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

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

The chemical composition and nickel,cobalt, copper,zinc and lead contents of Nanao Bay sediments

The contents of major and some of the minor elements, nickel, cobalt, copper, zinc and lead were studied on sediments collected from three inlets of Nanao Bay located at eastern side of Noto Peninsula. Little variation was found on the average contents of silicon, iron, titanium, aluminum, manganese, magnesium and potassium among the sediments of West, South and North Bays in Nanao Bay. Whereas significant difference was found on the contents of calcium, chlorine, sulfur and nitrogen among sediments of three bays.As to the minor elements, the average contents of nickel (20±5 ppm), cobalt (5±1 ppm), copper (18±5 ppm) and lead (17±8 ppm) are relatively low but zinc content is high in these sediments comparing with those of coastal deposit around Japan Island. From the results obtained here, it became clear that no environmental contamination of nickel, cobalt, copper and lead, and a little organic pollution were found in Nanao Bay sediments.     

Relation between mean and variance in catch numbers of fish egg and larva

In each of six areas with various horizontal scale from 0.4 to 15.6 nautical miles, many surveys with vertical net hauls are made for sampling fish eggs and larvae. Though values ofC _A are widely spread in each area, the variances ² and the meanm of catch numbers calculated from each survey follow approximately the relation from a Poisson mixture model (PMM).

Determination of Sr/Sr mass-dependent isotopic fractionation and radiogenic isotope variation of Sr/Sr in the Neoproterozoic Doushantuo Formation

We measured both mass-dependent isotope fractionation of δ⁸⁸Sr (⁸⁸Sr/⁸⁶Sr) and radiogenic isotopic variation of Sr (⁸⁷Sr/⁸⁶Sr) for the Neoproterozoic Doushantuo Formation that deposited as a cap carbonate immediately above the Marinoan-related Nantuo Tillite. The δ⁸⁸Sr and ⁸⁷Sr/⁸⁶Sr compositions showed three remarkable characteristics: (1) high radiogenic ⁸⁷Sr/⁸⁶Sr values and gradual decrease in the ⁸⁷Sr/⁸⁶Sr ratios, (2) anomalously low δ⁸⁸Sr values at the lower part cap carbonate, and (3) a clear correlation between ⁸⁷Sr/⁸⁶Sr and δ⁸⁸Sr values. These isotopic signatures can be explained by assuming an extreme greenhouse condition after the Marinoan glaciation. Surface seawater, mixed with a large amount of freshwater from continental crusts with high ⁸⁷Sr/⁸⁶Sr and lighter δ⁸⁸Sr ratios, was formed during the extreme global warming after the glacial event. High atmospheric CO₂ content caused sudden precipitation of cap carbonate from the surface seawater with high ⁸⁷Sr/⁸⁶Sr and lighter δ⁸⁸Sr ratios. Subsequently, the mixing of the underlying seawater, with unradiogenic Sr isotope compositions and normal δ⁸⁸Sr ratios, probably caused gradual decrease of the ⁸⁷Sr/⁸⁶Sr ratios of the seawater and deposition of carbonate with normal δ⁸⁸Sr ratios. The combination of ⁸⁷Sr/⁸⁶Sr and δ⁸⁸Sr isotope systematics gives us new insights on the surface evolution after the Snowball Earth.     

Earthquake‐related geomorphic environment and pond sediment information

Shaking during the 1995 Kobe earthquake caused surface material to be more mobile in catchment areas in the Rokko Mountains, Kobe, where there are some active fault lines. As a result, there were many landslides associated with the earthquake. The sedimentation rate in a pond in the mountains increased several fold, then exponentially decreased with seasonality over several years. Six years after the earthquake there were no marked surface movements related to the earthquake, even though the sedimentation rates had increased slightly. A new steady state for the structure of the earthquake‐modi?ed surface had evidently been reached. Copyright © 2004 John Wiley & Sons, Ltd.     

Carbon isotopes and petrography of kerogens in ∼3.5-Ga hydrothermal silica dikes in the North Pole area, Western Australia

More than 600 specimens of ∼3.5 Ga-old hydrothermal silica dikes from the North Pole area, Pilbara craton, Western Australia, have been studied petrographically. The kerogens in 44 samples have been analyzed isotopically (C and N) and chemically (C, N, and H). The silica dikes are composed mainly of fine-grained silica (modal abundance: >97%) and are classified into two types by minor mineral assemblages: B(black)-type and G(gray)-type. The B-type silica dikes contain kerogen (0.37 to 6.72 mgC/g; average 2.44 mgC/g, n = 21) and disseminated sulfides, dominantly pyrite and Fe-poor sphalerite. In some cases, carbonate and apatite are also present. Their silica-dominated and sulfide-poor mineral assemblages suggest precipitation from low-temperature reducing hydrothermal fluid (likely 100-200°C). On the other hand, the G-type silica dikes are sulfide-free and concentrations of kerogen are relatively low (0.05 to 0.41 mgC/g; average 0.17 mgC/g, n = 13). They typically contain Fe-oxide (mainly hematite) which commonly replaces cubic pyrite and rhombic carbonate. Some G-types occur along secondary quartz veins. These textures indicate that the G-type silica dikes were formed by postdepositional metasomatism (oxidation) of the B-types, and that the B-types probably possess premetasomatic signatures. The δ¹³C values of kerogen in the B-types are −38.1 to −33.1‰ (average −35.9‰, n = 21), which are ∼4‰ lower than those of the G-types (−34.5 to −30.0‰; average −32.2‰, n = 19), and ∼6‰ lower than bedded chert (−31.2 to −29.4‰; average −30.5‰, n = 4). This indicates the preferential loss of ¹²C during the metasomatism (estimated fractionation factor: 0.9985). Considering the metasomatic effect on carbon isotopes with probably minor diagenetic and metamorphic overprints, we conclude that the original δ¹³C values of the kerogen in the silica dikes would have been heterogeneous (∼5‰) and at least some material had initial δ¹³C values of ≤ −38‰. The inferred ¹³C-depletions of organic carbon could have been produced by anaerobic chemoautotrophs such as methanogen, but not by aerobic photoautotrophs. This is consistent with the estimated physical and chemical condition of the hydrothermal fluid, which was probably habitable for anaerobic and thermophilic/hyperthermophilic chemoautotrophs. Alternatively, the organic matter may have been possibly produced by abiological reaction such as Fischer-Tropsch Type (FTT) synthesis under the hydrothermal condition. However, the estimated condition is inconsistent with the presence of the effective catalysts for the FTT reaction (i.e., Fe-Ni alloy, magnetite, and hematite). These lines of evidence suggest the possible existence of biosphere in the ∼3.5 Ga sub-seafloor hydrothermal system.     

Polysynthetically-twinned structures of enstatite and wollastonite

Crystal structures of clinoenstatite, orthoenstatite, wollastonite-1T and wollastonite-2M (parawollastonite) were refined to an R factor 3–4 percent level. Molar volumes at room temperature are 31.270(15), 31.315(8), 39.842(5) and 39.901(10) cm³/MSiO₃, in the above-mentioned order, indicating that one-layer polytypes (clinoenstatite and wollastonite-1T) are stable at higher pressures than two-layer polytypes (orthoenstatite and wollastonite-2M). The polytypic relation of the enstatite polytypes can be described by four twinning operations — b glide ∥ to (110), a glide ∥ to (001), twofold screw axis ∥ to a (of orthoenstatite) and a twofold screw axis ∥ to c. For the wollastonite polytypes, twinning operations are twofold screw axis ∥ to b and a glide ∥ to (010). Structural adjustments after twinning are not necessarily the largest at the twin boundary (true in enstatite but not so in wollastonite). In both cases octahedral sites that involve bridging oxygens tend to show relatively large changes. Lattice strain ellipsoids associated with twinning are also different for enstatite and wollastonite, which implies that wollastonite may react differently from enstatite to non-hydrostatic pressure.