Microscale oxygen isotope variations in 1.9 Ga Gunflint cherts: Assessments of diagenesis effects and implications for oceanic paleotemperature reconstructions

Variations in the oxygen isotope composition (δ¹⁸O) of five cherts from the 1.9 Ga Gunflint iron formation (Canada) were studied at the micrometer scale by ion microprobe to try to better understand the processes that control δ¹⁸O values in cherts and to improve seawater paleotemperature reconstructions. Gunflint cherts show clearly different δ¹⁸O values for different types of silica with for instance a difference of ≈15‰ between detrital quartz and microquartz. Microquartz in the five samples is characterized by large intra sample variations in δ¹⁸O values, (δ¹⁸O of quartz varies from 4.6‰ to 6.6‰ at the 20 μm scale and from ≈12‰ to 14‰ at 2 μm scale). Isotopic profiles in microquartz adjacent to hydrothermal quartz veins demonstrate that microquartz more than ≈200 μm away from the veins has preserved its original δ¹⁸O value.At the micrometer spatial resolution of the ion probe, data reveal that microquartz has preserved a considerable δ¹⁸O heterogeneity that must be regarded as a signature inherited from its diagenetic history. Modelling of the δ¹⁸O variations produced during the diagenetic transformation of sedimentary amorphous silica precursors into microquartz allows us to calculate seawater temperature (T_sw at which the amorphous silica precipitated) and diagenesis temperature (T_diagenesis at which microquartz formed) that reproduce the δ¹⁸O distributions (mean, range and shape) measured at micrometer scale in microquartz. The two critical parameters in this modelling are the δ¹⁸O value and the mass fraction of the diagenetic fluid. Under these assumptions, the most likely ranges for T_sw and T_diagenesis are from 37 to 52 °C and from 130 to 170 °C, respectively.     

The ∼1100 Ma Sturgeon Falls paleosol revisited: Implications for Mesoproterozoic weathering environments and atmospheric CO2 levels

During the active rifting stage of the ∼1100 Ma Midcontinental Rift in North America, alluvial sediments were deposited intermittently between basalt flows on the north and south shores of present day Lake Superior. At times of depositional quiescence, paleosols developed in both areas on the alluvial sediments and on the antecedent basalt. New results from the Sturgeon Falls paleosol in Michigan characterizing the weathering processes at the time of its formation indicate moderate maturity, high degrees of hydrolysis and leaching, and a low degree of salinization. Geochemical provenance indices indicate a homogeneous source for the paleosols, and in contrast to earlier work, there is little evidence for K metasomatism. As a result, atmospheric CO₂ levels of 4–6× pre-industrial atmospheric levels were calculated using a mass-balance model. This result is consistent with previous calculations from nearly contemporaneous paleosols from the other side of the Keweenawan Rift and from the ∼100 Ma younger Sheigra paleosol in Scotland. The calculated CO₂ values are also consistent with the calculated weathering environment proxies that indicate weak to moderate weathering at this time frame and suggest that the higher greenhouse gas loads indicated by Paleoproterozoic paleosols had dissipated by the mid-late Mesoproterozoic.     

Quadruple sulfur isotope analysis of ca. 3.5 Ga Dresser Formation: New evidence for microbial sulfate reduction in the early Archean

Multiple sulfur isotope system is a powerful new tracer for atmospheric, volcanic, and biological influences on sulfur cycles in the anoxic early Earth. Here, we report high-precision quadruple sulfur isotope analyses (³²S/³³S/³⁴S/³⁶S) of barite, pyrite in barite, and sulfides in related hydrothermal and igneous rocks occurring in the ca. 3.5 Ga Dresser Formation, Western Australia. Our results indicate that observed isotopic variations are mainly controlled by mixing of mass-dependently (MD) and non-mass-dependently fractionated (non-MD) sulfur reservoirs. Based on the quadruple sulfur isotope systematics (δ³⁴S-Δ³³S-Δ³⁶S) for these minerals, four end-member sulfur reservoirs have been recognized: (1) non-MD sulfate (δ³⁴S = −5 ± 2‰; Δ³³S = −3 ± 1‰); (2) MD sulfate (δ³⁴S = +10 ± 3‰); (3) non-MD sulfur (δ³⁴S > +6‰; Δ³³S > +4‰); and (4) igneous MD sulfur (δ³⁴S = Δ³³S = 0‰). The first and third components show a clear non-MD signatures, thus probably represent sulfate and sulfur aerosol inputs. The MD sulfate component (2) is enriched in ³⁴S (+10 ± 3‰) and may have originated from microbial and/or abiotic disproportionation of volcanic S or SO₂. Our results reconfirm that the Dresser barites contain small amounts of pyrite depleted in ³⁴S by 15-22‰ relative to the host barite. These barite-pyrite pairs exhibit a mass-dependent relationship of δ³³S/δ³⁴S with slope less than 0.512, which is consistent with that expected for microbial sulfate reduction and is significantly different from that of equilibrium fractionation (0.515). The barite-pyrite pairs also show up to 1‰ difference in Δ³⁶S values and steep Δ³⁶S/Δ³³S slopes, which deviate from the main Archean array (Δ³⁶S/Δ³³S = −0.9) and are comparable to isotope effects exhibited by sulfate reducing microbes (Δ³⁶S/Δ³³S = −5 to −11). These new lines of evidence support the existence of sulfate reducers at ca. 3.5 Ga, whereas microbial sulfur disproportionation may have been more limited than recently suggested.     

Fluid-mobile trace element constraints on the role of slab melting and implications for Archaean crustal growth models

We use published and new trace element data to identify element ratios which discriminate between arc magmas from the supra-subduction zone mantle wedge and those formed by direct melting of subducted crust (i.e. adakites). The clearest distinction is obtained with those element ratios which are strongly fractionated during refertilisation of the depleted mantle wedge, ultimately reflecting slab dehydration. Hence, adakites have significantly lower Pb/Nd and B/Be but higher Nb/Ta than typical arc magmas and continental crust as a whole. Although Li and Be are also overenriched in continental crust, behaviour of Li/Yb and Be/Nd is more complex and these ratios do not provide unique signatures of slab melting. Archaean tonalite-trondhjemite-granodiorites (TTGs) strongly resemble ordinary mantle wedge-derived arc magmas in terms of fluid-mobile trace element content, implying that they did not form by slab melting but that they originated from mantle which was hydrated and enriched in elements lost from slabs during prograde dehydration. We suggest that Archaean TTGs formed by extensive fractional crystallisation from a mafic precursor. It is widely claimed that the time between the creation and subduction of oceanic lithosphere was significantly shorter in the Archaean (i.e. 20 Ma) than it is today. This difference was seen as an attractive explanation for the presumed preponderance of adakitic magmas during the first half of Earth's history. However, when we consider the effects of a higher potential mantle temperature on the thickness of oceanic crust, it follows that the mean age of oceanic lithosphere has remained virtually constant. Formation of adakites has therefore always depended on local plate geometry and not on potential mantle temperature.     

The five stable isotope compositions of Fig Tree barites: Implications on sulfur cycle in ca. 3.2 Ga oceans

The discovery of ³³S anomalies in Archean sedimentary rocks has established that the early Earth before ∼2.2 Ga (billion years ago) had a very different sulfur cycle than today. The origin of the anomalies and the nature of early sulfur cycle are, however, poorly known and debated. In this study, we analyzed the total sulfur and oxygen isotope compositions, the δ¹⁸O, Δ¹⁷O, δ³⁴S, Δ³³S, and Δ³⁶S, for the >3.2 Ga Fig Tree barite deposits from the Barberton Greenstone Belt, South Africa. The goal is to address two questions: (1) was Archean barite sulfate a mixture of ³³S-anomalous sulfate of photolysis origin and ³³S-normal sulfate of other origins? (2) did the underlying photochemical reactions that generated the observed ³³S anomalies for sulfide and sulfate also generate ¹⁷O anomalies for sulfate?We developed a new method in which pure barite sulfate is extracted for oxygen and sulfur isotope measurements from a mixture of barite sands, cherts, and other oxygen-bearing silicates. The isotope data reveal that (1) there is no distinct ¹⁷O anomaly for Fig Tree barite, with an average Δ¹⁷O value the same as that of the bulk Earth (−0.02 ± 0.07‰, N = 49); and (2) the average δ¹⁸O value is +10.6 ± 1.1‰, close to that of the modern seawater sulfate value (+9.3‰). Evidence from petrography and from the δ¹⁸O of barites and co-existing cherts suggest minimum overprinting of later metamorphism on the sulfate’s oxygen isotope composition. Assuming no other processes (e.g., biological) independently induced oxygen isotope exchange between sulfate and water, the lack of reasonable correlation between the δ¹⁸O and Δ³³S or between the δ³⁴S and Δ³³S suggests two mutually exclusive scenarios: (1) An overwhelming majority of the sulfate in the Archean ocean was of photolysis origin, or (2) The early Archean sulfate was a mixture of ³³S-normal sulfates and a small portion (<5%?) of ³³S-anomalous sulfate of photolysis origin from the atmosphere. Scenario 1 requires that sulfate of photolysis origin must have had only small ³³S or ³⁶S anomalies and no ¹⁷O anomaly. Scenario 2 requires that the photolysis sulfate have had highly negative δ³⁴S and Δ³³S values, recommending future theoretical and experimental work to look into photochemical processes that generate sulfate in Quadrant I and sulfide in Quadrant III in a δ³⁴S (X)-Δ³³S (Y) Cartesian plane. A total sulfur and oxygen isotope analysis has provided constraints on the underlying chemical reactions that produced the observed sulfate isotope signature as well as the accompanying atmospheric, oceanic, and biological conditions.     

Layered intrusions and volcanic sequences in Central Brazil: Geological and geochronological constraints for Mesoproterozoic (1.25 Ga) and Neoproterozoic (0.79 Ga) igneous associations

A 350-km long belt of layered complexes and associated volcano-sedimentary sequences forms a continental-scale feature exposed along the internal portion of the Neoproterozoic Brasília Belt in central Brazil. This study provides new geochronological results and a critical review of the available data of these igneous associations of central Brazil. Precise age dating combined with geological and petrological studies indicate that this belt consists of two distinct igneous rock associations. The 1.25 and 0.79 Ga igneous episodes are constrained by reliable U–Pb zircon ages (SHRIMP and ID-TIMS) obtained in different regions and lithotypes of this belt. Both igneous associations were affected by high-grade metamorphism and tectonism at ca. 0.76 Ga, which partially disrupted the original igneous stratigraphy of the layered complexes and volcano-sedimentary sequences. The present configuration of this belt results from later events, probably caused by final ocean closure and continental collision between the São Francisco and Amazonian continents at ca. 0.63 Ga.     

赣南中侏罗世流纹岩地球化学及成因研究：上地壳成因的的微量元素和Pb-Nd-Sr同位素地球化学制约

江西南部龙南-寻邬地区余田群菖蒲组的流纹岩形成于中侏罗世(164．8．1Ma～174．9Ma)，为双峰式火山岩组合的酸性端元，属弱过铝质(ACNK平均为1．04)钙碱性系列(σ平均为1．90)。稀土元素含量高(平均为278．9μg/g)，轻稀土富集(IMH平均为7．94)，Eu亏损中等(δEu平均为0．41)。微量元素以富集Rb，Ba，Th，U，Zr，Y，Pb，而亏损Sr，Nb为特征。Pb，Nd，Sr同位素组成为：(^206Pb/^204Pb)t=17．89～18．58，(^207Pb/^204Pb)t=15．58～15．70，(^208Pb/^204Pb)t=37．94～38．82；εNd(t)=-7．44～-11．9；ISr=0．71126～0．71228。对赣南流纹岩微量元素采用蛛网图和模糊聚类分析方法进行对比研究的结果及Pb-Nd-Sr同位素相关特征为其上地壳成因提供了地球化学佐证。赣南流纹岩是由进入上地壳内高位岩浆房的石英拉斑玄武岩浆的底侵作用直接使上地壳部分熔融形成的产物。     

Pb and nd isotope and trace element constraints on the origin of basic rocks in an early proterozoic igneous complex,minnesota

A suite of early Proterozoic basic to granitic rocks exposed near St. Cloud, Minnesota are cut by northeast-trending basaltic dikes. Pb isotope data for all of these rocks overlap and plot about an 1800 Ma PbPb correlation line. The basic rocks, which are light REE enriched, have ϵ_Nd values between +0.4 and −4.8. Petrogenetic considerations suggest that the basic rocks were derived from a light REE enriched source which had an Fe/Mg ratio greater than that for pyrolite. The enrichment in Fe/Mg is probably a result of the addition of basic melts to the source. The light REE enrichment may have a mantle origin by the addition of mantle-derived, light REE enriched basic melts or fluids; or a sedimentary origin by the addition of light REE enriched fluids or melts derived from subducted sediments with an early Proterozoic provenance. In either case, the Nd isotopes suggest that the light REE enriched component existed since c. 2300 Ma. The igneous complex may have formed at a convergent margin. An anorthositic gabbro near Mora, has an ϵ_Nd of +5 indicating that it was derived from a mantle source with a history of light REE depletion. This gabbro may have been part of an early Proterozoic ocean crust.     

Hypervelocity collisions into continental crust composed of sediments and an underlying crystalline basement: comparing the Ries (∼24 km) and Chicxulub (∼180 km) impact craters

The Chicxulub and Ries impact craters were excavated from layered continental terrains that were composed of carbonate-bearing sedimentary sequences and underlying crystalline silicate basement materials. The Chicxulub and Ries impact events were sufficiently large to produce complex peak-ring impact craters. The walls of transient craters and excavation cavities, with diameters of 12-16 km for the Ries and 90-100 km for Chicxulub, collapsed to form final crater diameters of ∼24 and ∼180 km, respectively. Debris from both the sedimentary and crystalline layers was ejected during crater formation, but the bulk of the melting occurred at depth, in the silicate basement. The volume of melt and proportion of melt among shock-metamorphosed debris was far larger at Chicxulub, producing a central melt sheet ∼3 km in depth. The central melt sheet was covered with melt-bearing polymict breccias and, at the Ries, similar breccias (crater suevites) filled the central cavity. Also at the Ries (and presumably at Chicxulub), large hill-size megablocks of crystalline basement material were deposited near the transient crater rim. Blocks and megablocks of sedimentary lithologies were ejected into the modification zone between the peak ring and final crater rim, while additional material was slumping inward during crater growth, and buried beneath a fallout deposit of melt-bearing polymict breccias. The melt and surviving clasts in the breccias are dominantly derived from the deeper, basement lithologies. At greater distances, however, the ejecta is dominated by near-surface sedimentary lithologies, large blocks of which landed with such high energy that they scoured and eroded the pre-existing surface. The excavation and ejecta pattern produced lithological and chemical variations with radial distance from the crater centers that evolve from basement components near the crater centers to sedimentary components far from the crater centers. In addition, carbonate (and anhydrite in the case of Chicxulub) was vaporized, producing environmentally active gases. The vaporized volume produced by the Ries impact event was too small to dramatically alter the evolution of life, but the vaporized volume produced by the Chicxulub impact event is probably a key factor in the Cretaceous-Tertiary boundary mass extinction event.     

Major and trace element, and Sr-Nd isotope constraints on the origin of Paleogene volcanism in South China prior to the South China Sea opening

Paleogene volcanic rocks crop out in three sedimentary basins, namely, Sanshui, Heyuan and Lienping, in the attenuated continental margin of south China. Lavas from the Sanshui basin which erupted during 64-43 Ma are bimodal, consisting of intraplate tholeiitic basalt and trachyte/rhyolite associations. Similar to Cretaceous A-type granites from the nearby region, the felsic member shows peralkaline nature [Na₂O + K₂O ≈ 10–12%; (Na + K)/Al≈ 0.98−1.08], general enrichment in the incompatible trace elements and significant depletion in Ba, Sr, Eu, P and Ti. Although both types of the Sanshui lavas have rather uniform Nd isotope compositions [_Nd(T) ≈ +6 to +4]that are comparable to Late Cenozoic basalts around the South China Sea, the felsic rocks possess apparently higher initial Sr isotope ratios (I_Sr up to 0.713) and form a horizontal array to the right in the Nd vs. Sr isotope plot. Closed system differentiation of mantle-derived magmas in a ‘double diffusive’ magma chamber is considered for the bimodal volcanism, in which the trachytes and rhyolites represent A-type melts after extensive crystal fractionation in the upper portion of the chamber. Such A-type melts were later contaminated by small amounts (1–3%) of upper crustal materials during ascent. On the other hand, composition of lavas in the other two basins varies from tholeiitic basalt to andesite. Their Sr and Nd isotope ratios [I_Sr ≈ 0.705 to 0.711; _Nd(T) ≈ +1 to − 5] and generally correlative Nb-Ta depletions suggest a distinct magma chamber process involving fractional crystallization concomitant with assimilation of the country rock. We conclude that these Paleogene volcanic activities resulted from the lithospheric extension in south China that migrated southwards and eventually led to opening of the South China Sea during 30-16 Ma.     

Pt-Re-Os and Sm-Nd isotope and HSE and REE systematics of the 2.7 Ga Belingwe and Abitibi komatiites

High-precision Pt-Re-Os and Sm-Nd isotope and highly siderophile element (HSE) and rare earth element (REE) abundance data are reported for two 2.7 b.y. old komatiite lava flows, Tony’s flow (TN) from the Belingwe greenstone belt, Zimbabwe, and the PH-II flow (PH) from Munro Township in the Abitibi greenstone belt, Canada. The emplaced lavas are calculated to have contained ∼25% (TN) and ∼28% (PH) MgO. These lavas were derived from mantle sources characterized by strong depletions in highly incompatible lithophile trace elements, such as light REE (Ce/Sm_N = 0.64 ± 0.02 (TN) and 0.52 ± 0.01 (PH), ε¹⁴³Nd(T) = +2.9 ± 0.2 in both sources). ¹⁹⁰Pt-¹⁸⁶Os and ¹⁸⁷Re-¹⁸⁷Os isochrons generated for each flow yield ages consistent with respective emplacement ages obtained using other chronometers. The calculated precise initial ¹⁸⁶Os/¹⁸⁸Os = 0.1198318 ± 3 (TN) and 0.1198316 ± 5 (PH) and ¹⁸⁷Os/¹⁸⁸Os = 0.10875 ± 17 (TN) and 0.10873 ± 15 (PH) require time-integrated ¹⁹⁰Pt/¹⁸⁸Os and ¹⁸⁷Re/¹⁸⁸Os of 0.00178 ± 11 and 0.407 ± 8 (TN) and 0.00174 ± 18 and 0.415 ± 5 (PH). These parameters, which by far represent the most precise and accurate estimates of time-integrated Pt/Os and Re/Os of the Archean mantle, are best matched by those of enstatite chondrites. The data also provide evidence for a remarkable similarity in the composition of the sources of these komatiites with respect to both REE and HSE. The calculated absolute HSE abundances in the TN and PH komatiite sources are within or slightly below the range of estimates for the terrestrial Primitive Upper Mantle (PUM). Assuming a chondritic composition of the bulk silicate Earth, the strong depletions in LREE, yet chondritic Re/Os in the komatiite sources are apparently problematic because early Earth processes capable of fractionating the LREE might also be expected to fractionate Re/Os. This apparent discrepancy could be reconciled via a two-stage model, whereby the moderate LREE depletion in the sources of the komatiites initially occurred within the first 100 Ma of Earth’s history as a result of either global magma ocean differentiation or extraction and subsequent long-term isolation of early crust, whereas HSE were largely added subsequently via late accretion. The komatiite formation, preceded by derivation of basaltic magmas, was a result of second-stage, large-degree dynamic melting in mantle plumes.     

Correlated microanalysis of zircon: Trace element, δO, and U-Th-Pb isotopic constraints on the igneous origin of complex >3900 Ma detrital grains

The origins of >3900 Ma detrital zircons from Western Australia are controversial, in part due to their complexity and long geologic histories. Conflicting interpretations for the genesis of these zircons propose magmatic, hydrothermal, or metamorphic origins. To test the hypothesis that these zircons preserve magmatic compositions, trace elements [rare earth elements (REE), Y, P, Th, U] were analyzed by ion microprobe from a suite of >3900 Ma zircons from Jack Hills, Western Australia, and include some of the oldest detrital zircons known (4400-4300 Ma). The same ∼20 μm domains previously characterized for U/Pb age, oxygen isotope composition (δ¹⁸O), and cathodoluminescence (CL) zoning were specifically targeted for analysis. The zircons are classified into two types based on the light-REE (LREE) composition of the domain analyzed. Zircons with Type 1 domains form the largest group (37 of 42), consisting of grains that preserve evolved REE compositions typical of igneous zircon from crustal rocks. Grains with Type 1 domains display a wide range of CL zoning patterns, yield nearly concordant U/Pb ages from 4400 to 3900 Ma, and preserve a narrow range of δ¹⁸O values from 4.7‰ to 7.3‰ that overlap or are slightly elevated relative to mantle oxygen isotope composition. Type 1 domains are interpreted to preserve magmatic compositions. Type 2 domains occur in six zircons that contain spots with enriched light-REE (LREE) compositions, here defined as having chondrite normalized values of La_N > 1 and Pr_N > 10. A subset of analyses in Type 2 domains appear to result from incorporation of sub-surface mineral inclusions in the analysis volume, as evidenced by positively correlated secondary ion beam intensities for LREE, P, and Y, which are anti-correlated to Si, although not all Type 2 analyses show these features. The LREE enrichment also occurs in areas with discordant U/Pb ages and/or high Th/U ratios, and is apparently associated with past or present radiation damage. The enrichment is not attributed to hydrothermal alteration, however, as oxygen isotope ratios in Type 2 domains overlap with magmatic values of Type 1 domains, and do not appear re-set as might be expected from dissolution or ion-exchange processes operating at variable temperatures. Thus, REE compositions in Type 2 domains where mineral inclusions are not suspected are best interpreted to result from localized enrichment of LREE in areas with past or present radiation damage, and with a very low fluid/rock ratio. Correlated in situ analyses allow magmatic compositions in these complex zircons to be distinguished from the effects of secondary processes. These results are additional evidence for preservation of magmatic compositions in Jack Hills zircons, and demonstrate the benefits of detailed imaging in studies of complicated detrital zircons of unknown origin. The data reported here support previous interpretations that the majority of >3900 Ma zircons from the Jack Hills have an origin in evolved granitic melts, and are evidence for the existence of continental crust very early in Earth’s history.     

Hf-Pb isotope and trace element constraints on the origin of the Jacupiranga Complex (Brazil): Insights into carbonatite genesis and multi-stage metasomatism of the lithospheric mantle

The Lower Cretaceous Jacupiranga complex, in the central-southeastern portion of the South American Platform, includes carbonatites in close association with silicate rocks (i.e. strongly and mildly silica-undersaturated series). Here we document the first hafnium isotope data on the Jacupiranga complex, together with new trace element and Pb isotope compositions. Even though liquid immiscibility from a carbonated silicate melt has been proposed for the genesis of several Brazilian carbonatites, isotopic and geochemical (e.g., Ba/La ratios, lack of pronounced Zr-Hf and Nb-Ta decoupling) information argues against a petrogenetic relationship between Jacupiranga carbonatites and their associated silicate rocks. Thus, an origin by direct partial melting of the mantle is considered. The isotopic compositions of the investigated silicate samples are coherent with a heterogeneously enriched subcontinental lithospheric mantle (SCLM) source of rather complex evolution. At least two metasomatic processes are constrained: (1) a first enrichment event, presumably derived from slab-related fluids introduced into the SCLM during Neoproterozoic times, as indicated by consistently old T_DM ages and lamprophyre trace signatures, and (2) a Mesozoic carbonatite metasomatism episode of sub-lithospheric origin, as suggested by εNd-εHf values inside the width of the terrestrial array. The Jacupiranga parental magmas might thus derive by partial melting of distinct generations of metasomatic vein assemblages that were hybridized with garnet peridotite wall-rocks.     

A Metamorphosed, Early Archaean Chromitite from West Greenland: Implications for the Genesis of Archaean Anorthositic Chromitites

An early Archaean (>3·81 Ga) chromitite–ultramaficlayered body from the Ujaragssuit nunât area, west Greenland,may represent the Earth’s oldest chromitite. The layeredbody occurs as a large xenolith (800 m x 100 m) entrained withintonalitic gneisses and preserves primary igneous layering andtextures. New Re–Os and Pb–Pb isotope results supportthe view that it has been metamorphosed twice, in the earlyand late Archaean at 3·75 Ga and 2·8 Ga. Mineralchemistry and textures indicate that the chromite compositionspreserve two different evolutionary trends. There is a mainmagmatic trend in which Cr/(Cr + Al) ratios remain relativelyconstant but in which there is strong enrichment in Fe³⁺, Fe²⁺and Ti with progressive differentiation. This trend is a compositeof magmatic-liquidus, magmatic-cooling and subsolidus re-equilibrationprocesses. A second trend is defined by chromites from harzburgitesin the upper part of the layered body. These chromites showmagmatic replacement textures in which Fe-rich chromites arealtered to aluminous chromites. Chromites showing magmatic replacementtextures are thought to have formed by reaction with a late,interstitial melt during the solidification of the layered body.The close association between the Fe³⁺–Cr-chromites ofthe main trend and Al-rich chromites of the type found in otherArchaean megacrystic anorthosites suggest a magmatic-geneticrelationship between the two types of chromite. We propose thatanorthositic chromites form in an Fe-rich basaltic melt derivedfrom a komatiitic, boninitic or basaltic parent magma throughreaction between the melt and early-formed Fe-rich chromite. KEY WORDS: chromite; anorthosite; Archaean; Greenland; Re–Os     

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

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 (REY_SN) exhibit positive La_SN, Gd_SN, and Y_SN 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.     

Anthropogenic versus natural control on trace element and Sr-Nd-Pb isotope stratigraphy in peat sediments of southeast Florida (USA), ∼1500 AD to present

Analysis of a well-dated peat core from Blue Cypress Marsh (BCM) provides a detailed record of natural and anthropogenic factors that controlled the geochemical cycles of a number of trace elements in Florida over the last five centuries. The trace elements were divided into “natural” and “anthropogenic” groups using concentration trends from the bottom to the top of the core. The “natural” group includes Li, Sc, Cr, Co, Ga, Ge, Zr, Nb, Cs, Ba, Hf, Y, Ta, Th, and REE (Rare Earth Elements). These elements show similar concentrations throughout the core, indicating that changes in human activities after European arrival in the “New World” did not affect their geochemical cycles. The “anthropogenic” group includes Pb, Cu, Zn, V, Sb, Sn, Bi, and Cd. Upcore enrichment of these elements indicates enhancement by anthropogenic activities. From the early 1500s to present, fluxes of the “anthropogenic” metals to the marsh increased significantly, with modern accumulation rates several-fold (e.g., V) to hundreds of times (e.g., Zn) greater than pre-colonial rates. The dominant input mechanism for trace elements from both groups to the marsh has been atmospheric deposition. Atmospheric input of a number of the elements, including the anthropogenic metals, was dominated by local sources during the last century. For several elements, long-distant transport may be important. For instance, REE and Nd isotopes provide evidence for long-range atmospheric transport dominated by Saharan dust.The greatest increase in flux of the “anthropogenic” metals occurred during the 20th century and was caused by changes in the chemical composition of atmospheric deposition entering the marsh. Increased atmospheric inputs were a consequence of several anthropogenic activities, including fossil fuel combustion (coal and oil), agricultural activities, and quarrying and mining operations. Pb and V exhibit similar trends, with peak accumulation rates in 1970. The principal anthropogenic source of V is oil combustion. The decline in V accumulation after 1970 in the BCM peat corresponds to the introduction of low-sulfur fuels and the change from heavy to distilled oils since the 1970s. After the 1920s, Pb distribution in the peat follows closely the history of alkyl lead consumption in the US, which peaked in the 1970s. Pb isotopes support this inference and furthermore, record changes in the ore sources used to produce leaded gasoline. Idaho ores dominated the peat Pb isotope record until the 1960s, followed by Pb from Mississippi Valley Type deposits from the 1960s to the 1980s. Enhanced fluxes of Cu, Zn, Cd, Sn, Sb, Bi, and to some extent Ni during the last century are likely also related to fossil fuel combustion. Local agricultural activities may also have influenced the geochemical cycles of Cu and Zn. The peat record shows enhanced U accumulation during the last century, possibly related to phosphate mining in western Florida. Sr isotopes in the peat core also reflect anthropogenic influence. The ⁸⁷Sr/⁸⁶Sr ratio decreases from natural background values in the basal part of the core to lower values in the upper part of the core. The Sr isotope shift is probably related to quarrying operations in Florida, and marks the first time an anthropogenic signal has been detected using the Sr isotope record in a peat core.     

Geochemistry of Late Mesozoic mafic dykes in western Fujian Province of China： Sr-Nd isotope and trace element constraints

The Bancun diabase dyke and the Bali hornblende gabbro dyke in western Fujian Province were emplaced in the Early and Late Cretaceous periods, respectively; the former is designated to calc-alkaline series and the latter to K-high-calc-alkaline rock series. Both the dykes are characterized by such geochemical characteristics as high Al and Na2O>K2O. As for the Bancun dyke, Al2O3=16.32%–17.54% and K2O/Na2O=0.65–0.77; as for the Bali dyke, Al2O3=16.89%–17.81% and K2O/Na2O=0.93–0.99. Both the Bancun and Bali mafic dykes are relatively enriched in LILE and LREE, but depleted in HSFE, displaying the geochemical characteristics of continental marginal arc, with high initial Sr isotopic ratios and low εNd (t) values. The (87Sr/86Sr)i ratios of the Bancun diabase dyke are within the range of 0.708556–0.70903 and their εNd (t) values vary between -6.8 and -6.3; those of the Bali hornblende dyke are within the range of 0.710726–0.710746 and their εNd (t) values are -4.7– -4.9, showing the characteristics of enriched mantle EM II. The isotope and trace element data showed that the mafic dykes have not experienced obvious crustal contamination, and metasomatism caused by subduction fluids is the main factor leading to LILE and LREE enrichments. The enriched mantle is the source region for the mafic dykes, and mixing of subduction fluid metasomatized enriched mantle and EM II-type mantle constituted the mantle source region of both the Bancun and Bali mafic dykes. Upwelling of the asthenosphere mantle provided sufficient heat energy for the generation of magmas. In accordance with the discrimination diagram of their tectonic settings as well as their trace element geochemical characteristics, it is considered that the dykes both at Bancun and Bali possess the characteristics of continental marginal arc, revealing the tectonic environment of formation of the mafic dykes, the continental dynamic background as an intraplate tensional belt in which the mafic dykes were emplaced. Meanwhile, it is also indicated that the tensional tectonic stress mechanism is responsible for the formation of the mafic dykes in western Fujian Province.     

Coupled trace element and SIMS sulfur isotope geochemistry of sedimentary pyrite:Implications on pyrite growth of Caixiashan Pb-Zn deposit

Colloform pyrite with core-rim texture is commonly deposited in carbonate platforms associated with the sulfide ores such as the Caixiashan Pb-Zn deposit.However,the genesis of colloform pyrite in Pb-Zn deposits,its growth controls and their geological implication are insufficiently understood.Integration of in-situ trace element and SIMS sulfur isotopes has revealed geochemical variations among these pyrite layers.These colloform pyrite occur as residual phases of core-rim aggregates,the cores are made up of very fine-grained anhedral pyrite particles,with some rims being made up of fine-grained and poorlycrystallized pyrite,while the other rims were featured with euhedral cubic pyrite.which are cemented by fine-grained calcite and/or dolomite with minor quartz.Sulfur isotope analysis shows that some wellpreserved rims have negative δ~(34)S values(-28.12‰to-0.49‰),whereas most of the cores and rims have positive δ~(34)S values(0 to+44.28‰;peak at+14.91‰).Integrating with the methane and sulfate were observed in previous fluid inclusion study,we suggest that the ~(34)S depleted rims were initially formed by bacteria sulfate reduction(BSR),whereas the positive δ~(34)S values were resulted from the sulfate reduction driven by anaerobic methane oxidation(AOM).The well-developed authigenic pyrite and calcite may also support the reaction of AOM.Combined with petrographic observations,trace element composition of the colloform pyrite reveals the incorporation and precipitation behavior of those high abundance elements in the pyrite:Pb and Zn were present as mineral inclusion and likely precipitated before Fe,as supported by the time-resolved Pb-Zn signal spikes in most of the analyzed pyrite grains.Other metals,such as Hg,Co and Ni,may have migrated as chloride complexes and entered the pyrite lattice.Arsenic and Sb,generally influenced by complex-forming reactions rather than substitution ones,could also enter the pyrite lattice,or slightly predate the precipitation of colloform pyrite as mineral inclusions,which are controlled by their hydrolysis constant in the ore fluids.The colloform pyrite may have grown inward from the rims.The successive BSR reaction process would enrich H_2~(32)S in the overlying water column but reduce the metal content,the nucleation of these pyrite rims was featured by strongly negative sulfur isotopes.The following AOM process should be activated by deformation like the turbidity sediment of the mudstone as the sulfide deposition are associated with fault activities that caused the emission of methane migration upward and simultaneously replenishing the metal in the column.The higher AOM reaction rate and the higher metal supply(not only Fe.but with minor other metals such as Pb and Zn) caused by sediment movement enhanced the metal concentration within the pyrite lattice.     

Carbon–oxygen isotope and trace element constraints on how fluids percolate faulted limestones from the San Andreas Fault system: partitioning of fluid sources and pathways

Understanding the way fluids flow in fault zones is of prime importance to develop correct models of earthquake mechanics, especially in the case of the abnormally weak San Andreas Fault (SAF) system. Because fluid flow can leave detectable signatures in rocks, geochemistry is essential to bring light on this topic. The present detailed study combines, for the first time, C–O isotope analyses with a comprehensive trace element data set to examine the geometry of fluid flow within a significant fault system hosted by a carbonate sequence, from a single locality across the Little Pine Fault–SAF system. Such a fault zone contains veins, deformation zones, and their host rocks. Stable isotope geochemistry is used to establish a relative scale of integrated fluid–rock ratios. Carbonate δ¹⁸O varies between 28‰ and 15‰ and δ¹³C between 5‰ and −7‰. From highest to lowest delta values, thus from least to most infiltrated, are the host rocks, the vein fillings, and the deformation zone fillings, respectively. Infiltration increases toward fault core. The fluids are H₂O–CO₂ mixtures. Two fluid sources, one internal and the other external, are found. The external fluid is inferred to come essentially from metamorphism of the Franciscan formation underneath. The internal (local) fluid is provided by a 30% volume reduction of the host limestones resulting from pressure solution and pore size reduction. Most trace elements, including the lanthanides, show enrichment at the 100-m scale in host carbonate rocks as fluid–rock ratios increase toward the fault core. In contrast, the same trace element concentrations are low, relative to host rocks, in veins and deformation zone carbonate fillings, and this difference in concentration increases as fluid–rock ratio increases toward the fault core. We suggest that the fluid trace elements are scavenged by complexation with organic matter in the host rocks. Elemental complexation is especially illustrated by large fractionation of Y–Ho and Nb–Ta geochemical pairs. Complexation associated with external fluid flow has a significant effect on trace element enrichment (up to 700% relative enrichment) while concentration by pressure solution associated with volume decrease of host rocks has a more limited effect (up to 40% relative enrichment). Our observations from the millimeter to the kilometer scale call for the partitioning of fluid sources and pathways, and for a mixed focused–pervasive fluid flow mechanism. The fluid mainly flows within veins and deformation zones and, simultaneously, within at least 10 cm from these channels, part of the fluid flows pervasively in the host rock, which controls the fluid composition. Scavenging of the fluid rare earth elements (REE) by host rocks is responsible for the formation of REE-depleted vein and deformation zone carbonate fillings. Fluid flow is not only restricted to veins or deformation zones as commonly believed. An important part of fluid flow takes place in host rocks near fault zones. Hence, the nature of the lithologies hosting fault zones must be considered in order to take into account the role of fluids in the seismic cycle.     

Experimental study and modeling of fluid reaction paths in the quartz-kyanite ± muscovite-water system at 0.7 GPa in the 350-550 °C range: Implications for Al selective transfer during metamorphism

In order to quantify Al transfer in response to fluid-mineral equilibration under evolving metamorphic conditions, isobaric (0.7 GPa) experiments were conducted in the 350-550 °C range. Disequilibrium was induced (1) by holding initially pure water and natural minerals (kyanite + quartz ± muscovite enclosed in a perforated inner capsule) under isothermal conditions and (2) by stepwise temperature variations. In all experiments, secondary Al-bearing phases crystallized in the external tube of a “tube-in-tube” setup (SEM characterization); they are interpreted as witnesses of the evolution of the fluid composition (fluid reaction path). These reaction paths and the subsequent amount of secondary crystallizations were modeled using thermodynamic data from SUPCRT92 and estimates of both starting-mineral dissolution rates and elemental diffusion coefficients from the literature. A major result is that the amount of aluminum transferred to secondary phases is a thousand times larger than the calculated Al concentration in the fluid. Although the crystallization of Al-bearing phases was expected as a response to a temperature decrease, the stepwise temperature increase (20 °C/day) also led to aluminum transfer towards secondary phases. In the course of re-equilibration, the fluid first becomes saturated with respect to aluminosilicates and then reaches silica saturation, due to the low solubility of Al-minerals. Consequently, aluminosilicates partly recrystallize in response to a temperature increase. Crystallization of secondary Al-phases in the external tube implies that aqueous aluminum was efficiently transported from the inner capsule, even in the pure Al₂O₃-SiO₂-H₂O system. Therefore, mass balance calculations considering a constant Al reference frame, i.e., postulating Al immobility, should be regarded with caution.