Imbalance in the carbonate budget of surficial sediments in the North Atlantic Ocean: variations over the last millenium?

Fluxes contributing to the particulate carbonate system in deep-sea sediments were investigated at the BENGAL site in the Porcupine Abyssal Plain (Northeast Atlantic). Deposition fluxes were estimated using sediment traps at a nominal depth of 3000 m and amounted to 0.37±0.1 mmol C m⁻² d⁻¹. Dissolution of carbonate was determined using flux of total alkalinity from in situ benthic chambers, is 0.4±0.1 mmol C m⁻² d⁻¹. Burial of carbonate was calculated from data on the carbonate content of the sediment and sedimentation rates from a model age based on ¹⁴C dating on foraminifera (0.66±0.1 mmol C m⁻² d⁻¹). Burial plus dissolution was three times larger than particle deposition flux which indicates that steady-state is not achieved in these sediments. Mass balances for other components (BSi, ²¹⁰Pb), and calculations of the focusing factor using ²³⁰Th, show that lateral inputs play only a minor role in this imbalance. Decadal variations of annual particle fluxes are also within the uncertainty of our average. Long-term change in dissolution may contribute to the imbalance, but can not be the main reason because burial alone is greater than the input flux. The observed imbalance is thus the consequence of a large change of carbonate input flux which has occured in the recent past. A box model is used to check the response time of the solid carbonate system in these sediments and the time to reach a new steady-state is in the order of 3 kyr. Thus it is likely that the system has been perturbed recently and that large dissolution and burial rates reflect the previously larger particulate carbonate deposition rates. We estimate that particulate carbonate fluxes have certainly decreased by a factor of at least 3 and that this change has occurred during the last few centuries.     

Chemical abundances from B-stars in the Magellanic Clouds

We observed near-Main-Sequence B-stars in the Magellanic Clouds with the 3.6 m telescope and CASPEC at La Silla. We obtained spectra of high resolution and high S/N-ratio. The stars are members of the blue globular clusters NGC 1818 (LMC) and NGC 330 (SMC). The spectra are used for differential abundance analyses using HER as galactic reference star. Apart from CNO the metals are underabundant by about a factor of three and four for the LMC and SMC star, respectively. The CNO pattern is interesting since in both stars oxygen is considerably more abundant than carbon.Based on observations collected at ESO, La Silla and on Calar Alto, Spain and on observations made with the International Ultraviolet Explorer.     

Source rock-crude oil correlation by isotopic type-curves

An isotopic type-curve has been defined based on the ${}^{13}\text{C}{}^{12}\text{C}$ ratios of the saturated, aromatic, heterocomponent (NOSs), and asphaltene fractions of crude oils. These fractions show ¹³C enrichments with increasing polarity or polarizability. This systematic pattern can be used to estimate the ${}^{13}\text{C}{}^{12}\text{C}$ ratio of the kerogen from which the oil had been generated. Genetically associated source rock oil pairs have been used to show that the difference between the measured and the estimated δ-values of kerogen is about ?0.5%., and between the δ-values of the kerogen and the asphaltene fraction is approximately +0.6%.     

Metal binding to dissolved organic matter and adsorption to ferrihydrite in shallow peat groundwaters: Application to diamond exploration in the James Bay Lowlands,Canada

The speciation and solubility of kimberlite pathfinder metals (Ni, Nd, Ba and K) in shallow peat groundwaters is investigated over the Yankee, Zulu and Golf kimberlites in the Attawapiskat region, James Bay Lowlands, Canada. The purpose of this study is to examine the relationship between dissolved organic matter (DOM) complexation with kimberlite pathfinder metals and determine the spatial distribution of those metals in shallow peat groundwaters along sampling transects over subcropping kimberlites. Nickel, Nd, Ba and K complexation with DOM and the adsorption of these metals onto ferrihydrite were calculated using Visual MINTEQ 3.0 and the NICA-Donnan database. Calculations predict almost 100% of soluble Nd, Ni and Ba form complexes with DOM at sampling sites with little to no contribution from upwelling groundwater (i.e., dissolved organic C (DOC) concentrations = 40–132 mg/L, pH = 3.9–5.5, and log ionic strength ??3). In only the most ombrotrophic peat groundwater conditions does a majority fraction of K bind to DOM. By contrast, under conditions with large contributions from upwelling groundwaters (i.e., DOC concentrations ?40 mg/L, pH = 5.5–6.5, and log ionic strength = ?3 to ?2), as little as 10% of Nd and Ni, and 0% K and Ba are predicted to complex with DOM. The modeling calculations suggest the dominant control on metal–DOM complexation, particularly with respect to Ni and Nd, is competitive effects for DOM binding sites due to elevated ionic strength where there is evidence of strong groundwater upwelling. Visual MINTEQ modeling of metal adsorption on ferrihydrite surfaces predicts that under strong upwelling conditions, Ni and Nd are scavenged from solution due to increased ferrihydrite precipitation and decreased fractions of metals complexed with DOM. Analytical geochemical data are consistent with model predictions of metal adsorption on ferrihydrite. Total dissolved Ni and Nd concentrations at sites of strong upwelling are up to five times lower than waters with little to no upwelling and log ferrihydrite saturation indices (logSI_ferr) indicate precipitation (values up to 5) at sites of strong groundwater upwelling. Where the majority of Ni and Nd complex with DOM and ferrihydrite is highly under saturated (logSI_ferr = ?18 to ?5), the concentrations of total Ni and Nd are elevated compared to other sites along sampling transects. Metal complexation with DOM effectively inhibits metal scavenging from solution via adsorption and/or from forming secondary mineral precipitates. Also, because alkaline earth metals do not compete strongly with Ni and Nd for adsorption sites on ferrihydrite surfaces, but do compete strongly for insoluble organic sites, Ni and Nd are more likely to adsorb onto ferrihydrite.     

Multi-angle backscatter classification and sub-bottom profiling for improved seafloor characterization

This study applies three classification methods exploiting the angular dependence of acoustic seafloor backscatter along with high resolution sub-bottom profiling for seafloor sediment characterization in the Eckernförde Bay, Baltic Sea Germany. This area is well suited for acoustic backscatter studies due to its shallowness, its smooth bathymetry and the presence of a wide range of sediment types. Backscatter data were acquired using a Seabeam1180 (180 kHz) multibeam echosounder and sub-bottom profiler data were recorded using a SES-2000 parametric sonar transmitting 6 and 12 kHz. The high density of seafloor soundings allowed extracting backscatter layers for five beam angles over a large part of the surveyed area. A Bayesian probability method was employed for sediment classification based on the backscatter variability at a single incidence angle, whereas Maximum Likelihood Classification (MLC) and Principal Components Analysis (PCA) were applied to the multi-angle layers. The Bayesian approach was used for identifying the optimum number of acoustic classes because cluster validation is carried out prior to class assignment and class outputs are ordinal categorical values. The method is based on the principle that backscatter values from a single incidence angle express a normal distribution for a particular sediment type. The resulting Bayesian classes were well correlated to median grain sizes and the percentage of coarse material. The MLC method uses angular response information from five layers of training areas extracted from the Bayesian classification map. The subsequent PCA analysis is based on the transformation of these five layers into two principal components that comprise most of the data variability. These principal components were clustered in five classes after running an external cluster validation test. In general both methods MLC and PCA, separated the various sediment types effectively, showing good agreement (kappa >0.7) with the Bayesian approach which also correlates well with ground truth data (r²?>?0.7). In addition, sub-bottom data were used in conjunction with the Bayesian classification results to characterize acoustic classes with respect to their geological and stratigraphic interpretation. The joined interpretation of seafloor and sub-seafloor data sets proved to be an efficient approach for a better understanding of seafloor backscatter patchiness and to discriminate acoustically similar classes in different geological/bathymetric settings.     

Zur Frage des Faltenbaues im oberschlesischen Steinkohlenbecken

Ohne Zusammenfassung     

Benthic Carbon Mineralization and Nutrient Turnover in a Scottish Sea Loch: An Integrative In Situ Study

Based on in situ microprofiles, chamber incubations and eddy covariance measurements, we investigated the benthic carbon mineralization and nutrient regeneration in a ~65-m-deep sedimentation basin of Loch Etive, UK. The sediment hosted a considerable amount of infauna that was dominated by the brittle star A. filiformis. The numerous burrows were intensively irrigated enhancing the benthic in situ O₂ uptake by ~50 %, and inducing highly variable redox conditions and O₂ distribution in the surface sediment as also documented by complementary laboratory-based planar optode measurements. The average benthic O₂ exchange as derived by chamber incubations and the eddy covariance approach were similar (14.9 ± 2.5 and 13.1 ± 9.0 mmol m^?2 day^?1) providing confidence in the two measuring approaches. Moreover, the non-invasive eddy approach revealed a flow-dependent benthic O₂ flux that was partly ascribed to enhanced ventilation of infauna burrows during periods of elevated flow rates. The ratio in exchange rates of ΣCO₂ and O₂ was close to unity, confirming that the O₂ uptake was a good proxy for the benthic carbon mineralization in this setting. The infauna activity resulted in highly dynamic redox conditions that presumably facilitated an efficient degradation of both terrestrial and marine-derived organic material. The complex O₂ dynamics of the burrow environment also concurrently stimulated nitrification and coupled denitrification rates making the sediment an efficient sink for bioavailable nitrogen. Furthermore, bioturbation mediated a high efflux of dissolved phosphorus and silicate. The study documents a high spatial and temporal variation in benthic solute exchange with important implications for benthic turnover of organic carbon and nutrients. However, more long-term in situ investigations with like approaches are required to fully understand how environmental events and spatio-temporal variations interrelate to the overall biogeochemical functioning of coastal sediments.     

Chemical and structural relations of epitaxial xenotime and zircon substratum in sedimentary and hydrothermal environments: a TEM study

Xenotime overgrowths on detrital zircon in siliciclastic sediments have been reported in numerous studies. However, in natural samples, solid solution of zircon and xenotime is limited to near-end-member compositions. In order to characterize the interface region between both minerals and to draw inferences on the growth mechanisms of authigenic xenotime, we studied xenotime overgrowths on detrital zircon grains from two Phanerozoic sandstone samples with contrasting post-depositional histories. In one sample, the small (≤10 μm), pyramidal xenotime overgrowths are of diagenetic origin and grew without major discontinuity on the detrital zircon grain. The second sample shows up to >50-μm-wide, porous and inclusion-rich, hydrothermal xenotime overgrowths on detrital zircon, whereas the transition zone between both minerals is accompanied by large pore volume. Chemical compositions of the xenotime precipitates from the two samples differ particularly in Y, REE, Th and Sc concentrations, whereas high MREE availability in the diagenetic sample and the presence of Sc in the hydrothermal sample, respectively, appear to have promoted xenotime growth. Transmission electron microscopy on electron-transparent foils cut from the interface region shows that both the diagenetic xenotime and the hydrothermal xenotime are crystalline and grew in optical and crystallographic continuity to their detrital zircon substrata. Only a narrow transition zone (≤90 nm—diagenetic sample, 200–300 nm—hydrothermal sample) between zircon and xenotime is in part made up of nanometre-scale crystalline domains that are slightly distorted and may have formed from dissolution–re-precipitation processes at the zircon rim along with precipitation from the respective fluid.     

Groundwater Pumping Is a Significant Unrecognized Contributor to Global Anthropogenic Element Cycles

Quantifying anthropogenic contributions to elemental cycles provides useful information regarding the flow of elements important to industrial and agricultural development and is key to understanding the environmental impacts of human activity. In particular, when anthropogenic fluxes reach levels large enough to influence an element's overall cycle the risk of adverse environmental impacts rises. While intensive groundwater pumping has been observed to affect a wide-range of environmental processes, the role of intensive groundwater extraction on global anthropogenic element cycles has not yet been characterized. Relying on comprehensive datasets of groundwater and produced water (groundwater pumped during oil/gas extraction) chemistry from the U.S. Geological Survey along with estimates of global groundwater usage, I estimate elemental fluxes from global pumping, consumptive use, and depletion of groundwater. I find that groundwater fluxes appreciably contribute to a number of elements overall cycles and thus these cycles were underestimated in prior studies, which did not recognize groundwater pumping's role. I also estimate elemental loadings to agricultural soils in the United States and find that in some regions, groundwater may provide a significant portion (more than 10%) of crop requirements of key nutrients (K, N). With nearly 40% of globally irrigated land under groundwater irrigation, characterizing nutrient and toxic element fluxes to these soils, which ultimately influence crop yields, is important to our understanding of agricultural production. Thus, this study improves our basic understanding of anthropogenic elemental cycles and demonstrates that quantification of groundwater pumping elemental fluxes provides valuable information about the potential for environmental impacts from groundwater pumping.