Upper bound solution of a laterally loaded rigid monopile in normally consolidated clay

A centrifuge test is performed to investigate the ultimate lateral capacity of a free-head rigid monopile foundation in normally consolidated (NC) clay. Based on the test result, an upper-bound velocity field is constructed to illustrate the evolution of the soil resisting mechanisms with the progressive rotation and the effect on reaction forces during loading. Simultaneously finite element analyses are also employed to model the centrifuge test and verify the conclusion of the upper bound analysis. Finally, an empirical expression is presented for predicting the upper-bound collapse loads of monopiles with different eccentricity/length ratios and length/diameter ratios in NC clay.     

A multiple-code simulation study of the long-term EDZ evolution of geological nuclear waste repositories

This simulation study shows how widely different model approaches can be adapted to model the evolution of the excavation disturbed zone (EDZ) around a heated nuclear waste emplacement drift in fractured rock. The study includes modeling of coupled thermal-hydrological-mechanical (THM) processes, with simplified consideration of chemical coupling in terms of time-dependent strength degradation or subcritical crack growth. The different model approaches applied in this study include boundary element, finite element, finite difference, particle mechanics, and elasto-plastic cellular automata methods. The simulation results indicate that thermally induced differential stresses near the top of the emplacement drift may cause progressive failure and permeability changes during the first 100 years (i.e., after emplacement and drift closure). Moreover, the results indicate that time-dependent mechanical changes may play only a small role during the first 100 years of increasing temperature and thermal stress, whereas such time-dependency is insignificant after peak temperature, because of decreasing thermal stress.     

内标校正-电感耦合等离子体发射光谱法测定磷矿石中的磷

采用电感耦合等离子体发射光谱法(ICP-OES)可以同时测定磷矿石中的主、次量元素,但在实际测量过程中,仪器的漂移以及基体效应引起的分析误差不容忽视。本文以碲为内标,对高含量磷的测定进行校正,可以有效降低由仪器漂移以及基体效应引起的分析误差,12次平行测定磷的相对标准偏差(RSD)为0.5%,与未经校正的RSD值(4.1%)相比,显著提高了分析精度,极大地降低了仪器波动对测定结果的影响,因此获得了更低的方法检出限(0.0044%)。实验还对比了王水溶样与盐酸-硝酸-氢氟酸-高氯酸(四酸)溶样两种样品前处理方法对磷矿石分析的影响,结果表明:以王水对磷矿石标准物质进行快速溶解,磷、钙、铁、镁、锰等元素的测定结果与标准值间的相对误差范围为-6.7%~1.6%,满足日常测定要求;而钾、钠、铝是否能够完全溶出与样品的矿物组成及氟含量存在联系,若需要分析钾、钠、铝等元素,如果样品中的硅酸盐矿物组成不多,氟含量较高时可以考虑采用王水溶解;四酸可以完全溶解样品,适合于磷、钙、铁、镁、铝、钾、钠、锰、锶等元素的同时测定。     

碱熔融-电感耦合等离子体发射光谱法测定高硫铝土矿中的硫

应用电感耦合等离子体发射光谱法(ICP-OES)测定高硫铝土矿(硫含量≤8%)中的硫时,由于硫存在-2、+4和+6等多种价态,常用的酸溶法和碱熔法处理高硫铝土矿时往往无法完全氧化硫而导致硫测定结果偏低。本文用过氧化钠熔融、热水浸取和盐酸酸化提取高硫铝土矿中的硫,使用基体匹配法绘制校准曲线补偿铝和钠对硫测定的光谱干扰,以S182.034 nm(184 nm)作为分析谱线,采用ICP-OES对硫进行测定。结果表明:3 g过氧化钠在700℃下熔融10 min,可以较好地氧化高硫铝土矿中的硫;校准曲线的线性相关系数为0.9999,方法检出限为0.025μg/m L,相对标准偏差(RSD,n=6)小于5%;与碳硫仪的测定结果相比较,两种方法无显著性差异。本方法溶样彻底,无样品损失,为今后实现应用ICP-OES同时测定高硫铝土矿中的硫和其他元素奠定了基础。     

电感耦合等离子体发射光谱法测定超贫磁铁矿和磁性物中有益有害组分及可选性评价

超贫磁铁矿是需要通过磁选富集后才能利用的铁矿石,磁性物是其磁选后的主要产品,磁性物中有益有害组分的含量是否满足规范要求是评价超贫磁铁矿可选性的前提,然而尚未引起足够的重视。本文采用电磁分选仪对超贫磁铁矿进行磁选,结合ICP-OES法对原矿和磁性物中有益有害组分(TFe、V_2O_5、TiO_2、P、Cu、Pb、Zn)进行了测定。结果表明,对于含量明显低于规范要求的V_2O_5、Cu、Pb、Zn,磁选后其含量虽有变化,但不影响冶炼及综合评价的结果;对于TFe、TiO_2、P,磁选后其含量发生明显变化,其中TFe由14.23%~16.60%提高至53.95%~69.86%,TiO_2由4.43%~5.02%降至0.84%~1.83%,P由0.11%~0.30%降至0.027%~0.048%,已对冶炼及综合评价的结果产生了影响,依据磁性物中TFe、TiO_2、P的含量更能切实反映超贫磁铁矿的可选性;所用超贫磁铁矿易于选别,通过单一弱磁选即可获得主要组分(TFe)及有害物质(P、Cu、Pb、Zn)满足炼铁用铁矿石工业要求的精矿;大部分TiO_2随弱磁选进入尾矿,后期应注意对尾矿中的TiO_2进行评价。该方法可快速获得超贫磁铁矿原矿及磁性物中有益有害组分的含量信息,既能从冶炼角度初步评价超贫磁铁矿的可选性,也可以确定后续综合利用研究的目标元素,对于超贫磁铁矿资源的合理开发利用具有重要的现实意义。     

碱熔共沉淀-电感耦合等离子体质谱法测定橄榄岩中的稀土元素

橄榄岩的稀土元素特征对研究岩石成因、岩浆作用过程具有重要的意义。橄榄岩中的稀土元素含量低(∑REEs=0.1~1μg/g),且存在镁、铁等基体元素的干扰,难以准确测定。前人通常利用高压密闭酸溶-离子交换法处理样品,将稀土元素与镁、铁等基体元素分离,达到了预富集的效果,但耗时长(消解时间接近7天)、操作步骤繁多,不利于大批量样品的分析。本文建立了过氧化钠碱熔、Fe(OH)_3和Mg(OH)_2共沉淀的样品前处理方法,通过离心使溶液与沉淀分离,从而实现了稀土元素与镁、铁等基体元素的快速分离,再采用电感耦合等离子体质谱法测定稀土元素含量。方法检出限为0.17~2.18 ng/g,加标回收率为95%~101%,国家标准物质(GBW07101和GBW07102)的测定值与标准值的相对误差小于20%,相对标准偏差(RSD,n=11)小于10%。该方法既减少了分步沉淀过程中带来的损失,也缩短了分析周期(消解时间仅需一天),操作简便,分析效率高。     

HPLC-ICP-MS法研究内蒙古锡盟和新疆塔城高碘地区地下水的总碘及碘形态特征

长期饮用高碘水将对人体造成危害,地下水总碘及碘形态分析对于高碘地区碘环境地球化学研究具有重要价值。本文采用高效液相色谱-电感耦合等离子体质谱联用技术对内蒙古锡盟与新疆塔城高碘地区地下水总碘及碘形态进行测定。研究表明:锡盟地区地下水中碘以I-形态为主,总碘量维持在200μg/L,个别点位达到600μg/L甚至1700μg/L,呈环状分布,从东北至西南呈现"低-高-低"的分布规律;塔城地区地下水中的碘以IO-3形态为主,总碘量不足100μg/L,个别点位接近200μg/L,呈层状分布,自东向西逐渐升高。分析认为,氧化性的条件利于不同碘形态之间的转化;溶解氧过高或过低都不利于碘的储存;碘会随着可溶性盐的流失而流失;沿河流的流向,下游地势较低,总碘得到积累。本研究结果对于锡盟和塔城地区科学预防甲状腺肿、制定法律法规具有指导作用。     

基于LA-ICP-MS多元素成像技术的早寒武世磷结核成因研究

我国下寒武统底部广泛发育磷结核、磷块岩等富磷沉积,为早寒武世最为重要的化学标志层之一,也代表了隐生宙—显生宙转折期地球表层系统的重大变革。当前对磷来源和富集机制的解释不一。为进一步明确该时期富磷沉积的形成机制,本文利用激光剥蚀电感耦合等离子体质谱联用技术(LA-ICP-MS)对贵州金沙地区牛蹄塘组黑色页岩中的磷结核进行多元素原位微区成像研究。结果表明:磷结核中各元素富集情况清晰地记录了磷结核形成过程中微环境的变化趋势。其中,磷结核内部Ca、P共富集以及Si亏损,指示P富集缘于自生磷灰石生成,P则来自于有机质含氧或厌氧降解释放;Mn、Zn与P共富集于磷结核内部,指示结核形成时的底部水体为含氧水体;As、Mo、V等元素主要富集于围岩或黑色页岩,指示缺氧含H_2S水体形成终止了结核生长。本研究显示,LA-ICP-MS原位多元素成像技术能够获取微区内丰富的地球化学信息,并提供高精度可视化证据,未来将在地质勘探和古环境研究等领域得到更广泛应用。     

Review on Advances in Chemical Osmosis in Clayey Sediments

Osmotic phenomena refer to water and solute transport processes that occur when transport of solute molecules or ions is restricted by the porous medium relative to that of water molecules. Chemical osmosis and reverse osmosis/ultrafiltration are osmotic phenomena. The studies of “coupled flow” caused by chemical osmosis have been widely applied in many fields, such as earth science, environmental science and civil engineering. This paper provided a review of the considerable advances in the field of chemical osmosis and clay semipermeable membrane since the 1950s. We summarized the research progress of chemical osmosis in clayey sediments into three aspects: theoretical basis, experimental research and numerical model. In particular, the laboratory equipment and measurement methods of the chemico-osmotic efficiency coefficient σ were described,. The existing discontinuous models based on the ‘diffusive double layer’ theory were summerized, as well as the various control factors of σ. It increases with Cation Exchange Capacity (CEC), compaction pressure and decreases by the increasing of porosity and solution concentration. This paper also summerized the contimuum models based on non-equilibrium thermodynamics, which are used to explain and predict anomalies of hydraulic head pressure and salinity in clayey environments. For the future development of this discipline, it is critical to find a reliable method to confirm the σ value. It is also critical to emphasize the research on chemical osmosis in complex conditions and the influence of chemical osmosis on groundwater flow and solute transpotation. China has just stepped into this research area and more efforts should be made if significant progress is desired. This review will be helpful to further research on groundwater numerical simulation integrated with chemical osmosis in China.     

过氧化钠碱熔-电感耦合等离子体质谱法测定原生矿石中的锡

原生锡矿石主要存在的矿床类型有矽卡岩型锡矿、斑岩型锡矿、锡石硅酸盐脉型锡矿、锡石硫化物脉型锡矿、石英脉及云英岩型锡矿。锡矿石一般不溶于盐酸、硝酸及王水体系,采用硫酸、氢氟酸处理时无法全部溶解。苯芴铜分光光度法和碘量法等传统测试方法存在受样品中伴生元素干扰大、稳定性差、检出限高、分析效率低等不足。本文建立了电感耦合等离子体质谱法测定原生矿石中锡元素含量的分析方法,用过氧化钠对样品进行熔融分解处理,热水浸取后用酒石酸-盐酸酸化,采用铑作为内标进行仪器信号漂移校正,同时用高倍稀释的方式来克服基体干扰。方法检出限为0.1μg/g,精密度小于5%,最低检出浓度为0.4μg/g,测试范围为12.5～12700μg/g。本方法操作简便,分析速度和数据质量都优于传统分析方法。