Geochemical investigations of sediment profiles in the Norwegian-Greenland Sea

High-, i.e. 15-140-yr-resolution climate records from sediment cores 23071, 23074, and PS2644 from the Nordic Seas were used to recon:;truct changes in the surface and deep water circulation during marine isotope stages 1-5.1, i.e. the last 82 000 yr. From this the causal links between the paleoceanographic signals and the Dansgaard-Oeschger events 1-21 revealed in 0180-ice-core records from Greenland were determined. The stratigraphy of the cores is based on the planktic 0180 curves, the minima of which were directly correlated with the GISP2-0180 record, numerous AMS 14C ages, and some ash layers. The planktic d18O and dl3C curves of all three cores reveal numerous meltwater events, the most pronounced of which were assigned to the Heinrich events 1-6. The meltwater events, among other things also accompanied by cold sea surface temperatures and high IRD concentration, correlate with the stadial phases of the Dansgaard-Oeschger cycles and in the western Iceland Sea also to colder periods or abrupt drops in 0180 within a few longer interstadials. Besides being more numerous, the meltwater events also show isotope values lighter in the Iceland Sea than in the central Norwegian Sea, especially if compared to core 23071. This implies a continuous inflow of relative warm Atlantic water into the Norwegian Sea and a cyclonic circulation regime.

(Table T1) Geochemical composition of coastal sediments from the Schleswig-Holstein Wadden Sea, Germany

Approximately quantitative values are presented on the mineral content of the clay and silt fractions of marine sediments from the Wadden Sea. Considering the extent of clay mineral transformation and neoformation in a marine environment, it is believed to be insignificant, because of the sea water and pore solutions of the sediments seem to represent - with the exception of a small Mg-surplus - a kind of equilibrium solution for three- and four-layer minerals, which neither favors a considerable base fixation nor base release. Therefore, illite neoformation during halmyrolysis or early diagenesis seems to be impossible, especially because of unfavourable relations of potassium to all other cations in the sea water. Obviously the neoformation of illite takes place only during later diagenetic stages. The processes of clay mineral neoformation in a marine environment are probably restricted to the formation of amorphous (Mg-)Fe-Si-particles which may be first steps in the formation of chamosites, chlorites or smectites.

Mineralogical, geochemical and magnetic signatures of surface sediments from the Canadian Beaufort Shelf and Amundsen Gulf (Canadian Arctic)

Mineralogical, geochemical, magnetic, and siliciclastic grain-size signatures of 34 surface sediment samples from the Mackenzie-Beaufort Sea Slope and Amundsen Gulf were studied in order to better constrain the redox status, detrital particle provenance, and sediment dynamics in the western Canadian Arctic. Redox-sensitive elements (Mn, Fe, V, Cr, Zn) indicate that modern sedimentary deposition within the Mackenzie-Beaufort Sea Slope and Amundsen Gulf took place under oxic bottom-water conditions, with more turbulent mixing conditions and thus a well-oxygenated water column prevailing within the Amundsen Gulf. The analytical data obtained, combined with multivariate statistical (notably, principal component and fuzzy c-means clustering analyses) and spatial analyses, allowed the division of the study area into four provinces with distinct sedimentary compositions: (1) the Mackenzie Trough-Canadian Beaufort Shelf with high phyllosilicate-Fe oxide-magnetite and Al-K-Ti-Fe-Cr-V-Zn-P contents; (2) Southwestern Banks Island, characterized by high dolomite-K-feldspar and Ca-Mg-LOI contents; (3) the Central Amundsen Gulf, a transitional zone typified by intermediate phyllosilicate-magnetite-K-feldspar-dolomite and Al-K-Ti-Fe-Mn-V-Zn-Sr-Ca-Mg-LOI contents; and (4) mud volcanoes on the Canadian Beaufort Shelf distinguished by poorly sorted coarse-silt with high quartz-plagioclase-authigenic carbonate and Si-Zr contents, as well as high magnetic susceptibility. Our results also confirm that the present-day sedimentary dynamics on the Canadian Beaufort Shelf is mainly controlled by sediment supply from the Mackenzie River. Overall, these insights provide a basis for future studies using mineralogical, geochemical, and magnetic signatures of Canadian Arctic sediments in order to reconstruct past variations in sediment inputs and transport pathways related to late Quaternary climate and oceanographic changes.

(Tables 1-3) Geochemical composition of seepage water in soils obtained in Schleswig-Holstein, Germany

Under defined laboratory and field conditions, the investigation of percolating water through soil columns (podsol, lessive and peat) down to groundwater table shows that the main factors which control the chemical characteristics of the percolates are: precipitation, evaporation, infiltration rate, soil type, depth and dissolved organic substances. Evaporation and percolation velocity influences the Na+, SO4**2- and Cl- concentrations. Low percolation velocity leads also to longer percolation times and water logging in less permeable strata, which results in lower Eh-values and higher CO2-concentrations due to low gas exchange with the atmosphere. Ca2+ and Mg2+ carbonate concentration depends on soil type and depth. Metamorphism and decomposition of organic substances involve NO3 reduction and K+, Mg2+, SO4**2-, CO2, Fe2+,3+ transport. The analytical data were evaluated with multi variate statistical methods.

Geochemical characterization and the voltammetric investigation of hydrothermal Iron speciation of samples gained during SONNE cruise SO229

Hydrothermal vent fluids are highly enriched in iron (Fe) compared to ambient seawater, and organic ligands may play a role in facilitating the transport of some hydrothermal Fe into the open ocean. This is important since Fe is a limiting micronutrient for primary production in large parts of the world's surface ocean. We have investigated the concentration and speciation of Fe in several vent fluid and plume samples from the Nifonea vent field, Coriolis Troughs, New Hebrides Island Arc, South Pacific Ocean using competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-AdCSV) with salicylaldoxime (SA) as the artificial ligand. Our results for total dissolved Fe (dFe) in the buoyant hydrothermal plume samples showed concentrations up to 3.86 µM dFe with only a small fraction between 1.1 and 11.8% being chemically labile. Iron binding ligand concentrations ([L]) were found in µM level with strong conditional stability constants up to logKFeL,Fe3+ of 22.9. Within the non-buoyant hydrothermal plume above the Nifonea vent field, up to 84.7% of the available Fe is chemically labile and [L] concentrations up to 97 nM were measured. [L] was consistently in excess of Felab, indicating that all available Fe is being complexed, which in combination with high Felab values in the non-buoyant plume, signifies that a high fraction of hydrothermal dFe is potentially being transported away from the plume into the surrounding waters, contributing to the global oceanic Fe budget.

The Evolution of the Los Negritos Porphyry Copper Deposit, Coquimbo, Chile: Geological, Geochronological, Mineralogical and Geochemical Evidence

The Los Negritos porphyry copper deposit is located ~ 4 km to the northeast of Carmen de Andacollo Mine in the Chilean Cretaceous metallogenic belt. The mineralization is hosted in andesite of the Quebrada Marquesa Formation and a series of at least four early to intramineral porphyry intrusive rock types: plagioclase quartz biotite porphyry (P1b and P1a dated at 109.60± 0.75 Ma and 107.22± 0.40 Ma); plagioclase biotite porphyry (P2: 106.30 ± 0.47 Ma); and quartz plagioclase biotite porphyry (P3: 106.19 ± 0.42 Ma). These units are cut by late‐ to post‐mineral plagioclase‐hornblende porphyritic rocks (P4b: 106.20 ± 0.69 Ma and P4a: 106.50 ± 0.68 Ma). The earliest intrusive units (P1) were affected by an initial stage of K‐feldspar‐biotite alteration, with chalcopyrite, molybdenite (date at 108.5 ± 0.5 Ma) and gold (up to 0.11 ppm), and the surrounding volcanic host rock was overprinted by chlorite‐epidote dominated (propylitic) alteration. Subsequent to the P2 and P3 intrusion, these rocks were affected by albite and then a second stage of potassic alteration. The Ti and Ba contents in hydrothermal biotite are notably lower (typically Ti = 0.100‐0.144 a.p.f.u. and Ba = 0.001‐0.005 a.p.f.u) than in magmatic ones (generally Ti = 0.186‐0.222 a.p.f.u. and Ba = 0.014‐0.023 a.p.f.u.), and constitute an excellent discriminant of the nature of biotite. These early stages of alteration were overprinted by copper‐molybdenum bearing chlorite‐sericite alteration at 106.60 ± 0.5 Ma (Re‐Os age in molybdenite) and by quartz‐sericite‐pyrite veins (phyllic), respectively in the southwest and northeast areas. The average temperature associated with these two alteration facies is estimated around 305 °C. Weak albite‐calcite alteration, spatially associated with sulfosalts and distributed along the margins of P3, overprinted the phyllic facies. The intrusive rock units at the Los Negritos and Carmen de Andacollo deposits are geochemically classified as diorite to granodiorite with a calc‐alkaline magmatic affinity, and formed in a volcanic arc setting from partial melting of a metasomatized mantle wedge. They are interpreted to be cogenetic, and related to a common long‐lived magma chamber that emplaced during a period of tectonic inversion known as the Subhercynian, Peruvian or Pacific event.

The Provenance and Geochemical Alteration of Bermudan Eolianites

Large calcareous eolianites cover the remote island of Bermuda, accounting for more than 90% of the limestone bedrock. This study examines the sedimentology and geochemistry of these eolianites to better understand Pleistocene oceanography and the meteoric alteration of subtropical carbonate sediments. Cluster analyses reveal that the eolian carbonate sediments fall into two natural groups that represent lagoonal and reefal end members of marine sediment production. Coral fragments are uncharacteristically absent, possibly destroyed prior to their incorporation into eolian deposits by endolithic microboring organisms or broken up during transport. Sediment assemblages lead to the following interpretations of the Bermudan offshore environment: (1) the Ledge Flats reef system along the southwestern coast has been active since MIS 11, contributing coralline algal-rich sediment to the northern beaches of Sandy’s Parish and acting as an energy barrier in the south, allowing for low energy sedimentation in the quiet back- reef region; (2) on the northeastern coast, the low energy back-reef region landward of the Ledge Flats has thrived since MIS 11; (3) during MIS 5e, slightly warmer water temperatures led to the hindrance of coralline algal growth along the southern coast and in the North Lagoon. These are the first interpretations of Pleistocene marine assemblages on Bermuda. Meteoric fluids progressively transformed the pristine carbonate sediments into hardened limestones in a predictable solubility-dependent manner. The progressive alteration is coincident with: (1) divergence of δ18O and δ13C values from those similar to unaltered sediment towards those of calcrete, due to interaction with CO2-charged meteoric fluids; (2) depletion of elements with low partitioning coefficients and low meteoric concentrations, such as barium, boron, magnesium, potassium, sodium, strontium, and uranium; (3) enrichment of iron from Terra Rossa-hosted iron oxides; (4) enrichment of aluminum via detrital minerals sourced from protosol horizons; and (5) manganese concentrations that remain uncharacteristically low, owing to the lack of a consistent manganese source. Elemental correlations are useful for characterizing meteoric diagenesis, assuming the primary mineralogy is recognized, all components have been fully altered, and inter-particle cements are ubiquitous.

Upper-Pleistocene terrace deposits in Mediterranean climate: geomorphological and source-rock control on mineral and geochemical signatures (Betic Cordillera, SE Spain)

Mineral and chemical composition of alluvial Upper-Pleistocene deposits from the Alto Guadalquivir Basin (SE Spain) were studied as a tool to identify sedimentary and geomorphological processes controlling its formation. Sediments located upstream, in the north-eastern sector of the basin, are rich in dolomite, illite, MgO and KB2BO. Downstream, sediments at the sequence base are enriched in calcite, smectite and CaO, whereas the upper sediments have similar features to those from upstream. Elevated rare-earth elements (REE) values can be related to low carbonate content in the sediments and the increase of silicate material produced and concentrated during soil formation processes in the neighbouring source areas. Two mineralogical and geochemical signatures related to different sediment source areas were identified. Basal levels were deposited during a predominantly erosive initial stage, and are mainly composed of calcite and smectite materials enriched in REE coming from Neogene marls and limestones. Then the deposition of the upper levels of the alluvial sequences, made of dolomite and illitic materials depleted in REE coming from the surrounding Sierra de Cazorla area took place during a less erosive later stage of the fluvial system. Such modification was responsible of the change in the mineralogical and geochemical composition of the alluvial sediments.

Coralline algae in a changing world: integrating ecological, physiological, and geochemical responses to global change

Coralline algae are globally distributed benthic primary producers that secrete calcium carbonate skeletons. In the context of ocean acidification, they have received much recent attention due to the potential vulnerability of their high-Mg calcite skeletons and their many important ecological roles. Herein, we summarize what is known about coralline algal ecology and physiology, providing context to understand their responses to global climate change. We review the impacts of these changes, including ocean acidification, rising temperatures, and pollution, on coralline algal growth and calcification. We also assess the ongoing use of coralline algae as marine climate proxies via calibration of skeletal morphology and geochemistry to environmental conditions. Finally, we indicate critical gaps in our understanding of coralline algal calcification and physiology and highlight key areas for future research. These include analytical areas that recently have become more accessible, such as resolving phylogenetic relationships at all taxonomic ranks, elucidating the genes regulating algal photosynthesis and calcification, and calibrating skeletal geochemical metrics, as well as research directions that are broadly applicable to global change ecology, such as the importance of community-scale and long-term experiments in stress response.

Coralline algae (Rhodophyta) in a changing world: integrating ecological, physiological, and geochemical responses to global change

Coralline algae are globally distributed benthic primary producers that secrete calcium carbonate skeletons. In the context of ocean acidification, they have received much recent attention due to the potential vulnerability of their high-Mg calcite skeletons and their many important ecological roles. Herein, we summarize what is known about coralline algal ecology and physiology, providing context to understand their responses to global climate change. We review the impacts of these changes, including ocean acidification, rising temperatures, and pollution, on coralline algal growth and calcification. We also assess the ongoing use of coralline algae as marine climate proxies via calibration of skeletal morphology and geochemistry to environmental conditions. Finally, we indicate critical gaps in our understanding of coralline algal calcification and physiology and highlight key areas for future research. These include analytical areas that recently have become more accessible, such as resolving phylogenetic relationships at all taxonomic ranks, elucidating the genes regulating algal photosynthesis and calcification, and calibrating skeletal geochemical metrics, as well as research directions that are broadly applicable to global change ecology, such as the importance of community-scale and long-term experiments in stress response.

Multivariate analysis of regional-scale geochemical data for environmental monitoring

A compositional multivariate approach is used to analyse regional scale soil geochemical data obtained as part of the Tellus Project generated by the Geological Survey Northern Ireland (GSNI). The multi-element total concentration data presented comprise XRF analyses of 6862 rural soil samples collected at 20cm depths on a non-aligned grid at one site per 2 km2. Censored data were imputed using published detection limits. Using these imputed values for 46 elements (including LOI), each soil sample site was assigned to the regional geology map provided by GSNI initially using the dominant lithology for the map polygon. Northern Ireland includes a diversity of geology representing a stratigraphic record from the Mesoproterozoic, up to and including the Palaeogene. However, the advance of ice sheets and their meltwaters over the last 100,000 years has left at least 80% of the bedrock covered by superficial deposits, including glacial till and post-glacial alluvium and peat. The question is to what extent the soil geochemistry reflects the underlying geology or superficial deposits. To address this, the geochemical data were transformed using centered log ratios (clr) to observe the requirements of compositional data analysis and avoid closure issues. Following this, compositional multivariate techniques including compositional Principal Component Analysis (PCA) and minimum/maximum autocorrelation factor (MAF) analysis method were used to determine the influence of underlying geology on the soil geochemistry signature. PCA showed that 72% of the variation was determined by the first four principal components (PC’s) implying “significant” structure in the data. Analysis of variance showed that only 10 PC’s were necessary to classify the soil geochemical data. To consider an improvement over PCA that uses the spatial relationships of the data, a classification based on MAF analysis was undertaken using the first 6 dominant factors. Understanding the relationship between soil geochemistry and superficial deposits is important for environmental monitoring of fragile ecosystems such as peat. To explore whether peat cover could be predicted from the classification, the lithology designation was adapted to include the presence of peat, based on GSNI superficial deposit polygons and linear discriminant analysis (LDA) undertaken. Prediction accuracy for LDA classification improved from 60.98% based on PCA using 10 principal components to 64.73% using MAF based on the 6 most dominant factors. The misclassification of peat may reflect degradation of peat covered areas since the creation of superficial deposit classification. Further work will examine the influence of underlying lithologies on elemental concentrations in peat composition and the effect of this in classification analysis.