The Northwest Africa (NWA) 5790 meteorite: A mesostasis‐rich nakhlite with little or no Martian aqueous alteration

Northwest Africa (NWA) 5790 is the most recently discovered member of the nakhlite group. Its mineralogy differs from the other nakhlites with a high abundance mesostasis (38.1 ± 3.6 vol%) and scarcity of olivine (4.0 ± 2.2 vol%). Furthermore, zoning of augite phenocrysts, and other petrographic and chemical characteristics suggest that NWA 5790 samples the chilled margin of its parent lava flow/sill. NWA 5790 contains calcite and rare clay minerals that are evidence for its exposure to liquid water. The calcite forms a cement to coatings of dust on the outer surface of the find and extends into the interior of the meteorite within veins. The presence of microbial remains within the coating confirms that the dust and its carbonate cement are terrestrial in origin, consistent with the carbon and oxygen isotope composition of the calcite. The clay minerals are finely crystalline and comprise ~0.003 vol% of the meteorite. δD values of the clay minerals range from ?212 ± 109‰ to ?96 ± 132‰, and cannot be used to distinguish between a terrestrial or Martian origin. As petrographic results are also not definitive, we conclude that secondary minerals produced by Martian groundwaters are at best very rare within NWA 5790. The meteorite has therefore sampled a region of the lava flow/sill with little or no exposure to the aqueous solutions that altered other nakhlites. This isolation could relate to the scarcity of olivine in NWA 5790 because dissolution of olivine in other nakhlites by Martian groundwaters enhanced their porosity and permeability, and provided solutes for secondary minerals.     

Proximity to ice fields and lake depth as modulators of paleoclimate records: a regional study from southwest Yukon,Canada

Pronounced climate warming during the past century has been well documented in high-latitude regions. Nonetheless, considerable heterogeneity exists in northern climate trends. We examined the roles of cryospheric landscape and lake depth in modulating the rate and magnitude of local climate responses through a paleolimnological study of lakes from southwest Yukon, Canada. By sampling lakes at varying distances from the Wrangell-St. Elias ice fields, we hypothesized that, for lakes of similar maximum depth, sites closest to the ice fields would be relatively complacent in terms of their chironomid and diatom assemblage changes over the past ~200 years. This hypothesis is based on the moderating effect of the glaciers on local climate, which would be most pronounced in the lakes nearest to the ice fields. However, given the known ecological differences between deep and shallow lakes, we further predicted that, for a given distance from the ice fields, a sediment record from a shallower lake would show the greatest change in stratigraphic subfossil assemblages. Because of the complicated shape of the ice fields, we applied the longitude for each site (which decreases from west to east) to approximate the proximity of our study lakes to the ice fields. Consistent with our predictions, we observed a space-transgressive pattern in the chironomid assemblage turnover that was associated with their proximity to the ice fields (r = ?0.75, P = 0.034, n = 8) across lakes of similar depth (mean maximum depth ± 1, SE = 18.1 ± 2.6 m). Considering a broader network of lakes that represented a greater range in maximum depth (4.9–29 m), we found that differences in subfossil chironomid assemblages between the modern and ca. AD 1800 sediment layers were strongly related to lake depth (r = ?0.77, P < 0.001, n = 15), but failed to detect a significant relationship with latitude or longitude (i.e. our proxy for proximity to the ice fields). Similarly, our comparative high-resolution analyses of two lakes with distinct lake morphometries, but similar proximities to the ice fields, demonstrated the predicted contrasting pattern: we observed pronounced post-1880 changes in the biotic assemblages in the shallow lake and a muted and delayed response (i.e. ~1970s) in the deeper lake. Our findings confirm that cryospheric landscape features can strongly modulate regional climate. Furthermore, our work shows that investigators need to be conscious of how climate change affects the structure and functioning of lakes of different typologies, which influences the way in which paleoclimate signals are recorded and interpreted.     

Bitumens associated with lead,zinc and flnorite ore minerals in North Derbyshire,England

A bitumen deposit in north Derbyshire, England, is described and studied using the techniques of gas chromatography, infra-red spectrophotometry and elemental analysis. The bitumens are associated with lead-zinc-fluorite ore minerals concentrated along an unconformable contact between the Carboniferous Limestone and the overlying shales. Three varieties of bitumen are distinguished and are compared with the dispersed bitumens in both the Carboniferous Limestone and the Edale Shales, with crude oils believed to be derived from these shales, and with inclusions in the hydrothermal mineral fiuorite, associated with the limestone-shale contact. One of the varieties recognized, a brittle brown solid, contains aliphatic hydrocarbons very similar to those of the shales and to those of the crude oils likely derived from these shales. The other two are a viscous oil and a brittle, black solid, which geologic evidence suggests were originally derived from the limestone. They contain a very complex mixture of aliphatic hydrocarbons quite different from those in the limestone, however. Aliphatic hydrocarbons isolated from fluorite, which is hydrothermally formed, in nearby massive deposits are almost identical to those of the limestone and shale. This observation indicates that alteration of the aliphatic hydrocarbons in the sediment by hydrothermal fluids is an unlikely explanation for the origin of the complex mixtures of hydrocarbons in the viscous oil and brittle, black solid. On the basis of indirect evidence of high nitrogen content, presence of unsaturated hydrocarbons, and suitability of the environment for bacterial growth, it is suggested that selective bacterial alteration of the aliphatic hydrocarbons is the main process responsible for their present composition. A geologic history for the deposit is postulated that involves a two-phase introduction of bitumens. Each phase is suggested to have begun as a pulse of warm saline fluids migrating along the shale-limestone unconformity passed through the topographic high at Windy Knoll. Microbial oxidation of the bitumens may have taken place during the deposition process or, more likely, as a recent secondary oxidation process.     

Geochemical and Sr–O isotopic constraints on magmatic differentiation at Gede Volcanic Complex, West Java, Indonesia

The Gede Volcanic Complex (GVC) of the Sunda island arc (West Java, Indonesia) consists of multiple volcanic centres and eruptive groups with complex magmatic histories. We present new petrological, mineralogical, whole-rock major and trace element and Sr–O isotopic data to provide constraints on the relative importance of fractional crystallisation and magma mixing in petrogenesis, as well as on the role and nature of the arc crust. Banded juvenile scoria from Young and Old Gede provide unequivocal evidence for the (late-stage) interaction of distinct magmas at Gede volcano. However, the relatively small-degree compositional zoning observed in plagioclase phenocrysts of all eruptive groups (up to ~20 mol% An) may be attributed to physical changes in magma properties (e.g. P, T, and PH₂O) rather than changes in melt composition. Major element and trace element variations within each eruptive series are inconsistent with magmatic evolution through simple mixing processes. Instead, mixing of variably fractionated magma batches is suggested to account for the significant scatter in some element variation diagrams. No correlation is observed between textural complexity and/or mineral disequilibrium and whole-rock geochemistry. REE data and geochemical modelling indicate that fractional crystallisation involving amphibole in the mid- to lower crust, and fractionation of plagioclase, clinopyroxene, Fe–Ti oxide ± olivine ± orthopyroxene provide strong control on the geochemical evolution of GVC rocks. Two-pyroxene geothermobarometry provides pre-eruption crystallisation temperatures of 891–1,046°C and pressures of 3.4–6.5 kbar, equivalent to ~13–24 km depth beneath the volcanoes (mid- to lower crust). Low, mantle-like clinopyroxene δ¹⁸O values of GVC lavas and poor correlation of Sr isotope ratios with indices of differentiation precludes significant assimilation of isotopically distinct crust during magmatic differentiation. Therefore, we suggest that the geochemical character of the moderately thick West Javan arc crust is relatively immature compared to typical continental crust. Trace element ratios and strontium isotopes show that the magmatic source composition of the older geographical units, Gegerbentang and Older Quaternary, is distinct from the other GVC groups.     

δC of low-molecular-weight organic acids generated by the hydrous pyrolysis of oil-prone source rocks

Low-molecular-weight (LMW) aqueous organic acids were generated from six oil-prone source rocks under hydrous-pyrolysis conditions. Differences in total organic carbon-normalized acid generation are a function of the initial thermal maturity of the source rock and the oxygen content of the kerogen (OI). Carbon-isotope analyses were used to identify potential generation mechanisms and other chemical reactions that might influence the occurrence of LMW organic acids. The generated LMW acids display increasing ¹³C content as a function of decreasing molecular weight and increasing thermal maturity. The magnitudes of observed isotope fractionations are source-rock dependent. These data are consistent with δ¹³C values of organic acids presented in a field study of the San Joaquin Basin and likely reflect the contributions from alkyl-carbons and carboxyl-carbons with distinct δ¹³C values. The data do not support any particular organic acid generation mechanism. The isotopic trends observed as a function of molecular weight, thermal maturity, and rock type are not supported by either generation mechanisms or destructive decarboxylation. It is therefore proposed that organic acids experience isotopic fractionation during generation consistent with a primary kinetic isotope effect and subsequently undergo an exchange reaction between the carboxyl carbon and dissolved inorganic carbon that significantly influences the carbon isotope composition observed for the entire molecule. Although generation and decarboxylation may influence the δ¹³C values of organic acids, in the hydrous pyrolysis system described, the nondestructive, pH-dependent exchange of carboxyl carbon with inorganic carbon appears to be the most important reaction mechanism controlling the δ¹³C values of the organic acids.     

Anoxic nitrification: Evidence from Humber Estuary sediments (UK)

Conventional understanding of the nitrogen cycle in marine sediments has changed in recent years with the discovery of an alternative pathway for ammonia oxidation via the reduction of manganese oxides (during anoxic nitrification). In anoxic sediments, the potential for manganese oxides to serve as oxidant for nitrification may be considerable yet previous work on manganese-rich sediments has suggested anoxic nitrification may not be significant. In this study, the potential for anoxic nitrification in a range of sediment types was investigated. Laboratory incubation of sediment from three sites on the Humber Estuary, a microbially diverse environment, showed anoxic accumulation of nitrate, nitrite and dinitrogen gas, with and without the addition of synthetic manganese oxides. Incubation experiments confirmed anoxic nitrification as microbially mediated, with heat-killed controls yielding negative results. The anoxic nitrification reaction significantly depleted ammonia concentrations, and occurred simultaneously with manganese-, iron- and sulphate reduction, and methanogenesis. Taken in conjunction with other studies, results suggest anoxic nitrification may not only be dependent on total manganese concentrations but on manganese dynamics. Anoxic nitrification may be explained as a non-steady state reaction, dependent on the recent stability of a sediment system. Physical perturbation of sediments may cause the redistribution and/or introduction of manganese oxides and promote anoxic nitrification. The significance and persistence of anoxic nitrification is likely to depend on the frequency and magnitude of sediment perturbation, which explains why the reaction varies so widely across studied sites, and why it may not occur in some manganese-rich sediment.     

How Well Does Chlorophyll Explain the Seasonal Variation in Phytoplankton Activity?

The seasonal variation in phytoplankton activity is determined by analysing 1385 primary production (PP) profiles, chlorophyll a (Chl) concentration profiles and phytoplankton carbon biomass concentrations (C) from the period 1998–2012. The data was collected at six different stations in the Baltic Sea transition zone (BSTZ) which is a location with strong seasonal production patterns with light as the key parameter controlling this productivity. We show that the use of Chl as a proxy for phytoplankton activity strongly overestimates the contribution from the spring production to annual pelagic carbon flow. Spring (February and March) Chl comprised 16–30% of the total annual Chl produced, whereas spring C was much lower (8–23%) compared to the annual C. Spring PP accounted for 10–18% of the total annual PP, while the July–August production contributed 26–33%, i.e. within the time frame when zooplankton biomass and grazing pressure are highest. That is, Chl failed in this study to reflect the importance of the high summer PP. A better proxy for biomass may be C, which correlated well with the seasonal pattern of PP (Pearson correlation, p < 0.05). Thus, this study suggests to account for the strong seasonal pattern in C/Chl ratios when considering carbon flow in coastal systems. Seasonal data for PP were fitted to a simple sinusoidal wave model describing the seasonal distribution of PP in the BSTZ and were proposed to present a better parameterizaton of PP in shallow stratified temperate regions than more commonly applied proxies.     

Microbial ecology of the stratified water column of the Black Sea as revealed by a comprehensive biomarker study

The stratified water column of the Black Sea is partitioned into oxic, suboxic, and euxinic zones, each characterized by different biogeochemical processes and by distinct microbial communities. In 2003, we collected particulate matter by large volume in situ filtration at the highest resolution to date for lipid biomarker analysis and bacterioplankton for enumeration of major prokaryotic groups. Abundances of several prokaryotic groups were estimated using CARD-FISH probes specific for Bacteria, Archaea (Crenarchaeota and Euryarchaeota), epsilonproteobacteria (mainly sulfide oxidizers) and sulfate reducing bacteria. We also measured a wide range of bacterial and archaeal lipid biomarkers. Depth distributions of diagnostic biomarkers are matched with zonation of microbial processes, including aerobic bacterial oxidation of methane, oxidation of ammonium by bacteria and archaea, metal reduction, and sulfide oxidation at the chemocline, and bacterial sulfate reduction and anaerobic oxidation of methane by archaea in the anoxic zone. Cell densities for archaea and sulfate reducing bacteria are estimated based on water column biomarker concentrations and compared with CARD-FISH results.     

Late Pleistocene Vertebrates and Other Fossils from Epiguruk, Northwestern Alaska

Sediments exposed at Epiguruk, a large cutbank on the Kobuk River about 170 km inland from Kotzebue Sound, record multiple episodes of glacial-age alluviation followed by interstadial downcutting and formation of paleosols. Vertebrate remains from Epiguruk include mammoth, bison, caribou, an equid, a canid, arctic ground squirrel, lemmings, and voles. Radiocarbon ages of bone validated by concordant ages of peat and wood span the interval between about 37,000 and 14,000 yr B.P. The late Pleistocene pollen record is dominated by Cyperaceae, with Artemisia, Salix, Betula, and Gramineae also generally abundant. The fossil record from Epiguruk indicates that the Kobuk River valley supported tundra vegetation with abundant riparian willows during middle and late Wisconsin time. Large herbivores were present during the height of late Wisconsin glaciation as well as during its waning stage and the preceding interstadial interval. The Kobuk River valley would have been a favorable refugium for plants, animals, and possibly humans throughout the last glaciation.