Biogeochemistry of dissolved carbon,major, and trace elements during spring flood periods on the Ob River     

Sergey N. Vorobyev  Oleg S. Pokrovsky  Larisa G. Kolesnichenko  Rinat M. Manasypov  Liudmila S. Shirokova  Jan Karlsson  Sergey N. Kirpotin 《水文研究》2019,33(11):1579-1594

Detailed knowledge of the flood period of Arctic rivers remains one of the few factors impeding rigorous prediction of the effect of climate change on carbon and related element fluxes from the land to the Arctic Ocean. In order to test the temporal and spatial variability of element concentration in the Ob River (western Siberia) water during flood period and to quantify the contribution of spring flood period to the annual element export, we sampled the main channel year round in 2014–2017 for dissolved C, major, and trace element concentrations. We revealed high stability (approximately ≤10% relative variation) of dissolved C, major, and trace element concentrations in the Ob River during spring flood period over a 1‐km section of the river channel and over 3 days continuous monitoring (3‐hr frequency). We identified two groups of elements with contrasting relationship to discharge: (a) DIC and soluble elements (Cl, SO₄, Li, B, Na, Mg, Ca, P, V, Cr, Mn, As, Rb, Sr, Mo, Ba, W, and U) negatively correlated (p < 0.05) with discharge and exhibited minimal concentrations during spring flood and autumn high flow and (b) DOC and particle‐reactive elements (Al, Fe, Ti, Y, Zr, Nb, Cs, REEs, Hf, Tl, Pb, and Th), some nutrients (K), and metalloids (Ge, Sb, and Te), positively correlated (p < 0.05) with discharge and showed the highest concentrations during spring flood. We attribute the decreased concentration of soluble elements with discharge to dilution by groundwater feeding and increased concentration of DOC and particle‐reactive metals with discharge to leaching from surface soil, plant litter, and suspended particles. Overall, the present study provides first‐order assessment of fluxes of major and trace elements in the middle course of the Ob River, reveals their high temporal and spatial stability, and characterizes the mechanism of river water chemical composition acquisition.  相似文献   

The 238U/235U Ratio as an Indicator of Redox Conditions in the Ediacaran Paleobasin (Sequence of the Chaya River,Baikal–Patom Highland,Southern Part of Central Siberia)     

Chugaev  A. V.  Chernyshev  I. V.  Pokrovsky  B. G.  Mandzhieva  G. V.  Gareev  B. I.  Sadasyuk  A. S.  Batalin  G. A. 《Doklady Earth Sciences》2019,485(1):336-340

Doklady Earth Sciences - Abstract—This article is devoted to a study of variations in the U isotopic composition (238U/235U) in the section of clastic–carbonate Ediacaran sediments...  相似文献   

Strontium and oxygen isotopic systems in waters of mud volcanoes of the Taman Peninsula     

M. I. Bujakaite  V. Yu. Lavrushin  B. G. Pokrovsky  O. E. Kikvadze  B. G. Polyak 《Lithology and Mineral Resources》2014,49(1):47-54

Ten of eleven analyzed water samples from mud volcanoes of the Taman Peninsula are characterized by ⁸⁷Sr/⁸⁶Sr ratio within 0.70734–0.70957, which overlaps the values typical of the Mesozoic and Cenozoic sedimentary carbonates, but sharply differs from the value in the clayey sediments of the Maikop Group (0.7157 ± 0.0022). These data indicate that the strontium isotopic composition is mainly defined by carbonate reservoirs, with relatively little effect of elision solutions, input of which is noticeable only in the water of Gladkovsky Volcano (⁸⁷Sr/⁸⁶Sr = 0.71076). The high δ¹⁸O in mud volcanic waters (up to 14.2‰) can also be attributed to ionic exchange with sedimentary carbonates at temperatures around 150°C.  相似文献   

Isotopic compositions of C,O, Sr,and S and problem of ages of the Katera and Uakit Groups,western Transbaikal region     

B. G. Pokrovsky  M. I. Bujakaite 《Lithology and Mineral Resources》2016,51(4):262-282

The age of the Katera Group, which occupies a large area in the western North Muya Range and occurs 100–150 km east of the Uakit Group, is a debatable issue. Based on geological correlations with reference sections of the Baikal Group and Patom Complex, the Katera and Uakit groups were previously considered nearly coeval units and assigned to Late Precambrian (Khomentovskii and Postnikov, 2002; Salop, 1964). This was supported partly by the Sm–Nd model datings (Rytsk et al., 2007, 2009, 2011). Finds of the Paleozoic flora substantiated the revision of age of the Uakit Group and its assignment to the Late Devonian–Early Carboniferous (Gordienko et al., 2010; Minina, 2003, 2012, 2014). We have established that Sr and C isotopic compositions in carbonates of these groups differ drastically, as suggested by their different ages. Sediments of the Nyandoni Formation (Katera Group), which contains carbonates characterized by minimum values of ⁸⁷Sr/⁸⁶Sr = 0.7056 and maximum values of δ¹³C = 4.9‰, were accumulated in the first half of Late Riphean (800–850 Ma ago), whereas the overlying Barguzin Formation (⁸⁷Sr/⁸⁶Sr_min = 0.70715, δ¹³C_max= 10.5‰) was deposited at the end of Late Riphean (700–750 Ma). Judging from the isotope data, the Nerunda Formation (Uakit Group), which contains carbonates with characteristics matching the most rigorous criteria of fitness for the chemostratigraphic correlation (Sr content up to 4390 μg/g, Mn/Sr < 0.1, δ¹⁸O = 23.0 ± 1.8‰), was deposited at the end of Vendian ~550–540 Ma ago). The sequence includes thick typical carbonate horizons with very contrast carbon isotopic compositions: the lower unit has anomalous high δ¹³C values (5.8 ± 1.0‰); the upper unit, by anomalous low δ¹³C values (–5.2 ± 0.5‰]). Their Sr isotopic composition is relatively homogeneous (⁸⁷Sr/⁸⁶Sr = 0.7084 ± 0.0001) that is typical of the Late Vendian ocean. The S isotopic composition of pyrites from the Nyandoni Formation (Katera Group) (δ³⁴S = 14.1 ± 6.8‰) and pyrites from the Mukhtunny Formation (Uakit Group) (δ³⁴S = 0.7 ± 1.4‰) does not contradict the C and Sr isotopic stratigraphic data.  相似文献   

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

O. S. Pokrovsky  J. Schott 《Chemical Geology》2002,190(1-4):141-179

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.  相似文献   

An X-ray absorption fine structure and nuclear magnetic resonance spectroscopy study of gallium-silica complexes in aqueous solution     

Gleb S Pokrovski  Jacques SchottJean-Louis Hazemann  François Farges  Oleg S Pokrovsky 《Geochimica et cosmochimica acta》2002,66(24):4203-4222

The influence of aqueous silica on gallium(III) hydrolysis in dilute (2 × 10⁻⁴ ≤ m_Ga ≤ 5 × 10⁻³) and moderately concentrated (0.02 ≤ m_Ga ≤ 0.3) aqueous solutions was studied at ambient temperature, using high resolution X-ray absorption fine structure (XAFS) and nuclear magnetic resonance (NMR) spectroscopies, respectively. Results show that, in Si-free acidic solutions (pH < 3), Ga is hexa-coordinated with oxygens of H₂O molecules and/or OH groups in the first coordination sphere of the metal. With increasing pH, these hydroxyl groups are progressively replaced by bridging oxygens (-O-), and polymerized Ga-hydroxide complexes form via Ga-O-Ga chemical bonds. In the 2.5-3.5 pH range, both XAFS and NMR spectra are consistent with the dominant presence of the Ga₁₃ Keggin polycation, which has the same local structure as A1₁₃. Under basic pH (pH > 8), Ga exhibits a tetrahedral coordination, corresponding to Ga(OH)₄⁻ species, in agreement with previous NMR and potentiometric studies. Major changes in Ga hydrolysis have been detected in the presence of aqueous silica. Ga is tetra-coordinated, both in basic and acid (i.e., at pH > 2.7) Si-bearing solutions (0.01 ≤ m_Si ≤ 0.2), and forms stable gallium-silicate complexes. In these species, Ga binds via bridging oxygen to 2 ± 1 silicons, with an average Ga-Si distance of 3.16 ± 0.05 Å, and to 2 ± 1 silicons, with an average Ga-Si distance of 3.39 ± 0.03 Å. These two sets of Ga-Si distances imply the formation of two types of Ga-silicate aqueous complex, cyclic Ga-Si_2-3 species (formed by the substitution of Si in its tri-, tetra- or hexa-cyclic polymers by Ga atoms), and chainlike GaSi_2-4 species (similar to those found for A1), respectively. The increase in the number of Si neighbors (a measure of the complex concentration and stability), in alkaline media, with increasing SiO₂(aq) content and decreasing pH is similar to that for A1-Si complexes found in neutral to basic solutions. At very acid pH and moderate silica concentrations, the presence of another type of Ga-Si complex, in which Ga remains hexa-coordinated and binds to the silicon tetrahedra via the GaO₆ octahedron corners, has also been detected. These species are similar to those found for Al³⁺ in acid solutions. Thus, as for aluminum, silicic acid greatly hampers Ga hydrolysis and enhances Ga mobility in natural waters via the formation of gallium-silicate complexes.  相似文献   

Experimental study of brucite dissolution and precipitation in aqueous solutions: surface speciation and chemical affinity control     

Oleg S. Pokrovsky  Jacques Schott 《Geochimica et cosmochimica acta》2004,68(1):31-45

Dissolution and precipitation rates of brucite (Mg(OH)₂) were measured at 25°C in a mixed-flow reactor as a function of pH (2.5 to 12), ionic strength (10⁻⁴ to 3 M), saturation index (−12 < log Ω < 0.4) and aqueous magnesium concentrations (10⁻⁶ to 5·10⁻⁴ M). Brucite surface charge and isoelectric point (pH_IEP) were determined by surface titrations in a limited residence time reactor and electrophoretic measurements, respectively. The pH of zero charge and pH_IEP were close to 11. A two-pK, one site surface speciation model which assumes a constant capacitance of the electric double layer (5 F/m²) and lack of dependence on ionic strength predicts the dominance of >MgOH₂⁺ species at pH < 8 and their progressive replacement by >MgOH° and >MgO⁻ as pH increases to 10-12. Rates are proportional to the square of >MgOH₂⁺ surface concentration at pH from 2.5 to 12. In accord with surface speciation predictions, dissolution rates do not depend on ionic strength at pH 6.5 to 11. Brucite dissolution and precipitation rates at close to equilibrium conditions obeyed TST-derived rate laws. At constant saturation indices, brucite precipitation rates were proportional to the square of >MgOH₂⁺ concentration. The following rate equation, consistent with transition state theory, describes brucite dissolution and precipitation kinetics over a wide range of solution composition and chemical affinity: