Reactions of alkoxy radicals under atmospheric conditions: The relative importance of decomposition versus reaction with O2

The reactions of alkoxy radicals determine to a large extent the products formed during the atmospheric degradations of emitted organic compounds. Experimental data concerning the decompositions, 1,5-H shift isomerizations and reactions with O₂ of several classes of alkoxy radicals are inconsistent with literature estimations of their absolute or relative rate constants. An alternative, although empirical, method for assessing the relative importance under atmospheric conditions of the reactions of alkoxy radicals with O₂ versus decomposition was derived. This estimation method utilizes the differences in the heats of reaction, (H)=(H_{decomposition}–H_{O 2 reaction}), between these two reactions pathways. For (H)[22–0.5(H_{O 2 reaction})], alkoxy radical decomposition dominates over the reaction with O₂ at room temperature and atmospheric pressure of air, while for (H)[25-0.5(H_{O 2 reaction})], the O₂ reaction dominates over decomposition (where the units of H are in kcal mol^–1). The utility and shortcomings of this approach are discussed. It is concluded that further studies concerning the reactions of alkoxy radicals are needed.     

离子吸附型稀土矿床形成的矿物表/界面反应机制

华南离子吸附型稀土矿床提供了全球超过90%的重稀土,是我国优势的战略性关键金属矿产资源。掌握这类矿床的成矿机制和禀赋特征,可为增加稀土资源储量和高效利用稀土资源提供理论支撑。离子吸附型稀土矿床主要发育在富稀土花岗岩、浅变质岩及火山岩的风化壳中。基岩中的(含)稀土矿物是风化壳中离子态稀土的主要来源,其矿物组合很大程度上决定了稀土矿床的禀赋和分异特征。在物理-化学风化和微生物作用下,造岩矿物、含稀土矿物和稀土独立矿物逐渐溶解,使稀土元素活化和再富集。一方面,母岩风化形成的黏土矿物和铁锰氧化物具有较大的比表面积和一定的表面电荷密度,是稀土离子的主要载体;另一方面,稀土离子通过离子交换、表面吸附与络合、共沉淀,以及形成次生稀土矿物等途径富集在次生矿物表面,其富集-分异特征和赋存状态受矿物类型、pH、微生物活动等因素所控制。利用高分辨透射电镜结合选区电子衍射和电子能量损失谱,以及同步辐射X射线吸收精细结构谱,有望在原子级尺度查明稀土的微观赋存状态。未来研究需更多关注基岩中(含)稀土矿物组合及其演化路径的制约因素、微生物风化对离子吸附型稀土矿床成矿作用的约束,以及稀土元素的微观赋存状态等问题。     

高盐强酸性地下水中复合苯系污染物原位芬顿氧化实验研究

在原位氧化过程中,实际场地地下水和含水介质的物化特征是影响氧化效果的重要因素,而目前对此影响的研究较少。以某场地实际高盐强酸性复合苯系污染地下水为研究对象,以地下水中2-硝基-4-甲氧基苯胺(2-nitro-4-methoxyaniline,2-N)和3-硝基-4-甲氧基苯胺(3-nitro-4-methoxyaniline,3-N)为特征污染物,探究芬顿(Fenton)试剂原位氧化特征,并研究液相环境因素(初始H2O2浓度、初始Fe2+浓度、初始pH值、初始醋酸(Acetic acid,HAc)浓度、初始SO4^2-浓度)以及含水层介质对Fenton法去除2-N和3-N的影响。结果显示:(1)Fenton法去除2-N和3-N效果显著,且在初始液相条件为c(H2O2)=7 mmol/L、c(Fe²⁺)=4 mmol/L、pH=4、c(HAc)=0 mg/L和c(SO4^2-)=0 mmol/L时去除效果最佳;(2)各因素对Fenton法氧化2-N和3-N的影响不同,加入H₂O₂和Fe²⁺使2-N和3-N去除率上升,增大HAc浓度使2-N和3-N去除率下降;(3)含水层介质对2-N和3-N具有一定吸附性,且对3-N的吸附性强于2-N,二者在本实验中最大吸附态占比分别为29%和42%,而吸附态的存在会抑制Fenton法对2-N和3-N的去除;(4)矿物分析结果显示介质含有少量黄铁矿,在硫酸环境下,介质腐蚀溶解释放Fe²⁺,在达到一定浓度后,无需额外添加Fe²⁺即可完成Fenton反应进而去除2-N和3-N。     

江陵凹陷古新世地下卤水型硼矿成因研究

中国探明硼资源主要分布于东北和青藏等地区,矿床品位低,共伴生矿物多,开发成本高,开发利用程度低,难以满足产业发展需求。目前,在江汉盆地江陵凹陷勘探中发现卤水中B2O3浓度达3 g/L,Li、K、Br、I、Rb、Cs含量超过工业品位,综合利用价值高。本文在前人研究的基础上,对江陵凹陷新生代卤水型硼矿开展水化学、同位素地球化学及实验地球化学分析,重点研究了古气候、构造和玄武岩等对卤水成矿的影响,探究其成因机制。研究初步认为,不同的储卤层岩性具有不同的地球化学和同位素特征,玄武岩有强烈的蚀变,说明地下流体对火成岩发生了交代作用,玄武岩的水-岩反应是富硼卤水矿的重要物质来源;一定盐度的流体有利于硼离子的活化,高盐度流体是硼成矿元素主要的迁移载体,表生环境下干热的古气候使含矿水体蒸发浓缩是富硼卤水富集成矿的重要形成机制。     

广州夏季雨水硝酸盐δ15N变化特征

通过对广州2007年夏季雨水硝酸盐δ15的研究,讨论了广州地区雨水硝酸盐的主要来源及与之有关的大气化学演变过程。雨水硝酸盐占δ15N的变化趋势与N2O5含量的相似。暗示雨水硝酸盐δ15N与氮氧化合物的大气化学过程之间存在某种联系。白天雨水硝酸盐δ15N值偏低,与OH自由基氧化NOx生成硝酸盐的“白天反应”为主要反应相一致;18：00以后硝酸盐δ15N值呈升高趋势,则与N2O5累积的“夜间反应”成为主导反应相一致。因“白天反应”生成的HNO3的δ15N值受同位素分馏影响较小,白天雨水硝酸盐占δ15N值更能准确反映大气NOx的来源。白天雨水硝酸盐占δ15N平均值为2．5‰±2．1‰,表明除火力发电厂和机动车尾气排放来源外,雷电以及海源对大气NOx可能也有潜在贡献。     

Metamorphic evolution of sapphirine‐ and orthoamphibole‐cordierite‐bearing gneiss,Okanogan dome,Washington, USA

Gneiss domes are commonly cored by quartzofeldspathic rocks that provide little information about the pressure–temperature–fluid history of the domes. Three northern Cordilleran migmatite domes (Thor‐Odin and Valhalla/Passmore, British Columbia, Canada; Okanogan, Washington, USA), however, contain Mg–Al‐rich orthoamphibole‐cordierite gneiss as layers and lenses that record metamorphic conditions and pressure–temperature (P–T) path information not preserved in the host migmatite. These Mg–Al‐rich rocks are therefore a valuable archive of metamorphic conditions during dome evolution, although refractory rocks such as these commonly contain reaction textures that may complicate the calculation of metamorphic conditions. In the Okanogan dome, Mg–Al‐rich layers are part of the Tunk Creek unit, which occurs at the periphery of an underlying migmatite domain. Bulk compositional layers (mm‐ to m‐scale) consist of gedrite‐dominated, hornblende‐dominated and biotite‐bearing layers that contain variable amounts of gedrite, hornblende, anorthite, cordierite, spinel, sapphirine, corundum, kyanite, biotite and/or staurolite. The presence of different compositional layers (some with reaction textures, some without) allows systematic analysis of metamorphic history by a combined petrographic and phase equilibrium analysis. Gedrite‐dominated layers containing relict kyanite preserve evidence of the highest‐P conditions; symplectitic and coronal reaction textures around kyanite indicate decompression at high temperature. Gedrite‐dominated layers lacking these reaction textures contain layers of sapphirine and spinel in apparent textural equilibrium and record a later high‐T–low‐P part of the path. Phase equilibria (pseudosection) analysis for layers that lack reaction textures indicates metamorphic conditions of 720–750 °C at a range of pressures (>8 to <4 kbar) following decompression. Elevated crustal temperatures and concordant structural fabrics in the Tunk Creek unit and underlying migmatite domain suggest that the calculated P–T conditions recorded in Tunk Creek rocks were coeval with anatexis, extension, and dome formation in Palaeocene–Eocene time. In contrast to orthoamphibole‐cordierite gneiss in the other Cordilleran domes, the Tunk Creek unit occurs as a discontinuous km‐scale layer rather than as smaller (m‐scale) pods, is more calcic, and lacks garnet. In addition, kyanite did not transform to sillimanite, and spinel commonly occurs as a blocky matrix phase in addition to vermicules in symplectite. These differences, along with the compositional layering, allow an analysis of bulk composition v. tectonic (P–T path) controls on mineral assemblages and textures. Pseudosection modelling of different layers in the Tunk Creek unit provides a basis for understanding the metamorphic history of these texturally complex, refractory rocks and their host gneiss domes, and other such rocks in similar tectonic settings.     

伊犁京希—伊尔曼德金矿床的热液蚀变及成矿流体演化特征

京希－伊尔曼德金矿床的热液蚀变在空间上有明显的分带性，中心蚀变带以强烈的硅化为主，典型的蚀变矿物组合为石英或玉髓和地开石，中间带为高级泥化带，以地开石－高岭石－石英或玉髓为特征；外带为以蒙脱石－高岭石－伊利石－其他粘土矿物等矿物组合为主的泥化带，蚀变强度和矿物组合的分带性是温度、压力和化学梯度的反映，是流体在不断的水或流体－岩石反应和成分交换的产物。该矿床成矿流体演化过程为：早期酸性（pH=2-3)含矿流体在沿断裂上升过程中，受围岩灰岩中的流体（pH为中性）缓冲，在其进入高渗透性的碎屑岩层时，流速和水－岩石或流休－岩石反应大大加快，并在与大气降水的混合作用下，pH值逐步升高（3－5），产生了流体的温度及成分梯度，在温度和压力迅速下降的条件下，金及蚀变矿物沉淀、结晶生长，形成了蚀变空间分带，中心带保存完好的多孔状石英和地开石等高级泥化矿物组合说明该矿床是高硫化热液体系作用下的产物。     

地下流体远场地震效应讨论

本文通过对５级地震前地下流体异常事例的研究得到，地下流体的远场效应是客观存在的。与近场效应相似，远场效应也显示出复杂性，同时远场效应与近场效应无明显差异，这就给地震预报，尤其判断未来震中，带来很大困难。为此有必要开展地震综合预报和地下流体地震综合观测。     

白云石的微化反应与有序度

试验证实白云石的微化反应特征明显受有序度的影响，白云石粉末在稀盐酸中的起泡程度随有序度的降低而加剧，在茜素红溶液中的染色程度和速度随有序度的降低而增强。低有序度白云石或完全无序的原白云石，其微化反应与方解石极为相似，反之，高有序度白云石与菱镁矿相似。另外还讨论白云石微化反应的机理。