The Neoarchaean surficial sulphur cycle: An alternative hypothesis based on analogies with 20th-century atmospheric lead.

We revisit the S-isotope systematics of sedimentary pyrite in a shaly limestone from the ca. 2.52 Ga Gamohaan Formation, Upper Campbellrand Subgroup, Transvaal, South Africa. The analysed rock is interpreted to have been deposited in a water depth of ca. 50-100 m, in a restricted sub-basin on a drowning platform. A previous study discovered that the pyrites define a nonzero intercept δ34 SV-CDT -Δ33 S data array. The present study carried out further quadruple S-isotope analyses of pyrite, confirming and expanding the linear δ34 SV-CDT -Δ33 S array with an δ34 S zero intercept at ∆33 S ca. +5. This was previously interpreted to indicate mixing of unrelated S-sources in the sediment environment, involving a combination of recycled sulphur from sulphides that had originally formed by sulphate-reducing bacteria, along with elemental sulphur. Here, we advance an alternative explanation based on the recognition that the Archaean seawater sulphate concentration was likely very low, implying that the Archaean ocean could have been poorly mixed with respect to sulphur. Thus, modern oceanic sulphur systematics provide limited insight into the Archaean sulphur cycle. Instead, we propose that the 20th-century atmospheric lead event may be a useful analogue. Similar to industrial lead, the main oceanic input of Archaean sulphur was through atmospheric raindown, with individual giant point sources capable of temporally dominating atmospheric input. Local atmospheric S-isotope signals, of no global significance, could thus have been transmitted into the localised sediment record. Thus, the nonzero intercept δ34 SV-CDT -Δ33 S data array may alternatively represent a very localised S-isotope signature in the Neoarchaean surface environment. Fallout from local volcanic eruptions could imprint recycled MIF-S signals into pyrite of restricted depositional environments, thereby avoiding attenuation of the signal in the subdued, averaged global open ocean sulphur pool. Thus, the superposition of extreme local S-isotope signals offers an alternative explanation for the large Neoarchaean MIF-S excursions and asymmetry of the Δ33 S rock record.

Does a Heavy Fe-Isotope Composition of Akilia Quartz-Amphibole-Pyroxene Rocks Necessitate a BIF Origin?

The age and origin of the quartz-amphibole-pyroxene (qap) gneiss from the island of Akilia, southern West Greenland, have been the subject of intense debate since the light C-isotope composition of graphite inclusions in apatite was interpreted to indicate the presence of Earth's earliest biological activity. Although this claim for biogenic relicts has been vigorously challenged, the possibility that the rocks might represent some of Earth's earliest water-lain sediments and, hence, a suitable repository for life remains an open question. While some workers have suggested that the entire sequence represents an originally mafic-ultramafic igneous precursor subsequently modified by metasomatism, quartz injection, high-grade metamorphism, and extreme ductile deformation, others maintain that at least a small part of the sequence retains geochemical characteristics indicative of a chemical sedimentary origin. Fractionated Fe isotopes with δ(56)Fe values similar to those observed in Isua BIF have been reported from high-SiO2 units of qap and used to support a chemical sedimentary protolith for the qap unit. Here, we present new Fe isotope data from all lithologic variants in the qap gneiss on Akilia, including layers of undisputed ultramafic igneous origin. Since the latter require introduction of fractionated Fe into at least part of the qap unit, we argue that Fe isotopes must therefore be treated with considerable caution when used to infer BIF for part or all of the qap protolith.

In situ trace metal analysis of Neoarchaean--Ordovician shallow-marine microbial-carbonate-hosted pyrites.

Pre-Cambrian atmospheric and oceanic redox evolutions are expressed in the inventory of redox-sensitive trace metals in marine sedimentary rocks. Most of the currently available information was derived from deep-water sedimentary rocks (black shale/banded iron formation). Many of the studied trace metals (e.g. Mo, U, Ni and Co) are sensitive to the composition of the exposed land surface and prevailing weathering style, and their oceanic inventory ultimately depends on the terrestrial flux. The validity of claims for increased/decreased terrestrial fluxes has remained untested as far as the shallow-marine environment is concerned. Here, the first systematic study of trace metal inventories of the shallow-marine environment by analysis of microbial carbonate-hosted pyrite, from ca. 2.65-0.52 Ga, is presented. A petrographic survey revealed a first-order difference in preservation of early diagenetic pyrite. Microbial carbonates formed before the 2.4 Ga great oxygenation event (GOE) are much richer in pyrite and contain pyrite grains of greater morphological variability but lesser chemical substitution than samples deposited after the GOE. This disparity in pyrite abundance and morphology is mirrored by the qualitative degree of preservation of organic matter (largely as kerogen). Thus, it seems that in microbial carbonates, pyrite formation and preservation were related to presence and preservation of organic C. Several redox-sensitive trace metals show interpretable temporal trends supporting earlier proposals derived from deep-water sedimentary rocks. Most notably, the shallow-water pyrite confirms a rise in the oceanic Mo inventory across the pre-Cambrian-Cambrian boundary, implying the establishment of efficient deep-ocean ventilation. The carbonate-hosted pyrite also confirms the Neoarchaean and early Palaeoproterozoic ocean had higher Ni concentration, which can now more firmly be attributed to a greater proportion of magnesian volcanic rock on land rather than a stronger hydrothermal flux of Ni. Additionally, systematic trends are reported for Co, As, and Zn, relating to terrestrial flux and oceanic productivity.

Micro-scale sulphur isotope evidence for sulphur cycling in the late Archean shallow ocean.

We report in situ secondary ion mass spectrometer sulphur isotope data for sedimentary pyrite from the 2.52 Ga Upper Campbellrand Subgroup, Transvaal, South Africa. The analysed sedimentary rocks represent a transition in depositional environment from very shallow to deeper water, with strong sedimentological, facies distribution and geochemical evidence for the presence of a shallow redox chemocline. Data were obtained directly in thin section in order to preserve petrographic context. They reveal a very large extent of isotopic fractionation both in mass-independent (MIF) and in mass-dependent fractionation (MDF) on unprecedentedly small scale. In the shallow-water microbical carbonates, three types of pyrite were identified. The texturally oldest pyrite is found as small, isotopically little fractionated grains in the microbial mats. Large (several mm) spheroidal pyrite concretions, which postdate the mat pyrite, record strong evidence for an origin by bacterial sulphate reduction. Rare pyrite surrounding late fenestral calcite is inferred to have formed from recycled bacterial pyrite on account of the slope of its correlated MIF and MDF array. This latter type of pyrite was also found in an interbedded black shale and a carbonate laminite. In a deeper water chert, pyrite with very heavy sulphur indicates partial to almost complete sulphate reduction across a chemocline whose existence has been inferred independently. The combined picture from all the studied samples is that of a sulphate availability-limited environment, in which sulphur was cycled between reservoirs according to changing redox conditions established across the chemocline. Cycling apparently reduced the extent of recorded sulphur isotope fractionation relative to what is expected from projection in the correlated MIF and MDF arrays. This is consistent with regionally relatively high free oxygen concentrations in the shallow water, permitting locally strong MDF. Our new observations add to the growing evidence for a complex, fluctuating evolution of free atmospheric oxygen between c. 2.7 Ga and 2.3 Ga.