Pyrite paragenesis and multiple sulfur isotope distribution in late Archean and early Paleoproterozoic Hamersley Basin sediments

The sulfur isotope record in late Archean and early Paleoproterozoic rocks is of considerable importance because it provides evidence for changes in early Earth atmospheric oxygen levels and potentially constrains the origin and relative impact of various microbial metabolisms during the transition from an anoxic to oxic atmosphere. Mass independently fractionated (MIF) sulfur isotopes reveal late Archean and early Paleoproterozoic sulfur sources in different pyrite morphologies in Western Australia's Hamersley Basin. Multiple sulfur isotope values in late Archean pyrite vary according to morphology. Fine grained pyrite has positive sulfur MIF, indicating a reduced elemental sulfur source, whereas pyrite nodules have negative sulfur MIF, potentially derived from soluble sulfate via microbial sulfate reduction. The Hamersley Basin δ³⁴S–Δ³³S record suggests that the extent of oxygenation of the surface ocean fluctuated through the Late Archean from at least 2.6 Ga, more than 150 million yr before the Great Oxidation Event. In the early Paleoproterozoic, there is less distinction between pyrite morphologies with respect to sulfur isotope fractionation, and pyrite from the Brockman Iron Formation trends toward modern sulfur isotope values. An important exception to this is the strong negative MIF recorded in layer parallel pyrite in Paleoproterozoic carbonate facies iron formation. This may suggest that deeper water hydrothermal environments remained anoxic while shallower water environments became more oxidised by the early Paleoproterozoic. The results of the current study indicate that sulfide paragenesis is highly significant when investigating Archean and early Paleoproterozoic multiple sulfur isotope compositions and sulfur sources.     

Preserved organic matter in a fossil Ocean Continent Transition in the Alps: the example of Totalp,SE Switzerland

Evidence from ultraslow spreading mid-ocean ridges and both fossil and present-day Ocean–Continent Transitions (OCT) demonstrates that mantle serpentinization resulting from the interaction of mantle rock and water during tectonic exhumation is widespread. Observations at white smokers in modern ocean settings suggest that methane produced by serpentinization can support methanotrophic bio-systems, which use methane as the only source of carbon. An important question is whether such bio-systems are more generally pervasive in their association with serpentinized mantle in the subsurface. In this study, we examined whether there is evidence for such a methanotrophic system in exhumed serpentinized mantle at a magma-poor rifted continental margin, by probing for characteristic biological markers in these and associated sedimentary rocks in the Totalp unit of SE Switzerland. This unit represents a remnant of the former OCT of the southern Alpine Tethyan margin and was chosen because of its mild Alpine tectonic and low-grade metamorphic overprint during Alpine orogeny, hence giving potential for the preservation of indigenous organic matter (OM). Totalp samples are characterized by low organic carbon contents of 11–647 ppm. The majority of the samples contain hydrocarbons in the form of n-alkanes in the range C₁₇–C₃₆. Some sediments contain isoprenoids, for example pristane and phytane and a suite of steranes that are consistent with a marine origin for the OM preserved in the rocks. Traces of marine planktonic and bacterial OM are preserved in the serpentinized mantle and overlying sediments of this ancient Tethyan OCT, but there is no evidence that the OM has been generated from methanotrophic bio-systems.     

Understanding river dune splitting through flume experiments and analysis of a dune evolution model

Forecasts of water level during river floods require accurate predictions of the evolution of river dune dimensions, because the hydraulic roughness of the main channel is largely determined by the bed morphology. River dune dimensions are controlled by processes like merging and splitting of dunes. Particularly the process of dune splitting is still poorly understood and – as a result – not yet included in operational dune evolution models. In the current paper, the process of dune splitting is investigated by carrying out laboratory experiments and by means of a sensitivity analysis using a numerical dune evolution model. In the numerical model, we introduced superimposed TRIAS ripples (i.e. triangular asymmetric stoss side‐ripples) on the stoss sides of underlying dunes as soon as these stoss sides exceed a certain critical length. Simulations with the model including dune splitting showed that predictions of equilibrium dune characteristics were significantly improved compared to the model without dune splitting. As dune splitting is implemented in a parameterized way, the computational cost remains low which means that dune evolution can be calculated on the timescale of a flood wave. Subsequently, we used this model to study the mechanism of dune splitting. Literature showed that the initiation of a strong flow separation zone behind a superimposed bedform is one of the main mechanisms behind dune splitting. The flume experiments indicated that besides its height also the lee side slope of the superimposed bedform is an important factor to determine the strength of the flow separation zone and therefore is an important aspect in dune splitting. The sensitivity analysis of the dune evolution model showed that a minimum stoss side length was required to develop a strong flow separation zone. Copyright © 2014 John Wiley & Sons, Ltd.     

Arsenic in an alkaline AMD treatment sludge: Characterization and stability under prolonged anoxic conditions

Lime treatment of acid mine drainage (AMD) generates large volumes of neutralization sludge that are often stored under water covers. The sludge consists mainly of calcite, gypsum and a widespread ferrihydrite-like Fe phase with several associated species of metal(loid) contaminants. The long-term stability of metal(loid)s in this chemically ill-defined material remains unknown. In this study, the stability and speciation of As in AMD sludge subjected to prolonged anoxic conditions is determined. The total As concentration in the sludge is 300 mg kg⁻¹. In the laboratory, three distinct water cover treatments were imposed on the sludge to induce different redox conditions (100%N₂, 100%N₂ + glucose, 95%N₂:5%H₂). These treatments were compared against a control of oxidized, water-saturated sludge. Electron micro-probe (EMP) analysis and spatially resolved synchrotron X-ray fluorescence (SXRF) results indicate that As is dominantly associated with Fe in the sludge. In all treatments and throughout the experiment, measured concentrations of dissolved As were less than 5 μg L⁻¹. Dissolved Mn concentration in the N₂ + glucose treatment increased significantly compared to other treatments. Manganese and As K-edge X-ray absorption near edge structure spectroscopy (XANES) analyses showed that Mn was the redox-active element in the solid-phase, while As was stable. Arsenic(V) was still the dominant species in all water-covered sludges after 9 months of anoxic treatments. In contrast, Mn(IV) in the original sludge was partially reduced into Mn(II) in all water-covered sludges. The effect was most pronounced in the N₂ + glucose treatment, suggesting microbial reduction. Micro-scale SXRF and XANES analysis of the treated sludge showed that Mn(II) accumulated in areas already enriched in Fe and As. Overall, the study shows that AMD sludges remain stable under prolonged anoxic conditions. External sources of chemical reductants or soluble C were needed to induce lower redox state in the systems, and even under these imposed treatments, only weakly reducing conditions (Mn threshold) developed. The results suggest that As(V) in AMD sludge will remain stable under prolonged anoxic conditions as long as Mn(IV) is present and organic matter accumulation is negligible.     

Strong variation in weathering of layered rock maintains hillslope‐scale strength under high precipitation

The evolution of volcanic landscapes and their landslide potential are both dependent upon the weathering of layered volcanic rock sequences. We characterize critical zone structure using shallow seismic V_p and V_s profiles and vertical exposures of rock across a basaltic climosequence on Kohala peninsula, Hawai’i, and exploit the dramatic gradient in mean annual precipitation (MAP) across the peninsula as a proxy for weathering intensity. Seismic velocity increases rapidly with depth and the velocity–depth gradient is uniform across three sites with 500–600 mm/yr MAP, where the transition to unaltered bedrock occurs at a depth of 4 to 10 m. In contrast, velocity increases with depth less rapidly at wetter sites, but this gradient remains constant across increasing MAP from 1000 to 3000 mm/yr and the transition to unaltered bedrock is near the maximum depth of investigation (15–25 m). In detail, the profiles of seismic velocity and of weathering at wet sites are nowhere monotonic functions of depth. The uniform average velocity gradient and the greater depths of low velocities may be explained by the averaging of velocities over intercalated highly weathered sites with less weathered layers at sites where MAP > 1000 mm/yr. Hence, the main effect of climate is not the progressive deepening of a near‐surface altered layer, but rather the rapid weathering of high permeability zones within rock subjected to precipitation greater than ~1000 mm/yr. Although weathering suggests mechanical weakening, the nearly horizontal orientation of alternating weathered and unweathered horizons with respect to topography also plays a role in the slope stability of these heterogeneous rock masses. We speculate that where steep, rapidly evolving hillslopes exist, the sub‐horizontal orientation of weak/strong horizons allows such sites to remain nearly as strong as their less weathered counterparts at drier sites, as is exemplified by the 50°–60° slopes maintained in the amphitheater canyons on the northwest flank of the island. Copyright © 2017 John Wiley & Sons, Ltd.     

The Monitor project: rotation of low-mass stars in the open cluster NGC 2547

We report on the results of an I -band time-series photometric survey of NGC 2547 using the MPG/ESO 2.2-m telescope with Wide Field Imager, achieving better than 1 per cent photometric precision per data point over  14 ≲ I ≲ 18  . Candidate cluster members were selected from a V versus V − I colour–magnitude diagram over  12.5 < V < 24  (covering masses from  0.9 M_⊙  down to below the brown dwarf limit), finding 800 candidates, of which we expect ∼330 to be real cluster members, taking into account contamination from the field (which is most severe at the extremes of our mass range). Searching for periodic variations in these gave 176 detections over the mass range  0.1 ≲ M /M_⊙≲ 0.9  . The rotation period distributions were found to show a clear mass-dependent morphology, qualitatively intermediate between the distributions obtained from similar surveys in NGC 2362 and 2516, as would be expected from the age of this cluster. Models of the rotational evolution were investigated, finding that the evolution from NGC 2362 to 2547 was qualitatively reproduced (given the uncertainty in the age of NGC 2547) by solid body and core-envelope decoupled models from our earlier NGC 2516 study without need for significant modification.     

Setting nutrient thresholds to support an ecological assessment based on nutrient enrichment, potential primary production and undesirable disturbance

The EU Water Framework Directive recognises that ecological status is supported by the prevailing physico-chemical conditions in each water body. This paper describes an approach to providing guidance on setting thresholds for nutrients taking account of the biological response to nutrient enrichment evident in different types of water. Indices of pressure, state and impact are used to achieve a robust nutrient (nitrogen) threshold by considering each individual index relative to a defined standard, scale or threshold. These indices include winter nitrogen concentrations relative to a predetermined reference value; the potential of the waterbody to support phytoplankton growth (estimated as primary production); and detection of an undesirable disturbance (measured as dissolved oxygen). Proposed reference values are based on a combination of historical records, offshore (limited human influence) nutrient concentrations, literature values and modelled data. Statistical confidence is based on a number of attributes, including distance of confidence limits away from a reference threshold and how well the model is populated with real data. This evidence based approach ensures that nutrient thresholds are based on knowledge of real and measurable biological responses in transitional and coastal waters.     

Sulfides in mantle peridotites from Penghu Islands, Taiwan: Melt percolation, PGE fractionation, and the lithospheric evolution of the South China block

Major elements, highly siderophile elements (HSE) and Re-Os isotope ratios were analysed in situ on individual sulfide grains in spinel peridotite xenoliths hosted by Miocene intraplate basalts from the Penghu Islands, Taiwan. The xenoliths represent texturally and compositionally different mantle domains, and the geochemical characteristics of the sulfides show changes in HSE distribution and Re-Os isotope systematics, produced as their host rocks were metasomatised by percolating fluids/melts. In prophyroclastic and partly metasomatised peridotites from the Kueipi (KP) locality, the sulfides have subchondritic to superchondritic ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os ratios. Many of these sulfides reflect fluid/melt interaction with residual MSS and/or crystallization of fractionated sulfide melts, which produced high contents of Cu and PPGEs and high Re/Os; inferred melt/rock ratios are low. In contrast, sulfides in equigranular and extensively metasomatised peridotites from the Tungchiyu (TCY) locality are mainly more sulfur-rich Ni-(Co)-rich MSS, with subchondritic to chondritic ¹⁸⁷Os/¹⁸⁸Os and subchondritic ¹⁸⁷Re/¹⁸⁸Os. These sulfides are interpreted as products of interaction between pre-existing MSS and percolating silicate melts. Melt/rock ratios were high and the percolating melt was less differentiated than the melt that percolated the KP peridotites. Sulfides in a TCY pyroxenite are mainly MSS; they have the lowest HSE contents, subchondritic to superchondritic ¹⁸⁷Os/¹⁸⁸Os and subchondritic ¹⁸⁷Re/¹⁸⁸Os, and may have precipitated from sulfide melts that segregated from basaltic melts under S-saturated conditions. In most sulfides melt percolation appears to have induced fractionation among the HSEs and disturbed Re-Os isotope compositions. Despite the metasomatic effects, rare residual MSS, sulfides that from crystallised sulfide melts and sulfides modified by addition of Re (with no evidence for Os addition) can still provide useful chronological information. Such sulfides yield T_RD age peaks of 1.9, 1.7-1.6, 1.4-1.3 and 0.9-0.8 Ga, which may record the timing of melt extraction and/or metasomatic events in the mantle. These periods are contemporaneous with the major crustal events recorded by U-Pb dates and Nd and Hf model ages in the overlying crust. This close correspondence indicates that the sulfide T_RD ages reflect the timing of lithosphere-scale tectonothermal events (such as melting and metasomatism) that affected both the lithospheric mantle and the overlying crust. The sulfide T_RD ages, taken together with the crustal data, suggest that most of the Cathaysia block had formed at least by Paleo-Proterozoic time, and that some domains are Archean in age.     

Inclusions in diamonds from the K14 and K10 kimberlites, Buffalo Hills, Alberta, Canada: diamond growth in a plume?

Analyses of mineral inclusions, carbon isotopes, nitrogen contents and nitrogen aggregation states in 29 diamonds from two Buffalo Hills kimberlites in northern Alberta, Canada were conducted. From 25 inclusion bearing diamonds, the following paragenetic abundances were found: peridotitic (48%), eclogitic (32%), eclogitic/websteritic (8%), websteritic (4%), ultradeep? (4%) and unknown (4%). Diamonds containing mineral inclusions of ferropericlase, and mixed eclogitic-asthenospheric-websteritic and eclogitic-websteritic mineral associations suggests the possibility of diamond growth over a range of depths and in a variety of mantle environments (lithosphere, asthenosphere and possibly lower mantle).

Eclogitic diamonds have a broad range of C-isotopic composition (δ¹³C=−21‰ to −5‰). Peridotitic, websteritic and ultradeep diamonds have typical mantle C-isotope values (δ¹³C=−4.9‰ av.), except for two ¹³C-depleted peridotitic (δ¹³C=−11.8‰, −14.6‰) and one ¹³C-depleted websteritic diamond (δ¹³C=−11.9‰). Infrared spectra from 29 diamonds identified two diamond groups: 75% are nitrogen-free (Type II) or have fully aggregated nitrogen defects (Type IaB) with platelet degradation and low to moderate nitrogen contents (av. 330 ppm-N); 25% have lower nitrogen aggregation states and higher nitrogen contents (30% IaB; <1600 ppm-N).

The combined evidence suggests two generations of diamond growth. Type II and Type IaB diamonds with ultradeep, peridotitic, eclogitic and websteritic inclusions crystallised from eclogitic and peridotitic rocks while moving in a dynamic environment from the asthenosphere and possibly the lower mantle to the base of the lithosphere. Mechanisms for diamond movement through the mantle could be by mantle convection, or an ascending plume. The interaction of partial melts with eclogitic and peridotitic lithologies may have produced the intermediate websteritic inclusion compositions, and can explain diamonds of mixed parageneses, and the overlap in C-isotope values between parageneses. Strong deformation and extremely high nitrogen aggregation states in some diamonds may indicate high mantle storage temperatures and strain in the diamond growth environment. A second diamond group, with Type IaA–IaB nitrogen aggregation and peridotitic inclusions, crystallised at the base of the cratonic lithosphere. All diamonds were subsequently sampled by kimberlites and transported to the Earth's surface.