Hafnium and neodymium isotopes in surface waters of the eastern Atlantic Ocean: Implications for sources and inputs of trace metals to the ocean

We present hafnium (Hf) and neodymium (Nd) isotopic compositions and concentrations in surface waters of the eastern Atlantic Ocean between the coast of Spain and South-Africa. These data are complemented by Hf and Nd isotopic and concentration data, as well as rare earth element (REE) concentrations, in Saharan dust.Hafnium concentrations range between a maximum of 0.52 pmol/kg in the area of the Canary Islands and a minimum value of 0.08 pmol/kg in the southern Angola Basin. Neodymium concentrations also show a local maximum in the area of the Canary Islands (26 pmol/kg) but are even higher between ∼20°N and ∼4°N reaching maximum concentrations of 35 pmol/kg. These elevated concentrations provide evidence of inputs from weathering of the Canary Islands and from the partial dissolution of dust from the Sahara/Sahel region. The inputs from ocean island weathering are also reflected in radiogenic Hf and Nd isotopes.The Hf isotopic compositions of dust samples themselves are highly variable, ranging between ε_Hf = −20 and −0.6. The combined Hf and Nd isotopic compositions of dust plot close to the “terrestrial array” during periods of appreciable dust load in the atmosphere. During low atmospheric dust loading combined Hf and Nd isotopic compositions similar to seawater are observed. Most of the variability can be explained in terms of variable degrees of zircon loss from the dust samples, which in turn is linked to sorting during atmospheric transport to the eastern Atlantic Ocean and possibly presorting by sedimentary redistribution on the continent. In addition, increasing relative proportions of radiogenic clay minerals with decreasing grain size may contribute to the radiogenic Hf isotopic compositions observed.While the Nd isotopic composition in the surface ocean reflects the Nd isotopic composition of the Saharan dust adjacent to the Sahara/Sahel region, the release of Hf from that dust appears to be incongruent and results in surface ocean Hf isotopic compositions which are ∼10 ε_Hf more radiogenic than the bulk dust. Radiogenic Hf appears to be released from clays and possibly from trace apatite. Rare earth element patterns of dust samples indicate the presence of apatite but provide no evidence for ferromanganese grain coatings, suggesting that such coatings are insignificant in the release of Hf and Nd from Saharan dust to the surface ocean.The Nd isotopic composition of the surface waters becomes less radiogenic south of the equator, most likely reflecting the release of Nd from Congo river sediments. The release of Hf from Saharan dust and the Congo river sediments, however, does not produce distinct Hf isotopic signatures in the surface ocean, implying that the mobile fraction of Hf integrated over large continental areas is isotopically uniform. The Hf isotopic uniformity in the surface ocean means that the limited variability in deep water isotopic compositions is consistent with a short deep water residence time and reflects homogenous continental inputs rather than efficient deep water homogenization.     

Trace elements in organic- and iron-rich surficial fluids of the boreal zone: Assessing colloidal forms via dialysis and ultrafiltration

On-site size fractionation of about 40 major and trace elements (TE) was performed on waters from boreal small rivers and their estuaries in the Karelia region of North-West Russia around the “Vetreny Belt” mountain range and in Paanajärvi National Park (Northern Karelia). Samples were filtered in the field using a progressively decreasing pore size (5 μm, 2.5 (3) μm, 0.22 (0.45) μm, 100 kDa, 10 and 1 kDa) by means of frontal filtration and ultrafiltration (UF) techniques and employing in-situ dialysis with 10 and 1 kDa membranes followed by ICP-MS analysis. For most samples, dialysis yields a systematically higher (factor of 2-3) proportion of colloidal forms compared to UF. Nevertheless, dialysis is able to provide a fast and artefact-free in-situ separation of colloidal and dissolved components.Similar to previous studies in European subarctic zones, poor correlation of iron concentration with that of organic carbon (OC) in (ultra)filtrates and dialysates reflect the presence of two pools of colloids composed of organic-rich and Fe-rich particles. All major anions and silica are present as dissolved species (or solutes) passing through the 1-kDa membrane. Size-separation ultrafiltration experiments show the existence of larger or smaller pools of colloidal particles different for each of the considered elements.The effect of rock lithology (acidic versus basic) on the colloidal speciation of TE is seen solely in the increase of Fe and some accompanying TE concentrations in catchment areas dominated by basic rocks compared to granitic catchments. Neither the ultrafiltration pattern nor the relative proportions of colloidal versus truly dissolved TE are affected by the lithology of the underlying rocks: within ±10% uncertainty, the two colloidal (10 kDa-0.22 μm and 1-10 kDa) and the truly dissolved (<1 kDa) pools show no difference in percentage of TE distribution between two types of bedrock lithology. The same conclusion is held for organic- and Fe-rich waters. In contrast, landscape context analysis demonstrated slight dominance, for most TE affected by UF, of large-size colloids (10 kDa-0.22 μm) in rivers and streams and small-size colloids and truly dissolved fractions in swamp stagnant surface waters. This supports the existence of two pathways of colloids formation: during the plant litter degradation in wetland zones and at the redox front in river riparian zone.     

On the elemental composition of suspended matter of the Severnaya Dvina River (White Sea region)

New data on the elemental composition of the Severnaya Dvina River, the largest one in the White Sea region, are presented. The elemental composition of the river water in May, the period of the snowmelt flood, is similar to the upper layer of the Earth’s continental crust due to the active erosion of the earth material in the catchment area. In August, the period of the summer low water, the impact of biogenic components increases and elevated concentrations of Cd, Sb, Mn, Zn, Pb, and Cu are observed. At other times, no significant pollution by heavy and rare-earth elements is registered.     

Molecular and isotopic partitioning of low-molecular-weight hydrocarbons during migration and gas hydrate precipitation in deposits of a high-flux seepage site

Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone.Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (> 99.85 mol.% of ∑[C₁–C₄, CO₂]). Molecular ratios of LMWHC (C₁/[C₂ + C₃] > 1000) and stable isotopic compositions of methane (δ¹³C = ? 53.5‰ V-PDB; D/H around ? 175‰ SMOW) indicated predominant microbial methane formation. C₁/C₂₊ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by > 0.03 mol.% (∑[C₁–C₄, CO₂]) relative to the other gas types and the virtual lack of ¹⁴C–CH₄ indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely.As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% ∑(C₁–C₄, CO₂)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of ¹⁴C–CH₄ (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.     

The Triassic age for oceanic eclogites in the Dabie orogen: Entrainment of oceanic fragments in the continental subduction

Low-temperature and high-pressure eclogites with an oceanic affinity in the western part of the Dabie orogen have been investigated with combined Lu–Hf and U–Pb geochronology. These eclogites formed over a range of temperatures (482–565 °C and 1.9–2.2 GPa). Three eclogites, which were sampled from the Gaoqiao country, yielded Lu–Hf ages of 240.7 ± 1.2 Ma, 243.3 ± 4.1 Ma and 238.3 ± 1.2 Ma, with a corresponding lower-intercept U–Pb zircon age of 232 ± 26 Ma. Despite the well-preserved prograde major- and trace-element zoning in garnets, these Lu–Hf ages mostly reflect the high-pressure eclogite-facies metamorphism instead of representing the early phase of garnet growth due to the occurrence of omphacite inclusions from core to rim and the shell effect. An upper-intercept zircon U–Pb age of 765 ± 24 Ma is defined for the Gaoqiao eclogite, which is consistent with the weighted-mean age of 768 ± 21 Ma for the country gneiss. However, the gneiss has not been subjected to successive high-pressure metamorphism. The new Triassic ages are likely an estimate of the involvement of oceanic fragments in the continental subduction.     

Continental crust in Gorny Altai: nature and composition of protoliths

The history of the Vendian–Early Paleozoic formation of protoliths of continental crust in the Gorny Altai segment of the Central Asian fold belt is considered, and their composition, isotopic characteristics, and formation mechanisms are estimated. We have established two stages of crust-forming processes in Gorny Altai: Early and Late Caledonian, with the different structures of formed geoblocks and nature and compositions of crustal protoliths. At the Early Caledonian stage, fragments of oceanic lithosphere of basic composition (MORB, OIT, OIB) (T_Nd(DM-2st) = 0.65–1.1 Ga) formed, as well as island arcs with andesite-basaltic and andesitic protoliths with low contents of incompatible elements (T_Nd(DM-2st) = 0.7–0.9 Ga). At the Late Caledonian stage, the redistribution of the substance of these blocks and the external supply of material led to the formation of heterogeneous crust of turbidite basins with an oceanic basement and andesite-dacitic upper-crustal protoliths (T_Nd(DM-2st) varies from 0.8–0.9 Ga in the framing of the volcanic arc of Altaids to 1.4–1.6 Ga at the boundary of the Altai–Mongolian microcontinent).     

4D architecture and tectonic evolution of the Laverton region,eastern Yilgarn Craton,Western Australia

The Laverton region, located in the eastern Yilgarn Craton (EYC) Western Australia, is second only to the Kalgoorlie region for gold endowment. The integration of high-density, potential-field data, regional- and camp-scale seismic reflection data, regional- and mine-scale structural analysis, and geochronologically-constrained stratigraphy, provided new insights into the 4D architecture and tectonic evolution of Laverton region.     

Decolorization of different azo dyes by Phanerochaete chrysosporium RP78 under optimal condition

Detoxification of synthetic dyes is one of the main challenges in clearing textile industry wastes. Biodegradation of azo-dyes using Phanerochaete chrysosporium is one the most environmentally friendly methods available. The main enzymes responsible for mycodecolorization process are lignin and manganese peroxidases. Here, optimization of expression conditions has been carried out with manipulating culture condition and nutrient sources. Therefore, the effects of buffer and temperature as well as nitrogen source on lignin peroxidase and manganese peroxidase production were investigated at two levels and four levels, respectively. For this purpose, P. chrysosporium RP78 based on Taguchi design of experiment has been applied. Maximum lignin and manganese peroxidase activities of 182 ± 2.5 U/L and 850 ± 41 U/L were obtained under predicted optimum conditions, respectively. Thereby, about 100 % decolorization was achieved after 24 h for two most widely used groups of azo dyes in textile industry consisting reactive and acidic. The physical adsorption of the azo dyes by mycelia was not significant which indicated that the enzymatic degradation of the dyes was occurred. Time profile of these enzymes showed that manganese peroxidase was peaked on 9^th day while lignin peroxidase peaked on 13^th day and remained stable in the culture. The extracellular expression profiles of both were studied by 2 dimensional gel electrophoresis to partially characterize the enzymes.