Asymmetrically zoned reaction rims: assessment of grain boundary diffusivities and growth rates related to natural diffusion-controlled mineral reactions

This study explores garnet coronas around hedenbergite, which were formed by the reaction plagioclase + hedenbergite→garnet + quartz, to derive information about diffusion paths that allowed for material redistribution during reaction progress. Whereas quartz forms disconnected single grains along the garnet/hedenbergite boundaries, garnet forms ～20‐μm‐wide continuous polycrystalline rims along former plagioclase/hedenbergite phase boundaries. Individual garnet crystals are separated by low‐angle grain boundaries, which commonly form a direct link between the reaction interfaces of the plagioclase|garnet|hedenbergite succession. Compositional variations in garnet involve: (i) an overall asymmetric compositional zoning in Ca, Fe²⁺, Fe³⁺ and Al across the garnet layer; and (ii) micron‐scale compositional variations in the near‐grain boundary regions and along plagioclase/garnet phase boundaries. These compositional variations formed during garnet rim growth. Thereby, transfer of the chemical components occurred by a combination of fast‐path diffusion along grain boundaries within the garnet rim, slow diffusion through the interior of the garnet grains, and by fast diffusion along the garnet/plagioclase and the garnet/hedenbergite phase boundaries. Numerical simulation indicates that diffusion of Ca, Al and Fe²⁺ occurred about three to four, four and six to seven orders of magnitude faster along the grain boundaries than through the interior of the garnet grains. Fast‐path diffusion along grain boundaries contributed substantially to the bulk material transfer across the growing garnet rim. Despite the contribution of fast‐path diffusion, bulk diffusion through the garnet rim was too slow to allow for chemical equilibration of the phases involved in garnet rim formation even on a micrometre scale. Based on published garnet volume diffusion data the growth interval of a 20‐μm‐wide garnet rim is estimated at ～10³–10⁴ years at the inferred reaction conditions of 760 ± 50 °C at 7.6 kbar. Using the same parameterization of the growth law, 100‐μm‐ and 1‐mm‐thick garnet rims would grow within 10⁵–10⁶ and 10⁶–10⁷ years respectively.     

An experimental study of the grain-scale processes of peridotite melting: implications for major and trace element distribution during equilibrium and disequilibrium melting

The grain-scale processes of peridotite melting were examined at 1,340°C and 1.5 GPa using reaction couples formed by juxtaposing pre-synthesized clinopyroxenite against pre-synthesized orthopyroxenite or harzburgite in graphite and platinum-lined molybdenum capsules. Reaction between the clinopyroxene and orthopyroxene-rich aggregates produces a melt-enriched, orthopyroxene-free, olivine + clinopyroxene reactive boundary layer. Major and trace element abundance in clinopyroxene vary systematically across the reactive boundary layer with compositional trends similar to the published clinopyroxene core-to-rim compositional variations in the bulk lherzolite partial melting studies conducted at similar P–T conditions. The growth of the reactive boundary layer takes place at the expense of the orthopyroxenite or harzburgite and is consistent with grain-scale processes that involve dissolution, precipitation, reprecipitation, and diffusive exchange between the interstitial melt and surrounding crystals. An important consequence of dissolution–reprecipitation during crystal-melt interaction is the dramatic decrease in diffusive reequilibration time between coexisting minerals and melt. This effect is especially important for high charged, slow diffusing cations during peridotite melting and melt-rock reaction. Apparent clinopyroxene-melt partition coefficients for REE, Sr, Y, Ti, and Zr, measured from reprecipitated clinopyroxene and coexisting melt in the reactive boundary layer, approach their equilibrium values reported in the literature. Disequilibrium melting models based on volume diffusion in solid limited mechanism are likely to significantly underestimate the rates at which major and trace elements in residual minerals reequilibrate with their surrounding melt. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Si diffusion in zircon

Self-diffusion of Si under anhydrous conditions at 1 atm has been measured in natural zircon. The source of diffusant for experiments was a mixture of ZrO₂ and ³⁰Si-enriched SiO₂ in 1:1 molar proportions; experiments were run in crimped Pt capsules in 1-atm furnaces. ³⁰Si profiles were measured with both Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis with the resonant nuclear reaction ³⁰Si(p,γ)³¹P. For Si diffusion normal to c over the temperature range 1,350–1,550°C, we obtain an Arrhenius relation D = 5.8 exp(−702 ± 54 kJ mol⁻¹/RT) m² s⁻¹ for the NRA measurements, which agrees within uncertainty with an Arrhenius relation determined from the RBS measurements [62 exp(−738 ± 61 kJ mol⁻¹/RT) m² s⁻¹]. Diffusion of Si parallel to c appears slightly faster, but agrees within experimental uncertainty at most temperatures with diffusivities for Si normal to c. Diffusion of Si in zircon is similar to that of Ti, but about an order of magnitude faster than diffusion of Hf and two orders of magnitude faster than diffusion of U and Th. Si diffusion is, however, many orders of magnitude slower than oxygen diffusion under both dry and hydrothermal conditions, with the difference increasing with decreasing temperature because of the larger activation energy for Si diffusion. If we consider Hf as a proxy for Zr, given its similar charge and size, we can rank the diffusivities of the major constituents in zircon as follows: D _Zr < D _Si << D _{O, dry} < D _{O, ‘wet’}.     

钱二块铀矿床采铀注液结垢趋势的理论分析与预测

用离子系数矩阵法对钱二块铀矿床地浸采铀试验注液中存在的独立离子反应进行了确定,由溶度积规则及反应平衡原理,借助Matlab编程,估算出了钱二块铀矿床地浸采铀试验注液可能会生成的沉淀物种类及数量,为防治结垢提供了一定的理论依据.     

Budgets of Mn,Cd and Cu in the macrotidal Gironde estuary (SW France)

The behavior and budget of Mn, Cd and Cu in the Gironde estuary were investigated through data from both the water column (WC) and sediment depth profiles. In the estuarine freshwater reaches, Mn and Cd removal from and Cu addition to the dissolved phase occurs with a magnitude equivalent to 10%, 30% and 25% of their respective annual fluvial gross dissolved input, respectively. In the saline estuary, diffusive benthic outflow is the main source of dissolved Mn (74% of the total gross dissolved input within the estuary) to the WC. In contrast, Cd (96%) and Cu (89%) are mainly released into the dissolved phase of the WC from fluvial, estuarine and dredging-related particles through complexation (Cd) and organic carbon mineralization (Cu). Anthropogenic activities (sediment dredging) induce pore water inputs, particulate sulfide oxidation and sediment resuspension, significantly contributing to the metal budget of the WC. The related amounts of metals released could be equivalent to 20–50% (Cd) and up to 70% (Cu) of their respective net dissolved addition. Mass balances suggest that a large part of the metals previously released into the dissolved phase from processes within the estuary are removed by suspended particles due to (co-)precipitation of Fe/Mn (oxy)hydroxides and scavenging on autochthonous organic matter. On an annual basis, the Gironde estuary acts as a net sink of dissolved Mn, removing 60% of the dissolved fluvial inputs, and as a net source of dissolved Cd and Cu, contributing ∼ 85% and 20–45% to the dissolved Cd and Cu fluxes to the ocean.     

海藻硫酸多糖911对小鼠脾淋巴细胞增殖反应及对细胞产生IL—2作用的影响

本文以~3H—TdR掺入法观察911对小鼠脾淋巴细胞增殖反应的影响并用CTLL细胞检测了其对IL—2的作用。体外实验结果表明,911对小鼠脾淋巴细胞增殖反应有明显的增强作用,以0.5μg/ml的浓度效果最为明显,相对增殖指数RPI可达200％;体内实验则以5mg/kg体重ip,连续7d效果最好,相对增殖指数RPI可达176％;911用药组小鼠IL—2的产生量均高于对照组,以5mg/kg和10mg/kg效果最好。以上实验证明,这一多糖是一种有希望的新免疫调节药物。     

The influence of salinity on the solubility of Zn and Cd sulphides in the Scheldt estuary

In the estuary of the river Scheldt, where an oxygen gradient exists in addition to the salinity gradient, redox processes will be of major importance for trace metal mobilisation. In this study, the influence of salinity and pH on the redox processes of dissolved Zn and Cd sulphides is investigated together with the effects on the ratio of the dissolved Zn and Cd concentrations. The speciation of these metals is calculated with the chemical equilibrium programme +. Zn sulphides are oxidised at lower oxygen concentrations than Cd sulphides, due to lower stability constants, causing a sudden increase or peak in the dissolved Zn/Cd ratio. The formation of dissolved Cd chloride complexes when oxidation occurs at high salinities (S=15) increases the mobility of Cd, causing a decrease in the Zn/Cd peak of the total dissolved concentrations. The peak is three to four times smaller at S=15 than when oxidation occurs at S=2. The simple model calculations compare very well with field data. The Scheldt estuary is suitable to illustrate these calculations. In the 1970s, the anoxic part of the estuary reached S=15–20, but since the early 1980s it has dropped to S=2–10. Historic data on metals in the estuary from 1978, 1987 and the 1990s were used to compare with the equilibrium calculations. The increase of the dissolved Zn/Cd peak at low salinity as a consequence, of the decreasing anoxic region is confirmed well by the data. The good agreement between model calculations and field data is a proof of the extreme importance of redox processes for the solubility of Zn and Cd sulphides in the estuary.     

尼罗罗非鱼对不同颜色定置网片的反应特性

本文初步研究了尼罗罗非鱼对红、黄、绿、蓝、青灰色定置网片反应特性,并探讨了该鱼对青灰色网片的适应特性。结果表明:绿色网片对罗非鱼的阻拦作用最大,青灰色网片次之,红、黄色网片再次,蓝色网片最小。罗非鱼对青灰色网片具明显的适应现象,它们完成整个适应过程所需的实验重复次数约为7次。     

菲降解菌的降解特性及酶促反应动力学研究

通过对取自MBR膜生物反应器中的活性污泥加入菲进行富集培养、驯化,分离、纯化出一株能以菲为唯一碳源和能源的短杆状革兰氏阴性菌J-1,细菌长2～5μm,宽1～3μm;研究了初始底物浓度、温度、pH对菌株J-1降解菲的影响,探讨了菌株J-1胞内酶对菲降解的底物抑制动力学。试验表明:菌株J-1在48h内能将不同浓度菲的水溶液中的菲完全降解;菲浓度增加,达到完全降解的时间延长。温度对细菌的降解能力影响较大,菌株J-1对菲降解的最佳温度为28℃。1.15mg·L-1的菲,28℃时48h内能完全降解,而相同时间内10℃时的降解率仅为36.65%。菌株J-1对pH的波动具有一定的适应性,pH在一定范围内(6.0～8.4)变化对菲降解的影响不大,降解反应的最佳pH为7.2。菌株J-1对菲的降解符合一级动力学反应方程。较高的底物浓度对酶促降解反应具有抑制作用,酶促反应的最大速率常数vm=1.17mg·L-1·h-1,米氏常数Km=61.70mg·L-1;底物抑制常数kS=49.60mg·L-1;最佳底物浓度[S]opt=55.32mg·L-1。     

Carbonyl products of the gas phase reaction of ozone with 1,1-disubstituted alkenes

Carbonyl products have been identified and their formation yields measured in experiments involving the gas phase reaction of ozone with 1,1-disubstituted alkenes at ambient T and p=1 atm. of air. Sufficient cyclohexane was added to scavenge the hydroxyl radical in order to minimize OH-alkene and OH-carbonyl reactions. Formation yields (carbonyl formed/ozone reacted) of primary carbonyls were close to the value of 1.0 that is consistent with the mechanism: O₃+R₁R₂C=CH₂ (HCHO+R₁R₂COO)+(1–)(R₁COR₂+H₂COO) where formaldehyde and the ketone R₁ COR₂ are the primary carbonyls and R₁R₂COO and H₂COO are the corresponding biradicals. Measured values of were 0.58–0.82 and indicate modest preferential formation of formaldehyde and the disubstituted biradical as compared to the ketone and the biradical H₂COO. Carbonyls other than the primary carbonyls were identified. Their formation is discussed in terms of subsequent reactions of the disubstituted biradicals R₁R₂COO. Similarities and differences between disubstituted and monosubstituted biradicals are outlined.