Mercury abundance and isotopic composition indicate subaerial volcanism prior to the end-Archean “whiff” of oxygen

Funding: This study was supported by National Aeronautics and Space Administration Exobiology Grant NNX16AI37G (R.B.) and by the MacArthur Professorship (J.D.B.) at the University of Michigan. M.A.K. acknowledges support from an Agouron Institute postdoctoral fellowship.Earth’s early atmosphere witnessed multiple transient episodes of oxygenation before the Great Oxidation Event 2.4 billion years ago (Ga) [e.g., A. D. Anbar et al., Science 317, 1903–1906 (2007); M. C. Koehler, R. Buick, M. E. Barley, Precambrian Res. 320, 281–290 (2019)], but the triggers for these short-lived events are so far unknown. Here, we use mercury (Hg) abundance and stable isotope composition to investigate atmospheric evolution and its driving mechanisms across the well-studied “whiff” of O2 recorded in the ∼2.5-Ga Mt. McRae Shale from the Pilbara Craton in Western Australia [A. D. Anbar et al., Science 317, 1903–1906 (2007)]. Our data from the oxygenated interval show strong Hg enrichment paired with slightly negative Δ199Hg and near-zero Δ200Hg, suggestive of increased oxidative weathering. In contrast, slightly older beds, which were evidently deposited under an anoxic atmosphere in ferruginous waters [C. T. Reinhard, R. Raiswell, C. Scott, A. D. Anbar, T. W. Lyons, Science 326, 713–716 (2009)], show Hg enrichment coupled with positive Δ199Hg and slightly negative Δ200Hg values. This pattern is consistent with photochemical reactions associated with subaerial volcanism under intense UV radiation. Our results therefore suggest that the whiff of O2 was preceded by subaerial volcanism. The transient interval of O2 accumulation may thus have been triggered by diminished volcanic O2 sinks, followed by enhanced nutrient supply to the ocean from weathering of volcanic rocks causing increased biological productivity.PostprintPeer reviewe

Mercury Stable Isotope Fractionation during Abiotic Dark Oxidation in the Presence of Thiols and Natural Organic Matter

Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/155770/1/Zheng_et_al_2018_mercury_stable.pd

Mercury abundance and isotopic composition indicate subaerial volcanism prior to the end-Archean “whiff” of oxygen

Earth’s early atmosphere witnessed multiple transient episodes of oxygenation before the Great Oxidation Event 2.4 billion years ago (Ga) [e.g., A. D. Anbar et al., Science 317, 1903–1906 (2007); M. C. Koehler, R. Buick, M. E. Barley, Precambrian Res. 320, 281–290 (2019)], but the triggers for these short-lived events are so far unknown. Here, we use mercury (Hg) abundance and stable isotope composition to investigate atmospheric evolution and its driving mechanisms across the well-studied “whiff” of O2 recorded in the ∼2.5-Ga Mt. McRae Shale from the Pilbara Craton in Western Australia [A. D. Anbar et al., Science 317, 1903–1906 (2007)]. Our data from the oxygenated interval show strong Hg enrichment paired with slightly negative Δ199Hg and near-zero Δ200Hg, suggestive of increased oxidative weathering. In contrast, slightly older beds, which were evidently deposited under an anoxic atmosphere in ferruginous waters [C. T. Reinhard, R. Raiswell, C. Scott, A. D. Anbar, T. W. Lyons, Science 326, 713–716 (2009)], show Hg enrichment coupled with positive Δ199Hg and slightly negative Δ200Hg values. This pattern is consistent with photochemical reactions associated with subaerial volcanism under intense UV radiation. Our results therefore suggest that the whiff of O2 was preceded by subaerial volcanism. The transient interval of O2 accumulation may thus have been triggered by diminished volcanic O2 sinks, followed by enhanced nutrient supply to the ocean from weathering of volcanic rocks causing increased biological productivity

From water to edible fish. Transfer of metals and metalloids in the San Roque Reservoir (Córdoba, Argentina). Implications associated with fish consumption

The concentration of Mn, Fe, Zn, Cu, Cd, Cr, Ni, Ag, Mo, Nd, Al, Ce, As, Sr, Pb, Pt and Hg was analysed in water, sediments, and aquatic organisms from the San Roque Reservoir (Córdoba-Argentina), sampled during the wet and dry season, to evaluate their transfer through the food web. Stable nitrogen (δ15N) isotopes were used to investigate trophic interactions. According to this, samples were divided into three trophic groups: plankton, shrimp (Palaemonetes argentinus) and fish (Silverside, Odontesthes bonariensis). Liver and gills are the main heavy metal storage tissues in fish. Hg and As concentrations in the muscle of O. bonariensis exceed the Oral Reference doses for metals established by USEPA (2009). Trophic magnification factors (TMFs) for each element were determined from the slope of the regression between trace element concentrations and δ15N. Calculated TMFs showed fundamental differences in the trophodynamics of the studied elements during the wet and dry season in the San Roque Reservoir. Concentrations of Ni, Cd, Cr, Al, Mn, Fe, Mo, Ce, Nd, Pt and Pb during both seasons, and Sr during the dry season, showed statistically significant decreases (TMF 1) in concentration with trophic level. Current results trigger the need for further studies to establish differential behaviour with different species within the aquatic web, particularly when evaluating the transfer of toxic elements to edible organisms, which could pose health risks to humans.Fil: Monferran, Magdalena Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; ArgentinaFil: Garnero, Paola Lorena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Diversidad y Ecología Animal. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Instituto de Diversidad y Ecología Animal; ArgentinaFil: Bistoni, Maria de Los Angeles. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Diversidad y Ecología Animal. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Instituto de Diversidad y Ecología Animal; ArgentinaFil: Anbar, Ariel A.. Arizona State University. Chemistry And Biochenistry; Estados UnidosFil: Gordon, Gwyneth W.. Arizona State University; Estados UnidosFil: Wunderlin, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Ciencia y Tecnología de Alimentos Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Ciencia y Tecnología de Alimentos Córdoba; Argentin

A Contemporary Microbially Maintained Subglacial Ferrous “Ocean”

An active microbial assemblage cycles sulfur in a sulfate-rich, ancient marine brine beneath Taylor Glacier, an outlet glacier of the East Antarctic Ice Sheet, with Fe(III) serving as the terminal electron acceptor. Isotopic measurements of sulfate, water, carbonate, and ferrous iron and functional gene analyses of adenosine 5′-phosphosulfate reductase imply that a microbial consortium facilitates a catalytic sulfur cycle. These metabolic pathways result from a limited organic carbon supply because of the absence of contemporary photosynthesis, yielding a subglacial ferrous brine that is anoxic but not sulfidic. Coupled biogeochemical processes below the glacier enable subglacial microbes to grow in extended isolation, demonstrating how analogous organic-starved systems, such as Neoproterozoic oceans, accumulated Fe(II) despite the presence of an active sulfur cycle.Chemistry and Chemical Biolog

Redox dynamics of later Cambrian oceans

A growing body of evidence suggests that the deep oceans during the early Paleozoic Era were widely oxygen deficient, despite evidence for increased marine oxygenation during the Neoproterozoic. However, the temporal and geographic extents and dynamics of reducing marine conditions within these oceans are not well understood. Here, we investigate marine redox history during the Drumian through the earliest Jiangshanian International Stages of the Cambrian Period, using concentrations of redox-sensitive metals (vanadium, uranium, and molybdenum), iron speciation, and Mo isotope stratigraphy of the Alum Shale Formation of Scandinavia. These data suggest a major perturbation occurred in trace metal cycling during the later Cambrian Period that was linked to a transient change in marine redox conditions coincident with the well-known Steptoean Positive Isotope Excursion or SPICE. The δ98Mo measurements of the Alum shale show systematic variations during the interval that contains the SPICE which are broadly consistent with a transient expansion of sulfidic, reducing marine environments — indicating a significant exacerbation of an already-common condition during the Cambrian Period. Additionally, iron speciation data record a local transition from predominantly anoxic, ferruginous (Fe+2 containing) to anoxic, euxinic (sulfide containing) water column conditions near the initiation of the SPICE. Trace metal abundances, however, appear to decline well before the start of the SPICE, suggesting an earlier initiation of the global expansion of reducing environments. More broadly, our data and modeling support the notion that significant portions of the oceans remained oxygen deficient throughout the later portion of the Cambrian, and that these oceans were also prone to transient intervals of more reducing conditions similar to the Oceanic Anoxic Events of the Mesozoic