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We determined highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, and Re) concentrations and 187Os/188Os ratios for ultramafic rocks distributed over the Eoarchean gneiss complex of the Saglek-Hebron area in northern Labrador, Canada in order to constrain to what extent variations in HSE abundances are recorded in Early Archean mantle that have well-resolved 182W isotope anomalies relative to the present-day mantle (∼+11 ppm: Liu et al., 2016). The samples analysed here have been previously classified into two suites: mantle-derived peridotites occurring as tectonically-emplaced slivers of lithospheric mantle, and metakomatiites comprising mostly pyroxenitic layers in supracrustal units dominated by amphibolites. Although previous Sm-Nd and Pb-Pb isotope studies provided whole-rock isochrons indicative of ∼3.8 Ga protolith formation for both suites, our whole-rock Re-Os isotope data on a similar set of samples yield considerably younger errorchrons with ages of 3612 ± 130 Ma (MSWD = 40) and 3096 ± 170 Ma (MSWD = 10.2) for the metakomatiite and lithospheric mantle suites, respectively. The respective initial 187Os/188Os = 0.10200 ± 18 for metakomatiites and 0.1041 ± 18 for lithospheric mantle rocks are within the range of chondrites. Re-depletion Os model ages for unradiogenic samples from the two suites are consistent with the respective Re-Os errorchrons (metakomatiite TRD = 3.4–3.6 Ga; lithospheric mantle TRD = 2.8–3.3 Ga). These observations suggest that the two ultramafic suites are not coeval. However, the estimated mantle sources for the two ultramafics suites are similar in terms of their broadly chondritic evolution of 187Os/188Os and their relative HSE patterns. In detail, both mantle sources show a small excess of Ru/Ir similar to that in modern primitive mantle, but a ∼20% deficit in absolute HSE abundances relative to that in modern primitive mantle (metakomatiite 74 ± 18% of PUM; lithospheric mantle 82 ± 10% of PUM), consistent with the ∼3.8 Ga Isua mantle source and Neoarchean komatiite sources around the world (∼70–86% of PUM). This demonstrates that the lower HSE abundances are not unique to the sources of komatiites, but rather might be a ubiquitous feature of Archean convecting mantle. This tentatively suggests that chondritic late accretion components boosted the convecting mantle HSE inventory after core separation in the Hadean, and that the Eoarchean to Neoarchean convecting mantle was depleted in its HSE content relative to that of today. Further investigation of Archean mantle-derived rocks is required to explore this hypothesis.

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.

We have determined U–Pb ages, trace element abundances and Hf isotopic compositions of approximately 1000 detrital zircon grains from the Mississippi, Congo, Yangtze and Amazon Rivers. The U–Pb isotopic data reveal the lack of >3.3 Ga zircons in the river sands, and distinct peaks at 2.7–2.5, 2.2–1.9, 1.7–1.6, 1.2–1.0, 0.9–0.4, and The striking attribute of our new data set is the non-uniformitarian secular change in Hf isotopes of granitoid crusts; Hf isotopic compositions of granitoid crusts deviate from the mantle evolution line from about 3.3 to 2.0 Ga, the deviation declines between 2.0 and 1.3 Ga and again increases afterwards. Consideration of mantle-crust mixing models for granitoid genesis suggests that the noted isotopic trends are best explained if the rate of crust generation globally increased in two stages at around (or before) 3.3 and 1.3 Ga, whereas crustal differentiation was important in the evolution of the continental crust at 2.3–2.2 Ga and after 0.6 Ga. Reconciling the isotopic secular change in granitoid crust with that in sedimentary rocks suggests that sedimentary recycling has essentially taken place in continental settings rather than active margin settings and that the sedimentary mass significantly grew through addition of first-cycle sediments from young igneous basements, until after ∼1.3 Ga when sedimentary recycling became the dominant feature of sedimentary evolution. These findings, coupled with the lack of zircons older than 3.3 Ga in river sands, imply the emergence of large-scale continents at about 3.3 Ga with further rapid growth at around 1.3 Ga. This resulted in the major growth of the sedimentary mass between 3.3 and 1.3 Ga and the predominance of its cannibalistic recycling later.

The redox state of Precambrian shallow seas has been linked with material cycle and evolution of the photosynthesis-based ecosystem. Iron is a redox-sensitive element and exists as a soluble Fe(II) species or insoluble Fe(III) species on Earth’s surface. Previous studies have shown that the iron isotopic ratio of marine sedimentary minerals is useful for understanding the ocean redox state, although the redox state of the Archean shallow sea is poorly known. This is partly because the conventional bulk isotope analytical technique has often been used, wherein the iron isotopic record may be dampened by the presence of isotopically different iron-bearing minerals within the same sample. Here we report a microscale iron isotopic ratio of individual pyrite grains in shallow marine stromatolitic carbonates over geological time using a newly developed, near-infrared femtosecond laser ablation multicollector ICP-MS technique (NIR-fs-LA-MC-ICP-MS). We have determined that the grain-scale iron isotopic distribution of pyrite from coeval samples shows a bimodal (2.7 and 2.3 Ga) or unimodal pattern (2.9, 2.6, and 0.7 Ga). In particular, pyrite from the 2.7 Ga Fortescue Group shows a unique bimodal distribution with highly positive (+1.0‰ defined as Type 1) and negative δ56Fe values (−1.8‰ defined as Type 2). Type 1 and 2 pyrites occasionally occur within different siliceous layers in the same rock specimen. Layer-scale iron isotopic heterogeneity indicates that the iron isotopic ratios of the two types of pyrite are not homogenized by diagenesis after deposition. Some cubic pyrites have a core with a positive δ56Fe value (1‰) and a rim with a crustal δ56Fe value (0‰). The observed isotopic zoning suggests that the positive δ56Fe value is a primary signature at the time of stromatolite formation, while secondary pyrite precipitated during diagenesis. The positive δ56Fe value of Type 1 and the large iron isotopic difference between Type 1 and 2 (2.8‰.) suggest partial Fe(II) oxidation in the 2.7-Ga shallow sea, i.e., pyritization of 56Fe-enriched ferric oxyhydroxide (Type 1) and 56Fe depleted Fe2+aq in seawater (Type 2). Type 2 pyrite was probably not produced by microbial iron redox cycling during diagenesis because this scenario requires a higher abundance of pyrite with δ56Fe of 0‰ than of −1.8‰. Consequently, the degree of Fe(II) oxidation in the 2.7-Ga shallow sea can be estimated by a Fe2+aq steady-state model. The model calculation shows that half the Fe2+aq influx was oxidized in the seawater. This implies that O2 produced by photosynthesis would have been completely consumed by oxidation of the Fe2+aq influx. Grain-scale iron isotopic distribution of pyrite could be a useful index for reconstructing the redox state of the Archean shallow sea.

Exposure of the ca . 6 Ma Taitao ophiolite, Chile, located ∼50 km south of the Chile Triple Junction, allows detailed chemical and isotopic study of rocks that were recently extracted from the depleted mantle source of mid-ocean ridge basalts (DMM). Ultramafic and mafic rocks are examined for isotopic (Os, Sr, Nd, and O), and major and trace element compositions, including the highly siderophile elements (HSE). Taitao peridotites have compositions indicative of variable extents of partial melting and melt extraction. Low δ 18 O values for most whole rock samples suggest some open-system, high-temperature water–rock interaction, most likely during serpentinization, but relict olivine grains have δ 18 O values consistent with primary mantle values. Most of the peridotites analyzed for Nd–Sr isotopes have compositions consistent with estimates for the modern DMM, although several samples are characterized by 87 Sr/ 86 Sr and 143 Nd/ 144 Nd indicative of crustal contamination, most likely via interactions with seawater. The peridotites have initial 187 Os/ 188 Os ratios that range widely from 0.1168 to 0.1288 ( γ Os = −8.0 to +1.1), averaging 0.1239 ( γ Os = −2.4), which is comparable to the average for modern abyssal peridotites. A negative correlation between the Mg # of relict olivine grains and Os isotopic compositions of whole rock peridotites suggests that the Os isotopic compositions reflect primary mantle Re/Os fractionation produced by variable extents of partial melting at approximately 1.6 Ga. Recent re-melting at or near the spatially associated Chile Ridge further modified these rocks, and Re, and minor Pt and Pd were subsequently added back into some rocks by late-stage melt–rock or fluid–rock interactions. In contrast to the peridotites, approximately half of the mafic rocks examined have whole rock δ 18 O values within the range of mantle compositions, and their Nd and Sr isotopic compositions are all generally within the range of modern DMM. These rocks have initial 187 Os/ 188 Os ratios, calculated for 6 Ma, that range from 0.126 ( γ Os = −1) to as high as 0.561 ( γ Os = +342). The Os isotopic systematics of each of these rocks may reflect derivation from mixed lithologies that include the peridotites, but may also include pyroxenites with considerably more radiogenic Os than the peridotites. This observation supports the view that suprachondritic Os present in MORB derives from mixed mantle source lithologies, accounting for some of the worldwide dichotomy in 187 Os/ 188 Os between MORB and abyssal peridotites. The collective results of this study suggest that this >500 km 3 block of the mantle underwent at least two stages of melting. The first stage occurred at ∼1.6 Ga, after which the block remained isolated and unmixed within the DMM. A final stage of melting recently occurred at or near the Chile Ridge, resulting in the production of at least some of the mafic rocks. Convective stirring of this mantle domain during a >1 Ga period was remarkably inefficient, at least with regard to Os isotopes.

In-situ ion microprobe measurements of carbon isotopic compositions of graphite were made in seven metasediments and two carbonate rocks from the ca. 3.8 Ga Isua supracrustal belt, West Greenland. The δ13C values of micron-scale graphite globules in the metasediments and the carbonate rocks vary from –18 to +2‰ and from –7 to –3‰, respectively. The maximum δ13C value of graphite globules in the metasediment rises from –14 to –5‰, as the metamorphic grade increases from epidote-amphibolite to upper amphibolite facies. In a single hand specimen, the δ13C values of graphite inclusions in garnet are ∼7‰ lower on average than those outside garnet. Similarly, graphite armored by quartz apparently shows a few permil lower δ13C values than those on grain boundaries between noncarbonate minerals. The fact that early crystallized minerals include relatively 13C-depleted graphite indicates that the regional metamorphism increased the δ13C values of the Isua graphite. This is consistent with the regional trend of 13C-enrichment accompanied by the increase of metamorphic grade. The minimum fractionation between graphite and carbonate is consistent with the equilibrium fractionation at about 400 to 550 °C. These observations indicate that isotopic exchange with isotopically heavy carbonate caused 13C-enrichment of Isua graphite. The δ13C values of graphite reported here (δ13C > –18‰) were produced either as a metamorphic modification of organic carbon with initially much lower δ13C values, or as an abiological reaction such as decomposition of carbonate. If the isotopic exchange between carbonate and graphite during regional metamorphism controlled the 13C-enrichment of Isua graphite, previously reported large 13C-depletion of graphite, especially armored by apatite (Mojzsis et al., 1996) was probably premetamorphic in origin. This supports the existence of life at Isua time (ca. 3.8 Ga).