hydrogeological constraints on the formation of palaeoproterozoic banded iron formations banded iron formations are critical to track changes in archaean to palaeoproterozoic ocean chemistry with deposition triggered by water column iron oxidation recently however it was suggested that reduced iron minerals were the primary precipitates and these were subsequently oxidized by oxygen bearing groundwater if true this would cast doubt on our understanding of how banded iron formations were deposited and their ability to record early ocean chemistry here we present a hydrogeological box model based on the approximately 2 5 billion year old hamersley basin of western australia developed to evaluate the plausibility of secondary iron oxidation the box model calculates the time required for groundwater to flux enough oxygen through the basin to oxidize a given amount of ferrous iron less than 9 of nearly four million model iterations returned oxidation times less than the age of the basin successful simulations required simultaneously steep hydraulic gradients high permeability and elevated oxygen concentrations our simulations show that the postdepositional oxidation of large banded iron formations is unlikely except on a limited scale that is during secondary ore formation and that oxidized iron phases were probably the precursor to large palaeoproterozoic banded iron formations banded iron formations could not have formed by postdepositional oxidation according to four million hydrogeological box model iterations that failed to reproduce secondary oxidation on reasonable timescales

episodic speleothem deposition tracks the terrestrial impact of millennial scale last glacial climate variability in sw ireland abstract eighty four new u th ages are presented for twenty randomly selected broken displaced and reworked calcite speleothems retrieved from clastic sedimentary fill and from isolated bedding plane shelves in crag cave sw ireland the dated pre holocene samples span much of the last glacial ranging in age from 85 15 0 60 to 23 45 0 17 ka speleothem deposition requires the presence of liquid water and because crag cave is a shallow system deposition is considered likely only when mean annual air temperatures maat exceed the freezing point of water deposition at this mid latitude ocean marginal site occurred episodically during mis5a through to mis2 synchronously within dating uncertainties with the timing of greenland interstadials gi in the latter part of marine isotope stage 3 mis3 deposition was particularly intense consistent with regional scale climate amelioration inferred previously from radiocarbon ages for sparse mis3 organic and freshwater surficial deposits in n ireland a brief episode of speleothem deposition at c 23 40 0 22 ka coincides with gi 2 demonstrating the sensitivity of the site to brief climate amelioration episodes in greenland during mis2 conditions favourable for speleothem deposition occurred periodically during the last glacial indicating temperature changes of at least 10 c between stadials and interstadials at this mid latitude site deposition ceased during greenland stadials gs including during periods of ice rafting in the adjacent n atlantic ocean heinrich events oxygen and carbon isotope ratios of the last glacial speleothems are generally elevated reflecting non equilibrium isotope fractionation effects however establishment of low 13c values often occurred within a few decades of climate amelioration indicating that biogenic co2 production resumed rapidly at this site particularly during mis3 speleothem 18o variability was driven largely by long term changes in the 18o value of the adjacent north atlantic surface water in turn largely reflecting changes in global ice volume in common with published speleothem datasets warming episodes in ireland associated with gi events typically pre date their timing in the gicc05 and gicc05modelext time scales but lie comfortably within the maximum counting uncertainties of these ice core age models

chemical processes affecting the mobility of major minor and trace elements during weathering of granitic rocks abstract the behaviour of 38 major and trace elements as well as changes in the mineralogy have been examined in 10 weathering profiles developing on some portuguese granitic rocks element mobilities are calculated from geochemical data normalized with respect to ti in the fresh parent rock chemical elements are divided into two groups immobile and mobile on the basis of their geochemical distribution during weathering elements that are immobile during weathering are zr hf fe al th nb sc and the ree very mobile are ca na p k sr ba rb mg and si mobile elements are derived mainly from leachable minerals such as feldspars micas and apatites whereas immobile elements are either concentrated in resistate phases or strongly adsorbed by secondary minerals the geochemical behaviour of mn cr v fe and ce is very dependent on redox conditions redox transformations of these elements can be used to set limits on the oxidation state of a weathering suite the ree are mobilized or fractionated during late stages of weathering but not during moderate stages of weathering this fractionation is caused by selective leaching of rocks composed of both stable and unstable minerals containing ree

could bacteria have formed the precambrian banded iron formations banded iron formations bifs are prominent sedimentary deposits of the precambrian but despite a century of endeavor the mechanisms of their deposition are still unresolved interactions between microorganisms and dissolved ferrous iron in the ancient oceans offer one plausible means of mineral precipitation in which bacteria directly generate ferric iron either by chemolithoautotrophic iron oxidation or by photoferrotrophy on the basis of chemical analyses from bif units of the 2 5 ga hamersley group western australia we show here that even during periods of maximum iron precipitation most if not all of the iron in bifs could be precipitated by iron oxidizing bacteria in cell densities considerably less than those found in modern fe rich aqueous environments those ancient microorganisms would also have been easily supported by the concentrations of nutrients p and trace metals v mn co zn and mo found within the same iron rich bands these calculations highlight the potential importance of early microbial activity on ancient metal cycling

siderite cannot be used as co2 sensor for archaean atmospheres abstract it was proposed to utilize siderite feco3 in mid to late archaean superior type banded as a proxy to constrain the co2 partial pressure of archaean atmospheres implicit in this proposition is that siderite was a primary carbonate mineral that crystallized directly from fe2 enriched archaean seawater in equilibrium with atmospheric co2 to our knowledge that proposition has not been demonstrated to be valid we test with water gas exchange experiments under controlled co2 partial pressures if siderite can be stabilized as a primary mineral in fe2 bearing seawater reduced seawater proxies enriched in fe2 and mn2 are equilibrated with reduced n2 ch4 co2 h2 gas phases with variable co2 the solid phases stabilized in fe2 enriched water compositions are amorphous ferrous iron hydroxy carbonates crystalline siderite feco3 is not found to be a stable phase the phases precipitating from mn2 enriched water include crystalline rhodochrosite mnco3 and possibly amorphous mn enriched phases based on these results we advise against using siderite in banded iron formations as a co2 sensor for the archaean atmosphere

climatic changes in areas adjacent to the north atlantic during the last glacial interglacial transition 14 9 ka bp a contribution to igcp 253 this paper presents a summary of the evidence for climatic changes during the last glacial interglacial transition 14 9 ka bp in land areas adjacent to the north atlantic it is a synthesis of the results of the 12 regional summaries compiled by contributors to the north atlantic seaboard programme of igcp 253 that are published separately in this issue of journal of quaternary science eighteen palaeotemperature curves are compared and arranged in three transects one from southern europe to spitsbergen a second from ireland to poland and the third from southern new england to the labrador baffin shelf area ten maps are presented that summarise the synoptic climatic conditions of the region in 500 year time periods the purpose of the exercise is to examine the extent to which any emerging patterns support the ruddiman and mclntyre model of large scale shifts in the position of the oceanic polar front during the last glacial interglacial transition some broad agreement emerges although the influence of oceanic changes is diminished in areas that lay in close proximity to the laurentide and fennoscandian ice sheets attention is drawn to limitations in the compilations and to the potential for improved models in the future

the flickering switch of late pleistocene climate change polar ice contains a unique record of past climate variations previous greenland ice cores have documented relatively warm interstadial periods during the last glaciation and short centuryscale returns to colder conditions during the glacial to interglacial warming see for example ref 1 these climate features have also been observed to varying degrees in ocean sediment cores2 4 and terrestrial pollen and insect records5 7 here we report electrical conductivity measurements from a new greenland ice core which confirm these previous observations and also reveal a hitherto unrecognized mode of rapid climate variation fluctuations in ice conductivity on the scales of 5 20 years reflect rapid oscillations in the dust content of the atmosphere this flickering between two preferred states would seem to require extremely rapid reorganizations in atmospheric circulation

abrupt increase in greenland snow accumulation at the end of the younger dryas event the warming at the end of the last glaciation was characterized by a series of abrupt returns to glacial climate the best known of which is the younger dryas event1 despite much study of the causes of this event and the mechanisms by which it ended many questions remain unresolved1 oxygen isotope data from greenland ice cores2 4 suggest that the younger dryas ended abruptly over a period of about 50 years dust concentrations2 4 in these cores show an even more rapid transition 20 years this extremely short timescale places severe constraints on the mechanisms underlying the transition but dust concentrations can reflect subtle changes in atmospheric circulation which need not be associated with a large change in climate here we present results from a new greenland ice core gisp2 showing that snow accumulation doubled rapidly from the younger dryas event to the subsequent preboreal interval possibly in one to three years we also find that the accumulation rate change from the oldest dryas to the bo11ing allerod warm period was large and abrupt the extreme rapidity of these changes in a variable that directly represents regional climate implies that the events at the end of the last glaciation may have been responses to some kind of threshold or trigger in the north atlantic climate system

decoupling photochemical fe ii oxidation from shallow water bif deposition abstract oxidized fe minerals in archean paleoproterozoic banded iron formations bifs are commonly taken to indicate the presence of biogenic o 2 or photosynthetic fe ii oxidizing bacteria in the oceans photic zone however at least one viable abiogenic oxidation mechanism has been proposed prior to the rise of atmospheric oxygen and the development of a protective ozone layer the earth s surface was subjected to high levels of ultraviolet radiation bulk ocean waters that were anoxic at this time could have supported high concentrations of dissolved fe ii under such conditions dissolved ferrous iron species such as fe 2 and fe oh would have absorbed radiation in the 200 400 nm range leading to the formation of dissolved ferric iron fe iii which in turn would have hydrolyzed to form ferric hydroxide fe oh 3 at circumneutral ph cairns smith a g 1978 precambrian solution photochemistry inverse segregation and banded iron formations nature 76 807 808 braterman p s cairns smith a g and sloper r w 1983 photo oxidation of hydrated fe 2 significance for banded iron formations nature 303 163 164 this process has been invoked to account for bif deposition without need for biology francois l m 1986 extensive deposition of banded iron formations was possible without photosynthesis nature 320 352 354 here we evaluate the potential importance of photochemical oxidation using a combination of experiments and thermodynamic models the experiments simulate the chemistry of ambient precambrian seawater mixing with fe ii rich hydrothermal fluids with and without uv irradiation we find that if fe ii was effused from relatively shallow seamount type vent systems directly into an anoxic photic zone the photochemical contribution to solid phase precipitation would have been negligible instead most of the fe ii would have precipitated rapidly as an amorphous precursor phase to the ferrous silicate mineral greenalite fe 3 si 2 o 5 oh 4 and or the ferrous carbonate siderite feco 3 depending on different simulated atmospheric pco 2 levels conversely in experiments where fe ii was exposed either to phototrophic fe ii oxidizing bacteria or to o 2 ferric hydroxide formed rapidly and the precipitation of ferrous iron phases was not observed if as suggested on mass balance grounds bif deposition requires that fe be sourced from shallow seamount type systems then we are driven to conclude that oxide facies bif are the product of a rapid non photochemical oxidative process the most likely candidates being direct or indirect biological oxidation and that a significant fraction of bif could have initially been deposited as ferrous minerals

a re evaluation of the vegetation history of the eastern pyrenees france from the end of the last glacial to the present abstract fourteen pollen records obtained from 10 sites in the eastern pyrenees are presented along with the results of 40 new radiocarbon dates of samples obtained from these sites the data 784 pollen spectra provide a more comprehensive evaluation of the vegetation history of the region than has hitherto been possible the salient elements of the regional plant succession are described in the light of a study of regional pollen rain vegetation relationships vegetational developments during the last glacial interglacial transition and the holocene are compared with those of other regions in france and the western mediterranean this approach therefore provides a new synthesis of published and unpublished information over a large area a consistent and coherent pattern emerges and the new evidence indicates a number of previously held views on the vegetation history of the pyrenees to be erroneous

207pb 206pb zircon ages and the evolution of the singhbhum craton eastern india an ion microprobe study1this paper is dedicated to prof a k saha one of the senior co authors who passed away after submission of the paper 1 abstract we used an ion microprobe to measure 207 pb 206 pb ages of single zircons from four key lithologies from the singhbhum craton of eastern india detrital zircons from the oldest recognized sedimentary sequence of the craton the older metamorphic group yielded 3 5 3 6 ga ages indicating that crustal formation had already been initiated by 3 6 ga in this region this data also established an older limit of 3 5 ga for the age of sediment deposition the first appearance of extensive continental crust in the singhbhum region marked by the emplacement of the older metamorphic tonalite gneisses is dated at 3 44 ga our data from both of these units reveal that a 3 2 ga event induced overgrowths within each of these pre existing zircon populations we determine an age of 3328 7 ma for the singhbhum granite phase ii the most widespread of this granite s three phases the emplacement of the two phases of the mayurbhanj granite marking the youngest major episode of acid plutonism in this craton took place in rapid succession at 3 1 ga marking the broad scale stabilization of this terrain

wisconsinan late glacial environmental change in southern new england a regional synthesis a synthesis of vegetational and climatic history during the wisconsinan late glacial 13 9 ka bp is presented for the southern new england region the interpretations are based on a number of pollen stratigraphical investigations supported by plant macrofossil data chronology is based partly on ams dates of plant macrofossils reference is made briefly to the controversial nature of the evidence for deglaciation in the region a curve representing mean july temperature changes in the region during the period 13 9 ka bp is provided

cerium anomalies in lateritic profiles the ree geochemistry and mineralogy have been studied in four lateritic profiles one derived from a syenite akongo sw cameroon the others being developed on a gneissic basement and located along a soil toposequence goyoum e cameroon there is a fractionation between lree and hree in the lateritic samples during weathering the weathered residual products being enriched in lree from la to eu and depleted in hree from gd to lu sampled waters are enriched in hree in relation to the syenite host rock a positive ce anomaly has been found systematically at the top of the saprolite beneath a zone of iron oxide accumulation in the laterite up to 2000 ppm ce may be present in the akongo profile cerianite ceo2 is present as very fine coatings in non ferruginous clayey domains primary ree bearing accessory minerals are weathered at the bottom of the profile specifically allanite and apatite are transformed into florencite and rhabdophane but these phases have no ce anomaly all the data are interpreted as the result of the following processes 1 1 ree leaching in a reducing environment 2 2 oxidation of ce3 to ce4 in an oxidizing environment 3 3 deposition of cerium as cerianite whereas the other ree remain in solution

a late weichselian stable isotope stratigraphy compared with biostratigraphical data a case study from southern sweden late weichselian lake sediments from a site in southern sweden were analysed for stable carbon and oxygen isotopes as well as plant macrofossils and insect remains by comparison of independent d

authigenic precipitation of ferric oxyhydroxides and greenalite in archean oceans abstract the initial mineral phases of banded iron formations bifs were mostly altered during diagenesis and metamorphism the initial iron mineral whether it was hydrous ferric oxides hfo or hydrous ferrous silicates hfs is a matter of debate each of those being the primary iron mineral offers us considering completely different biogeochemical conditions of archean oceans some archean greenstone bifs of badampahar 3 2 ga singhbhum craton and nuvvuagittuq 3 8 ga northern quebec consist alternating grunerite magnetite and quartz rich authigenic sedimentary bands the minerals appear to be co crystallized during metamorphism and show evidence of being originated from different precursor minerals e g magnetite from hfo and grunerite from hfs the process of such episodic hfo and hfs precipitations apparently related to two different fe si cycles in the archean oceans is not understood yet in situ trace element geochemistry of the minerals proves their authigenic origin and shows some characteristic geochemical differences e g grunerite having higher contents of hydrothermally sourced trace elements whereas magnetite being rich in elements involved in marine biogenic cycles the origin of mineralogically different e g quartz grunerite and magnetite rich bands of the studied bifs is explained with a model of hfs rich precipitation during episodic hydothermalism subsequent hfo rich precipitation by microbial oxidation and silica rich precipitation during no hydrothermal activity or non depositional period of iron minerals

the continental tree ring record absolute chronology 14c calibration and climatic change at 11 ka abstract tree ring chronologies are unique archives for various parameters indicating climatic change the wood structure of trees deposited in river gravel below the water table is well preserved even after several millennia and it provides information on a time scale of solar years during the past 25 years in the hohenheim tree ring laboratory long tree ring chronologies have been constructed now reaching back to 11 400 yr dendro b p in this contribution we demonstrate the evidence for climatic change in the early holocene which can be obtained both from botanical properties e g parameters of ring growth and from the isotopic information recorded in tree rings

iron formations a global record of neoarchaean to palaeoproterozoic environmental history abstract iron formations if represent an iron rich rock type that typifies many archaean and proterozoic supracrustal successions and are chemical archives of precambrian seawater chemistry and post depositional iron cycling given that if accumulated on the seafloor for over two billion years of earth s early history changes in their chemical mineralogical and isotopic compositions offer a unique glimpse into environmental changes that took place on the evolving earth perhaps one of the most significant events was the transition from an anoxic planet to one where oxygen was persistently present within the marine water column and atmosphere linked to this progressive global oxygenation was the evolution of aerobic microbial metabolisms that fundamentally influenced continental weathering processes the supply of nutrients to the oceans and ultimately diversification of the biosphere and complex life forms many of the key recent innovations in understanding if genesis are linked to geobiology since biologically assisted fe ii oxidation either directly through photoferrotrophy or indirectly through oxygenic photosynthesis provides a process for if deposition from mineral precursors the abundance and isotope composition of fe ii bearing minerals in if additionally suggests microbial fe iii reduction a metabolism that is deeply rooted in the archaea and bacteria linkages among geobiology hydrothermal systems and deposition of if have been traditionally overlooked but now form a coherent model for this unique rock type this paper reviews the defining features of if and their distribution through the neoarchaean and palaeoproterozoic this paper is an update of previous reviews by bekker et al 2010 2014 that will improve the quantitative framework we use to interpret if deposition in this work we also discuss how recent discoveries have provided new insights into the processes underpinning the global rise in atmospheric oxygen and the geochemical evolution of the oceans

wisconsinan late glacial environmental change on the southeast baffin shelf southeast baffin island and northern labrador the importance of the baffin labrador region is explained in terms of the channelling through this area of the mass flux of meltwater from the laurentide ice sheet and the probable effects of this on the thermohaline circulation of the north atlantic the chronology of glaciation and deglaciation in the region is summarised reference is made to recent marine records from the baffin shelf isotopic changes recorded in foraminiferal assemblages obtained from marine sediments in the baffin shelf labrador sea area indicate the timing and possible magnitude of meltwater fluxes during the period 14 0 11 0 ka bp

geochemistry and sedimentology of a facies transition from limestone to iron formation deposition in the early proterozoic transvaal supergroup south africa this study deals with the geochemistry and sedimentology of a facies transition from interbedded carbonate shale to banded iron formation in the campbellrand carbonate sequence to the overlying kuruman iron formation of the transvaal supergroup in south africa which is approximately 2 3 ga old four major lithologies are 1 limestone and dolomite 2 shale and interbedded shale carbonate 3 siderite rich banded iron formation and 4 iron oxide rich banded iron formation these rocks are unaltered and essentially unmetamorphosed with a maximum metamorphic diagenetic overprint ranging in temperature from 110 degrees to 170 degrees c and with pressures of not more than 2 kbars the oldest rocks are limestones and lesser dolomite with abundant cryptalgalaminae and intraclastic textures interbedded with the limestones and dolomites are carbonaceous shales some of which are unusually ferruginous or pyrite rich these carbonates and shales are overlain by meso and microbanded siderite chert iron formation which grades upward into magnetite chert and carbonate rich iron formation the averages for major and trace elements and rare earth element ree contents of the limestones dolomites and shales are distinct from those of the two types of iron formation the two most chemically diverse rock types are the shales enriched in alkalis and most trace elements and the two iron formation types siderite and magnetite rich which are almost totally depleted in all elements except si fe mg and ca and co 2 the high al 2 o 3 contents of the shales avg 9 55 wt correlate well with their high organic carbon contents avg 3 91 wt the limestones and dolomites have average al 2 o 3 and organic carbon contents of about 3 0 and 0 7 wt percent respectively the two iron formation types have al 2 o 3 average values of 0 099 wt percent siderite rich and 0 066 wt percent magnetite rich and corresponding averages for organic carbon of 0 080 wt percent siderite rich and 0 012 wt percent magnetite rich the ree are generally concentrated in the shales by a factor of about 10 over the iron formations the limestones and dolomites have intermediate values and the iron formations are most depleted the iron formation ree patterns in a ratio with north american shale composite nasc have pronounced positive eu anomalies and slight negative ce anomalies both of these anomalies are absent in the shales but the limestones and dolomites show slight positive eu anomalies the siderite rich iron formations consist of chert siderite ankerite or ferroan dolomite with traces of pyrite and stilpnomelane the siderite in these commonly microbanded assemblages is very fine grained along well defined bedding planes it is concluded from petrographic study that siderite is a primary precipitate the ankerites and ferroan dolomites in these siderite rich occurrences are commonly euhedral rhombohedral much coarser grained and appear to be of later diagenetic origin the magnetite rich iron formations consist of chert magnetite ankerite or ferroan dolomite or siderite or hematite or stilpnomelane or minnesotaite in these oxide rich iron formations the ankerites and ferroan dolomites are similarly much coarser grained than the finely banded siderite on the basis of the geochemical data and a reconstruction of the depositional basin for the carbonate shale to iron formation transition we conclude that the limestone dolomite shale lithologies originated in a water column quite distinct from that in which the iron formations were precipitated we propose a model with a stratified water column in which the surface waters during a regressive stage in the depositional basin were the site of much organic carbon productivity and the locus of cryptalgal limestones and intraclastic limestone deposition with at somewhat greater depth below the chemocline deposition of pyritic carbonaceous shale our model depicts the deeper waters during a transgressive stage of the basin with the kaapvaal craton more deeply submerged as the site for iron formation deposition these deeper waters were depleted in organic carbon and enriched in dissolved ferrous iron relative to the shallower water mass with continued availability of oxygen along the chemocline separating the two water masses the ultimate source of the iron and probably the sio 2 in the iron formations appears to be a very dilute hydrothermal input in the deep ocean waters as concluded from mixing calculations of ree values for modern atlantic ocean water and hydrothermal solutions from the east pacific rise

the silica cycle in the precambrian abstract whereas the modem silica cycle is heavily dependent on the biology of silica secreting organisms such as the diatoms the precambrian silica cycle was dominated by inorganic reactions among dissolved silica clay and zeolite minerals and organic matter there is no evidence for deposition of a layered amorphous silica but abundant evidence for diagenetic silicification in the neoproterozoic the time period chosen for this analysis the influx of silica to the neoproterozoic ocean would have been governed as today by the balance among tectonism weathering and hydrothermal input the evidence of neoproterozoic rocks favors tectonic and weathering regimes not very dissimilar to those of the early phanerozoic and hydrothermal inputs significantly altered at certain periods one flux would have been very different the present diffusional influx of silica from interstitial waters into the oceans would have been altered to an efflux from the oceans to interstitial waters reactions of dissolved silica with inorganic phases would have controlled silica concentrations at a level of about 60 ppm this figure is based on experimental determinations of solubility and silica sorption on clay minerals and zeolites as silica in interstitial waters was lowered by opal ct precipitation a diffusional efflux from the ocean into the sediment was set up silicification would have started in early diagenesis as opal ct precipitated from interstitial waters diffusion of silica from overlying seawater declined as the sediment was buried a few hundred meters and the diffusion path lengthened during this still relatively shallow burial silicification continued but this time powered by hydrologie transport of dissolved silica from coastal plain sediments during transgressions and regressions thus the major removal of silica from the neoproterozoic ocean took place by diagenetic reactions

iron silicate microgranules as precursor sediments to 2 5 billion year old banded iron formations banded iron formations bifs are chemical sedimentary rocks comprising alternating layers of iron rich and silica rich minerals that have been used to infer the composition of the early precambrian ocean and ancient microbial processes however the identity of the original sediments and their formation is a contentious issue due to postdepositional overprinting and the absence of modern analogues petrographic examination of the ca 2 5 ga dales gorge member of the brockman iron formation hamersley group western australia reveals the presence of abundant silt sized microgranules composed of stilpnomelane the microgranules are most common in the least altered bif where they define sedimentary laminations implying a depositional origin we suggest that the precursor mineral was an iron rich silicate that formed either in the water column or on the seafloor the microgranular texture may have developed due to clumping of amorphous mud forming silt sized floccules the microgranules were resedimented by dilute density currents and deposited in lamina sets comprising a basal microgranular rich lamina overlain by amorphous mud with dispersed microgranules the lamina sets collectively define plane lamination structure probably of the lower flow regime the microgranular textures are preserved only where early diagenetic silica prevented the compaction of lamina sets episodic resedimentation of iron silicates alternating with periods of nondeposition and seafloor silicification provides an explanation for some of the characteristic banding in bif we propose that for most of the early precambrian the persistence of ferruginous oceans with elevated silica concentrations favored the widespread growth of iron silicate minerals which in environments starved of continental sediments formed extensive deposits of the precursor sediment to iron formation

chemical sedimentary protoliths in the 3 75 ga nuvvuagittuq supracrustal belt quebec canada abstract analyses of chemical sedimentary precipitates such as banded iron formation bif provide a direct means to explore the nature and composition of the early hydrosphere the recently discovered 3750 myr old nuvvuagittuq supracrustal belt nsb in the northeast superior province quebec canada hosts a suite of iron oxide rich pyroxene and amphibole units that are interpreted to be the metamorphosed equivalents of fe oxide facies bif and a collection of bif like ca fe mg silicate rocks the nsb rocks provide a rare glimpse of trace metal availability in eoarchean ca 3800 ma seawater as they may be contemporaneous with the relatively well studied isua supracrustal belt of southern west greenland their comparison provides an opportunity to enhance our basic understanding of the eoarchean oceans at a global scale work since the initial discovery of the nsb in 2001 has established the basic lithological geochemical and petrographic characteristics of these bif and bif like rocks here we review the current state of knowledge of nsb rocks of probable chemical sedimentary origin including aspects of their geology likely origin and age we conclude by examining the implications of results thus far for our understanding of early seawater compositions and for the emergence of life in the context of early metallo enzyme evolution

making magnetite late again evidence for widespread magnetite growth by thermal decomposition of siderite in hamersley banded iron formations abstract banded iron formations bifs are marine chemical sedimentary rocks that were widely deposited before the start of the great oxidation event 2 45 2 32 ga they represent an important archive into the chemistry of the precambrian oceans and atmosphere and the evolution of the marine biosphere it is believed that bifs were derived from ferric oxides hydroxides that were deposited by iron oxidizing bacteria or by reaction with oxygen released by cyanobacteria hematite is traditionally interpreted to represent the dehydrated product of the ferric oxide hydroxide precipitate whereas magnetite is thought to have formed from ferric oxides hydroxides via bacterial iron reduction and oxidation of microbial biomass however studies are equivocal about when and how magnetite formed in bifs we present the results of a detailed petrographic study of magnetite in bifs of the hamersley group western australia we find no evidence that magnetite was precipitated from seawater or was a product of bacterial iron reduction instead most of the magnetite formed by replacement of siderite and other ferrous rich minerals after burial our observations suggest that magnetite growth was linked to the breakdown of siderite during metamorphism published experimental data indicate that in the presence of water and under the metamorphic conditions experienced in the southern pilbara craton 200 350 c the thermal decomposition of siderite could account for much of the magnetite in the hamersley bifs 3feco3 h2o fe3o4 3co2 h2 the relationship between magnetite and the primary precipitates which are preserved as greenalite nanoparticles and microgranules in chert bands suggests that much of the magnetite formed in siderite rich iron silicate bands that developed by compaction of non silicified iron silicate muds these bands acted as reactive pathways for fluid flow and the formation of magnetite if most of the magnetite formed after burial then it is necessary to reassess assumptions about the chemistry of the original precipitates and the role of microbial life in the redox cycling of iron our results are consistent with models for the deposition of bifs that center around a precursor sediment comprising greenalite precipitates and diagenetic siderite that was partially replaced by magnetite and hematite after burial

the role of ocean atmosphere reorganizations in glacial cycles abstract a case is made that glacial to interglacial transitions involve major reorganizations of the ocean atmosphere system such reorganizations constitute jumps between stable modes of operation which cause changes in the greenhouse gas content and albedo of the atmosphere only in this way can the rapidity of glacial terminations the hemispheric synchroneity and symmetry of mountain glaciation and the large polar air temperature and dustiness variations be accounted for if these reorganizations are driven in some fashion by orbitally induced seasonal insolation changes then the connection between insolation and climate is most likely through impacts of fresh water transport on the ocean s salinity distribution

allerod younger dryas lake temperatures from midge fossils in atlantic canada remains of freshwater midges are abundant in lake sediments and their species distributions are closely related to the surface water temperature of lakes their distributions thus provide a powerful tool for paleoclimatology the distribution of species in a core from splan pond in atlantic canada indicates that there were abrupt transitions in late glacial temperatures between warm and cold states the transitions are correlative with the well known warm allerod and cold younger dryas events in europe these data thus confirm the inference from palynological data that these events affected regions on both sides of the atlantic

rare earth element systematics of the chemically precipitated component in early precambrian iron formations and the evolution of the terrestrial atmosphere hydrosphere lithosphere system irrespective of provenance age and metamorphic grade the chemically precipitated component in early precambrian 2 3 ga iron formations ifs displays smyb cn 1 which reflects the corresponding ratios of contemporaneous seawater in conjunction with end if end shale jacobsen and pimentel klose 1988a b this rare earth element ree signature reveals that the ree distribution in early precambrian ifs must be explained by mixing between a marine bottom and a surface water component and that the rees and by analogy the fe cannot be derived from weathering of a continental source eusm n ratios of detritus free ifs are controlled by the marine bottom water component where eusm cn 1 results from ree input from high temperature high t hydrothermal fluids which received their ree signature during high t alteration of oceanic crust at spreading centres decreasing eusm cn of ifs with decreasing depositional age reflect the vaning importance of high t compared to low t 200 c hydrothermal fluids hence oceanic crust alteration for the ree budget of marine bottom waters and are related to decreasing upper mantle temperatures smyb n ratios of detritus free ifs are controlled by the marine surface water component whose ree distribution is affected by the same processes which operate today in the entire ocean mixing calculations reveal that smyb cn in early precambrian marine surface waters was significantly lower than it is today to explain this difference two mechanisms are discussed on the basis of higher pco2 and lower po2 levels of the precambrian atmosphere 1 1 higher co32 in precambrian river and coastal waters and 2 2 redox cycling of the rees at an oceanwide chemocline which separated anoxic and oxic water masses however these processes are synergetic and could have operated in unison the ree distribution in precambrian ifs is described as a result of mixing in a multicomponent system where high t and low t hydrothermal fluids contributed to the marine bottom water and ree input from the dissolved ree pool in river waters after some modification in estuaries dominated the ree distribution in marine surface waters after mixing of bottom and surface waters their combined ree load was quantitatively scavenged onto precipitating iron oxihydroxides or iron carbonates and deposited with the chemically precipitated component after addition of variable amounts of clastic detritus this eventually resulted in the ree distribution observed in precambrian ifs

paleoclimatic inferences from glacial fluctuations on svalbard during the last 20 000 years the climate history of western spitsbergen svalbard is deduced from variations of glaciers during the last 20 000 years a major depression of the regional equilibrium line altitude ela occurred during the late weichselian glacial maximum 18000 13000y ago when low summer temperatures may have caused year round snow accumulation on the ground this rapid expansion of the glaciers also indicates nearby moisture sources suggesting partly open conditions in the norwegian sea during the summers a rapid glacial retreat around 13 000 12 500 y bp was caused by a sudden warming during the younger dryas the ela along the extreme western coast of spitsbergen was not significantly lower than at present in contrast to fennoscandia the british isles and the alps there is no evidence for readvance of local glaciers during younger dryas on western spitsbergen this difference is attributed to a much dryer climate on spitsbergen and probably only slight changes in sea surface temperatures in addition summer melting in this high arctic area is more sensitive to orbitally increased insolation around 10 000 y bp another rapid warming occurred and during early and mid holocene the summer temperatures were significantly higher than at present a temperature decline during the late holocene caused regrowth of the glaciers which reached their maximum holocene position during the last century

rare earth elements in hamersley bif minerals abstract minerals from the hamersley banded iron formation western australia were analyzed for y and rare earth elements yrees by laser ablation icp ms to investigate diagenetic pathways from precursor phases to bif minerals one group of apatites carries the seawater ree signature giving evidence that p and rees thoroughly scavenged from the water column by si ferrihydrite particles were released upon microbial fe 3 reductive dissolution of si ferrihydrite in pore water and finally sequestered mainly in authigenic apatite the absence of fractionation between apatite and seawater suggests that ree were first incorporated into an amorphous calcium phosphate as fully hydrated cations i e as outer sphere complexes the iron oxides and carbonates carry only a small fraction of the whole rock ree budget their ree patterns are distinctly enriched in yb and show some m type tetrad effect consistent with experimental k d ree between solid and saline solution with low carbonate ion concentrations it is deduced that hematite formed at an incipient stage of fe 2 catalyzed dissolution of si ferrihydrite via a dissolution reprecipitation pathway the ree pattern of greenalite found as sub micron particles in quartz in a chert siderite sample is consistent with its authigenic origin by precipitation in pore water after dissolution of a small amount of si ferrihydrite magnetite carries very low yrees ppb level has an homogeneous pattern distinctly enriched in the mid rees compared to hematite and includes a late population depleted in light rees ba and as magnetite forming aggregates and massive laminae is tentatively interpreted as reflecting some fluid aided hematite magnetite re equilibration or transformation at low grade metamorphic temperatures

episodic negative anomalies of cerium at the depositional onset of the 2 65 ga itabira iron formation quadrilatero ferrifero of minas gerais brazil abstract magnetite bands in sericitic phyllite of the batatal formation mark the transition to the overlying 2 65 ga itabira iron formation or caue itabirite in the quadrilatero ferrifero of minas gerais brazil the magnetite bands have low non crustal th u ratios suprachondritic y ho ratios and sporadic anomalies of ce that are characterised as truly negative the data point to mild oxygenation of sea water at the depositional onset of the itabira iron formation some 200 ma before the great oxidation event

the nature of mesoproterozoic central indian tectonic zone with exhumed and reworked older granulites abstract the ese wnw trending central indian tectonic zone citz divides the indian subcontinent into southern and northern crustal provinces its narrow northern belt consists of closed early proterozoic mahakoshal rift zone which is presently confined between two moho reaching faults that characterize the son narmada sona lineament the mesoproterozoic sausar mobile belt smb the chhotanagpur granite gneiss complex cggc and the gneissic complex of northeast india represent the wider southern belt the mahakoshal rift belt has a thick pile of mafic ultramafic rocks and possibly oceanic components the basin closed due to a south directed subduction creating a magmatic arc that was sutured to its southern boundary during 1 8 1 7 ga a south dipping ductile shear zone known as the son narmada south fault affects both its supracrustals and intrusive granitoids the son narmada south fault generally delimits the northern boundary of the gondwana basins whereas the son narmada north fault delineates the northern boundary of the mahakoshal mobile belt and the southern boundary of the meso neoproterozoic vindhyan basin the smb representing the southern belt of the citz in the central sector comprises strongly folded and metamorphosed non volcanic and mn rich sausar sediments intermixed with reworked basement gneisses migmatites and granulites representing the pre sausar assemblage the sausar orogeny closed during terminal mesoproterozoic ca 1 0 ga on the other hand metamorphism in the basement gneiss migmatites and northern and southern granulite belts pre dates the sausar orogeny the earliest structure of the smb truncates and rotates the n s oriented structures of the southward located sakoli and the dongargarh belts of neoarchaean palaeoproterozoic age the northern granulite belt of the smb and the cggc and the high grade supracrustals from the sonapahar area in ne india all indicate very high p t conditions during 1 7 1 5 ga peak metamorphism which was followed by decompressional cooling the setting resembles continental collision which was followed by tectonic exhumation and denudation on the other hand the southern granulite belt from the smb documents a late archaean 2 6 ga event and a later 1 4 ga event the dalma volcanic belt located close to the southern tectonized boundary of the cggc belt and possibly the assemblage of copious mafic enclaves within the ca 550 ma granite plutons from ne india represent back arc like setting during 1 6 1 5 ga the setting is caused due to the southward subduction of the north indian block beneath the southern block leading to continental collision the metasedimentary belt located further to the south of the dalma volcanic belt and flanking the archaean singbhum craton to the north on the other hand is palaeoproterozoic in age but has been metamorphosed during ca 1 6 ga because of the northern collision related orogeny reworking and incorporation of basement gneisses and granulites from the mid crust level to the younger sausar cover sediments denote renewed spell of thrust tectonics that remobilized the collision zone rocks of the earlier orogeny the tectonic transport was from the north to the south with north dipping thrusts thus there was a reversal in the direction of convergence from the preceding orogeny the sausar orogeny closed during ca 1 0 ga it caused anatectic event producing granitoid plutons migmatites and charnockites in the cggc belt and migmatites in the gneissic complex in ne india

wisconsinan late glacial environmental change in newfoundland a regional review the distribution of 75 lake and bog sites from which pollen stratigraphical evidence relevant to the late quaternary of newfoundland has been obtained is presented the detailed records of lithology pollen and diatoms supplemented by geochemical data are discussed for three of the sites southwest brook lake woody hill brook pond and leading tickles and interpretations made are based on vegetational history relative climatic changes and extent of ice cover radiocarbon data from 14 sites are summarised a summary chart of late glacial environmental changes including a qualitative palaeotemperature curve is provided

primary hematite in neoarchean to paleoproterozoic oceans banded iron formations bifs are ironand silica rich chemical sedimentary rocks formed throughout the archean and paleoproterozoic eras the presence of hematite fe2o3 and magnetite fe3o4 in bifs has led to the widespread assumption that fe ii oxidation must have occurred in the ancient oceans via either a biological or chemical mechanism however it is unclear whether the ferric iron now present in bif represents the original ferric oxyhydroxide e g ferrihydrite fe oh 3 precipitated in the water column or if it is the result of later stage circulation of oxidizing fl uids through the sediment pile in this study we conducted high resolution microscopic investigations on bif from the 2728 ma abitibi greenstone belt located in the superior province of the canadian shield and the 2460 ma kuruman iron formation in south africa to ascertain the timing and paragenesis of the hematite three types of hematite are identifi ed by high resolution electron microscopic characterization and selected area electron diffraction 1 3 5 nm ultrafi ne hematite particles in the iron oxide rich bands h1 2 submicrometer subhedral to euhedral hema tite crystals randomly distributed in the chert matrix of transitional zones between iron oxide and chert rich bands h2 and 3 needle like radial and fi brous hematite that replaced stilpnomelane or carbonates and is distributed along fractures or layer boundaries h3 we interpret the fi rst two types as primary minerals dehydrated from precursor ferric oxyhydroxides h1 remains ultrafi ne in size while h2 has undergone an ostwald coarsening process facilitated by internal fl uids produced during amorphous silica to quartz transformation h3 is a later stage mineral formed by external fl uid mediated replacement of iron silicates or carbonates these results indicate that a signifi cant fraction of the hematite in the bif originated from ferric oxyhydroxide precursors importantly this implies that photosynthetic fe ii oxidation by either a direct or indirect biological mechanism did exist in seawaters from which some bif material was deposited

alternating si and fe deposition caused by temperature fluctuations in precambrian oceans precambrian banded iron formations contain thin alternating layers of iron and silica rich minerals microbial culture experiments show that these alternations could be caused by changes in the relative dominance of microbial iron oxidation and abiotic silica precipitation driven by fluctuating ocean temperature

lateglacial and early holocene pollen stratigraphy of the northern apennines italy a contribution to the north atlantic seaboard programme of igcp 253 termination of the pleistocene abstract pollen diagrams supported by 25 radiocarbon dates are presented for four sites in the ligurian emilian apennines northern italy which collectively span the late weichselian lateglacial and holocene coleopteran evidence is available for the lateglacial and early holocene sediments from one of the sites collectively the data provide a an internally consistent series of local pollen assemblages zones such that regional pollen assemblage zones are defined b a detailed chronology of vegetation changes in the region c an impression of environmental changes during the lateglacial holocene transition of particular note is the clear evidence for a marked younger dryas event which together with evidence from other parts of southern europe indicates that the climatic severity of this event did not diminish southwards on the european continent also of significance is the pollen and coleopteran evidence for mixed woodland in the region during the lateglacial interstadial which is not in keeping with previous reconstructions

late weichselian environmental change in southern sweden and denmark a synthesis is presented of the envronmental and climatic variations that are inferred to have occurred in southern sweden up to latitude 59 n and denmark during the weichselian late glacial 14 9 ka bp the chronology and characteristics of the main phases of deglaciation sea level change periglacial activity soil development vegetation cover and climate change are summarised a curve representing the main changes in temperature including quantitative estimates based upon beetle data and using the mutual climatic range method is presented

the quaternary deposits and landforms of scotland and the neighbouring shelves a review abstract a thick sequence of quaternary sediments up to 1000 m has been deposited in the north sea basin and perhaps five major glacial episodes the first occurring prior to ca 1 8 2 1 ma bp and the last during the late devensian can be recognised between the glacial events periods of low salinity arctic marine or glacio marine sedimentation have been dominant although episodes of ameliorated climate when north atlantic drift waters had access to the north sea have been identified a number of horizons in separate boreholes have been correlated with the last interglacial oxygen isotope stage 5e and a sequence of water mass movements around the scottish coasts can be reconstructed for the last ca 125 ka on land sequences of quaternary deposits relating to several glacial and non glacial terrestrial and marine events occur in different areas but due to poor dating correlation between these sequences cannot yet be achieved in particular north east scotland has a complex glacial history with evidence for ice sheet glaciation on at least four occasions evidence from the outer hebrides north east scotland and the north sea basin indicates that the late devensian scottish ice sheet had a rather restricted extent only reaching a short distance offshore along much of the east and west coasts at this time ice free areas existed in north east scotland on the isle of lewis and probably in caithness and orkney whilst part of the outer shelf around st kilda was dry land a marine embayment extended down the east coast of scotland between the scottish and scandinavian ice sheets and independent ice caps existed on the outer hebrides and probably on shetland deglaciation of the greater part of the country took place prior to ca 13 ka bp whilst the climate was still very cold the ice retreat appears to have been orderly with stagnant ice masses being trapped only in topographically suitable locations a number of retreat stages or minor readvances occurred during the general deglaciation the firth of clyde was one of the last areas outside the highlands to be deglaciated and this occurred in a rapid possibly catastrophic fashion shortly prior to ca 13 ka bp despite the mild climate at the start of the lateglacial interstadial it is not known if there was complete deglaciation prior to the loch lomond readvance the readvance glaciers however may have started to advance during the latter part of the interstadial when declining terrestrial temperatures coincided with a period of mild marine conditions the loch lomond readvance maximum can only be dated to some time after ca 10 9 ka bp and it is likely that final ice free conditions were not achieved until the earliest holocene

sudden changes in north atlantic circulation during the last deglaciation sudden changes in the flow of warm atlantic surface waters into the norwegian sea occurred frequently during the last deglaciation typically involving shifts in sea surface temperature of 5 c in fewer than 40 years these led to equally large and rapid changes in atmospheric temperatures and to shifts in atlantic deep thermo haline circulation and ice sheet melting rates

the archaean nucleus of singhbhum the present state of knowledge abstract the supracrustal rocks of the older metamorphic group omg consisting of metasediments and ortho amphibolite constitute the oldest unit in the archaean nucleus of singhbhum however there are indications that still older 3 4 3 8 ga crust of both sialic and mafic composition existed in this region the omg ortho amphibolites were formed by partial melting of mantle with near chondritic composition ca 3 3 ga ago probably as a result of plume activity shortly afterwards partial melting of the underplated mafic material produced a tonalitic melt older metamorphic tonalitic gneiss omtg which intruded the omg supracrustals and the entire suite was deformed and metamorphosed to upper amphibolite facies subsequent to this melting of the omg ortho amphibolites and the lower crustal material of probable andesitic composition produced melts varying in composition from tonalite to granite and these intruded in different phases to produce plutons of singhbhum granite bonai granite and kaptipada granite which together form volumetrically the major part of the archaean nucleus the older omg and omtg occur as enclaves within these younger granitoids the time difference between the emplacements of the omtg and the early phases of younger granitic intrusion was of the order of 100 200 ma thus serial additions of juvenile material led to the formation of a stable microcontinent by 3 2 ga thermally triggered stretching in this microcontinent produced basins peripheral to the present day singhbhum granite pluton and in these basins the younger supracrustal rocks of the iron ore group iog consisting of bif associated argillaceous and subordinate arenaceous rocks and mafic lavas were laid down there is inadequate field or geochronological evidence to resolve the issue of whether the different iron ore basins were coeval or not meagre geochronological data suggest that some of the bifs are older than ca 3 1 ga post iog activity is confined to the intrusion of mafic dyke swarms and formation of intracratonic basins the ages of both being uncertain

the formation of magnetite in the early archean oceans abstract banded iron formations bifs are iron and silica rich chemical sedimentary rocks that were deposited throughout much of the precambrian the biological oxidation of dissolved fe ii led to the precipitation of a ferric oxyhydroxide phase such as ferrihydrite in the marine photic zone upon burial ferrihydrite was either transformed into hematite through dehydration or it was reduced to magnetite via biological or abiological fe iii reduction coupled to the oxidation of buried microbial biomass however it has always been intriguing as to why the oldest bifs are characteristically magnetite rich while bifs formed after the neoarchean are dominated by hematite here we propose that some magnetite in early archean bif could have precipitated directly from seawater through the reaction of settling ferrihydrite and hot fe ii rich hydrothermal fluids that existed in the deeper waters we conducted experiments that showed the reaction of fe ii with biogenic ferric iron mats under strict anoxic conditions lead to the formation of a metastable green rust phase that within hours transformed into magnetite our model further posits that with the progressive cooling and oxidation of the earth s oceans the above reaction shuts off and magnetite was subsequently restricted to reactions associated with diagenesis and metamorphism

simulating precambrian banded iron formation diagenesis abstract post depositional diagenetic alteration makes the accurate interpretation of key precipitation processes in ancient sediments such as precambrian banded iron formations bifs difficult while microorganisms are proposed as key contributors to bif deposition the diagenetic transformation of precursor fe iii minerals associated with microbial biomass had not been experimentally tested we incubated mixtures of ferrihydrite proxy for biogenic ferric oxyhydroxide minerals and glucose proxy for microbial biomass in gold capsules at 1 2 kbar and 170 c both wet chemical analysis and mineralogical methods microscopy x ray diffraction and mossbauer spectroscopy were used to analyze the reaction products under these conditions ferrihydrite fe iii oh 3 transforms to hematite fe 2 iii o 3 magnetite fe ii fe 2 iii o 4 and siderite fe ii co 3 silica coated ferrihydrite prepared at conservative si fe ratios as predicted for the precambrian oceans and mixed with glucose yielded hematite and siderite whereas magnetite could not be identified microscopically our results show that electron transfer from organic carbon to fe iii minerals during temperature pressure diagenesis can drive the production of key bif minerals our results also demonstrate that the post depositional mineralogy of bif does not directly archive the oceanic or atmospheric conditions present on earth during their lithification as a consequence atmospheric composition regarding concentrations of methane and co 2 during the time of bif mineral deposition cannot be directly inferred from bif mineralogical data alone

dating the oldest greenstone in india a 3 51 ga precise u pb shrimp zircon age for dacitic lava of the southern iron ore group singhbhum craton abstract this article reports a precise 3506 8 2 3 ma u pb shrimp zircon age for dacitic lava in a well preserved low grade metamorphic and low strained greenstone belt succession of the southern iron ore group singhbhum craton india this age makes the succession the oldest known greenstone belt succession in india and one of the oldest low strain greenstone successions in the world after the 3 51 ga coonterunah group of the pilbara craton western australia and the moderately deformed 3 54 ga theespruit formation of the barberton greenstone belt kaapvaal craton south africa the geochemical composition of the dacitic lava and related volcanic rocks suggests that they formed in a volcanic arc setting the succession also contains a major 120 m thick oxide facies banded iron formation that distinguishes it from the slightly older successions of the pilbara and kaapvaal cratons this banded iron formation may well be one of the oldest and most well preserved and together with associated volcanics

online preconcentration icp ms analysis of rare earth elements in seawater the rare earth elements rees with their systematically varying properties are powerful tracers of continental inputs particle scavenging intensity and the oxidation state of seawater however their generally low pmol kg concentrations in seawater and fractionation potential during chemical treatment makes them difficult to measure here we report a technique using an automated preconcentration system which efficiently separates seawater matrix elements and elutes the preconcentrated sample directly into the spray chamber of an icp ms instrument the commercially available seafast system elemental scientific inc makes use of a resin with ethylenediaminetriacetic acid and iminodiacetic acid functional groups to preconcentrate rees and other metals while anions and alkali and alkaline earth cations are washed out repeated measurements of seawater from 2000 m water depth in the southern ocean allows the external precision 2 of the technique to be estimated at 23 for all rees and 15 for most comparison of nd concentrations with isotope dilution measurements for 69 samples demonstrates that the two techniques generally agree within 15 accuracy was found to be good for all rees by using a five point standard addition analysis of one sample and comparing measurements of mine water reference materials diluted with a nacl matrix with recommended values in the literature this makes the online preconcentration icp ms technique advantageous for the minimal sample preparation required and the relatively small sample volume consumed 7 ml thus enabling large data sets for the rees in seawater to be rapidly acquired

the rainbow vent fluids 36 14 n mar the influence of ultramafic rocks and phase separation on trace metal content in mid atlantic ridge hydrothermal fluids fluids were collected from the rainbow vent field 36 14 n on the mid atlantic ridge mar during the 1997 diving flores cruise this vent field in ultramafic rocks at a depth of 2300 m is composed of 10 black smokers emitting acidic ph 2 8 fluids at 365 c the low ph of the hot temperature rainbow fluids likely results from seawater ultramafic rock interaction that releases h ions into reducing hydrothermal fluids fluid chemistry is strongly influenced by phase separation generating cl rich brines clem 750 mm strongly enriched with mn fe co ni cu zn ag cd cs pb y and rare earth elements ree ree and transition metal abundance particularly fe and mn in the rainbow fluids is dramatically higher than in other mar fluids the abundance of trace element and ree enrichment is due to the greater solubility of these elements that is strongly favored by cl complexation at low ph and high temperature conditions chondrite normalized ree patterns show strong lree enrichment with evidence of the typical eu anomaly this ree partitioning suggests that either 1 ultramafic rocks represent only a part of rocks leached during hydrothermal alteration and or 2 that the unique rainbow fluid temperature ph and redox state issued from the ultramafic character of leached substratum can produce unique ree partitioning

the composition of earth s oldest iron formations the nuvvuagittuq supracrustal belt quebec canada abstract the composition of iron formations in the 3 75 ga yr old nuvvuagittuq supracrustal belt in northern quebec provides a proxy for seawater composition of the eoarchean and perhaps hadean oceans as well as constraints on the types of nutrients available to earth s earliest life forms integrated petrologic and geochemical relationships mapped between mineral phases in thin section and whole rock chemistry provide a framework for interpreting bulk and micro scale variations in these chemical sedimentary precipitates results show that there are two distinct chemical sedimentary units in the nuvvuagittuq belt i a banded iron formation bif consisting of alternating micro bands of magnetite ca mg fe silicates and quartz and ii a more silicate rich fe poor unit the banded silicate formation bsf of alternating micro bands of quartz and ca mg fe silicates precursor bif and bsf deposits were likely layered amorphous silica and ferric oxyhydroxides fine grained carbonate oozes and or ca mg fe rich silicate gels deposited in a marine setting low al2o3 tio2 and hfse concentrations show that they are relatively detritus free with distinctively seawater like ree y profiles and consistently positive eu anomalies these features suggest that the rocks preserved their seawater like compositions despite metamorphic overprinting the most significant trace elements in the sediments are ni and zn experimentally derived partitioning coefficients show that ni was enriched in eoarchean seawater as compared to today up to 300 nm while zn was fairly similar up to 20 nm compositional resemblances between the nuvvuagittuq sediments and those documented in the ca 3 8 ga isua supracrustals west greenland provide a plausible case that global ocean processes in terms of trace metal abundances had reached steady state by the eoarchean

the weichselian late glacial in southwestern europe iberian peninsula pyrenees massif central northern apennines this paper presents a summary of late glacial environmental changes in southwestern europe lberian peninsula pyrenees massif central and the northern apennines the emphasis is on palaeoclimatic interpretations inferred from key sites in the region from which the most detailed records are available and which have been radiocarbon dated the earliest evidence for climatic improvement following the end of the last glacial stage is dated to ca 15 ka bp and is found at a few sites only by 13 ka bp a more widespread and marked climatic improvement is evident although it is difficult to be precise in the timing and magnitude of the event there are significant variations in detail between the late glacial records but evidence for a significant cooling correlated with the younger dryas event is widespread throughout the region just two sites in the region provide evidence for an earlier less emphatic phase of climatic cooling which is tentatively equated with the older dryas of continental northern europe dry conditions appear to have predominated throughout the region in the later part of the younger dryas and the early holocene

retreat velocity of the north atlantic polar front during the last deglaciation determined by 14 c accelerator mass spectrometry the glacial oscillations which dominate the quaternary global climate are closely related to changes in incoming solar radiation but the details of palaeoclimatic spectra suggest that other parameters usually referred to as feedback have significantly increased the climatic response to extraterrestrial forcing1 the last deglaciation appears to be one of the more characteristic examples of nonlinearity because its abruptness strongly contrasts with the smooth shape of the associated solar radiation maximum dated at 11 000 yr bp in addition the presence of the younger dryas cold event concomitant with the solar radiation maximum could be interpreted as a transitory phenomenon caused by the rapid meltwater influx linked to the first phase of the ice sheet s disintegration2 3 here using accelerator mass spectrometry we date precisely the movements of the polar front during the whole period of glacial retreat 15 000 8 000 yr bp our results show that the polar front has moved between 35 n and 55 n in 1 000 yr for the earliest retreat 12 500 12 000 bp and moved almost instantaneously that is 400 yr during the two abrupt climatic changes associated with the younger dry as cold event

a key role for green rust in the precambrian oceans and the genesis of iron formations iron formations deposited in marine settings during the precambrian represent large sinks of iron and silica and have been used to reconstruct environmental conditions at the time of their formation however the observed mineralogy in iron formations which consists of iron oxides silicates carbonates and sulfides is generally thought to have arisen from diagenesis of one or more mineral precursors ferric iron hydroxides and ferrous carbonates and silicates have been identified as prime candidates here we investigate the potential role of green rust a ferrous ferric hydroxy salt in the genesis of iron formations our laboratory experiments show that green rust readily forms in early seawater analogue solutions as predicted by thermodynamic calculations and that it ages into minerals observed in iron formations dynamic models of the iron cycle further indicate that green rust would have precipitated near the iron redoxcline and it is expected that when the green rust sank it transformed into stable phases within the water column and sediments we suggest therefore that the precipitation and transformation of green rust was a key process in the iron cycle and that the interaction of green rust with various elements should be included in any consideration of precambrian biogeochemical cycles large iron deposits formed episodically in the archaean oceans experimental data and geochemical modelling suggest that green rust was an important contributor to the formation of these deposits and the archaean iron cycle in general

scales of disequilibrium and rates of equilibration during metamorphism mounting evidence suggests that partial disequilibrium meaning disequilibrium for some elements but not for others may be a common but rarely detected phenomenon during metamorphic mineral growth even in ordinary prograde reactions that progress to completion detailed examination of compositional variations in garnet crystals over a range of metamorphic grade suggests distinctly different scales of equilibration for common elements with strong temperature dependence under lower greenschist facies conditions fe and mg may equilibrate at hand sample scale whereas mn and ca may not equilibrate even at millimeter scale although mn may achieve hand sample scale equilibration under upper greenschist facies conditions ca and many trivalent cations e g rees may not do so until temperatures exceed those of the middle amphibolite facies even in the lower granulite facies some elements e g y yb show indications of disequilibrium at sub centimeter scales during garnet growth analysis and numerical modeling of undisputed disequilibrium textures demonstrate that the most common impediment to equilibration during metamorphism is the sluggishness of intergranular diffusion the same mechanism known to govern porphyroblast crystallization in many metamorphic environments despite this importance to petrology few quantitative determinations exist of inter granular diffusion rates under metamorphic conditions using numerical simulations of coupled intergranular and intracrystalline diffusion processes in coronal textures around partially resorbed garnet crystals from the llano uplift u s a a very precise and relatively accurate estimate is obtained for the rate of intergranular diffusion of al in fluid undersaturated systems this result and an earlier estimate for fluid saturated systems provide bracketing values for al diffusivity during metamorphism

greenalite precipitation linked to the deposition of banded iron formations downslope from a late archean carbonate platform banded iron formations bifs were deposited as deep water facies distal to the late archean campbellrand carbonate platform transvaal supergroup south africa they are traditionally interpreted to have formed from iron oxides hydroxides and silica that precipitated when upwelling hydrothermal water enriched in fe2 and silica mixed with cooler shallow seawater enriched in dissolved oxygen the ferric oxides hydroxides were then converted to hematite or in the presence of organic matter reduced and incorporated into siderite new high resolution microscopy of bifs from distal facies of the campbellrand platform questions that interpretation revealing the presence of abundant greenalite nanoparticles interpreted to represent primary precipitates from ferruginous seawater consistent with recent results from equivalent aged bifs of the hamersley group western australia the particles locally define primary sedimentary lamination and are engulfed in diagenetic chert that preserves shrinkage structures considered to have formed during dehydration and recrystallization of amorphous silica cement the replacement of greenalite nanoparticles by coarser grained oxide silicate and carbonate minerals with destruction of primary textures and structures indicates that iron silicate muds were originally much more widespread based on our findings we propose a new model for the deposition of the bifs involving iron silicate precipitation from seawater followed by diagenetic silica cementation on the seafloor we suggest that ferrous iron and silica were transported in hydrothermal plumes sourced from acidic vent fluids upon mixing with cooler more alkaline seawater the solubility of ferrous iron and silica fell to levels that favored rapid nucleation and the precipitation of iron silicate nanoparticles over vast areas of the seafloor the close association between iron and silica during the deposition of bifs may be explained by the precipitation of iron silicate nanoparticles and possible sorption of silica onto the surfaces of sinking nanoparticles furthermore on the seafloor iron silicate nanoparticles presumably acted as nucleation sites for dissolved silica promoting early diagenetic silica precipitation and cementation of the iron rich muds our results indicate that iron silicates were important primary precipitates and suggest that changes in alkalinity rather than redox state played a key role in the precipitation of the precursor sediments of bifs

paleoceanographic reconstructions of surface ocean conditions in the greenland iceland and norwegian seas through the last 14 ka based on diatoms prior reconstructions of the last glacial maximum and the holocene did not include detailed paleoclimate data from the greenland iceland and norwegian gin seas which cover sensitive areas for oceanographic boundaries sea ice distribution and deep water formation in order to fill this gap we studied nine well dated sediment cores from this area and reconstructed the paleoceanographic conditions of the surface gin seas at 2000 year intervals since 13 400 bp based on the diatom record results show that a n s extending sea ice free corridor had opened along norway already at 13 400 bp indicating a northward flow of a branch of the north atlantic drift possibly caused by a change in the jet stream flow due to the decreased height of the north american ice sheet a major change of climatic conditions occurred over the gin seas as the insolation anomaly reached its maximum around 9000 bp when the sea ice cover and the oceanic fronts retreated to a northwesterly position along greenland and the ocean temperatures rose the first half of the holocene is recorded as the warmest period during the last 13 400 bp in the gin seas the duration of this climatic optimum decreased both toward the north and toward the margins of the area the second half of the holocene is characterized by a cooling trend in step with the decreasing insolation these results support the proposal of imbrie et al 1992 that the gin seas region acts as an initial responder to insolation changes

continentally derived solutes in shallow archean seawater rare earth element and nd isotope evidence in iron formation from the 2 9 ga pongola supergroup south africa abstract the chemical composition of surface water in the photic zone of the precambrian ocean is almost exclusively known from studies of stromatolitic carbonates while banded iron formations ifs have provided information on the composition of deeper waters here we discuss the trace element and nd isotope geochemistry of very shallow water if from the pongola supergroup south africa to gain a better understanding of solute sources to mesoarchean shallow coastal seawater the pongola supergroup formed on the stable margin of the kaapvaal craton 2 9 ga ago and contains banded iron formations ifs that represent the oldest documented superior type iron formations the ifs are near shore pure chemical sediments and shale normalized rare earth and yttrium distributions reysn exhibit positive lasn gdsn and ysn anomalies which are typical features of marine waters throughout the archean and proterozoic the marine origin of these samples is further supported by super chondritic y ho ratios average y ho 42 relative to older isua ifs 3 7 ga from greenland and younger kuruman ifs 2 5 ga also from south africa the pongola ifs are depleted in heavy rare earth elements hree and appear to record variations in solute fluxes related to sea level rise and fall sm nd isotopes were used to identify potential sediment and solute sources within pongola shales and ifs the nd t for pongola shales ranges from 2 7 to 4 2 and nd t values for the coeval iron formation samples range 1 9 to 4 3 are generally indistinguishable from those of the shales although two if samples display nd t as low as 8 1 and 10 9 the similarity in nd isotope signatures between the shale and iron formation suggests that mantle derived rey were not a significant nd source within the pongola depositional environment though the presence of positive eu anomalies in the if samples indicates that high t hydrothermal input did contribute to their rey signature isotopic mass balance calculations indicate that most 72 of the nd in these seawater precipitates was derived from continental sources if previous models of fe nd distributions in archean ifs are applied then the pongola ifs suggest that continental fluxes of fe to archean seawater were significantly greater than are generally considered