Stability,transformations and stabilizing potential of an amorphous manganese oxide and its surface-modified form in contaminated soils

A surface-modified amorphous manganese oxide (SM-AMO) was prepared to increase the stability of a previously studied promising stabilizing agent and to compare its immobilizing efficiency with respect to contaminating metals with the original material. To synthesize the SM-AMO, the AMO surface was synthetically covered with a coating of MnCO₃ because newly formed rhodochrosite precipitates were previously found to increase the stability of AMO particles in soils. A preliminary experiment evaluating the long-term stability of both materials in pure water suggested higher stability for the SM-AMO particles, showing a smaller release of Mn compared to the original AMO. An adsorption kinetics study focused on As, Cd, Pb and Zn showed lower adsorption rates and adsorption capacity for Zn, probably as a result of partial surface passivation. In comparison to these results for simple controlled systems, different effects were recorded when the two materials were applied to contaminated soils. When incubated in soil, a constantly lower mass loss was recorded in the case of SM-AMO. There were no significant differences in the release of Mn and DOC into the soil solution or in the stabilizing efficiency with regard to contaminating metal(loid)s between the original and surface-modified materials. Concerning the potential solid phase transformations in soil conditions, we observed a gradual equilibration between the surface composition of both materials. While the newly formed rhodochrosite precipitated on the AMO surface, the MnCO₃ coatings on SM-AMO gradually dissolved. Both amendments also effectively supported microbial activity, especially in the more contaminated soil sample. Thus, despite the smaller mass loss, the effectiveness of both materials is comparable in the long term.     

春季黄、渤海沉积物中CH4和N2O的垂向分布特征研究

本研究分别利用顶空平衡法与qPCR技术测定了2018年春季黄、渤海5个典型站位柱状沉积物中甲烷(CH₄)和氧化亚氮(N₂O)浓度及产甲烷菌与硫酸盐还原菌功能基因拷贝数,并分析了其与间隙水中相关环境因子的关系。沉积物上方水文条件的差异以及其中复杂的碳氮生物地球化学过程使得CH₄和N₂O浓度呈现出明显的空间和垂直变化。结果显示,沉积物中CH₄浓度为0.23~0.92 μmol·kg^-1,N₂O浓度为18.90~104.96 nmol·kg^-1。总体来说,渤海沉积物中CH₄和N₂O平均浓度高于黄海。垂向分布上,CH₄浓度均随深度增加逐渐升高, $\text{SO}_{4}^{2-}$浓度随深度增加逐渐降低,并与CH₄浓度呈镜像关系,产甲烷菌与硫酸盐还原菌的丰度也遵循着同样规律,这表明沉积物中产甲烷作用受$\text{SO}_{4}^{2-}$浓度的抑制。 mcrA基因拷贝数平均值为渤海低于黄海。除3500-7站外,沉积物中mcrA基因拷贝数随深度增加而升高。各站位mcrA 基因丰度与CH₄浓度均无显著相关性,且mcrA丰度与$\text{SO}_{4}^{2-}$浓度之间也未检测到显著相关性。dsrB基因拷贝数远高于mcrA基因拷贝数,且两者相差至少两个数量级。 dsrB基因拷贝数随深度逐渐增加,直至10 cm左右,随后至沉积物底部逐渐减少。各站位dsrB基因拷贝数与CH₄浓度剖面略有镜像关系,但均未检测到显著负相关性。以上结果均表明沉积物中存在着同时消耗沉积物中$\text{SO}_{4}^{2-}$与CH₄的其他作用。N₂O浓度随深度增加先降低,在深度30 cm以下逐渐升高。间隙水中$\text{NO}_{3}^{-}$和$\text{NO}_{2}^{-}$浓度均随深度减小,同时$\text{NH}_{4}^{+}$浓度与其呈相反趋势。沉积物中N₂O与$\text{NO}_{2}^{-}$及$\text{NO}_{3}^{-}$浓度均呈正相关,且前者相关性较高,说明反硝化作用是沉积物中N₂O产生的主要过程。这些结果为进一步了解近岸陆架海域沉积物中CH₄和N₂O的来源、分布及碳氮生物地球化学循环提供了参考资料。     

Hydration vs. oxidation: Modelling implications for Fe–Ti oxide crystallisation in mafic intrusions, with specific reference to the Panzhihua intrusion, SW China

Recent work on the Panzhihua intrusion has produced two separate models for the crystallisation of the intrusion:（1） low-Ti,high CaO and low H₂O（0.5 wt.%） parent magma（equivalent to Emeishan low-Ti basalt） at FMQ;and（2） high-Ti,low CaO and higher H₂O（>1.5 wt.%） parent magma（equivalent to Emeishan high-Ti basalt） at FMQ + 1.5.Modelling of these parent magma compositions produces significantly different results. We present here detailed f（O₂） and H₂O modelling for average compositions of both Emeishan high-Ti and low-Ti ferrobasalts in order to constrain the effects on crystallisation sequences for Emeishan ultra-mafic -mafic layered intrusions.Modelling is consistent with numerous experimental studies on ferro-basaltic magmas from other localities（e.g.Skaergaard intrusion）.Modelling is compared with the geology of the Panzhihua intrusion in order to constrain the crystallisation of the gabbroic rocks and the Fe-Ti oxides ore layers.We suggest that the gabbroic rocks at the Panzhihua intrusion can be best explained by crystallisation from a parent magma similar to that of the high-Ti Emeishan basalt at moderate H₂O contents（0.5-1 wt.%） but at the lower end of TiO₂ content for typical high-Ti basalts（2.5 wt.%TiO₂）. Distinct silicate disequilibrium textures in the Fe-Ti oxide ore layers suggest that an influx of H₂O may be responsible for changing the crystallisation path.An increase in H₂O during crystallisation of gabbroic rocks will result in the depression of silicate liquidus temperatures and resultant disequilibrium with the liquid.Continued cooling of the magma with high H₂O then results in precipitation of Mt-Uv alone. The H₂O content of parent magmas for mafic layered intrusions associated with the ELIP is an important variable.H₂O alters the crystallisation sequence of the basaltic magmas so that at high H₂O and f（O₂） Mt -Uv crystallises earlier than plagioclase and clinopyroxene.Furthermore,the addition of H₂O to an anhydrous magma can explain silicate disequilibrium texture observed in the Fe-Ti oxide ore layers.     

氧化铬对铝型材厂碱蚀渣制备铝方柱石材料结构的影响

利用铝型材厂碱蚀渣为主要原料,采用二步煅烧工艺制备铝方柱石材料。探索二次煅烧温度对铝型材厂碱蚀渣制备铝方柱石材料相组成、结晶度、微观结构的影响,进而研究氧化铬对铝方柱石材料相组成、微观结构的影响。采用同步热分析、X射线衍射、扫描电镜及相关分析软件表征制备的铝方柱石材料的相组成和显微结构。结果表明：铝型材厂碱蚀渣中有大量可烧失成分,物料需要进行致密化处理,再经过1500℃煅烧后的铝方柱石材料结构中具有明显的铝方柱石条柱状结构,结晶度增大,铝方柱石相对含量达到91%。随着氧化铬加入量增加,结构中的铝铬酸钙相增加。当氧化铬加入量为2%时,试样中结晶相的结晶度最高,形成条柱状铝方柱石相与立方状铝铬酸钙相共存的结构。当氧化铬加入量4%时,试样中铝方柱石相几乎消失,结晶度降低。     

Provenance Study of Fe–Ti Oxide Minerals in the Quaternary Sediments in Yichang Area and Its Implication of Formation Time of the Yangtze Three Gorges, China

The Three Gorges are considered to be critical to understand the formation of Yangtze River. Recent research results suggest that the Yangtze Three Gorges was created during the Quaternary but the exact time is debatable. Fe–Ti oxide minerals are seldom used to study sediment provenance, expecially using scanning electron microscopy(SEM), and energy dispersive spectrometer(EDS). In this study, the provenance of Quaternary sediments in Yichang area, which is located to the east of the Yangtze Three Gorges, was investigated by using SEM and EDS to research Fe–Ti oxides. The Panzhihua vanadium titanomagnetite and Emeishan basalt outcrop are located to the west of the Three Gorges. Further, the materials from them are observed in the Quaternary sediments of Yichang area. Fe–Ti oxide minerals from the Huangling granite are observed in the Yunchi and Shanxiyao Formations, which were formed before 0.75 Ma B.P., whereas Fe–Ti oxide minerals from the Huangling granite, Panzhihua vanadium titanomagnetite, and Emeishan basalt are observed in the riverbed and fifth-terrace sediments of the Yangtze River, which were formed after 0.73 Ma B.P.. Thus, we can infer that the Three Gorges formed after the deposition of the Shanxi Formation and before the fifth-terrace; i.e., 0.75–0.73 Ma B.P..     

广西荣华锰矿床地质特征及发现意义

广西荣华锰矿位于三叠系百逢组,在该地层中发现的工业锰矿床尚未见报道。通过对该矿区大比例尺地质填图,并结合地质工程和测试分析等手段,对矿床地质背景、沉积环境、矿体和矿石特征、沉积演化等进行分析研究,推测荣华锰矿为沉积-淋滤锰帽型矿床,矿体顺层分布于靠近罗楼组碳酸盐岩的百逢组第一段泥岩、泥质粉砂岩中,严格受地层和构造控制。矿石主要由偏锰酸矿、软锰矿等组成,矿石品位偏低,伴生Co等金属元素。百逢组之下的碳酸盐岩和百逢组第一段浊积砾岩层可作为该类锰矿上下界线典型的找矿标志。中三叠世桂西北处于盆包台构造格局,中晚古生代富含锰的台地在三叠纪遭受风化剥蚀,成矿元素被带入弧后盆地。随着特提斯洋闭合,挤压作用使盆地面积变小,水位加深,氧化还原界面波动,在百逢组第一段锰元素初步富集。后右江盆地抬升露出水面遭受剥蚀,风化淋滤作用最终形成该区顺层分布的氧化锰矿床。桂西广泛出露百逢组地层,其第一段具有良好的找矿前景。     

第一原理计算过渡金属掺杂尖晶石型LiMn2O4的电子结构

尽管对过渡金属掺杂锰酸锂后放电平台的升高现象有众多实验研究,但对其机理的研究却鲜见报道.采用第一原理的密度泛函理论,计算了过渡金属M(M=Ti、Cr、Fe、Co、Ni、Cu、Zn)掺杂尖晶石型LiMn2O4的电子结构,并以此分析放电平台的升高机理.电子态密度分析发现由于M-3d能带的诱导作用,出现了新的O-2p能带,而锂脱出时获得的电子,主要是由费米能级附近O-2p能带提供的.当过渡金属M由Ti变化到Zn时,M-3d能带逐渐向低能量的方向移动,新的O-2p能带出现的位置也随之下移,当Li脱出时,需要更多的能量才能从低能量的O-2p能带上获得电子,因而体系能够获得较高的嵌入电压.     

南海沉积物漫反射光谱反映的220ka以来东亚夏季风变迁

对南海越南岸外“太阳号”95航次17954孔220ka以来的沉积样品进行了漫反射光谱分析, 并从中提取F1和F2两个主因子及亮度和红度等漫反射光谱特征值, 发现漫反射光谱F1值和亮度反映了沉积物中的碳酸盐含量, 而漫反射光谱F2值和红度反映了沉积物中的铁氧化物含量, 后者可用作东亚夏季风的替代性指标.17954孔沉积物的漫反射光谱F2值显示, 倒数第二次冰消期东亚夏季风快速增长时间约在129ka; 本次工作还发现东亚夏季风在两次冰消期前的氧同位素2阶段和6阶段晚期各有一个异常强盛的时期.漫反射分析结果显示东亚夏季风主要受控于太阳辐射强度变化, 并明显地受低纬地区气候的影响.      

晚二叠世峨眉山地幔柱岩浆成矿作用

晚二叠世峨眉山地幔柱岩浆作用同时形成了Cu-Ni-PGE硫化物矿床和V-Ti-Fe氧化物矿床等不同类型的岩浆矿床。从硫化物矿床的PGE富集型、Cu-Ni-PGE富集型到Cu-Ni富集型,再到钒钛磁铁矿矿床,成矿基性-超基性岩体中基性岩石比例逐渐增加,PGE含量降低。铜镍铂族硫化物矿床具Nb和Ta负异常,岩浆流体组分含量较高,含有较高的H₂;而钒钛磁铁矿矿床具Nb、Ta和Ti正异常,Zr和Hf负异常,岩浆流体组分含量较低,含有较高的H₂O、CO₂和H₂。两类矿床强不相容元素和轻稀土元素(LREE)富集,Sr-Nd同位素组成与峨眉山玄武岩的演化趋势一致。Sr-Nd-Os-C-He同位素组成揭示岩浆上升过程中经历了不同程度的地壳混染,高钛玄武岩和钒钛磁铁矿矿床成矿岩体的地壳混染程度较低,部分低钛玄武岩和铜镍硫化物矿床存在明显的地壳混染。这两类岩浆矿床的形成与峨眉山地幔柱玄武岩浆有关,岩浆介质环境中H₂含量较高,V-Ti-Fe 氧化物矿床的形成与分离结晶、高含量的水和氧逸度的升高有关,Cu-Ni-(PGE)硫化物矿床的形成与还原性流体介质、结晶分异和地壳混染作用有关。     

Origin of Fe-Ti Oxide Ores in Mafic Intrusions: Evidence from the Panzhihua Intrusion, SW China

Economic concentrations of Fe–Ti oxides occur as massive,conformable lenses or layers in the lower part of the Panzhihuaintrusion, Emeishan Large Igneous Province, SW China. Mineralchemistry, textures and QUILF equilibria indicate that oxidesin rocks of the intrusion were subjected to extensive subsolidusre-equilibration and exsolution. The primary oxide, reconstructedfrom compositions of titanomagnetite in the ores and associatedintergrowths, is an aluminous titanomagnetite (Usp₄₀) with 40wt % FeO, 34 wt % Fe₂O₃, 16·5 wt % TiO₂, 5·3 wt% Al₂O₃, 3·5 wt % MgO and 0·5 wt % MnO. This compositionis similar to the bulk composition of the oxide ore, as inferredfrom whole-rock data. This similarity strongly suggests thatthe ores formed from accumulation of titanomagnetite crystals,not from immiscible oxide melt as proposed in earlier studies.The occurrence of oxide ores in the lower parts of the Panzhihuaintrusion is best explained by settling and sorting of densetitanomagnetite in the ferrogabbroic parental magma. This magmamust have crystallized Fe–Ti oxides relatively early andabundantly, and is likely to have been enriched in Fe and Tibut poor in SiO₂. These features are consistent with fractionationof mantle-derived melts under relatively high pressures (10kbar), followed by emplacement of the residual magma at 5 kbar.This study provides definitive field and geochemical evidencethat Fe–Ti oxide ores can form by accumulation in ferrogabbro.We suggest that many other massive Fe–Ti oxide depositsmay have formed in a similar fashion and that high concentrationsof phosphorus or carbon, or periodic fluctuation of fO₂ in themagma, are of secondary importance in ore formation. KEY WORDS: ELIP; Fe–Ti oxide ore; layered intrusion; Panzhihua; QUILF