TitaniQ under pressure: the effect of pressure and temperature on the solubility of Ti in quartz

Quartz and rutile were synthesized from silica-saturated aqueous fluids between 5 and 20 kbar and from 700 to 940°C in a piston-cylinder apparatus to explore the potential pressure effect on Ti solubility in quartz. A systematic decrease in Ti-in-quartz solubility occurs between 5 and 20 kbar. Titanium K-edge X-ray absorption near-edge structure (XANES) measurements demonstrate that Ti⁴⁺ substitutes for Si⁴⁺ on fourfold tetrahedral sites in quartz at all conditions studied. Molecular dynamic simulations support XANES measurements and demonstrate that Ti incorporation onto fourfold sites is favored over interstitial solubility mechanisms. To account for the P–T dependence of Ti-in-quartz solubility, a least-squares method was used to fit Ti concentrations in quartz from all experiments to the simple expression

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.     

Aerobic oxidation of mackinawite (FeS) and its environmental implication for arsenic mobilization

Oxidation of mackinawite (FeS) and concurrent mobilization of arsenic were investigated as a function of pH under oxidizing conditions. At acidic pH, FeS oxidation is mainly initiated by the proton-promoted dissolution, which results in the release of Fe(II) and sulfide in the solution. While most of dissolved sulfide is volatilized before being oxidized, dissolved Fe(II) is oxidized into green rust-like precipitates and goethite (α-FeOOH). At basic pH, the development of Fe(III) (oxyhydr)oxide coating on the FeS surface inhibits the solution-phase oxidation following FeS dissolution. Instead, FeS is mostly oxidized into lepidocrocite (γ-FeOOH) via the surface-mediated oxidation without dissolution. At neutral pH, FeS is oxidized via both the solution-phase oxidation following FeS dissolution and the surface-mediated oxidation mechanisms. The mobilization of arsenic during FeS oxidation is strongly affected by FeS oxidation mechanisms. At acidic pH (and to some extent at neutral pH), the rapid FeS dissolution and the slow precipitation of Fe (oxyhydr)oxides results in arsenic accumulation in water. In contrast, the surface-mediated oxidation of FeS at basic pH leads to the direct formation of Fe (oxyhydr)oxides, which provides effective adsorbents for As under oxic conditions. At acidic and neutral pH, the solution-phase oxidation of dissolved Fe(II) accelerates the oxidation of the less adsorbing As(III) to the more adsorbing As(V). This study reveals that the oxidative mobilization of As may be a significant pathway for arsenic enrichment of porewaters in sulfidic sediments.     

Ferrous phosphate surface precipitates resulting from the reduction of intragrain 6-line ferrihydrite by Shewanella oneidensis MR-1

The reductive biotransformation of 6-line ferrihydrite located within porous silica (intragrain ferrihydrite) by Shewanella oneidensis MR-1 was investigated and compared to the behavior of 6-line ferrihydrite in suspension (free ferrihydrite). The effect of buffer type (PIPES and NaHCO₃), phosphate (P), and an electron shuttle (AQDS) on the extent of reduction and formation of Fe(II) secondary phases was investigated under anoxic conditions. Electron microscopy and micro X-ray diffraction were applied to evaluate the morphology and mineralogy of the biogenic precipitates and to study the distribution of microorganisms on the surface of porous silica after bioreduction. Kinetic reduction experiments with free and intragrain ferrihydrite revealed contrasting behavior with respect to the buffer and presence of P. The overall amount of intragrain ferrihydrite reduction was less than that of free ferrihydrite [at 5 mmol L⁻¹ Fe(III)_T]. Reductive mineralization was not observed in the intragrain ferrihydrite incubations without P, and all biogenic Fe(II) concentrated in the aqueous phase. Irrespective of buffer and AQDS addition, rosettes of Fe(II) phosphate of approximate 20-30 μm size were observed on porous silica when P was present. The rosettes grew not only on the silica surface but also within it, forming a coherent spherical structure. These precipitates were well colonized by microorganisms and contained extracellular materials at the end of incubation. Microbial extracellular polymeric substances may have adsorbed Fe(II) promoting Fe(II) phosphate nucleation with subsequent crystal growth proceeding in different directions from a common center.     

Unsteady diagenetic processes and sulfur biogeochemistry in tropical deltaic muds: Implications for oceanic isotope cycles and the sedimentary record

Sedimentary S cycling is usually conceptualized and interpreted within the context of steadily accreting (1-D) transport-reaction regimes. Unsteady processes, however, are common in many sedimentary systems and can result in dramatically different S reaction balances and diagenetic products than steady conditions. Globally important common examples include tropical deltaic topset and inner shelf muds such as those extending from the Amazon River ∼1600 km along the Guianas coast of South America. These deposits are characterized by episodic reworking of the surface seabed over vertical depths of ∼0.1-3 m. Reworked surface sediments act as unsteady, suboxic batch reactors, unconformably overlying relict anoxic, often methanic deposits, and have diagenetic properties largely decoupled from net accumulation of sediment. Despite well-oxygenated water and an abundant reactive organic matter supply, physical disturbance inhibits macrofauna, and benthic communities are dominated by microbial biomass across immense areas. In the surficial suboxic layer, molecular biological analyses, tracer experiments, sediment C/S/Fe compositions, and δ³⁴S, δ¹⁸O of pore water indicate close coupling of anaerobic C, S, and Fe cycles. δ¹⁸O- can increase by 2-3‰ during anaerobic recycling without net change in δ³⁴S-, demonstrating reduction coupled to complete anaerobic reoxidation to and a δ¹⁸O- reduction + reoxidation fractionation factor?12‰ (summed magnitudes). S reoxidation must be coupled to Fe-oxide reduction, contributing to high dissolved Fe²⁺ (∼1 mM) and Fe mobilization-export. The reworking of Amazon-Guianas shelf muds alone may isotopically alter δ¹⁸O- equivalent in mass to?25% of the annual riverine delivery of to the global ocean. Unsteady conditions result in preservation of unusually heavy δ³⁴S isotopic compositions of residual Cr reducible S, ranging from 0‰ to >30‰ in physically reworked deposits. In contrast, bioturbated facies adjacent to physically reworked regions accumulate isotopically light S (δ³⁴S to −20‰) in otherwise similar decomposition regimes. The isotopic patterns of both physically and biologically reworked regions can be simulated with simple diagenetic models. Heavy S isotopic signatures are largely a consequence of unsteady diffusion and progressive anaerobic burndown into underlying deposits, whereas isotopically depleted bioturbated deposits predominantly reflect biogenic diffusive scaling and isotopic distillation/diffusive pumping associated with reoxidation in burrow walls immediately adjacent to reduced zones. The S isotopic transition from unsteady physically controlled regions of the Amazon delta moving laterally into bioturbated facies mimics the transition of S isotopic patterns temporally in the geologic record during the rise of bioturbation. No special role for S disproportionation is required to explain these differences. The potential role of unsteady, suboxic diagenesis and dynamic reworking of sediments has been largely ignored in models of the evolution of surficial elemental cycling and interpretations of the geologic record.     

干旱半干旱区土壤含水量反演与验证

基于MODIS遥感影像和表观热惯量法,以新疆为研究区,建立了适用于干旱半干旱区1 m土体的土壤含水量反演模型。模型根据高表观热惯量,高土壤含水量,低表观热惯量,低土壤含水量这一理论,通过日地表温差和宽波段反照率确定土壤含水量的时空变化。假设通过1 m土体的土壤水通量正比于上下底层土壤含水量的差值,利用水平衡方程建立土壤表面和底层土壤含水量关系方程,并利用中国土壤类型特点确定优化模型。通过验证结果表明,壤土和壤质粘土这两类土壤含水量接近真实值,砂土在区域验证中,模拟与实测差值为2.16%,整个模型模拟精度较好,能够准确地从时空上反演干旱半干旱地区1 m土体的土壤水分情况。     

The growth of the continental crust: Constraints from zircon Hf-isotope data

A worldwide database of over 13,800 integrated U–Pb and Hf-isotope analyses of zircon, derived largely from detrital sources, has been used to examine processes of crustal evolution on a global scale, and to test existing models for the growth of continental crust through time. In this study we introduce a new approach to quantitatively estimating the proportion of juvenile material added to the crust at any given time during its evolution. This estimate is then used to model the crustal growth rate over the 4.56 Ga of Earth's history. The modelling suggests that there was little episodicity in the production of new crust, as opposed to peaks in magmatic ages. The distribution of age-Hf isotope data from zircons worldwide implies that at least 60% of the existing continental crust separated from the mantle before 2.5 Ga. However, taking into consideration new evidence coming from geophysical data, the formation of most continental crust early in Earth's history (at least 70% before 2.5 Ga) is even more probable. Thus, crustal reworking has dominated over net juvenile additions to the continental crust, at least since the end of the Archean. Moreover, the juvenile proportion of newly formed crust decreases stepwise through time: it is about 70% in the 4.0–2.2 Ga time interval, about 50% in the 1.8–0.6 Ga time interval, and possibly less than 50% after 0.6 Ga. These changes may be related to the formation of supercontinents.