Iron colloids/organic matter associated transport of major and trace elements in small boreal rivers and their estuaries (NW Russia)

The chemical status of major and trace elements (TE) in various boreal small rivers and watershed has been investigated along a 1500-km transect of NW Russia. Samples were filtered in the field through a progressively decreasing pore size (5, 0.8 and 0.22 μm; 100, 10, and 1 kD) using a frontal filtration technique. All major and trace elements and organic carbon (OC) were measured in filtrates and ultrafiltrates. Most rivers exhibit high concentration of dissolved iron (0.2–4 mg/l), OC (10–30 mg/l) and significant amounts of trace elements usually considered as immobile in weathering processes (Ti, Zr, Th, Al, Ga, Y, REE, V, Pb). In (ultra)filtrates, Fe and OC are poorly correlated: iron concentration gradually decreases upon filtration from 5 μm to 1 kD whereas the major part of OC is concentrated in the <1–10 kD fraction. This reveals the presence of two pools of colloids composed of organic-rich and Fe-rich particles. According to their behavior during filtration and association with these two types of colloids, three groups of elements can be distinguished: (i) species that are not affected by ultrafiltration and are present in the form of true dissolved inorganic species (Ca, Mg, Li, Na, K, Sr, Ba, Rb, Cs, Si, B, As, Sb, Mo) or weak organic complexes (Ca, Mg, Sr, Ba), (ii) elements present in the fraction smaller than 1–10 kD prone to form inorganic or organic complexes (Mn, Co, Ni, Zn, Cu, Cd, and, for some rivers, Pb, Cr, Y, HREE, U), and (iii) elements strongly associated with colloidal iron in all ultrafiltrates (P, Al, Ga, REE, Pb, V, Cr, W, Ti, Ge, Zr, Th, U). Based on size fractionation results and taking into account the nominal pore size for membranes, an estimation of the effective surface area of Fe colloids was performed. Although the total amount of available surface sites on iron colloids (i.e., 1–10 μM) is enough to accommodate the nanomolar concentrations of dissolved trace elements, very poor correlation between TE and surface sites concentrations was observed in filtrates and ultrafiltrates. This strongly suggests a preferential transport of TE as coprecipitates with iron oxy(hydr)oxides. These colloids can be formed on redox boundaries by precipitation of Fe(III) from inflowing Fe(II)/TE-rich anoxic ground waters when they meet well-oxygenated surface waters. Dissolved organic matter stabilizes these colloids and prevents their aggregation and coagulation. Estuarine behavior of several trace elements was studied for two small iron- and organic-rich rivers. While Si, Sr, Ba, Rb, and Cs show a clear conservative behavior during mixing of freshwaters with the White sea, Al, Pb and REE are scavenged with iron during coagulation of Fe hydroxide colloids.     

Abundance and distribution of PGE and Au in the island-arc mantle: implications for sub-arc metasomatism

Ultramafic xenoliths from a veined mantle wedge beneath the Kamchatka arc have non-chondritic, fractionated chondrite-normalized platinum-group element (PGE) patterns. Depleted (e.g., low bulk-rock Al₂O₃ and CaO contents) mantle harzburgites show clear enrichment in the Pd group relative to the Ir group PGEs and, in most samples, Pt relative to Rh and Pd. These PGE signatures most likely reflect multi-stage melting which selectively concentrates Pt in Pt–Fe alloys while strongly depleting the sub-arc mantle wedge in incompatible elements. Elevated gold concentrations and enrichment of strongly incompatible enrichment (e.g., Ba and Th) in some harzburgites suggest a late-stage metasomatism by slab-derived, saline hydrous fluids. Positive Pt, Pd, and Au anomalies coupled with Ir depletions in heavily metasomatized pyroxenite xenoliths probably reflect the relative mobility of the Pd and Ir groups (especially Os) during sub-arc metasomatism which is consistent with Os systematics in arc mantle nodules. Positive correlations between Pt, Pd, and Au and various incompatible elements (Hf, U, Ta, and Sr) also suggest that both slab-derived hydrous fluids and siliceous melts were involved in the sub-arc mantle metasomatism beneath the Kamchatka arc.     

Post-mid-Cretaceous eastern North Sea evolution inferred from 3D thermo-mechanical modelling

The Late Cretaceous–Cenozoic evolution of the eastern North Sea region is investigated by 3D thermo-mechanical modelling. The model quantifies the integrated effects on basin evolution of large-scale lithospheric processes, rheology, strength heterogeneities, tectonics, eustasy, sedimentation and erosion.

The evolution of the area is influenced by a number of factors: (1) thermal subsidence centred in the central North Sea providing accommodation space for thick sediment deposits; (2) 250-m eustatic fall from the Late Cretaceous to present, which causes exhumation of the North Sea Basin margins; (3) varying sediment supply; (4) isostatic adjustments following erosion and sedimentation; (5) Late Cretaceous–early Cenozoic Alpine compressional phases causing tectonic inversion of the Sorgenfrei–Tornquist Zone (STZ) and other weak zones.

The stress field and the lateral variations in lithospheric strength control lithospheric deformation under compression. The lithosphere is relatively weak in areas where Moho is deep and the upper mantle warm and weak. In these areas the lithosphere is thickened during compression producing surface uplift and erosion (e.g., at the Ringkøbing–Fyn High and in the southern part of Sweden). Observed late Cretaceous–early Cenozoic shallow water depths at the Ringkøbing–Fyn High as well as Cenozoic surface uplift in southern Sweden (the South Swedish Dome (SSD)) are explained by this mechanism.

The STZ is a prominent crustal structural weakness zone. Under compression, this zone is inverted and its surface uplifted and eroded. Contemporaneously, marginal depositional troughs develop. Post-compressional relaxation causes a regional uplift of this zone.

The model predicts sediment distributions and paleo-water depths in accordance with observations. Sediment truncation and exhumation at the North Sea Basin margins are explained by fall in global sea level, isostatic adjustments to exhumation, and uplift of the inverted STZ. This underlines the importance of the mechanisms dealt with in this paper for the evolution of intra-cratonic sedimentary basins.     

Hydrothermal Redistribution of Rare—Earth Elements in Pingxiang Dacite,Guangxi

Distribution of the rare-earth elements (REE) in dacite has been studied so as to get a better understanding of the migration behavior of REE during alteration. Both unaltered and altered samples were collected in an unpolluted area of Guangxi Zhuang Autonomous Region, southwest China. The REE concentrations were analyzed by ICP-MS. It is concluded that the REE were enriched during dacite alteration in varying degrees. The chondrite-normalized REE patterns of altered samples approximately maintain the characteristics of unaltered samples. However, if we normalize the REE concentrations of altered samples with unaltered dacite, fractionation of REE will appear. The LREE are more enriched than HREE in all altered samples with the LREE possibly precipitated as carbonate minerals. Both positive and negative Eu anomalies exist. Enrichment, immobility and depletion are noticed for the element Lu. Heavy mineral alteration, difference in stability constant between carbonate LREE and HREE complexes, downward migration of weathering fluid and microenvironment change may be responsible for the fractionation of REE in the altered dacite.     

Rare earth elements in waters from the albitite-bearing granodiorites of Central Sardinia, Italy

With the aim of contributing to the knowledge of the geochemical behaviour and mobility of the rare earth element (REE) in the natural water systems, the ground and surface waters of the Ottana-Orani area (Central Sardinia, Italy) were sampled. The study area consists of albititic bodies included in Hercynian granodiorites. The waters have pH in the range of 6.0-8.6, total dissolved solid (TDS) of between 0.1 and 0.6 g/l, and major cation composition dominated by Ca and Na, whereas predominant anions are Cl and/or HCO₃.The pH and the major-element composition of the waters are the factors affecting the concentration of REE in solution. The concentrations of ∑REE+Y in the samples filtered at 0.4 μm vary between 140 and 1600 ng/l, with La of between 14 and 314 ng/l, and Yb of between <6 and 12 ng/l. A negative Ce anomaly, especially marked at high pH, is observed in the groundwaters. The surface waters show lower REE concentrations, which are independent of pH, and negligible Ce anomaly.Speciation calculations, carried out with the EQ3NR computer program, showed that the complexes with the CO₃²⁻ ligand are the dominant REE species at pH in the range of 6.7-8.6. The REE³⁺ ions dominate the speciation at pH <6.7 and only in the light REE (LREE).The relative concentrations of REE in water roughly reflect those in the aquifer host rocks. However, when concentrations of REE in water are normalised relative to the parent rocks, a preferential fractionation of heavy REE (HREE) into the water phase can be observed, suggesting the greater mobility and stability of HREE in aqueous solution.     

Method of Data Reduction and Uncertainty Estimation for Platinum-Group Element Data Using Inductively Coupled Plasma-Mass Spectrometry

A data reduction method is described for determining platinum-group element (PGE) abundances by inductively coupled plasma-mass spectrometry (ICP-MS) using external calibration or the method of standard addition. Gravimetric measurement of volumes, the analysis of reference materials and the use of procedural blanks were all used to minimise systematic errors. Internal standards were used to correct for instrument drift. A linear least squares regression model was used to calculate concentrations from drift-corrected counts per second (cps). Furthermore, mathematical manipulations also contribute to the uncertainty estimates of a procedure. Typical uncertainty estimate calculations for ICP-MS data manipulations involve: (1) Carrying standard deviations from the raw cps through the data reduction or (2) calculating a standard deviation from multiple final concentration calculations. It is demonstrated that method 2 may underestimate the uncertainty estimate of the calculated data. Methods 1 and 2 do not typically include an uncertainty estimate component from a regression model. As such models contribute to the uncertainty estimates affecting the calculated data, an uncertainty estimate component from the regression must be included in any final error calculations. Confidence intervals are used to account for uncertainty estimates from the regression model. These confidence intervals are simpler to calculate than uncertainty estimates from method 1, for example. The data reduction and uncertainty estimation method described here addresses problems of reporting PGE data from an article in the literature and addresses both precision and accuracy. The method can be applied to any analytical technique where drift corrections or regression models are used.     

Production of selected cosmogenic radionuclides by muons: 2. Capture of negative muons

We have determined the production yields for radionuclides in Al₂O₃, SiO₂, S, Ar, K₂SO₄, CaCO₃, Fe, Ni and Cu targets, which were irradiated with slow negative muons at the Paul Scherrer Institute in Villigen (Switzerland). The fluences of the stopped negative muons were determined by measuring the muonic X-rays. The concentrations of the long-lived and short-lived radionuclides were measured with accelerator mass spectrometry (AMS) and γ-spectroscopy, respectively. Special emphasis was put on the radionuclides ¹⁰Be, ¹⁴C and ²⁶Al produced in quartz targets, ²⁶Al in Al₂O₃ and S targets, ³⁶Cl in K₂SO₄ and CaCO₃ targets, and ⁵³Mn in Fe₂O₃ targets. These targets were selected because they are also the naturally occurring target minerals for cosmic ray interactions in typical rocks. We also present results of calculations for depth-dependent production rates of radionuclides produced after cosmic ray μ⁻ capture, as well as cosmic ray-induced production rates of geologically relevant radionuclides produced by the nucleonic component, by μ⁻ capture, by fast muons and by neutron capture.     

Gravity and magnetic signatures of volcanic plugs related to Deccan volcanism in Saurashtra, India and their physical and geochemical properties

The Bouguer anomaly and the total intensity magnetic maps of Saurashtra have delineated six circular gravity highs and magnetic anomalies of 40-60 mGal (10⁻⁵m/s²) and 800-1000 nT, respectively. Three of them in western Saurashtra coincide with known volcanic plugs associated with Deccan Volcanic Province (DVP), while the other three in SE Saurashtra coincide with rather concealed plugs exposed partially. The DVP represents different phases of eruption during 65.5±2.5 Ma from the Reunion plume. The geochemical data of the exposed rock samples from these plugs exhibit a wide variation in source composition, which varies from ultramafic/mafic to felsic composition of volcanic plugs in western Saurashtra and an alkaline composition for those in SE Saurashtra. Detailed studies of granophyres and alkaline rocks from these volcanic plugs reveal a calc-alkaline differentiation trend and a continental tectonic setting of emplacement. The alkaline plugs of SE Saurashtra are associated with NE-SW oriented structural trends, related to the Gulf of Cambay and the Cambay rift basin along the track of the Reunion plume. This indicates a deeper source for these plugs compared to those in the western part and may represent the primary source magma. The Junagadh plug with well differentiated ring complexes in western Saurashtra shows well defined centers of magnetic anomaly while the magnetic anomalies due to other plugs are diffused though of the same amplitude. This implies that other plugs are also associated with mafic/ultramafic components, which may not be differentiated and may be present at subsurface levels. Paleomagnetic measurements on surface rock samples from DVP in Saurashtra suggest a susceptibility of 5.5×10⁻² SI units with an average Koenigsberger ratio (Q_n) of almost one and average direction of remanent magnetization of D=147.4° and I=+56.1°. The virtual geomagnetic pole (VGP) position computed from the mean direction of magnetization for the volcanic plugs and Deccan basalt of Saurashtra is 30°N and 74°W, which is close to the VGP position corresponding to the early phases of Deccan eruption. Modeling of gravity and magnetic anomalies along two representative profiles across Junagadh and Barda volcanic plugs suggest a bulk density of 2900 and 2880 kg/m³, respectively and susceptibility of 3.14×10⁻² SI units with a Q_n ratio of 0.56 which are within the range of their values obtained from laboratory measurements on exposed rock samples. The same order of gravity and magnetic anomalies observed over the volcanic plugs of Saurashtra indicates almost similar bulk physical properties for them. The inferred directions of magnetization from magnetic anomalies, however, are D=337° and 340° and I=−38° and −50° which represent the bulk direction of magnetization and also indicate a reversal of the magnetic field during the eruption of these plugs. Some of these plugs are associated with seismic activities of magnitude ≤4 at their contacts. Based on this analysis, other circular/semi-circular gravity highs of NW India can be qualitatively attributed to similar subsurface volcanic plugs.     

昆明城市气候水平空间分布特征

以昆明城市为研究对象，对城市西南-东北剖线的实测资料比较研究，从气温、水汽压、相对湿度、风速、风向等方面分析了昆明城市气候特征、变化规律及城市热岛效应。研究表明：在昆明存在热岛效应，以夜间最为明显，其最强度效应可达5.0℃，出现时刻（3时）与国内外多数研究结果（傍晚）有所不同；昆明城市昼间呈现明显的干岛效应。所得结论可为探讨昆明城市气候特片和形成机制，城市环境污染防治及建筑规划、设计等提供依据。     

跨国公司地区总部职能与亚洲地区总部的区位研究

跨国公司建立地区总部制度是跨国公司应对经营“全球化”和“本地化”的要求而进行的一项组织变革。由于跨国公司地区总部承担着制定区域性经营战略和协调区域内众多子公司生产、销售、物流、研究与开发、资金筹供、人力资源培养等经营活动的职能，它的区位对东道国及其所在城市经济带来广泛影响。本文从跨国公司和地区总部职能特点入手，分析了该职能的区位因素，并探讨了跨国公司亚洲地区总部的区位特点，最后对中国大陆的国际商务职能建设提出了若干建议。