Seasonal dynamics of microbial sulfate reduction in temperate intertidal surface sediments: controls by temperature and organic matter

The role of microbial sulfate reduction on organic matter oxidation was studied quantitatively in temperate intertidal surface sediments of the German Wadden Sea (southern North Sea) on a seasonal base in the years 1998–2007. The sampling sites represent the range of sediments found in the back-barrier tidal area of Spiekeroog Island: sands, mixed and muddy flats. The correspondingly different contents in organic matter, metals, and porosities lead to significant differences in the activity of sulfate-reducing bacteria with volumetric sulfate reduction rates (SRR) in the top 15 cm of up to 1.4 μmol cm^?3 day^?1. Depth-integrated areal SRR ranged between 0.9 and 106 mmol m^?2 day^?1, with the highest values found in the mudflat sediments and lower rates measured in sands at the same time, demonstrating the impact of both temperature and organic matter load. According to a modeling approach for a 154-km² large tidal area, about 39, 122, and 285 tons of sulfate are reduced per day, during winter, spring/autumn, and summer, respectively. Hence, the importance of areal benthic organic matter mineralization by microbial sulfate reduction increases during spring/autumn and summer by factors of about 2 and 7, respectively, when compared to winter time. The combined results correspond to an estimated benthic organic carbon mineralization rate via sulfate reduction of 78 g C m^?2 year^?1.     

Biomarker responses as indication of contaminant effects in blue mussel (Mytilus edulis) and female eelpout (Zoarces viviparus) from the southwestern Baltic Sea

During a field study performed in spring and autumn 2001 and 2002, blue mussels (Mytilus edulis) and female eelpout (Zoarces viviparus) were collected at three locations in the Wismar Bay (Baltic Sea), and several biomarkers of contaminant effects were analysed. Besides seasonal and inter-annual variations, biomarker signals were most pronounced at the location closest to Wismar Harbour (Wendorf) in both species. Lysosomal membrane stability (LMS) was lowest and acetylcholinesterase activity (AChE) was significantly reduced. Frequency of micronuclei (MN) was significantly higher (in blue mussels), indicating mutagenic effects. In eelpout elevated levels of DNA adducts, EROD induction and PAH-metabolites were measured. Metallothionein (MT), biomarker for trace metal exposure, showed a gradient only in spring. Organochlorine contaminant analyses (PCBs, DDTs) corresponded to the observed biomarker levels. The results obtained clearly demonstrate pollution effects in the southwestern Baltic Sea. Moreover, they show that a multibiomarker approach is also applicable in a brackish water environment.     

Iron isotope fractionation in a buoyant hydrothermal plume, 5°S Mid-Atlantic Ridge

Fe isotopes are a potential tool for tracing the biogeochemical redox cycle of Fe in the ocean. Specifically, it is hypothesized that Fe isotopes could enable estimation of the contributions from multiple Fe sources to the dissolved Fe budget, an issue that has received much attention in recent years. The first priority however, is to understand any Fe isotope fractionation processes that may occur as Fe enters the ocean, resulting in modification of original source compositions. In this study, we have investigated the Fe inputs from a basalt-hosted, deep-sea hydrothermal system and the fractionation processes that occur as the hot, chemically reduced and acidic vent fluids mix with cold, oxygen-rich seawater.The samples collected were both end-member vent fluids taken from hydrothermal chimneys, and rising buoyant plume samples collected directly above the same vents at 5°S, Mid-Atlantic Ridge. Our analyzes of these samples reveal that, for the particulate Fe species within the buoyant plume, 25% of the Fe is precipitated as Fe-sulfides. The isotope fractionation caused by the formation of these Fe-sulfides is δ_Fe(II)–FeS = +0.60 ± 0.12‰.The source isotope composition for the buoyant plume samples collected above the Red Lion vents is calculated to be −0.29 ± 0.05‰. This is identical to the value measured in end-member vent fluids collected from the underlying “Tannenbaum” chimney. The resulting isotope compositions of the Fe-sulfide and Fe-oxyhydroxide species in this buoyant plume are −0.89 ± 0.11‰ and −0.19 ± 0.09‰, respectively. From mass balance calculations, we have been able to calculate the isotope composition of the dissolved Fe fraction, and hypothesize that the isotope composition of any stabilised dissolved Fe species exported to the surrounding ocean may be heavier than the original vent fluid. Such species would be expected to travel some distance from areas of hydrothermal venting and, hence, contribute to not only the dissolved Fe budget of the deep-ocean but also it’s dissolved Fe isotope signature.     

New model calculations for the production rates of cosmogenic nuclides in iron meteorites

Abstract— Here we present the first purely physical model for cosmogenic production rates in iron meteorites with radii from 5 cm to 120 cm and for the outermost 1.3 m of an object having a radius of 10 m. The calculations are based on our current best knowledge of the particle spectra and the cross sections for the relevant nuclear reactions. The model usually describes the production rates for cosmogenic radionuclides within their uncertainties; exceptions are ⁵³Mn and ⁶⁰Fe, possibly due to normalization problems. When an average S content of about 1 ± 0.5% is assumed for Grant and Carbo samples, which is consistent with our earlier study, the model predictions for ³He, ²¹Ne, and ³⁸Ar are in agreement. For ⁴He the model has to be adjusted by 24%, possibly a result of our rather crude approximation for the primary galactic α particles. For reasons not yet understood the modeled ³⁶Ar/³⁸Ar ratio is about 30–40% higher than the ratio typically measured in iron meteorites. Currently, the only reasonable explanation for this discrepancy is the lack of experimentally determined neutron induced cross sections and therefore the uncertainties of the model itself. However, the new model predictions, though not yet perfect, enable determining the radius of the meteoroid, the exposure age, the sulphur content of the studied sample as well as the terrestrial residence time. The determination of exposure ages is of special interest because of the still open question whether the GCR was constant over long time scales. Therefore we will discuss in detail the differences between exposure ages determined with different cosmogenic nuclides. With the new model we can calculate exposure ages that are based on the production rates (cm³STP/(gMa)) of noble gases only. These exposure ages, referred to as noble gas exposure ages or simply ^3,4He, ²¹Ne, or ^36,38Ar ages, are calculated assuming the current GCR flux. Besides calculating noble gas ages we were also able to improve the ⁴¹K‐⁴⁰K‐and the ³⁶Cl‐³⁶Ar dating methods with the new model. Note that we distinguish between ³⁶Ar ages (calculated via ³⁶Ar production rates only) and ³⁶Cl‐³⁶Ar ages. Exposure ages for Grant and Carbo, calculated with the revised ⁴¹K‐⁴⁰K method, are 628 ± 30 Ma and 841 ± 19 Ma, respectively. For Grant this is equal to the ages obtained using ³He, ²¹Ne, and ³⁸Ar but higher than the 3⁶Ar‐ and ³⁶Cl‐³⁶Ar ages by ?30%. For Carbo the ⁴¹K‐⁴⁰K age is ?40% lower than the ages obtained using ³He, ²¹Ne, and ³⁸Ar but equal to the ³⁶Ar age. These differences can either be explained by our still insufficient knowledge of the neutron‐induced cross sections or by a long‐term variation of the GCR.     

Noble gases in Grant and Carbo and the influence of S‐ and P‐rich mineral inclusions on the 41K‐40K dating system

Abstract— Cosmogenic He, Ne, and Ar were measured in the iron meteorites Grant (IIIAB) and Carbo (IID) to re‐determine their preatmospheric geometries and exposure histories. We also investigated the influence of sulphur‐ and/or phosphorus‐rich inclusions on the production rates of cosmogenic Ne. Depth profiles measured in Grant indicate a preatmospheric center location 117 mm left from the reference line and 9 mm below bar B, which is clearly different (?10 cm) from earlier results (?165 mm left from the reference line on bar F). For Carbo the preatmospheric center location was found to be 120 mm right of the reference line and 15 mm above bar J, which is in agreement with literature data. The new measurements indicate a spherical preatmospheric shape for both meteorites and, based on literature ³⁶C1 data, the radii were estimated to be about 32 cm and 70 cm for Grant and Carbo, respectively. We demonstrate that minor elements like S and P have a significant influence on the production rates of cosmogenic Ne. In our samples, containing on average 0.5% S and/or P, about 20% of ²¹Ne was produced from these minor elements. Using measured ²¹Ne concentrations and endmember ²²Ne/²¹Ne ratios for Fe + Ni and S + P, respectively, we show that it is possible to correct for ²¹Ne produced from S and/or P. The thus corrected data are then used to calculate new ⁴¹K‐⁴⁰K exposure ages—using published K data—which results in 564 ± 78 Ma for Grant and 725 ± 100 Ma for Carbo. The correction always lowers the ²¹Ne concentrations and consequently decreases the ⁴¹K‐⁴⁰K exposure ages. The discrepancies between ³⁶Cl‐³⁶Ar and ⁴¹K‐⁴⁰K ages are accordingly reduced. The existence of a significant long‐term variation of the GCR, which is based on a former 30–50% difference between ⁴¹K‐⁴⁰K and ³⁶Cl‐³⁶Ar ages, may warrant re‐investigation.     

Sorption of Np(V) and Np(IV) onto kaolinite: Effects of pH,ionic strength,carbonate and humic acid

The sorption of Np(V) and Np(IV) onto kaolinite has been studied in the absence and presence of humic acid (HA) in a series of batch equilibrium experiments under different experimental conditions: [Np]₀: 1.0 × 10^-6 or 1.0 × 10^-5 M, [HA]₀: 0 or 50 mg/L, I: 0.01 or 0.1 M NaClO₄, solid to liquid ratio: 4 g/L, pH: 6–11, anaerobic or aerobic conditions, without or with carbonate. The results showed that the Np(V) sorption onto kaolinite is affected by solution pH, ionic strength, Np concentration, presence of carbonate and HA. In the absence of carbonate, the Np(V) uptake increased with pH up to ∼96% at pH 11. HA further increased the Np(V) sorption between pH 6 and 9 but decreased the Np(V) sorption between pH 9 and 11. In the presence of carbonate, the Np(V) sorption increased with pH and reached a maximum of 54% between pH 8.5 and 9. At higher pH values, the Np(V) sorption decreased due to the presence of dissolved neptunyl carbonate species with a higher negative charge that were not sorbed onto the kaolinite surface which is negatively charged in this pH range. HA again decreased the Np(V) uptake in the near-neutral to alkaline pH range due to formation of aqueous neptunyl humate complexes. The decrease of the initial Np(V) concentration from 1.0 × 10⁻⁵ M to 1.0 × 10⁻⁶ M led to a shift of the Np(V) adsorption edge to lower pH values. A higher ionic strength increased the Np(V) uptake onto kaolinite in the presence of carbonate but had no effect on Np(V) uptake in the absence of carbonate.     

Geochemistry and Sr, Nd, Pb isotopic composition of the Central Atlantic Magmatic Province (CAMP) in Guyana and Guinea

The Central Atlantic Magmatic Province (CAMP) is one of the largest igneous provinces on Earth, extending more than 5000 km north to south, on both sides of the Atlantic Ocean. Its emplacement occurred about 200 Ma ago, at the Triassic–Jurassic boundary, and is linked to the initial breakup of Pangaea. Two areas of the province are studied here: French Guyana/Surinam (South America) and Guinea (West Africa), in order to document the petrogenesis and geodynamical significance of high-Ti and low-Ti basaltic magmas from the CAMP.

In Guyana, doleritic and gabbroic dykes are located on the edge of the Guiana Shield, and represent limited volumes of magma. They display low SiO₂ (47–50%), high TiO₂ (2.5–3.5%) and high FeO tholeiitic trends and show variably enriched trace element patterns ((La/Yb)_n=1.5–5.1). Their isotopic signature and ratios of very incompatible elements (εNd_i=+5.8 to +4.2, (⁸⁷Sr/⁸⁶Sr)_i=0.703–0.705, (²⁰⁷Pb/²⁰⁴Pb)_i=15.46–15.64) match a depleted PREMA (prevalent mantle)-like source. Their genesis can be modeled by ca. 15% partial melting of a lherzolite source, and a subsequent limited fractional crystallization (5–10%) or a slight upper crustal assimilation–fractional crystallization (AFC, r=0.1, Proterozoic contaminant). In Guinea, in contrast, huge volumes of CAMP magmas were intruded along the Rockelides suture and the West African craton, forming the Fouta Djalon sills and the Kakoulima laccolith. The laccolith is more than 1000 m thick. These features consist of gabbros, dolerites, diorites and mafic (gabbro) and ultramafic (dunite, wherlite) cumulates. Guinean tholeiites show high SiO₂ (51–58%), low TiO₂ (0.7–1.2%) and FeO trends, with high LILE/HFSE ratios and slight negative Nb–Ta anomalies. Isotopic signatures (εNd_i=+0.4 to −5.3, (⁸⁷Sr/⁸⁶Sr)_i=0.705–0.710, (²⁰⁷Pb/²⁰⁴Pb)_i=15.57–15.66) indicate a more enriched source than for Guyana as well as a higher rate of magma–upper crust interaction through an AFC process (r=0.3, Birimian crust contaminant) and, probably, an additional upper crustal contamination for the most differentiated sample.

This geochemical study supports the prevalence in Guinea, as for other low-Ti CAMP tholeiites, of a lithospheric mantle source, previously enriched during ancient subduction events, and preferentially reactivated in late Triassic times by edge-driven convection between cratonic and mobile belt domains. A larger contribution from a depleted asthenospheric source is required to generate high-Ti tholeiites in Guyana, which may reflect the development of CAMP rifting towards the initiation of the Central Atlantic oceanic crust.     

Eemian crustal deformation in the eastern Baltic area in the light of the new sites at Peski, Russia and Põhja-Uhtju, Estonia

Several Eemian (Mikulino) marine deposits are known from the northwestern part of Russia and from Estonia. The best-known deposits are situated at Mga, Russia and at Prangli, Estonia. Two new sites with clayey and silty deposits covered by till were studied for pollen and diatoms at Peski, Russia and Põhja-Uhtju, Estonia. At Peski, the deposit representing the Eemian Interglacial is 3.8 m thick at the depth of 13.4–9.6 m above present sea-level. At Põhja-Uhtju, the deposit representing the Eemian is 3.5 m thick at the depth of 47.9–51.4 m below present sea-level. Although Peski is situated at a higher altitude than Põhja-Uhtju at present, the diatom stratigraphy at these sites indicates deeper and more saline conditions in the Peski area than at Põhja-Uhtju during the Eemian. This result is similar to some previous studies, which indicate, that although the Russian deposits (e.g. Peski, Mga) are now at a higher altitude than those in Estonia (Põhja-Uhtju and Prangli), the diatoms in the Russian deposits are indicative of a considerable depth of water during the time of deposition. These deposits suggest that the Eemian shore levels ascend from Estonia eastwards, while the Late Weichselian and Holocene shorelines tilt downwards in the same general direction. The present material from Estonia and northwestern part of Russia shows marked differences between the Eemian and Late Weichselian/Holocene crustal deformations, which probably resulted from different ice loads during the final glaciation phases and probably also from different deglaciation patterns during the Saalian and Late Weichselian.     

Extremes of near-surface wind speed over Europe and their future changes as estimated from an ensemble of RCM simulations

In this study, we analyse the uncertainty of the effect of enhanced greenhouse gas conditions on windiness projected by an ensemble of regional model simulations driven by the same global control and climate change simulations. These global conditions, representative for 1961–1990 and 2071–2100, were prepared by the Hadley Centre based on the IPCC SRES/A2 scenario. The basic data sets consist of simulated daily maximum and daily mean wind speed fields (over land) from the PRUDENCE data archive at the Danish Meteorological Institute. The main focus is on the results from the standard 50 km-resolution runs of eight regional models. The best parameter for determining possible future changes in extreme wind speeds and possible change in the number of storm events is maximum daily wind speed. It turned out during this study that the method for calculating maximum daily wind speed differs among the regional models. A comparison of simulated winds with observations for the control period shows that models without gust parameterisation are not able to realistically capture high wind speeds. The two models with gust parametrization estimate an increase of up to 20% of the number of storm peak (defined as gusts?≥?8 Bft in this paper) events over Central Europe in the future. In order to use a larger ensemble of models than just the two with gust parameterisation, we also look at the 99th percentile of daily mean wind speed. We divide Europe into eight sub-regions (e.g., British Isles, Iberian Peninsula, NE Europe) and investigate the inter-monthly variation of wind over these regions as well as differences between today’s climate and a possible future climate. Results show differences and similarities between the sub-regions in magnitude, spread, and seasonal tendencies. The model ensemble indicates a possible increase in future mean daily wind speed during winter months, and a decrease during autumn in areas influenced by North Atlantic extra-tropical cyclones.     

Vertical distributions of sulfur species simulated by large scale atmospheric models in COSAM: Comparison with observations

A comparison of large‐scale models simulating atmospheric sulfate aerosols (COSAM) was conducted to increase our understanding of global distributions of sulfate aerosols and precursors. Earlier model comparisons focused on wet deposition measurements and sulfate aerosol concentrations in source regions at the surface. They found that different models simulated the observed sulfate surface concentrations mostly within a factor of two, but that the simulated column burdens and vertical profiles were very different amongst different models. In the COSAM exercise, one aspect is the comparison of sulfate aerosol and precursor gases above the surface. Vertical profiles of SO₂, SO²⁻₄, oxidants and cloud properties were measured by aircraft during the North Atlantic Regional Experiment (NARE) experiment in August/September 1993 off the coast of Nova Scotia and during the Second Eulerian Model Evaluation Field Study (EMEFSII), in central Ontario in March/April 1990. While no single model stands out as being best or worst, the general tendency is that those models simulating the full oxidant chemistry tend to agree best with observations although differences in transport and treatment of clouds are important as well.