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Post-GOE deep-water Fe-Si precipitates associated with volcanogenic massive sulfide deposits are an important feature of the Proterozoic rock record. Although it is clear that these enigmatic deposits formed in oxygen-deficient and hydrothermally influenced deep-water settings, the oxidation mechanism(s) resulting in their precipitation remain(s) unclear. Whilst existing genetic models typically couple direct and/or bacterially-mediated iron oxidation with abiotic silica precipitation, low temperature diffuse hydrothermal fluids offer a potential mechanistic alternative to explain the observed layering. Herein, via combination of petrographic observations with elemental and isotopic data (Fe, Si, and O), we explore the genesis of the primary mineral phases present within recent Fe-Si precipitates obtained from the Southwest Indian Ridge. Formation of ferrihydrite and opal-A in these precipitates provides insight into the genesis of widely invoked precursor minerals to post-GOE deep-water Fe-Si precipitates. Specifically, we find that the mineralogical layers that typify these Fe-Si precipitates may have originated via biologically mediated ferrihydrite precipitation and abiotic precipitation of opal-A from oversaturated fluids during diffuse flow. By analogy, we propose that diffuse hydrothermal fluid flow played an important role in the formation of post-GOE deep-water Fe-Si precipitates.

Stable thallium (Tl) isotope data from organic-rich siliciclastic sedimentary rocks have the potential to track ocean redox state on a broad scale. Here, we report new Tl isotope data from the Mesoproterozoic Velkerri Formation (Roper Group) and the Paleoproterozoic Wollogorang Formation (Tawallah Group), McArthur Basin, Northern Territory, Australia, and interpret these in the context of rhenium-osmium (Re-Os) geochronometry on the same sample suite. Previous work has shown that marine black shales from the Velkerri Formation provide evidence for closed-system Re-Os systematics, yielding a precise isochron with an age of 1361 ± 21 Ma that agrees well with independent age constraints for the unit. The isotopic composition of authigenic Tl in euxinic black shales from the upper Velkerri Formation (e205Tl = −2.4 ± 0.8, 2SD) indicates that the Tl isotope composition of local seawater at 1.36 Ga was within a plausible range for Tl inputs to the ocean. Isotope mass-balance modeling of the Tl isotope system within a Monte Carlo framework suggests that the Tl isotopic composition of seawater at 1.36 Ga was homogenous on a global scale and that the burial of Mn-oxides exerted minimal isotopic leverage on the Tl isotope composition of seawater at 1.36 Ga. Taken together with existing Mo, Cr, and U isotope data from the same samples, these observations are consistent with a low-O2 ocean-atmosphere system during this period of the Mesoproterozoic. Previous work has shown that the Re-Os systematics of black shales from the older (1.73 Ga) Wollogorang Formation are scattered and yield an erroneously young isochron age of 1359 ± 150 Ma, which has been attributed to post-depositional hydrothermal alteration at ∼1640 Ma. We observe no systematic relationship between stable Tl isotope compositions and the extent of alteration as gauged by open-system Re-Os behavior (−4.7 ± 1.4 for the upper Wollogorang Formation and −4.8 ± 0.4 for the lower Wollogorang Formation), in marked contrast to previous observations for the molybdenum (Mo) and uranium (U) isotope systems. The invariant signature of the Tl isotope data suggests the Tl isotope system was largely unperturbed during hydrothermal alteration. However, it remains difficult to definitively rule out the possibility that authigenic Tl isotope signatures have been overprinted by later localized hydrothermal fluid alteration in the Wollogorang Formation shales. These observations highlight the potential insights afforded by evaluating open-system behavior via radiogenic isotope systems together with other stable isotope tracers in efforts to reconstruct the redox landscape of Earth’s oceans over time.

Osmium isotopes, whole rock and mineral geochemical data from peridotite xenoliths from two Miocene McMurdo Volcanic Group cinder cones in the Transantarctic Mountains (TAM) in Southern Victoria Land, Antarctica, reveal that the underlying mantle preserves evidence for major mid-Proterozoic lithosphere formation despite the crust being dominated by late Neoproterozoic-Ordovician (~0.65–0.47 Ga) rocks. The Hooper Crags xenolith suite is dominated by harzburgites with highly refractory olivine Mg# (up to 92.3) and depleted bulk rock major and platinum group element + Re abundances, with 187Os/188Os ratios indicating depletion in the mid-Proterozoic. Pipecleaner Glacier xenoliths, 18 km distant, are lherzolites with olivine Mg# ( 250 km) East Antarctic Craton lithosphere shielding the immediately adjacent circum-cratonic mantle from being affected by convective asthenosphere-driven erosion. This contrasts with mantle lithosphere accreted distally to the East Antarctic Craton (represented by the now-detached Zealandia continent), which did not attain extreme thickness and has therefore been more susceptible to tectonic reworking and lateral translation.

The scavenging of dissolved trace metals such as chromium (Cr), molybdenum (Mo) and tungsten (W) and their authigenic enrichment in sedimentary archives mainly occur by particle shuttling that cause resolvable isotope fractionation. Because their scavenging is also dependent on the local marine redox potential and the overall marine chemical environment, the stable isotope composition of these elements in Archean sediments is widely used as paleoredox proxy. Tungsten, a new element in this tool box, is dissolved as the oxyanion tungstate (WO42−) at extremely low marine redox potentials and can thus help to reconstruct the earliest changes in the marine redox state. We tested the applicability of stable W isotopes as a new paleoredox proxy of the atmosphere–ocean system. We analyzed the δ186/184W of Precambrian igneous rocks to investigate the detrital background δ186/184W signature. This Precambrian igneous inventory (PII) shows δ186/184W values between −0.007 and +0.097‰, identical to the range of modern igneous crustal rocks, which indicates that the average Earth’s crust δ186/184W remained constant over billions of years. Furthermore, we present δ186/184W values of euxinic sediments from the Black Sea as a modern sedimentary analog, which we then compare with δ186/184W data of Archean and Proterozoic black shales (3.47–2.3 Ga). Modern Black Sea sapropels reveal crustal-like δ186/184W values between +0.050 and +0.071‰ suggesting limited authigenic enrichment of W in euxinic environments. Similarly, post-Great Oxidation Event shales (2.3 Ga) show crustal- or PII-like δ186/184W values indicating the deposition in euxinic or oxic environment. However, the Archean shale sample suites show elevated W concentrations and fractionated δ186/184W values up to +0.246‰, which we attribute to authigenic enrichment of heavy seawater W in a ferruginous setting. Thus, black shales δ186/184W values can help to distinguish between anoxic-ferruginous and euxinic depositional environments. Furthermore, we combine previously published Cr and Mo isotope data with new Cr and W isotope data to quantify the evolution of the marine redox state during the Archean. By combining the Eh-pH stability fields of W and Mo with the δ186/184W and δ98/95Mo values of Precambrian sediments, we suggest a 3-step evolution of the Precambrian ocean. (1) From 3.47 to 3.0 Ga, the Eh of a dominantly ferruginous ocean was between −0.4 V and −0.25 V, enabling the persistence of soluble WO42− but not MoO42− and thus only the authigenic enrichment of isotopically fractionated W. (2) Starting from 3.0 Ga, the Eh of some shallow-marine environments increased above −0.25 V, as indicated by δ98/95Mo values above the detrital background in shallow-marine sediments, while the Eh of the deep ocean still remained below −0.25 V indicated by the lack of authigenic Mo enrichment and fractionated δ98/95Mo values in deep-sea shales. (3) After 2.7 Ga elevated δ98/95Mo and δ186/184W values in deep-marine sediments suggest that the Eh of the ferruginous open-ocean now also increased above −0.25 V. We therefore suggest that the combination of δ98/95Mo and δ186/184W values of shales is a very promising tool to investigate earliest changes in marine redox conditions during the Archean.

The Archean-Proterozoic transition marks a time of fundamental geologic, biologic, and atmospheric changes to the Earth system, including oxygenation of the atmosphere (termed the Great Oxygenation Event; GOE), and the emergence of continents above sea level. The impacts of the GOE on Earth’s surface environment are imprinted on the geologic record, including the disappearance of mass-independent fractionation of sulfur isotopes (S-MIF). Temporally overlapping geologic and geochemical observations (e.g. a change in oxygen isotope ratio of sediments and an increase in subaerial volcanism) imply the widespread subaerial emergence of continents was coeval with atmospheric oxygenation. Here we present triple sulfur isotope ratios in pyrite and oxygen isotope ratios in garnet and zircon in a global suite of Archean and Proterozoic granitoids derived from the partial melting of sedimentary protoliths. These crustal melts record an increase in average garnet and zircon δ18O from 7.2‰ before 2.3 Ga to 10.0‰ post-2.3 Ga. Pre-2.3 Ga granitoids show small S-MIF signatures with Δ33S ranging from −0.29‰ to 0.13‰, whereas post-2.3 Ga granitoids record S-MDF (i.e. Δ33S = 0‰). The combination of sulfur and oxygen isotope signatures in the same sample with zircon U-Pb geochronology provides new insights on a potential causal link between the emergence of continents and Paleoproterozoic atmospheric oxygenation.

The Proterozoic rock record displays secular change from ferruginous to an oxic hydrosphere over the course of 2 billion years; however, debate continues on the periodicity, rate of change and steps in following atmospheric oxygenation that ultimately led to an oxygenated ocean. This is partly due to poor preservation of the Paleoproterozoic marine sedimentary record in the few hundred million years after the Great Oxidation Event. Whereas the 2.0 Ga rock record preserves only rare chemical sediments, it contains significant mafic igneous provinces, which are known to locally host volcanogenic massive sulfide (VMS) deposits. These hydrothermal environments fossilize the ancient interaction at the seafloor interface between volcanic rocks and seawater. In this context, the 2.01 Ga Degrussa VMS deposit of the Paleoproterozoic Capricorn Orogen, Western Australia offers an opportunity to probe the ancient ocean composition. The Degrussa VMS deposit preserves massive sulfide mineralisation (pyrite – chalcopyrite – pyrrhotite ± sphalerite ± galena) hosted in turbiditic sedimentary rocks interlayered with basaltic flows and cut by numerous gabbroic sills. Exhalite layers are composed of hematite and jasper associated with magnetite. This study documents the multiple sulfur isotope composition of the Degrussa VMS deposit through an integrated analytical approach, which comprises bulk fluorination gas chromatography isotope ratio mass spectrometry and in situ secondary ion mass spectrometry. By comparing the ultra-high precision bulk measurements (n = 21) with in situ measurements of variably-textured grains of pyrite, chalcopyrite and pyrrhotite (n = 252), we determine that VMS mineralisation yields δ34S between +2‰ and +5‰ with a peak at ∼+2.9‰, and negative Δ33S signal ranging from −0.08 to 0.00‰. A two component δ34S-Δ33S mixing model indicates 11% of H2S derived from thermochemically reduced seawater sulfate mixed with magmatic H2S. The most negative Δ33S values must be explained by interaction with sulfate in the near-surface, undergoing complex dissolution-reprecipitation reactions, necessitating a minimum seawater sulfate reservoir of ∼2 mmol/L, or 7% modern seawater at 2.01 Ga.

The sedimentary Mo and U isotope systems have been commonly used as novel global ocean redox tracers due to their long oceanic residence times and redox-sensitive behavior. However, local sedimentary environments and global ocean redox conditions both influence the Mo and U isotope compositions of euxinic organic-rich mudrocks (ORM). Here, we further develop the coupled use of Mo and U isotope data from euxinic ORM to more robustly infer coeval global ocean redox conditions. We measured δ238U from eight late Neoproterozoic to middle Paleozoic ORM units that have previously reported Mo isotope and Fe speciation data. Integration of our new data with previously published Proterozoic and Phanerozoic Mo and U isotope data reveals that there is no overall correlation between the Mo and U isotope compositions of euxinic ORM. This observation confirms that the extent to which local versus global environments influenced the preserved Mo and U isotope compositions in ORM was variable. Individual ORM units can have negative, positive, or no correlation between δ98Mo and δ238U. A negative correlation between δ98Mo and δ238U in the Upper Devonian Kettle Point Formation is similar to the observations from modern euxinic basins, reflecting a major control on the Mo-U isotope systematics by changes in the local depositional environment, such as bottom-water sulfide concentrations. A positive correlation between δ98Mo and δ238U observed in the Upper Ordovician Fjacka Shale is best explained by changes in global ocean redox conditions that simultaneously shifted the Mo and U isotope compositions of the global seawater and the Fjacka Shale ORMs in the same direction. No correlations between δ98Mo and δ238U for euxinic ORM may be caused by specific local depositional changes, a lack of or a combination of local and global environmental changes, and/or is an artifact of limited data. For example, a vertical trend (variable δ98Mo but similar δ238U) is shown by most samples from Member IV of the Ediacaran Doushantuo Formation, implying a strong influence on the Mo isotope data by an Fe-Mn particulate shuttle. A horizontal trend (similar δ98Mo but variable δ238U) is observed from the Paleoproterozoic Zaonega Formation, implying that relatively constant bottom water sulfide concentrations caused similar magnitudes of Mo isotope fractionations whereas other factors (e.g., U reduction pathways, aqueous U species, productivity) were responsible for variable U isotope fractionations. Relatively constant elemental concentrations and isotope compositions from the Tanezzuft Formation are indicative of stable conditions at local and global scales. We further propose a method to estimate the coeval seawater Mo and U isotope compositions based on a coupled Mo-U isotope mass balance model and the observations from modern euxinic basins. The coupled Mo-U isotope data from euxinic ORMs provide more insights on the local and global environmental controls on the preservation of both isotope systems than previously realized. Our study highlights the importance of examining the local depositional environment and using large datasets of coupled Mo-U isotope compositions from euxinic ORM intervals to reconstruct paleocean redox conditions.

The Paleoproterozoic Barney Creek Formation, which is currently interpreted as a restricted, deep marine paleoenvironment, plays a disproportionate role in our understanding of Proterozoic ocean chemistry and the rise of complex life. The Barney Creek Formation hosts several unusual biomarker features, specifically its methylhopane and carotenoid signatures. Herein, we demonstrate that the saline lacustrine Eocene Green River Formation shares a similar distribution of methylhopanes and carotenoids, which is characteristic of saline lacustrine organic matter more generally. These distinct methylhopane and carotenoid patterns are not observed together in marine organic matter of any geologic age. These results imply a saline lacustrine depositional environment for the Barney Creek Formation, which agrees with earlier but now abandoned depositional models of this formation. As a result, models of Proterozoic ocean chemistry and emergence of complex life that rely on a marine Barney Creek Formation should be reexamined. Alternatively, if Paleoproterozoic marine biomarker signatures resemble those of younger saline lacustrine systems, then this must be recognized to accurately interpret geologic biomarker and paleoenvironmental records.

International audience; The eastern part of Asia between the North China and Siberian cratons contains orogenic belts formed by the Paleo-Asian and Pacific subduction and older continental blocks. A fundamental question regarding these and all mobile belts is the fate of the continental lithospheric mantle (CLM) during their formation, i.e. whether, or to what extent the CLM may be formed, replaced or affected during orogeny. Insights into these processes can be obtained from mantle xenoliths hosted by Cenozoic basalts in the Proterozoic Khanka block in the far eastern Russia between NE China and the Pacific coast of Asia. We report petrographic, chemical, and Os-Sr-Nd isotope data for spinel peridotite xenoliths at two Khanka sites: Sviyagin and Podgelban. The modal abundances and chemical compositions suggest that the peridotites are residues of low to moderate degrees of melt extraction from fertile mantle. They show an 187Os/188Os vs. 187Re/188Os correlation with an apparent 1.9 Ga age; the 187Os/188Os ratios are positively correlated with Al2O3 and other melt extraction indices. These results provide the first robust CLM age constraints for the eastern Central Asian Orogenic Belt (CAOB). The ages suggest that the ancient CLM of the Khanka block may be roughly coeval with reworked CLM at Hannuoba (North China craton), and that it persisted through the Phanerozoic orogenies. Moreover, despite the proximity to Phanerozoic subduction zones, the Khanka CLM shows little post-melting enrichment, e.g. the clinopyroxenes are typically LREE-depleted and have Sr-Nd isotope ratios typical of the MORB mantle. We posit that the metasomatism of the CLM, earlier proposed for North China xenolith suites and ascribed to the effects of Pacific or older subduction and related mantle upwelling, may not be widespread in the CAOB. In general, Proterozoic blocks composed of residual peridotites may be more common in the CLM of the SE Siberia and northern China, and possibly other orogenic belts, than previously thought.

Numerous geologic proxies for Earth system processes track dramatic changes at the atmosphere-lithosphere or atmosphere-ocean interface during the early Paleoproterozoic Era. The presence of a geodynamic driver for these changes and how this might have affected the deeper lithosphere is more cryptic. Here we present temporally constrained δ18O and eHf in detrital zircon from Paleoproterozoic sedimentary successions in Western Australia and Canada that chart a rapid change in the oxygen isotopic composition from

In the Neoproterozoic Era there was widespread deposition of iron formations in close association with global or near glaciations. These ‘Snowball Earth’ glaciations likely played a key role in iron formation distribution and deposition. However, the environmental conditions, Fe sources, and formation mechanisms remain debated. Here we present the rare earth element geochemistry and Fe isotope composition of the synglacial iron formation within the Neoproterozoic Fulu Formation, South China. The Fulu iron formation consists of layers of authigenic minerals (mainly hematite) and detrital components (quartz, feldspars, Fe chlorite, and minor biotite). Positive Eu anomalies in one of the Fulu localities indicate a hydrothermal influence, suggesting that Fe was mainly sourced from distal hydrothermal systems. The bulk-rock Fe isotope composition of the Fulu iron formation shows a large range, with δ56Fe from −0.23 to +1.78‰. Correlation between bulk-rock δ56Fe values and Al/Fe ratios demonstrates that δ56Fe variability reflects, in part, varying proportions of authigenic versus detrital components. The Fe isotope composition of authigenic hematite is calculated by a linear regression and shows δ56Fe between +0.83 and +2.21‰, with an average at +1.54 ± 0.50‰ (2σ, n = 41). Using a dispersion-reaction model, the high δ56Fe values of hematite constrain local dissolved O2 concentrations of the ocean to less than 0.4 nmol/L, even in the shallow part of the water column. This relationship is consistent with highly reducing conditions in the Neoproterozoic oceans favored by isolation from the atmosphere by a sea ice. We attribute the extremely positive values to partial iron oxidation in waters that were cold relative to modern surface oceans. The dominant occurrence of hematite supports an abiotic precipitation pathway, given that biological activity would have introduced organic matter to the sediments and led to partial reduction of Fe(III) oxides and subsequent formation of magnetite and/or siderite, as is observed in Archean and Paleoproterozoic iron formations. Oxic glacial meltwater and/or O2 vertical transfer from the atmosphere to the upper ocean linked to ice dynamics is likely to have mediated the abiotic oxidation. We propose that vertical transfer of O2 resulted from the deposition of snow that trapped air bubbles at the top of the glacier coupled to a melting of the bottom of the glacier, which in combination delivered a limited but continuous amount of O2 to the ocean.

While the mantle roots directly beneath Archean cratons have been relatively well studied because of their economic importance, much less is known about the genesis, age, composition and thickness of the mantle lithosphere beneath the regions that surround the cratons. Despite this knowledge gap, it is fundamentally important to establish the nature of relationships between this circum-cratonic mantle and that beneath the cratons, including the diamond potential of circum-cratonic regions. Here we present mineral and bulk elemental and isotopic compositions for kimberlite-borne mantle xenoliths from the Parry Peninsula and Central Victoria Island, Arctic Canada. These xenoliths provide key windows into the lithospheric mantle underpinning regions to the North and Northwest of the Archean Slave craton, where the presence of cratonic material has been proposed. The mantle xenolith data are supplemented by mineral concentrate data obtained during diamond exploration. The mineral and whole rock chemistry of peridotites from both localities is indistinguishable from that of typical cratonic mantle lithosphere. The cool mantle paleogeotherms defined by mineral thermobarometry reveal that the lithospheric mantle beneath the Parry Peninsula and Central Victoria Island terranes extended well into the diamond stability field at the time of kimberlite eruption, and this is consistent with the recovery of diamonds from both kimberlite fields. Bulk xenolith Se and Te contents, and highly siderophile element (including Os, Ir, Pt, Pd and Re) abundance systematics, plus corresponding depletion ages derived from Re-Os isotope data suggest that the mantle beneath these parts of Arctic Canada formed in the Paleoproterozoic Era, at ∼2 Ga, rather than in the Archean. The presence of a diamondiferous Paleoproterozoic mantle root is part of the growing body of global evidence for diamond generation in mantle roots that stabilized well after the Archean. In the context of regional tectonics, we interpret the highly depleted mantle compositions beneath both studied regions as formed by mantle melting associated with hydrous metasomatism in the major Paleoproterozoic Wopmay-Great Bear-Hottah arc systems. These ∼2 Ga arc systems were subsequently accreted along the margin of the Slave craton to form a craton-like thick lithosphere with diamond potential thereby demonstrating the importance of subduction accretion in building up Earth’s long-lived continental terranes.

The construction of mountain belts by continent-continent collision is a fundamental phase of the supercontinent cycle and an inevitable consequence of subduction-driven plate tectonics on Earth. Yet, quantitative estimation of the rate and duration of prograde orogenic metamorphism in high-grade collisional belts has proven elusive to constrain. Differences in the chemical partitioning and diffusive behavior of elements associated with the 147Sm-143Nd and 176Lu-176Hf isotopic systems in metamorphic garnet can provide valuable insights on the time scales over which this mineral grows and cools in regionally metamorphosed terranes. Here, we present new Sm-Nd and Lu-Hf isotopic results from multiple garnet and whole-rock aliquots from a granulite-grade metasedimentary rock from the Proterozoic Putumayo Orogen of South America. Using a combination of internal isochron dating by these two decay systems, combined with apatite U-Pb dating and pressure-temperature-time (P-T-t) constraints from mineral equilibria and chemical diffusion geospeedometry, we provide first-order insights into the time scales of a Proterozoic continent-continent collisional metamorphic event in Amazonia associated with its incorporation to the Supercontinent Rodinia. Our results indicate that these metasediments attained peak granulite-grade metamorphic conditions of nearly 0.62 GPa and 680 °C at approximately 1035 Ma, and started to cool slowly, presumably during exhumation, at a rate of ∼5 K/Myr. Simple diffusion scaling relationships and numerical modeling of Sm-Nd and Lu-Hf in garnet indicate that, while Sm and Nd were both fully re-equilibrated at peak temperatures and therefore date cooling, Lu and Hf underwent diffusive decoupling due to incomplete Hf re-equilibration. By modeling the impact of this differential re-equilibration in the development of the Sm-Nd and Lu-Hf isochrons, we constraint the duration of the prograde metamorphic path and argue that garnet growth in this sample took place over millions of years—approximately 25 Myr according to our preferred interpretation. The determined apatite U-Pb date vs. grain-size relationship cannot be reconciled with the thermal history described above when modeled using the existing experimental diffusion data, and instead suggest that much slower Pb diffusivities in this mineral compared to those predicted by the existing experimental data may have inhibited its resetting. We note that the inferred temperature-time history for the metamorphic loop of this segment of the Putumayo basement is comparable to that proposed for the metamorphism and exhumation of metasediments in the India-Asia collision zone, suggesting that similar tectonic processes and rates likely operated during the Mesoproterozoic Putumayo orogeny.

The final publication is available at Elsevier via https://doi.org/10.1016/j.gca.2018.01.036 © 2018. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/

Iron isotopes have been widely applied to investigate the redox evolution of Earth’s surface environments. However, it is still unclear whether iron cycling in the water column or during diagenesis represents the major control on the iron isotope composition of sediments and sedimentary rocks. Interpretation of isotopic data in terms of oceanic redox conditions is only possible if water column processes dominate the isotopic composition, whereas redox interpretations are less straightforward if diagenetic iron cycling controls the isotopic composition. In the latter scenario, iron isotope data is more directly related to microbial processes such as dissimilatory iron reduction. Here we present bulk rock iron isotope data from late Proterozoic marine shales from Svalbard, northwestern Canada, and Siberia, to better understand the controls on iron isotope fractionation in late Proterozoic marine environments. Bulk shales span a δ 56Fe range from −0.45 ‰ to +1.04 ‰ . Although δ 56Fe values show significant variation within individual stratigraphic units, their mean value is closer to that of bulk crust and hydrothermal iron in samples post-dating the ca. 717–660 Ma Sturtian glaciation compared to older samples. After correcting for the highly reactive iron content in our samples based on iron speciation data, more than 90% of the calculated δ 56Fe compositions of highly reactive iron falls in the range from ca. −0.8 ‰ to +3 ‰ . An isotope mass-balance model indicates that diagenetic iron cycling can only change the isotopic composition of highly reactive iron by 1 ‰ , suggesting that water column processes, namely the degree of oxidation of the ferrous seawater iron reservoir, control the isotopic composition of highly reactive iron. Considering a long-term decrease in the isotopic composition of the iron source to the dissolved seawater Fe(II) reservoir to be unlikely, we offer two possible explanations for the Neoproterozoic δ 56Fe trend. First, a decreasing supply of Fe(II) to the ferrous seawater iron reservoir could have caused the reservoir to decrease in size, allowing a higher degree of partial oxidation, irrespective of increasing environmental oxygen levels. Alternatively, increasing oxygen levels would have led to a higher proportion of Fe(II) being oxidized, without decreasing the initial size of the ferrous seawater iron pool. We consider the latter explanation as the most likely. According to this hypothesis, the δ 56Fe record reflects the redox evolution of Earth’s surface environments. δ 56Fe values in pre-Sturtian samples significantly heavier than bulk crust and hydrothermal iron imply partial oxidation of a ferrous seawater iron reservoir. In contrast, mean δ 56Fe values closer to that of hydrothermal iron in post-Sturtian shales reflects oxidation of a larger proportion of the ferrous seawater iron reservoir, and by inference, higher environmental oxygen levels. Nevertheless, significant iron isotopic variation in post-Sturtian shales suggest redox heterogeneity and possibly a dominantly anoxic deep ocean, consistent with results from recent studies using iron speciation and redox sensitive trace metals. However, the interpretation of generally increasing environmental oxygen levels after the Sturtian glaciation highlights the need to better understand the sensitivity of different redox proxies to incremental changes in oxygen levels to enable us to reconcile results from different paleoredox proxies.

The Olympic Dam Cu–U–Au–Ag deposit in the Archean–Proterozoic Gawler Craton (South Australia) is a type example of the iron oxide–copper–gold (IOCG) spectrum of deposits and one of the largest Cu–U–Au resources known. Mineralization is hosted in a lithologically and texturally diverse, hematite-rich breccia complex developed within a granite of the 1.59 Ga Gawler Silicic Province. Emerging evidence indicates that both the breccia complex and its metal content developed over ∼1000 Ma, responding to major tectonic events, e.g., at 1300–1100, 825 and 500 Ma. However, metal sources and exact mechanism/s of ore formation remain poorly known. New high-precision 238U/235U data for a set of 40 whole rock samples representing all major lithological facies of the breccia complex show a narrow range (δ238UCRM112a = −0.56‰ to +0.04‰). At the scale of sampling, there is no correlation of δ238U with lithology, degree of alteration or U mineralogy, although ores with U > 5 wt.% have subtly higher δ238U values (−0.20‰ to 0.00) than the majority of samples (5 wt.% U, U/Sm ≫ 500) Olympic Dam ores define a neutron capture line, with correlated depletions in 149Sm (up to ∼2e units) and excesses in 150Sm (up to ∼ 4e units), but fission fragment contributions to Sm are below detection. These observations provide evidence for small-scale neutron-capture effects, with calculated neutron fluences of 1015 to 1016 n cm−2, similar to those observed in several Proterozoic and Phanerozoic U deposits. The apparent lack of fission fragment contributions in Olympic Dam high-grade ores can be explained with an age of U deposition, or re-deposition that is substantially younger than the initial 1.59 Ga age of the oldest IOCG-style mineralization. The results presented here thus (i) suggest uranium sources in common (likely igneous) upper crustal lithologies, (ii) support geochronological evidence for gradual addition of U in several stages over 1000 Ma at elevated temperatures of mineralization, and (iii) do not show the high δ238U signatures expected from low-temperature reworking of older low- δ238U ores.

Many Proterozoic anorthosite massifs show crustal isotopic signatures that have, for decades, fuelled debate regarding the source of these temporally-restricted magmas. Are these signatures indicative of lower crustal melting or of significant assimilation of crustal material into mantle-derived magmas? Traditional whole rock isotopic tracers (Sr, Nd, Pb and Os), like other geochemical, petrological and experimental tools, have failed to identify unambiguously the origins of the crust-like signature and resolve the source controversies for these feldspathic, cumulate intrusives. We make use of high precision Sr, Nd and Pb isotopic compositions of mineral phases (plag, opx, mag) and comagmatic, high-pressure orthopyroxene megacrysts as well as whole rock anorthosites/leuconorites from the Mealy Mountains Intrusive Suite (MMIS) and the Nain Plutonic Suite (NPS) to probe the origin of the crustal isotopic signatures and assess the importance of differentiation at lower crustal depths. This selection of samples represents fragments from various stages of the polybaric ascent of the magmas, while the study of the Mealy Mountains Intrusive Suite and the Nain Plutonic Suite is instructive as each is intruded into crust of significantly different age and isotopic composition. We observe marked differences in the whole-rock isotopic composition of Proterozoic anorthosites and high-pressure megacrysts (e.g. e Nd;T = +2 to −10) intruded into crustal terranes of different ages and isotopic compositions. Evidence for varying degrees of internal isotopic disequilibrium (ΔNd, ΔSr, ΔPb) in anorthosites from these different terranes reinforces the notion that crustal contamination, and more importantly, the nature of the crustal assimilant, has a profound influence on the chemical signature of Proterozoic anorthosites. While most samples from the MMIS and NPS show significant and measurable ΔNd and ΔPb disequilibrium, ΔSr compositions cluster around zero. This decoupling in disequilibrium geometries cannot be explained by melting of the lower crust. Assimilation of crust with distinctive Sr, Nd and Pb isotopic compositions does, however, explain the origin of decoupling in internal mineral isotopic compositions. We also find unexpected patterns of internal isotopic disequilibrium, such as isotopically radiogenic orthopyroxene relative to plagioclase and differences in plagioclase isotopic disequilibrium between orthopyroxene- and olivine-bearing samples. These various lines of evidence provide strong support for the generation of crustal isotopic signatures through assimilation, and not anatexis, of the lower crust. These isotopic data show that anorthosite petrogenesis likely involves significant differentiation and solidification at lower crustal depths, followed by ascent of high-crystallinity bodies (⩾50% crystallinity) to mid- or upper crustal levels. We show that protracted lower crustal differentiation imparts a clear chemical and isotopic signature on mantle-derived magmas of Proterozoic anorthosites and that this process is central in the development of such slowly ascending, plagioclase-rich magmas.

Trace elements are central components of enzymes that catalyze many of the essential reactions mediated by life. The redox sensitive nature of trace elements also permits their use as a record of ancient ocean conditions preserved in the geologic record. Trace element geochemistry in modern stratified systems is often used as a proxy for the redox state of the ancient oceans, which are thought to have been largely anoxic. In the present study, we examined trace element behavior of simultaneously collected samples at a heretofore unprecedented depth resolution (1–0.25 m intervals) throughout the redox-stratified water column of Fayetteville Green Lake, N.Y. (FGL), a 53 m deep meromictic lake under euxinic conditions similar to those thought to have been prevalent in Proterozoic oceans. Among characterized Proterozoic ocean analogs, FGL represents an understudied proxy in terms of trace elements, with characteristics of low salinity and high sulfate. In the FGL water column, spikes in the concentration of dissolved Mn, Fe and Co are coincident with the transition from oxic to euxinic conditions, and are associated with a decrease in dissolved Mo concentration. In contrast, the concentration of dissolved Ni did not vary across this transition despite the dramatic shift in redox state. From these data we present a one dimensional model for element transport and cycling through the water column to the sediments. Collectively, this comprehensive analysis of water column geochemistry provides insight into the effects of biogeochemical cycling in stratified systems on dissolved trace element concentrations in the water column. This study, in concert with characterization of other early Earth analogs, will greatly enhance the use of trace elements in interpreting the geologic record.

Lithium concentrations and isotopic compositions of 38 carbonatites and associated syenites from the Maoniuping, Lizhuang, and Dalucao in western Sichuan, along with previously published and new Pb–Sr–Nd–C–O isotope data and whole-rock analyses, are used to constrain their mantle source and genesis. Carbonatites and syenites are characterized by extremely varying Li concentrations (0.8–120 ppm) and highly variable Li isotopic compositions (−4.5‰ to +10.8‰). Among them, the majority of the carbonatites and syenites have δ7Li values between +0.2‰ and +5.8‰, which overlap with the reported values for MORB and OIB; 3 carbonatites have higher δ7Li values between +8.7‰ and +10.8‰; 5 carbonatites and 4 syenites have lighter δ7Li values between −4.5‰ and −0.3‰. These highly variable δ7Li compositions could not have been produced by diffusive-driven isotopic fractionation of Li and thus may record the isotopic signature of the late Proterozoic subcontinental lithospheric mantle (SCLM). This paper demonstrates the existence of anomalous δ7Li within the late Proterozoic subcontinental lithospheric mantle, suggesting that the ancient SCLM beneath western Sichuan was modified by interaction with fluids derived from the subducted oceanic crust and marine sediments. The modeling curves of fluids derived from a dehydrated slab (ratios: AOC80–SED20 to AOC40–SED60) with a representative mantle composition can account for the majority of lithium compositional variations. Some samples with unusual Pb–Sr–Nd–O isotopic compositions and highly variable δ7Li compositions are affected by significant involvement of marine sediments in their source region, not contaminated by crustal materials. The carbonatites and syenites in western Sichuan were generated by the partial melting of subcontinental lithospheric mantle, which was metasomatized by the Li-rich fluids derived from the subducted oceanic crust and marine sediments. This melting was most likely triggered by a Cenozoic asthenospheric mantle diapir related to Indian-Asian continental collision and post- or late-collisional stress relaxation in the Oligocene.

To improve estimates of the extent of ocean oxygenation during the late Ediacaran Period, we measured the U and Mo isotope compositions of euxinic (anoxic and sulfidic) organic-rich mudrocks (ORM) of Member IV, upper Doushantuo Formation, South China. The average δ 238 U of most samples is 0.24 ± 0.16‰ (2SD; relative to standard CRM145), which is slightly higher than the average δ 238 U of 0.02 ± 0.12‰ for restricted Black Sea (deep-water Unit I) euxinic sediments and is similar to a modeled δ 238 U value of 0.2‰ for open ocean euxinic sediments in the modern well-oxygenated oceans. Because 238 U is preferentially removed to euxinic sediments compared to 235 U, expanded ocean anoxia will deplete seawater of 238 U relative to 235 U, ultimately leading to deposition of ORM with low δ 238 U. Hence, the high δ 238 U of Member IV ORM points to a common occurrence of extensive ocean oxygenation ca. 560 to 551 Myr ago. The Mo isotope composition of sediments deposited from strongly euxinic bottom waters ([H 2 S] aq >11 μM) either directly records the global seawater Mo isotope composition (if Mo removal from deep waters is quantitative) or represents a minimum value for seawater (if Mo removal is not quantitative). Near the top of Member IV, δ 98 Mo approaches the modern seawater value of 2.34 ± 0.10‰. High δ 98 Mo points to widespread ocean oxygenation because the preferential removal of isotopically light Mo to sediments occurs to a greater extent in O 2 -rich compared to O 2 -deficient marine environments. However, the δ 98 Mo value for most Member IV ORM is near 0‰ (relative to standard NIST SRM 3134 = 0.25‰), suggesting extensive anoxia. The low δ 98 Mo is at odds with the high Mo concentrations of Member IV ORM, which suggest a large seawater Mo inventory in well-oxygenated oceans, and the high δ 238 U. Hence, we propose that the low δ 98 Mo of most Member IV ORM was fractionated from contemporaneous seawater. Possible mechanisms driving this isotope fractionation include: (1) inadequate dissolved sulfide for quantitative thiomolybdate formation and capture of a seawater-like δ 98 Mo signature in sediments or (2) delivery of isotopically light Mo to sediments via a particulate Fe–Mn oxyhydroxide shuttle. A compilation of Mo isotope data from euxinic ORM suggests that there were transient episodes of extensive ocean oxygenation that break up intervals of less oxygenated oceans during late Neoproterozoic and early Paleozoic time. Hence, Member IV does not capture irreversible deep ocean oxygenation. Instead, complex ocean redox variations likely marked the transition from O 2 -deficient Proterozoic oceans to widely oxygenated later Phanerozoic oceans.

To improve our understanding of ocean chemistry and biogeochemical cycling following the termination of large-scale Paleoproterozoic iron formation (IF) deposition (∼1.85 billion years ago [Ga]), we conducted a Fe–S–C–Mo geochemical study of the ∼1.65 Ga Chuanlinggou Formation, Yanshan Basin, North China. Despite the cessation of IF deposition, our results suggest the presence of anoxic but non-euxinic (ferruginous) conditions persisted below the surface mixed layer for the deepest portion of the continental rifting basin and that this pattern is apparently independent of the local organic carbon content. However, our paired S-isotope data of carbonate-associated sulfate and pyrite suggest presence of sulfate in pore fluids, which is not consistent with insufficient sulfate for bacterial sulfate reduction in the water column. Despite evidence for deposition under anoxic conditions, sedimentary molybdenum (Mo) concentrations are mostly not enriched relative to average continental crust. This relationship is consistent with the notion that sulfide-dominated conditions in the water column and/or the sediments are required for Mo enrichment and validates past assertions that Mo enrichment patterns in ancient shales track both the local presence and global distribution of euxinia specifically. In addition, we identified extensive diagenetic carbonate precipitation in the upper Chuanlinggou Formation with only moderately negative δ 13 C values (−3.4 ± 1.4‰). We propose, with support from a numerical model, that these diagenetic carbon isotope values were most likely derived from precipitation of carbonates dominantly in the methanic zone within the sediments. Diagenetic carbonate precipitation in the methanic zone is likely to have been more extensive in the Proterozoic than the Phanerozoic due to porewater oxidant limitation.

Dolomite precipitation models and kinetics are debated and complicated due to the complex and temporally fluctuating fluid chemistry and different diagenetic environments. Using well-established isotope systems (δ18O, δ13C, 87Sr/86Sr), fluid inclusions and elemental data, as well as a detailed sedimentological and petrographic data set, we established the precipitation environment and subsequent diagenetic pathways of a series of Proterozoic to Pleistocene syn-depositional marine evaporative (sabkha) dolomites, syn-depositional non-marine evaporative (lacustrine and palustrine) dolomites, altered marine (“mixing zone”) dolomites and late diagenetic hydrothermal dolomites. These data form the prerequisite for a systematic investigation of dolomite magnesium isotope ratios (δ26Mgdol). Dolomite δ26Mg ratios documented here range, from −2.49‰ to −0.45‰ (δ26Mgmean = −1.75 ± 1.08‰, n = 42). The isotopically most depleted end member is represented by earliest diagenetic marine evaporative sabkha dolomites (−2.11 ± 0.54‰ 2σ, n = 14). In comparing ancient compositions to modern ones, some of the variation is probably due to alteration. Altered marine (−1.41 ± 0.64‰ 2σ, n = 4), and earliest diagenetic lacustrine and palustrine dolomites (−1.25 ± 0.86‰ 2σ, n = 14) are less negative than sabkha dolomites but not distinct in composition. Various hydrothermal dolomites are characterized by a comparatively wide range of δ26Mg ratios, with values of −1.44 ± 1.33‰ (2σ, n = 10). By using fluid inclusion data and clumped isotope thermometry (Δ47) to represent temperature of precipitation for hydrothermal dolomites, there is no correlation between fluid temperature (∼100 to 180 °C) and dolomite Mg isotope signature (R2 = 0.14); nor is there a correlation between δ26Mgdol and δ18Odol. Magnesium-isotope values of different dolomite types are affected by a complex array of different Mg sources and sinks, dissolution/precipitation and non-equilibrium fractionation processes and overprinted during diagenetic resetting. Further progress on the use of δ26Mgdol as a proxy will require new theoretical and experimental data for Δ26Mgfluid-dol that includes dehydration effects of the free Mg aquo ion versus fluid temperature. In ancient diagenetic systems, complex variables must be considered. These include fluid chemistry and physical properties, Mg sources and sinks, temporal changes during precipitation and post-precipitation processes including open and closed system geochemical exchange with ambient fluids. All of these factors complicate the application of δ26Mgdol as proxy for their depositional or diagenetic environments. Nevertheless, the data shown here also indicate that δ26Mgdol can in principle be interpreted within a detailed framework of understanding.

HIMU (high- μ ; 238 U/ 204 Pb) is a mantle reservoir that has been thought to form by subduction and subsequent storage of ancient oceanic crust and lithosphere in the mantle. In order to constrain the processes that acted on subducted materials over several billion years, we present precise Pb–Sr–Nd–Hf–He isotopic data together with 40 Ar/ 39 Ar and K/Ar ages of HIMU lavas from St. Helena in the Atlantic. Clinopyroxene separates were analyzed together with whole-rock samples to better describe the geochemical characteristics of the HIMU component. Although isotopic variations are small in the St. Helena lavas (20.6–21.0 for 206 Pb/ 204 Pb) between 12 and 8 Ma, the younger lavas have more HIMU-like isotopic compositions than the older lavas. The mixing arrays defined by these lavas are remarkably similar to those observed in HIMU lavas from Austral Islands in the Pacific, suggesting that the two HIMU reservoirs located in different mantle domains are characterized by similar isotopic compositions with radiogenic 206 Pb/ 204 Pb and 208 Pb/ 204 Pb, enriched Nd and Hf isotopes, depleted Sr isotopes, and radiogenic 3 He/ 4 He. However, there is a significant difference between the St. Helena and Austral Islands lavas in 207 Pb/ 204 Pb. The St. Helena lavas show systematically higher 207 Pb/ 204 Pb for a given 206 Pb/ 204 Pb. Lead isotope evolution models suggest that both HIMU reservoirs formed around 2 Ga; however, the HIMU reservoir for St. Helena is about 0.3 Ga older than that for Austral Islands. The relation between 206 Pb/ 204 Pb and 208 Pb/ 204 Pb could reflect the time-integrated κ ( 232 Th/ 238 U) in the components. The HIMU components for St. Helena and Austral Islands have κ values between 3.3 and 3.7, which are intermediate between the present-day fresh mid-ocean ridge basalts (MORB; 2.6–3.2) and the chondritic silicate Earth (∼4). This is consistent with the model that the HIMU precursor is subducted oceanic crust created around 2 Ga from depleted upper mantle, in which κ monotonously decreased from the chondritic to the present-day values since late Archean or early Proterozoic, because of enhanced U recycling from the Earth’s surface back to the mantle in response to the increasing oxygen levels in the hydrosphere. Moreover, the fact that the HIMU components have much higher κ than the present-day hydrothermally altered MORB (0.2–2) suggests that either the HIMU precursor was an unaltered ancient oceanic crust, or more likely, an altered oceanic crust with minimal U enrichment by hydrothermal fluids in the less oxic marine environment of the late Archean or early Proterozoic. The unradiogenic 87 Sr/ 86 Sr of the HIMU components also suggests formation of ancient oceanic crust altered with hydrothermal fluids having much lower 87 Sr/ 86 Sr in that eon than at present, followed by removal of Rb from it by subduction dehydration.

The formation of sedimentary exhalative (SEDEX) Pb/Zn deposits is linked to ocean euxinia, but recent evidence suggests that ferruginous conditions may have dominated the deep ocean during the Middle Proterozoic, a maximum period for SEDEX distribution. Biomarkers of sulfate-reducing and sulfide-oxidising bacteria are valuable indicators of euxinic conditions in such settings. Organic matter (OM) from SEDEX deposits is often affected by alteration and/or migration, but OM entrapped within the kerogen/mineral matrix (Bitumen II) may be less affected than the freely-extractable OM (Bitumen I). We analysed Bitumen II from the Paleoproterozoic Here’s Your Chance (HYC) Pb/Zn/Ag deposit to find evidence of euxinic conditions in the depositional environment. n -Alkane distributions in Bitumen II are markedly distinct from previously-reported Bitumen I. Bitumen II contains long-chain n -alkanes (up to C 36 or C 38 ) and a strong even-over-odd distribution in a number of samples, which are 4‰ to 7‰ depleted in 13 C compared to n -alkanes in Bitumen I and verified as indigenous by comparison with δ 13 C of isolated kerogen. These features are interpreted as evidence of sulfate-reducing and sulfide-oxidising bacteria, confirming that HYC was deposited under euxinic conditions. Bitumen II has the potential to reveal information from OM that is degraded and/or overprinted in Bitumen I. Commonly-used methylphenanthrene maturity ratios give conflicting information as to the relative maturity of Bitumens I and II. Bitumen I contains a far higher proportion of methylated phenanthrenes than Bitumen II. As Bitumen II is sequestered within the kerogen/mineral matrix it may have restricted access to the ‘methyl pool’ of organic compounds that can donate methyl groups to aromatic hydrocarbons. Parameters that include both phenanthrene and methylphenanthrenes do not appear suitable to compare the maturity of Bitumens I and II; hence there is no clear evidence that Bitumen II is of lower thermal maturity than Bitumen I.

Hydrocarbons and organic biomarkers extracted from black shales and other carbonaceous sedimentary rocks are valuable sources of information on the biodiversity and environment of early Earth. Howe ...

We report Si-isotopic compositions of 75 sedimentologically and petrographically characterized chert samples with ages ranging from similar to 2600 to 750 Ma using multi-collector inductively coupled plasma mass spectrometry. delta Si-30 values of the cherts analyzed in this study show a similar to 7 parts per thousand range, from -4.29 to +2.85. This variability can be explained in part by (1) simple mixing of silica derived from continental (higher delta Si-30) and hydrothermal (lower delta Si-30) sources, (2) multiple mechanisms of silica precipitation and (3) Rayleigh-type fractionations within pore waters of individual basins. We observe similar to 3 parts per thousand variation in peritidal cherts from a single Neoproterozoic sedimentary basin (Spitsbergen). This variation can be explained by Rayleigh-type fractionation during precipitation from silica-saturated porewaters. In some samples, post-dissolution and reprecipitation of silica could have added to this effect. Our data also indicate that peritidal cherts are enriched in the heavier isotopes of Si whereas basinal cherts associated with banded iron formations (BIF) show lower delta Si-30. This difference could partly be due to Si being derived from hydrothermal sources in BIFs. We postulate that the difference in delta Si-30 between non-BIF and BIF cherts is consistent with the contrasting genesis of these deposits. Low delta Si-30 in BIF is consistent with laboratory experiments showing that silica adsorbed onto Fe-hydroxide particles preferentially incorporates lighter Si isotopes. Despite large intrabasinal variation and environmental differences, the data show a clear pattern of secular variation. Low delta Si-30 in Archean cherts is consistent with a dominantly hydrothermal source of silica to the oceans at that time. The monotonically increasing delta Si-30 from 3.8 to 1.5 Ga appears to reflect a general increase in continental versus hydrothermal sources of Si in seawater, as well as the preferential removal of lighter Si isotopes during silica precipitation in iron-associated cherts from silica-saturated seawater. The highest delta Si-30 values are observed in 1.5 Ga peritidal cherts; in part, these enriched values could reflect increasing sequestration of light silica during soil-forming processes, thus, delivering relatively heavy dissolved silica to the oceans from continental sources. The causes behind the reversal in trend towards lower delta Si-30 in cherts younger than 1.5 Ga old are less clear. Cherts deposited 1800-1900 Ma are especially low delta Si-30, a possible indication of transiently strong hydrothermal input at this time. (C) 2012 Elsevier Ltd. All rights reserved.

Most geochemical proxies and models of atmospheric evolution suggest that the amount of free O2 in Earth’s atmosphere stayed below 10−5 present atmospheric level (PAL) until the Great Oxidation Event (GOE) that occurred between ∼2.2 and 2.4 Ga, at which time free O2 in the atmosphere increased to approximately 10−1 to 10−2 PAL. Although photosynthetically produced “O2 oases” have been proposed for the photic zone of the oceans prior to the GOE, it has been difficult to constrain absolute O2 concentrations and fluxes in such paleoenvironments. Here we constrain free O2 levels in the photic zone of a Late Archean marine basin by the combined use of Fe and Mo isotope systematics of Ca–Mg carbonates and shales from the 2.68 to 2.50 Ga Campbellrand–Malmani carbonate platform of the Kaapvaal Craton in South Africa. Correlated Fe and Mo isotope compositions require a key role for Fe oxide precipitation via oxidation of aqueous Fe(II) by photosynthetically-derived O2, followed by sorption of aqueous Mo to the newly formed Fe oxides. A dispersion/reaction model illustrates the effects of Fe oxide production and Mo sorption to Fe oxides, and suggests that a few to a few tens of μM free O2 was available in the photic zone of the Late Archean marine basin, consistent with some previous estimates. The coupling of Fe and Mo isotope systematics provides a unique view into the processes that occurred in the ancient shallow ocean after production of free O2 began, but prior to oxygenation of the deep ocean, or significant accumulation of free O2 in the atmosphere. These results require oxygenic photosynthesis to have evolved by at least 2.7 Ga and suggest that the Neoarchean ocean may have had a different oxygenation history than that of the atmosphere. The data also suggest that the extensive iron formation deposition that occurred during this time was unlikely to have been produced by anoxygenic photosynthetic Fe(II) oxidation. Finally, these data indicate that the ocean had significant amounts of O2 at least 150 Myr prior to previously proposed “whiffs” of O2 at the Archean to Proterozoic transition.

Fe isotopes can provide new insight into redox-dependent biogeochemical processes. Precambrian iron formations (IF) are deserving targets for Fe isotope studies because they are composed predominantly of authigenic Fe phases and record a period of unprecedented iron deposition in Earth’s history. We present Fe isotope data for bulk samples from 24 Archean and Proterozoic IF and eight Phanerozoic Fe oxide-rich deposits. These data reveal that many Archean and early Paleoproterozoic iron formations were a sink for isotopically heavy Fe, in contrast to later Proterozoic and Phanerozoic Fe oxide-rich rocks. The positive δ 56 Fe values in IF are best explained by delivery of particulate ferric oxides formed in the water column to the sediment–water interface. Because IF are a net sink for isotopically heavy Fe, there must be a corresponding pool of isotopically light Fe in the sedimentary record. Earlier work suggested that Archean pyritic black shales were an important part of this light sink before 2.35 billion years ago (Ga). It is therefore likely that the persistently and anomalously low δ 56 Fe values in shales are linked with the deposition of isotopically heavy Fe in IF in the deeper parts of basins. IF deposition produced a residual isotopically light dissolved Fe pool that was captured by pyritic Fe in shales. Local dissimilatory Fe reduction in porewater and associated diagenetic reactions resulting in pyrite and carbonate precipitation may have further enhanced Fe isotope heterogeneity in marine sediments, and an ‘iron shuttle’ may have transported isotopically light Fe from shelf sediments to the basin. Nevertheless, water-column processing of hydrothermally delivered Fe likely had the strongest influence on the bulk iron isotope composition of Archean and Paleoproterozoic iron formations and other marine sediments.

Radiogenic isotope compositions of Hf and Nd are typically coupled in Phanerozoic and Proterozoic mafic rocks due to a similar behaviour of Lu–Hf and Sm–Nd during mantle melting. Eoarchean rocks, for instance those from southern West Greenland, exhibit an apparent decoupling of Hf and Nd isotope compositions. This apparent decoupling may either indicate metamorphic disturbance or, alternatively, mirror early differentiation processes in the silicate Earth. To evaluate the issue, we performed combined measurements of Hf–Nd isotope compositions together with major and trace element concentrations for well preserved >3720 to >3800 Ma old tholeiitic metabasalts and gabbros from the ∼3700 Ma and ∼3800 Ma old terranes of the Isua Supracrustal Belt, southern West Greenland. In contrast to younger mafic rocks, calculated initial eHf–eNd values of the Isua tholeiites show similar spreads and are both near chondritic to strongly depleted (−0.7 to +6.3 and −0.8 to +4.4, respectively), also in contrast to previously reported more depleted signatures in nearby boninite-like metabasalts of the Garbenschiefer unit. An evaluation of alteration effects based on preserved major and trace element arrays reveals pristine magmatic trends and therefore the measured isotope compositions indeed in most cases characterize contrasting Eoarchean mantle sources. In accord with this view, compositions of the Isua metabasalts yield Eoarchean regression ages in Sm–Nd and Lu–Hf isochron spaces, overlapping with emplacement ages inferred from crosscutting relationships with tonalites. Lutetium–Hf systematics of the Isua metabasalts studied here, yield clear isochron relationships. For both terranes, there is some scatter in Sm–Nd space, indicating early disturbance of the Sm–Nd system close in time to the extrusion ages, possibly by seafloor alteration. Trace element compositions of the metabasalts indicate an arc setting and a strong source overprint by melt-like subduction components. It is likely, that the source overprint may have caused partial decoupling of the eHf–eNd values, due to selective addition of Nd as observed in modern subduction settings. In this case, the most radiogenic initial eNd and eHf isotope values characterize the most depleted mantle sources, and less radiogenic values would reflect increased contributions of isotopically more enriched subduction components. However, the most depleted samples still exhibit decoupled Hf–Nd compositions, making a case for the presence of even older mantle heterogeneities. A proposed superchondritic composition of the silicate Earth (SCHEM), however, cannot account for the most depleted sample compositions. Conversely, a depleted upper mantle formed by crystallization of perovskite-rich cumulates in the early Hadean may well explain these observed compositions. A literature survey reveals an overlap in initial Hf–Nd compositions between southern West Greenland TTGs and the metabasalts analyzed here. This overlap suggests a genetic relationship between these lithologies, where the TTGs may have inherited their unusual Hf–Nd compositions from mafic precursors isotopically similar in composition to the Isua tholeiites.

Brines in Cambrian sandstones and Ordovician dolostones of the St-Lawrence Lowlands at Becancour, Quebec, Canada were sampled for analysis of all stable noble gases in order to trace their origin and migration path, in addition to quantifying their residence time. Major ion chemistry indicates that the brines are of Na–Ca–Cl type, possibly derived from halite dissolution. 87 Sr/ 86 Sr ratios and Ca excess indicate prolonged interactions with silicate rocks of the Proterozoic Grenville basement or the Cambrian Potsdam sandstone. The brines constrain a 2–3% contribution of mantle 3 He and large amounts of nucleogenic 21 Ne ∗ and 38 Ar ∗ and radiogenic 4 He and 40 Ar ∗ . 4 He/ 40 Ar ∗ and 21 Ne ∗ / 40 Ar ∗ ratios, corrected for mass fractionation during incomplete brine degassing, are identical to their production ratios in rocks. The source of salinity (halite dissolution), plus the occurrence of large amounts of 40 Ar ∗ in brines constrain the residence time of Becancour brines as being older than the Cretaceous. Evaporites in the St-Lawrence Lowlands likely existed only during Devonian–Silurian time. Brines might result from infiltration of Devonian water leaching halite, penetrating into or below the deeper Cambrian–Ordovician aquifers. During the Devonian, the basin reached temperatures higher than 250 °C, allowing for thermal maturation of local gas-prone source rocks (Utica shales) and possibly facilitating the release of radiogenic 40 Ar ∗ into the brines. The last thermal event that could have facilitated the liberation of 40 Ar ∗ into fluids and contributed to mantle 3 He is the Cretaceous Monteregian Hills magmatic episode. For residence times younger than the Cretaceous, it is difficult to find an appropriate source of salinity and of nucleogenic/radiogenic gases to the Becancour brines.

The noble gases (He, Ne, Ar, Kr and Xe) are powerful geochemical tracers because they have distinctive isotopic compositions in the atmosphere, crust and mantle. This study illustrates how noble gases can be used to trace fluid origins in high-temperature metamorphic and mineralising environments; and at the same time provides new information on the composition of noble gases in deeper parts of the crust than have been sampled previously. We report data for H2O and CO2 fluid inclusions trapped at greenschist to amphibolite facies metamorphic conditions associated with three different styles of mineralisation and alteration in the Proterozoic Mt Isa Inlier of Australia. Sulphide fluid inclusions are dominated by crustal 4He. However, co-variations in fluid inclusion 20Ne/22Ne, 21Ne/22Ne, 40Ar/36Ar and 136Xe/130Xe indicate noble gases were derived from three or more reservoirs. In most cases, the fluid inclusions elemental noble gas ratios (e.g. Ne/Xe) are close to the ranges expected in sedimentary and crystalline rocks. However, the elemental ratios have been modified in some of the samples providing evidence for independent pulses of CO2, and interaction of CO2 with high-salinity aqueous fluids. Compositional variation is attributed to mixing of: (i) magmatic fluids (or deeply sourced metamorphic fluids) characterised by basement-derived noble gases with 20Ne/22Ne ∼ 8.4, 21Ne/22Ne ∼ 0.4, 40Ar/36Ar ∼ 40,000 and 136Xe/130Xe ∼ 8; (ii) basinal–metamorphic fluids with a narrow range of compositions including near-atmospheric values and (iii) noble gases derived from the meta-sedimentary host-rocks with 20Ne/22Ne ∼ 8–9.8, 21Ne/22Ne These data provide the strongest geochemical evidence available for the involvement of fluids from two distinct geochemical reservoirs in Mt Isa’s largest ore deposits. In addition the data show how noble gases in fluid inclusions can provide information on fluid origins, the composition of the crust’s major lithologies, fluid–rock interactions and fluid–fluid mixing or immiscibility processes.

Detrital zircons from the Ob, Yenisey, Lena, Amur, Volga, Dnieper, Don and Pechora rivers have been analyzed for U–Th–Pb, O and Lu–Hf isotopes to constrain the growth rate of the preserved continental crust in Greater Russia. Four major periods of zircon crystallization, 0.1–0.55, 0.95–1.3, 1.45–2.0 and 2.5–2.9 Ga, were resolved from a compilation of 1366 zircon U/Pb ages. The Archean zircons have δ18O values lying between 4.53‰ and 7.33‰, whereas Proterozoic and Phanerozoic zircons have a larger range of δ18O values in each of the recognized U/Pb time intervals with maximum δ18O values up to 12‰. We interpret the zircons with δ18O between 4.5‰ and 6.5‰ to have been derived from a magmatic precursor that contains little or no sedimentary component. The variable δ18O values of the zircons were used to constrain the 176Lu/177Hf ratios of the crustal source region of the zircons, which, in turn, were used to calculate Hf model ages (TDMV). The crustal incubation time, the time difference between primitive crust formation (dated by TDMV) and crustal melting (dated by zircon U/Pb age), varies between 300 to 1000 Myr for the majority of analyzed zircon grains, but can be up to 2500 Myr. The average TDMV Hf model age weighted by the fraction of zircons in the river load is 2.12 Ga, which is in reasonable agreement with the area-weighted average of 2.25 Ga. The TDMV Hf model age crustal growth curve for zircons with mantle-like δ18O values (4.5–6.5‰), weighted by area, shows that growth of the Great Russian continental crust started at 4.2 Ga, and that there are two principal periods of crustal growth, 3.6–3.3 Ga and 0.8–0.6 Ga, which are separated by an interval of low but more or less continuous growth. An alternative interpretation, in which the average 176Lu/177Hf ratio (0.0115) of the continental crust is used for the Paleoproterozoic zircons from the Lena River, lowers the average TDMV age of these grains by about 500 Myr and delays the onset of significant crustal growth to 3.5 Ga. The two principal growth periods recognized in Greater Russia differ from those identified from the Gondwana and the Mississippi river basin, which show peaks at 1.7–1.9 and 2.9–3.1 Ga ( Hawkesworth and Kemp, 2006a ) and 1.6–2.2 and 2.9–3.4 Ga ( Wang et al., 2009 ), respectively. The older 3.6–3.3 Ga or 3.5–3.3 Ga peak for Greater Russia is slightly older than the older Gondwana-Mississippi peaks, whereas the younger 0.8–0.6 Ga peak is distinctly younger than the youngest peak in either Gondwana or the Mississippi river basin. This suggests that the two major peaks of crustal growth identified in Gondwana and the Mississippi river basin may not be global periods of enhanced continental growth and that the major periods of crustal growth may differ from continent to continent.

The consensus view is that the O 2 concentration of the Archean atmosphere was very low and that it rose to its present level of 21% in a series of steps, two of which dwarf the others in importance. The first, known as the Great Oxidation Event, occurred at ∼2.4 Ga. It involved an increase in the relative abundance of O 2 , which has been estimated at three orders of magnitude, and it is important because it led to the first surface weathering. The second, although less important in relative terms, involved the addition of 9 × 10 17 kg of O 2 to the atmosphere, at least ten times as much as that required to produce the Great Oxidation Event. Its importance lies in the fact that it correlates with the rise of animals in the Ediacaran and Early Cambrian periods. Although it is widely accepted that an increase in atmospheric O 2 facilitated the appearance of animals at ∼575 Ma, followed by the Cambrian Explosion ∼50 Myr later, the cause of this increase remains controversial. We show that the surge in the O 2 level near the Precambrian–Cambrian boundary correlates with major episodes of continent–continent collision associated with Gondwana’s amalgamation, including convergence between East and West Gondwana, which produced the 8000-km-long Transgondwanan Supermountains. The eroded roots of these mountains include the oldest lawsonite-bearing blueschists and eclogites, and ultra high-pressure metamorphic rocks. The sudden appearance of these low-thermal gradient, high-pressure metamorphic rocks implies that the Gondwanan orogenic zones were cooler and stronger than those associated with the assembly of earlier supercontinents and therefore capable of supporting higher mountains. There is a log-linear relationship between relief and erosion rate, and a linear relationship between sedimentation rate and organic C burial. Taken together these two relationships imply a log-linear relationship between relief and C sequestration. We suggest that the Gondwanan supermountains were higher than those produced during the assembly of earlier supercontinents and that rapid erosion of these mountains released a large flux of essential nutrients, including Fe and P, into the rivers and oceans, which triggered an explosion of algae and cyanobacteria. This, in turn, produced a marked increase in the production rate of photosynthetic O 2 . Rapid sedimentation during this period promoted high rates of burial of biogenic pyrite and organic matter generated during photosynthesis so that they could not back react with O 2 , leading to a sustained increase in atmospheric O 2 .

Clay minerals formed through chemical weathering have long been implicated in the burial of organic matter (OM), but because diagenesis and metamorphism commonly obscure the signature of weathering-derived clays in Precambrian rocks, clay mineralogy and its role in OM burial through much of geologic time remains incompletely understood. Here we have analyzed the mineralogy, geochemistry and total organic carbon (TOC) of organic rich shales deposited in late Archean to early Cambrian sedimentary basins. Across all samples we have quantified the contribution of 1M and 1Md illite polytypes, clay minerals formed by diagenetic transformation of smectite and/or kaolinite-rich weathering products. This mineralogical signal, together with corrected paleo-weathering indices, indicates that late Archean and Mesoproterozoic samples were moderately to intensely weathered. However, in late Neoproterozoic basins, 2M1 illite/mica dominates clay mineralogy and paleo-weathering indices sharply decrease, consistent with an influx of chemically immature and relatively unweathered sediment. A late Neoproterozoic switch to micaceous clays is inconsistent with hypotheses for oxygen history that require an increased flux of weathering-derived clays (i.e., smectite or kaolinite) across the Precambrian–Cambrian boundary. Compared to previous studies, our XRD data display the same variation in Schultz Ratio across the late Neoproterozoic, but we show the cause to be micaceous clay and not pedogenic clay; paleo-weathering signals cannot be recovered from bulk mineralogy without this distinction. We find little evidence to support a link between these mineralogical variations and organic carbon in our samples and conclude that modal clay mineralogy cannot by itself explain an Ediacaran increase in atmospheric oxygen driven by enhanced OM burial.

Joint application of the Mo isotope paleoredox proxy and Re–Os deposition-age geochronometer to euxinic black shales has potential for tracing the evolution of ocean redox chemistry over geological time. Here, we report new Re–Os and Mo isotope data for the Mesoproterozoic Velkerri Formation (Roper Group) and Paleoproterozoic Wollogorang Formation (Tawallah Group), McArthur Basin, northern Australia. New Re–Os ages of 1361 ± 21 Ma (2σ, n = 14, mean square of weighted deviates [MSWD] = 1.3, Model 1) and 1417 ± 29 Ma (2σ, n = 12, MSWD = 1.3, Model 1) constrain the depositional age of the Velkerri Formation and its contained biomarkers, as well as acritarchs and microfossils from the Roper Group. Black shales from the upper Velkerri Formation have high Mo abundances (105–119 ppm) and degree of pyritization [DOP] values (0.90–0.92) implying quantitative conversion of molybdate (MoO42−) to thiomolybdate (MoS42−) in overlying bottom waters. The average δ97/95Mo (0.72 ± 0.10‰, 2σ, n = 6) of these shales is consistent with previous data, but represents a significantly more precise determination for global seawater δ97/95Mo at 1.4 Ga. This value is lighter than present-day seawater by ∼0.85‰ and reflects expanded strongly euxinic deep ocean conditions ([H2S]aq > 11 μM) relative to oxic, suboxic, and weakly/intermittently euxinic ([H2S]aq

Detrital zircons from the Mississippi River have been analyzed for U–Th–Pb, Lu–Hf and O isotopes to constrain the rate of growth of the preserved North American continental crust. One hundred and forty two concordant zircon U/Pb dates on grains mounted in epoxy, obtained by Excimer laser ablation ICP-MS method, resolved six major periods of zircon crystallization: 0–0.25, 0.3–0.6, 0.95–1.25, 1.3–1.5, 1.65–1.95 and 2.5–3.0 Ga. These age ranges match the ages of the recognized lithotectonic units of the North American continent in the hinterland of the Mississippi River. Ninety-six zircons mounted on tape, which show no age zonation and were within 7.5% of concordance, were selected to represent the six U/Pb age time intervals and analyzed for Lu–Hf and O isotope by laser ablation MC-ICP-MS and SHRIMP II, respectively. The δ18O values of the zircons show a small step increase in the maximum δ18O values at the Archean-Proterozoic boundary from 7.5‰ in the Archean to 9.5‰, and rarely 13‰, in the Proterozoic and Phanerozoic. However, the average value of δ18O in zircons changes little with time, showing that the increase in the maximum δ18O values between 2.5 and 2.0 Ga, which can be attributed to an increase in the sediment content of the source regions of younger granitoids, is largely balanced by an increase in zircons with anomalously low δ18O, which can be attributed to hydrothermally altered crust in the granitoid source region. eHfi values for the zircons range from 13.1 to −26.9. Zircons derived from juvenile crust, which we define as having mantle δ18O (4.5–6.5‰) and lying within error of the Hf depleted mantle growth curve, are rare or absent in the Mississippi basin. The overwhelming majority of zircons crystallized from melted pre-existing continental crust, or mantle-derived magmas that were contaminated by continental crust. The average time difference between primitive crust formation and remelting for each of the recognized lithotectonic time intervals, which is defined as crustal incubation time in this study, is 890 ± 460 Myr. There is also a suggestion that the crustal incubation time increases with decreasing age in the Mississippi basin, which is consistent with the declining role of radioactive heat production in the lower crust with time. The average Hf model age (1.94 Ga), weighted by fraction of zircons in the river load is in reasonable agreement with the Nd model age (1.7 Ga) for the Mississippi River. However, if the zircons are weighted by the area of North America covered by the six recognized periods of zircon crystallization the average model age is 2.35 Ga, which compares favorably with an area weighted Nd model age of 2.36 Ga. Our preferred approach is to use the measured O isotope values to constrain variations in the 176Lu/177Hf ratio of the granitic source region from which the zircons crystallized, making the assumption that zircons with mantle-like O isotopic ratios have higher 176Lu/177Hf than zircons with higher O isotope values. This method gives an average Hf model age of 2.53 Ga, which is 180 Myr older than the constant 176Lu/177Hf calculation. The area weighted zircon Hf model ages show two distinct periods of crust formation for the North American continent, 1.6–2.2 and 2.9–3.4 Ga. At least 50% of the preserved North American continental crust was extracted from the mantle by 2.9 Ga and 90% by 1.6 Ga. Two similar periods of crustal growth are also recognized in Gondwana (Hawkesworth C. J. and Kemp A. I. S. (2006) Using hafnium and oxygen isotopes in zircons to unravel the record of crustal evolution. Chem. Geol. 226, 144–162.), suggesting that these may be periods of global continental crustal growth. However, we stress that more data from other continents are required before the hypothesis of episodic global continental growth can be accepted with confidence.

Thirty-four silicate and oxide inclusions large enough for in situ WDS electron microprobe analysis were exposed by grinding/polishing of 19 diamonds from the Kelsey Lake Mine in the Colorado-Wyoming State Line Kimberlite district. Eighteen olivines, seven Cr-pyropes, four Mg-chromites, and one orthopyroxene in 15 stones belong to the peridotite (P) suite and three garnets and one omphacite in three stones belong to the eclogite (E) suite. The fact that this suite is dominated by the peridotite population is in stark contrast to the other diamond suites studied in the State Line district (Sloan, George Creek), which are overwhelmingly eclogitic. Kelsey Lake olivine inclusions are magnesian (17 of 18 grains in 9 stones are in the range Fo 92.7–93.1), typical of harzburgitic P-suite stones worldwide, but unlike the more Fe-rich (lherzolitic) Sloan olivine suite. Mg-chromites (wt% MgO = 12.8–13.8; wt% Cr 2 O 3 = 61.4–66.6) are in the lower MgO range of diamond inclusion chromites worldwide. Seven harzburgitic Cr-pyropes in five stones have moderately low calcium contents (wt% CaO = 3.3–4.3) but are very Cr-rich (wt% Cr 2 O 3 = 9.7–16.7). A few stones have been analyzed by SIMS for carbon isotope composition and nitrogen abundance. One peridotitic stone is apparently homogeneous in carbon isotope composition (δ 13 C PDB = −6.2‰) but with variable nitrogen abundance (1296–2550 ppm). Carbon isotopes in eclogitic stones range from “normal” for the upper mantle (δ 13 C PDB = −5.5‰) to somewhat low (δ 13 C PDB = −10.2‰), with little internal variation in individual stones (maximum difference is 3.6‰). Nitrogen contents (2–779 ppm) are lower than in the peridotitic stone, and are lower in cores than in rims. As, worldwide, harzburgite-suite diamonds have been shown to have formed in Archean time, we suggest that the Kelsey Lake diamond population was derived from a block of Archean lithosphere that, at the time of kimberlite eruption, existed beneath the Proterozoic Yavapai province. The mixed diamond inclusion populations from the State Line kimberlites appear to support models in which volumes of Wyoming Craton Archean mantle survive buried beneath Proterozoic continental crust. Such material may be mixed with eclogitic/lherzolitic regimes emplaced beneath or intermingled with the Archean rocks by Proterozoic subduction.

The voluminous 2.5 Ga banded iron formations (BIFs) from the Hamersley Basin (Australia) and Transvaal Craton (South Africa) record an extensive period of Fe redox cycling. The major Fe-bearing minerals in the Hamersley–Transvaal BIFs, magnetite and siderite, did not form in Fe isotope equilibrium, but instead reflect distinct formation pathways. The near-zero average δ56Fe values for magnetite record a strong inheritance from Fe3+ oxide/hydroxide precursors that formed in the upper water column through complete or near-complete oxidation. Transformation of the Fe3+ oxide/hydroxide precursors to magnetite occurred through several diagenetic processes that produced a range of δ56Fe values: (1) addition of marine hydrothermal Fe 2 + aq , (2) complete reduction by bacterial dissimilatory iron reduction (DIR), and (3) interaction with excess Fe 2 + aq that had low δ56Fe values and was produced by DIR. Most siderite has slightly negative δ56Fe values of ∼ −0.5‰ that indicate equilibrium with Late Archean seawater, although some very negative δ56Fe values may record DIR. Support for an important role of DIR in siderite formation in BIFs comes from previously published C isotope data on siderite, which may be explained as a mixture of C from bacterial and seawater sources. Several factors likely contributed to the important role that DIR played in BIF formation, including high rates of ferric oxide/hydroxide formation in the upper water column, delivery of organic carbon produced by photosynthesis, and low clastic input. We infer that DIR-driven Fe redox cycling was much more important at this time than in modern marine systems. The low pyrite contents of magnetite- and siderite-facies BIFs suggests that bacterial sulfate reduction was minor, at least in the environments of BIF formation, and the absence of sulfide was important in preserving magnetite and siderite in the BIFs, minerals that are poorly preserved in the modern marine record. The paucity of negative δ56Fe values in older (Early Archean) and younger (Early Proterozoic) BIFs suggests that the extensive 2.5 Ga Hamersley–Transvaal BIFs may record a period of maximum expansion of DIR in Earth’s history.

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 not, vert, similar2.9 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 epsilon (Porson)Nd(t) for Pongola shales ranges from −2.7 to −4.2, and epsilon (Porson)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 epsilon (Porson)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 (greater-or-equal, slanted72%) 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.

This study is a comprehensive, stable isotope survey of the marine carbonate-dominated, upper Paleo- to lower Neoproterozoic stratigraphy of Jixian County, China. Carbonate-associated sulfate (CAS) was extracted and measured for δ 34 S CAS using the same samples analyzed for δ 13 C carbonate . This integrated proxy approach is a step towards a more comprehensive picture of secular variation in the composition of Proterozoic seawater. We specifically sampled marine carbonate intervals from the lower section of the Chuanlinggou Formation, Changcheng Group (ca. 1700 Ma) to the top of the Jingeryu Formation, Qingbaikou Group (ca. 800 Ma). δ 13 C carbonate values are mostly negative in the upper Paleoproterozoic Changcheng Group, with an ascending trend from −3‰ to 0‰. We observed variation of approximately 0 ± 1‰ in the Mesoproterozoic Jixian Group, and positive values of +2 ± 2‰ characterize the lower Neoproterozoic Qingbaikou Group. Stratigraphic variations in δ 34 S CAS are more remarkable in their ranges and magnitudes, including conspicuously high values exceeding +30‰ in the three intervals at ca. 1700 Ma, 1300–1100 Ma, and 1000–900 Ma. In the Changcheng Group, δ 34 S CAS values are typically higher than +25‰, with only a few values of less than +15‰. In contrast, most of the data spanning from the Mesoproterozoic Tieling Formation of the Jixian Group to the lower Neoproterozoic Jingeryu Formation of the Qingbaikou Group are highly variable between +10‰ and +25‰, with some values exceeding +25‰. In the late Paleoproterozoic (1700–1600 Ma), a >10‰ decrease in δ 34 S CAS and ∼3‰ increase in δ 13 C carbonate are coincident with, and likely related to, the breakup of Columbia, a supercontinent that predated Rodinia. Carbon and sulfur isotope data from the Mesoproterozoic, when global tectonic activity was comparatively weaker, fall mostly in the ranges of +15 ± 10‰ and 0 ± 1‰, respectively, but fluctuations of >20‰ for δ 34 S CAS and >3‰ for the δ 13 C carbonate at ca. 1450–1400 Ma may reflect subduction and large-scale magmatic activity in island arcs marking the end of Columbia breakup. From the late Mesoproterozoic (ca. 1300–1100 Ma) to the early Neoproterozoic (ca. 800 Ma), the δ 13 C and δ 34 S of seawater increased gradually with increasing variability. Most impressive are δ 34 S CAS values that exceed +30‰ in two intervals at ca. 1300–1100 Ma and ca. 1000–900 Ma, which may reflect the assembly and early breakup of Rodinia. Although gaps in the record remain, and studies of even higher resolution are warranted, our results suggest that changes in paleoceanographic conditions linked to global tectonics strongly influenced the biogeochemical cycles of C and S. Furthermore, periods of the Proterozoic previously noted for their isotopic invariability show clear isotopic expressions of this tectonic activity.

The argon isotope systematics of vein-quartz samples with two different K-reservoirs have been evaluated in detail. Potassium is hosted by ultra-high-salinity fluid inclusions in quartz samples from the Eloise and Osborne iron-oxide-copper-gold (IOCG) deposits of the Mt Isa Inlier, Australia. In contrast, K is hosted by accidentally trapped mica within lower-salinity fluid inclusions of a sample selected from the Railway Fault, 13 km south of the Mt Isa copper mine, Australia. Imprecise apparent ages have been obtained for all of the samples studied and conclusively demonstrate that quartz fluid inclusions are retentive to Ar and have not leaked over billions of years. IOCG samples that host K in fluid inclusions only, have K/Cl values of

Rare earth elements (REE) concentrations of Archean and Proterozoic chemical sediments are commonly used as proxies to study secular trends in the geochemistry of Precambrian seawater. In addition, similarities in the REE signatures of Archean chemical sediments and modern seawater have led researchers to argue that some Archean rocks originated as biochemical precipitates (i.e., microbial carbonates) in shallow marine (e.g., peritidal) environments. However, terrestrial waters, including river water and groundwater, also commonly exhibit REE fractionation patterns that resemble modern seawater. Here, we present the seawater-like REE data for ground

Mantle xenoliths and xenocrysts from Guaniamo, Venezuela kimberlites record equilibration conditions corresponding to a limited range of sampling in the lithosphere (100–150 km). Within this small range, however, compositions vary considerably, but regularly, defining a strongly layered mantle sequence. Major and trace element compositions suggest the following lithologic sequence: highly depleted lherzolite from 100 to 115 km, mixed ultra-depleted harzburgite and lherzolite from 115 to 120 km, relatively fertile lherzolite from 120 to 135 km, and mixed depleted harzburgite and relatively fertile lherzolite from 135 to 150 km. Based on comparison with well-documented mantle peridotites and xenocrysts from elsewhere, we conclude that the Meso-proterozoic Cuchivero Province (host to the Guaniamo kimberlites) is underlain by depleted and ultra-depleted shallow Archean mantle that was underplated, and uplifted, by Proterozoic subduction, perhaps more than once. These Proterozoic subduction events introduced less-depleted oceanic lithosphere beneath the Archean section, which remains there and is the source of the abundant Guaniamo eclogite-suite diamonds that have ocean-floor geochemical signatures. Although diamond-indicative low-Ca Cr-pyrope garnets are abundant, they are derived primarily from the shallow depleted layer within the field of graphite stability, and the rare peridotite-suite diamonds are either metastably preserved at these shallow depths, or were derived from the small amount of depleted lithosphere sampled by these kimberlites that remains within the diamond stability field (the mixture of Archean and Proterozoic mantle in the depth range 135–150 km).

Concentrations of oceanic and atmospheric oxygen have varied over geologic time as a function of sulfur and carbon cycling at or near the Earth's surface. This balance is expressed in the sulfur isotope composition of seawater sulfate. Given the near absence of gypsum in pre-Phanerozoic sediments, trace amounts of carbonate-associated sulfate (CAS) within limestones or dolostones provide the best available constraints on the isotopic composition of sulfate in Precambrian seawater. Although absolute CAS concen- trations, which range from those below detection to 120 ppm sulfate in this study, may be compromised by diagenesis, the sulfur isotope compositions can be buffered sufficiently to retain primary values. Stratigraphically controlled 34 S measurements for CAS from three mid-Proterozoic carbonate successions (1.2 Ga Mescal Limestone, Apache Group, Arizona, USA; 1.45-1.47 Ga Helena and Newland formations, Belt Supergroup, Montana, USA; and 1.65 Ga Paradise Creek Formation, McNamara Group, NW Queens- land, Australia) show large isotopic variability (9.1‰ to 18.9‰, 1.1‰ to 27.3‰, and 14.1‰ to 37.3‰, respectively) over stratigraphic intervals of 50 to 450 m. This rapid variability, ranging from scattered to highly systematic, and overall low CAS abundances can be linked to sulfate concentrations in the mid-Proterozoic ocean that were substantially lower than those of the Phanerozoic but higher than values inferred for the Archean. Results from the Belt Supergroup specifically corroborate previous arguments for seawater contributions to the basin. Limited sulfate availability that tracks the oxygenation history of the early atmosphere is also consistent with the possibility of extensive deep-ocean sulfate reduction, the scarcity of bedded gypsum, and the stratigraphic 34 S trends and 34 S enrichments commonly observed for iron sulfides of mid-Proterozoic age. Copyright © 2005 Elsevier Ltd