulphidic euxinic sediment this is taken to indicate the presence of sulphidic bottom waters during the deposition of the lower black shales including the ni mo ore layer in contrast anoxic non sulphidic conditions occurred during the deposition of the upper black shales taking all these geochemical data together we suggest that the early cambrian south china seaway was strongly stratified and stagnant and that euxinic bottom water conditions may have led to enrichment of the redox sensitive metals such as u v and mo in the lower black shales and in one case the occurrence of a polymetallic ni mo sulphide ore bed bearing an extraordinarily extreme metal enrichment which according to the mo toc and ni toc ratios and much other geochemical evidence may have been additionally influenced by hydrothermal input of metals within the rift basin as suggested by a number of previous studies

sedimentology and environmental significance of the cryogenian successions of the yangtze platform south china block abstract the neoproterozoic glaciations during sturtian c 720 ma and marinoan c 600 635 ma times are considered events of extreme climate change of global dimension sometimes interpreted according to the snowball earth hypothesis here we present for the first time a detailed sedimentological description and facies analysis of the deposits of both glacial events recorded on the yangtze platform of the south china block the yangtze platform was located at c 40 latitude during the older glaciation and close to the equator during the younger one the studied successions of nanhuan sinian age including both diamictite bearing units vary in thickness from 90 m to 1800 m and show some remarkable differences between the deposits of sturtian and marinoan age in general both diamictite bearing successions are composed of diamictites debris flow deposits turbidites structureless or laminated sand and siltstones and mudstones however diamictites of the lower unit were deposited from proglacial debris flows whereas those of the upper unit formed as lodgement deposits of the grounded zone laminated sand and siltstones containing dropstones are abundant in the lower unit and very rare in the upper one deposits of subaqueous mass flows are present in both units the lower diamictite unit is not overlain by cap carbonates the upper diamictite unit grades transgressively into 3 to 8 m thick successions of thin bedded and partly clast rich carbonate rocks representing the basal strata of the ediacaran doushantuo formation in view of a conformable contact between the upper diamictite unit and these carbonate layers and their similar lithostratigraphic position to those on other continents we consider them to represent cap carbonates our sedimentological data indicate different patterns of development of the two glaciations the sturtian event in south china is characterized by deposition of ice rafted debris distal to ice margins thus indicating ample open ocean space available for iceberg drift the marinoan record in south china registers depositional processes proximal to ice margins including lodgement deposits in consideration of the palaeogeographic position of the yangtze platform in intermediate sturtian and low marinoan latitudes during neoproterozoic time there were probably significant differences in intensity and extent between the glaciations the older one being less severe and characterized by regionally limited ice centres there is no evidence of a shutdown of the hydrological cycle during the deposition of the two diamictite units in conclusion our sedimentological data neither support a sturtian nor a marinoan hard snowball earth glaciation