Redox control on the tungsten isotope composition of seawater.

Free oxygen represents an essential basis for the evolution of complex life forms on a habitable Earth. The isotope composition of redox-sensitive trace elements such as tungsten (W) can possibly trace the earliest rise of oceanic oxygen in Earth's history. However, the impact of redox changes on the W isotope composition of seawater is still unknown. Here, we report highly variable W isotope compositions in the water column of a redox-stratified basin (δ186/184W between +0.347 and +0.810 ‰) that contrast with the homogenous W isotope composition of the open ocean (refined δ186/184W of +0.543 ± 0.046 ‰). Consistent with experimental studies, the preferential scavenging of isotopically light W by Mn-oxides increases the δ186/184W of surrounding seawater, whereas the redissolution of Mn-oxides causes decreasing seawater δ186/184W. Overall, the distinctly heavy stable W isotopic signature of open ocean seawater mirrors predominantly fully oxic conditions in modern oceans. We expect, however, that the redox evolution from anoxic to hypoxic and finally oxic marine conditions in early Earth's history would have continuously increased the seawater δ186/184W. Stable W isotope compositions of chemical sediments that potentially preserve changing seawater W isotope signatures might therefore reflect global changes in marine redox conditions.

Recycled selenium in hot spot-influenced lavas records ocean-atmosphere oxygenation.

Oxygenation of Earth's oceans and atmosphere through time has consequences for subducted surface signatures that are now stored in the mantle. Here, we report significant mass-dependent selenium isotope variations in modern hot spot-influenced oceanic lavas. These variations are correlated with tracers of mantle source enrichment, which can only be explained by incorporation of abyssal pelagic sediments subducted from a redox-stratified mid-Proterozoic ocean. Selenium geochemical signatures of these sediments have mostly been preserved during long-term recycling and may therefore complement the global surface sediment record as ancient oxygen archives. Combined deep mantle and surface perspectives, together with emerging models for atmospheric oxygen based on selenium systematics, further imply a significantly oxygenated ocean-atmosphere system throughout the mid-Proterozoic.

Evidence for local carbon-cycle perturbations superimposed on the Toarcian carbon isotope excursion.

A Jurassic negative carbon isotope excursion (CIE), co-evolved with Toarcian Oceanic Anoxic Event (OAE) at ~183 Ma, is suggested to be linked to a global carbon-cycle perturbation and is well documented for Toarcian terrestrial fossil woods and marine sediments around the globe. A theoretically coupled δ13 Ccarb -δ13 Corg pattern due to such dubbed global carbon-cycle event from the negative CIE in Dotternhausen Toarcian stratigraphic profile (southwest Germany) is unexpectedly disturbed by two-step δ13 Ccarb -δ13 Corg decoupling in which the last step, upper in the stratigraphic order, is of higher magnitude. However, the trigger(s) for these sudden decoupling disturbances are still poorly constrained. Here, connecting new carbon and oxygen isotope data with documentary lipid biomarkers shows that the global carbon cycle during the Toarcian OAE was disturbed by enhanced green sulfur bacteria (GSB) metabolisms and early diagenesis at local scales. The first step δ13 Ccarb -δ13 Corg decoupling was induced in the initial stage of the GSB bloom. The second step of much larger δ13 Ccarb -δ13 Corg decoupling arising from a GSB prosperity was, however, exaggerated by early diagenesis through the respiration of sulfate-reducing bacteria (SRB). Paleo-geographically distinct localities of the Tethys region show contrasting decoupled δ13 Ccarb -δ13 Corg patterns, which implies that the second-order carbon-cycle perturbations have pervasively and independently impacted the global carbon event during the Toarcian OAE.

Weathering, alteration and reconstructing Earth's oxygenation.

Deciphering the role-if any-that free oxygen levels played in controlling the timing and tempo of the radiation of complex life is one of the most fundamental questions in Earth and life sciences. Accurately reconstructing Earth's redox history is an essential part of tackling this question. Over the past few decades, there has been a proliferation of research employing geochemical redox proxies in an effort to tell the story of Earth's oxygenation. However, many of these studies, even those considering the same geochemical proxy systems, have led to conflicting interpretations of the timing and intensity of oxygenation events. There are two potential explanations for conflicting redox reconstructions: (i) that free oxygen levels were incredibly dynamic in both time and space or (ii) that collectively, as a community-including the authors of this article-we have frequently studied rocks affected by secondary weathering and alteration (particularly secondary oxidation) while neglecting to address the impact of this alteration on the generated data. There are now multiple case studies that have documented previously overlooked secondary alteration, resolving some of the conflicting constrains regarding redox evolution. Here, an analysis of a large shale geochemistry database reveals significant differences in cerium (Ce) anomalies, a common palaeoredox proxy, between outcrop and drill core samples. This inconsistency provides support for the idea that geochemical data from altered samples are frequently published in the peer-reviewed literature. As individuals and a geochemical community, most of us have been slow to appreciate how pervasive the problem is but there are examples of other communities that have faced and met the challenges raised by such quality control crises. Further evidence of the high potential for alteration of deep-time geochemical samples, and recognition of the manner in which this may lead to spurious results and palaeoenvironmental interpretations, indicate that sample archiving, in publicly accessible collections needs to become a prerequisite for publication of new palaeoredox data. Finally, the geochemical community need to think about ways to implement additional quality control measures to increase the fidelity of palaeoredox proxy work.

Selenium isotopes as tracers of a late volatile contribution to Earth from the outer Solar System.

The origin of Earth's volatiles has been attributed to a late addition of meteoritic material after core-mantle differentiation. The nature and consequences of this 'late veneer' are debated, but may be traced by isotopes of the highly siderophile, or iron-loving, and volatile element selenium. Here we present high-precision selenium isotope data for mantle peridotites, from double spike and hydride generation multi-collector inductively coupled plasma mass spectrometry. These data indicate that the selenium isotopic composition of peridotites is unaffected by petrological processes, such as melt depletion and melt-rock reaction, and thus a narrow range is preserved that is representative of the silicate Earth. We show that selenium isotopes record a signature of late accretion after core formation and that this signature overlaps only with that of the CI-type carbonaceous chondrites. We conclude that these isotopic constraints indicate the late veneer originated from the outer Solar System and was of lower mass than previously estimated. Thus, we suggest a late and highly concentrated delivery of volatiles enabled Earth to become habitable.

Limited oxygen production in the Mesoarchean ocean.

The Archean Eon was a time of predominantly anoxic Earth surface conditions, where anaerobic processes controlled bioessential element cycles. In contrast to "oxygen oases" well documented for the Neoarchean [2.8 to 2.5 billion years ago (Ga)], the magnitude, spatial extent, and underlying causes of possible Mesoarchean (3.2 to 2.8 Ga) surface-ocean oxygenation remain controversial. Here, we report δ15N and δ13C values coupled with local seawater redox data for Mesoarchean shales of the Mozaan Group (Pongola Supergroup, South Africa) that were deposited during an episode of enhanced Mn (oxyhydr)oxide precipitation between ∼2.95 and 2.85 Ga. Iron and Mn redox systematics are consistent with an oxygen oasis in the Mesoarchean anoxic ocean, but δ15N data indicate a Mo-based diazotrophic biosphere with no compelling evidence for a significant aerobic nitrogen cycle. We propose that in contrast to the Neoarchean, dissolved O2 levels were either too low or too limited in extent to develop a large and stable nitrate reservoir in the Mesoarchean ocean. Since biological N2 fixation was evidently active in this environment, the growth and proliferation of O2-producing organisms were likely suppressed by nutrients other than nitrogen (e.g., phosphorus), which would have limited the expansion of oxygenated conditions during the Mesoarchean.

Combined zinc-lead isotope and trace-metal assessment of recent atmospheric pollution sources recorded in Irish peatlands.

Atmospherically-fed Earth surface archives such as ombrotrophic peatlands, lake sediments, and ice consistently show an upward increase in Zn concentrations of hitherto unclear origin. Here, we present a combined stable Zn isotope and trace element (Zn, Cd, Ni, Cu, Cr, V, Ta, Pb) dataset for a historically polluted, near-urban bog (Liffey Head) from the east coast of Ireland. This peat record is compared to an archive from a rural site at the west coast of Ireland (Brackloon Wood). Both archives show a clear near-surface increase in Zn deposition, accompanied by periodic deposition in Cr, Ni, Mo, and V suggesting a co-genetic origin of these elements. In the Liffey Head site, biologic upward distillation of nutrients can be excluded as the origin of the elemental enrichments. The differences in the excess metal ratios between the two sites (e.g., Zn/Cd of 426-1564, east, and 77-106, west) are attributed to a higher contribution from traffic emissions (diesel, petrol) and oil-burning at the near-urban site, and dominant atmospheric influence from solid fossil fuel combustion emissions (e.g., mixed fuel, coal and wood) at the rural site. The Zn isotope composition in the historically-polluted Liffey Head bog evolved from δ66/64ZnJMC-Lyon values of 0.72 ±â€¯0.03‰ in the peat accumulated during the 19th century to lighter ratios (0.18 ±â€¯0.03‰) towards the top of the monolith (i.e., recent). Zinc-isotope ratios are positively correlated with excess metal/Cd ratios and also with 206Pb/207Pb, collectively fingerprinting the gradual change from a mining-dominated to a traffic-dominated atmospheric pollution at the east coast over the past century. A prevalent input, interpreted to represent combustion emissions from diesel engines, is observed for the past 15 years. Combined with trace elements and radiogenic Pb isotopes, the information obtained with the Zn isotope systematics adds towards an in-depth characterisation of the pollution signals.

Heavy metal mobility and valuable contents of processed municipal solid waste incineration residues from Southwestern Germany.

As conventional end-of-life disposal, municipal solid waste (MSW) incineration residues can be problematic due to potential release of toxic compounds into the environment. Using municipal solid waste incineration residues as urban-mine of valuable metals (e.g. precious metals) could provide a trash-to-treasure possibility. The objectives of the study are to (i) determine the contents of different contaminant metallic elements (Zn, Cu, Ba, Pb, Cr and Ni) in four size fractions of MSW incineration residues and discuss their mobility potential by using the modified BCR sequential extraction method; (ii) investigate the level of valuable critical contents (precious metals, rare earth elements, etc.) in these wastes. We also characterized mineralogy and elemental composition of four different grain size fractions (0-0.5, 0.5-2.0, 2.0-4.0 and 4.0-16.0 mm) of processed municipal solid waste incineration residue (PIR) from the Southwestern region of Germany, using X-ray fluorescence, X-ray powder diffraction and different spectroscopic techniques. Among all studied size fractions, grains smaller than 2 mm contained higher amounts of total extractable heavy metals in most cases. The most important finding of the study is that the total contents of Cu, Au and Pt in the incineration residues reached economically profitable levels (5.1 g/kg, 21.69 mg/kg and 17.45 mg/kg, respectively).

A case study for late Archean and Proterozoic biogeochemical iron- and sulphur cycling in a modern habitat-the Arvadi Spring.

As a consequence of Earth's surface oxygenation, ocean geochemistry changed from ferruginous (iron(II)-rich) into more complex ferro-euxinic (iron(II)-sulphide-rich) conditions during the Paleoproterozoic. This transition must have had profound implications for the Proterozoic microbial community that existed within the ocean water and bottom sediment; in particular, iron-oxidizing bacteria likely had to compete with emerging sulphur-metabolizers. However, the nature of their coexistence and interaction remains speculative. Here, we present geochemical and microbiological data from the Arvadi Spring in the eastern Swiss Alps, a modern model habitat for ferro-euxinic transition zones in late Archean and Proterozoic oceans during high-oxygen intervals, which enables us to reconstruct the microbial community structure in respective settings for this geological era. The spring water is oxygen-saturated but still contains relatively elevated concentrations of dissolved iron(II) (17.2 ± 2.8 µM) and sulphide (2.5 ± 0.2 µM) with simultaneously high concentrations of sulphate (8.3 ± 0.04 mM). Solids consisting of quartz, calcite, dolomite and iron(III) oxyhydroxide minerals as well as sulphur-containing particles, presumably elemental S0 , cover the spring sediment. Cultivation-based most probable number counts revealed microaerophilic iron(II)-oxidizers and sulphide-oxidizers to represent the largest fraction of iron- and sulphur-metabolizers in the spring, coexisting with less abundant iron(III)-reducers, sulphate-reducers and phototrophic and nitrate-reducing iron(II)-oxidizers. 16S rRNA gene 454 pyrosequencing showed sulphide-oxidizing Thiothrix species to be the dominating genus, supporting the results from our cultivation-based assessment. Collectively, our results suggest that anaerobic and microaerophilic iron- and sulphur-metabolizers could have coexisted in oxygenated ferro-sulphidic transition zones of late Archean and Proterozoic oceans, where they would have sustained continuous cycling of iron and sulphur compounds.

Elemental and isotopic behaviour of Zn in Deccan basalt weathering profiles: Chemical weathering from bedrock to laterite and links to Zn deficiency in tropical soils.

Zinc (Zn) is a micronutrient for organisms and essential for plant growth, therefore knowledge of its elemental cycling in the surface environment is important regarding wider aspects of human nutrition and health. To explore the nature of Zn cycling, we compared its weathering behaviour in a sub-recent regolith versus an ancient laterite profile of the Deccan Traps, India - an area of known soil Zn deficiency. We demonstrate that progressive breakdown of primary minerals and the associated formation of phyllosilicates and iron oxides leads to a depletion in Zn, ultimately resulting in a loss of 80% in lateritic residues. This residue is mainly composed of resistant iron oxides and hydroxides ultimately delivering insufficient amounts of bio-available Zn. Moreover, (sub)-tropical weathering in regions experiencing extended tectonic quiescence (e.g., cratons) further enhance the development of old and deep soil profiles that become deficient in Zn. This situation is clearly revealed by the spatial correlation of the global distribution of laterites, cratons (Africa, India, South America and Australia) and known regions of Zn deficient soils that result in health problems for humans whose diet is derived from such land. We also investigate whether this elemental depletion of Zn is accompanied by isotope fractionation. In the saprolitic horizons of both weathering profiles, compositions of δ66ZnJMC-Lyon lie within the "crustal average" of +0.27±0.07‰ δ66ZnJMC-Lyon. By contrast, soil horizons enriched in secondary oxides show lighter isotope compositions. The isotopic signature of Zn (Δ66Znsample-protolith up to ~ -0.65‰) during the formation of the ferruginous-lateritic weathering profile likely resulted from a combination of biotically- and kinetically-controlled sorption reactions on Fe-oxyhydroxides. Our findings suggest that oxide rich soil types/horizons in (sub)-tropical regions likely exert a control on riverine Zn isotope compositions such that these become heavier than the crustal average. This isotopic behaviour invites a broader study of global soils to test whether light isotope composition alone could serve as an indicator for reduced bioavailability of Zn.

Preparation and purification of organic samples for selenium isotope studies.

Selenium (Se) is an important micronutrient but also a strong toxin with a narrow tolerance range for many organisms. As such, a globally heterogeneous Se distribution in soils is responsible for various disease patterns (i.e. Se excess and deficiency) and environmental problems, whereby plants play a key role for the Se entrance into the biosphere. Selenium isotope variations were proved to be a powerful tracer for redox processes and are therefore promising for the exploration of the species dependent Se metabolism in plants and the Se cycling within the Critical Zone. Plant cultivation setups enable systematic controlled investigations, but samples derived from them-plant tissue and phytoagar-are particularly challenging and require specific preparation and purification steps to ensure precise and valid Se isotope analytics performed with HG-MC-ICP-MS. In this study, different methods for the entire process from solid tissue preparation to Se isotope measurements were tested, optimized and validated. A particular microwave digestion procedure for plant tissue and a vacuum filtration method for phytoagar led to full Se recoveries, whereby unfavorable organic residues were reduced to a minimum. Three purification methods predominantly described in the literature were systematically tested with pure Se solution, high concentrated multi-element standard solution as well as plant and phytoagar as target matrices. All these methods efficiently remove critical matrix elements, but differ in Se recovery and organic residues. Validation tests doping Se-free plant material and phytoagar with a reference material of known Se isotope composition revealed the high impact of organic residues on the accuracy of MC-ICP-MS measurements. Only the purification method with no detectable organic residues, hydride generation and trapping, results in valid mass bias correction for plant samples with an average deviation to true δ82/76Se values of 0.2 ‰ and a reproducibility (2 SD) of ± 0.2 ‰. For phytoagar this test yields a higher deviation of 1.1 ‰ from the true value and a 2 SD of ± 0.1 ‰. The application of the developed methods to cultivated plants shows sufficient accuracy and precision and is a promising approach to resolve plant internal Se isotope fractionations, for which respective δ82/76Se values of +2.3 to +3.5 ‰ for selenate and +1.2 to +1.9 ‰ for selenite were obtained.

Hereditary hemochromatosis is reflected in the iron isotope composition of blood.

It has recently been shown that the iron isotopic composition of blood differs between individuals and sexes, which is supposed to reflect individual differences in iron metabolism. We hypothesized that patients suffering from hereditary hemochromatosis would demonstrate alterations in the iron isotopic composition of blood due to persistent up-regulation of intestinal iron absorption. Blood from 30 patients with homozygous C282Y hemochromatosis was analyzed for iron isotopic composition by a newly developed technique using multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS). Blood of patients with hemochromatosis is characterized by a higher 56Fe/54Fe isotope ratio than blood of healthy individuals, which are either members of an age-matched control group (n = 10; P < .001) or young adults (n = 36; P < .001). In patients with hereditary hemochromatosis, the 56Fe/54Fe isotope ratio of blood significantly correlates with total-body iron accumulation, severity of clinical disease, and the need for regular phlebotomies to prevent iron reaccumulation. We conclude that blood of patients with hereditary hemochromatosis contains more of the heavier iron isotopes than blood of healthy individuals. The primary determinant of the iron isotopic composition of blood appears to be isotope-sensitive iron absorption in the intestine and the efficiency of this process.

Tungsten isotope evidence from approximately 3.8-Gyr metamorphosed sediments for early meteorite bombardment of the Earth.

The 'Late Heavy Bombardment' was a phase in the impact history of the Moon that occurred 3.8 4.0 Gyr ago, when the lunar basins with known dates were formed. But no record of this event has yet been reported from the few surviving rocks of this age on the Earth. Here we report tungsten isotope anomalies, based on the (182)Hf (182)W system (half-life of 9 Myr), in metamorphosed sedimentary rocks from the 3.7 3.8-Gyr-old Isua greenstone belt of West Greenland and closely related rocks from northern Labrador, Canada. As it is difficult to conceive of a mechanism by which tungsten isotope heterogeneities could have been preserved in the Earth's dynamic crust mantle environment from a time when short-lived (182)Hf was still present, we conclude that the metamorphosed sediments contain a component derived from meteorites.