金活动态提取剂提取-电感耦合等离子体质谱法测定深穿透地球化学样品中的金

金的地球化学勘查基于金的准确测定,地球化学样品中金含量通常处于ng/g水平,需先进行分离富集,再采用电感耦合等离子体质谱法(ICP-MS)或石墨炉原子吸收光谱法(GFAAS)进行测定。当前,隐伏矿床勘查是地球化学探测技术的发展前沿,金活动态提取技术是寻找隐伏金矿的有效手段之一。相比于全量分析,金的活动态含量更低,需要解决选择性提取、高效预富集与准确测定等一系列难题。本文采用柠檬酸铵与土壤中黏土矿物及次生矿物作用促使吸附和可交换组分的金进入提取液,以硫脲和硫代硫酸钠络合金使活动态金向提取液中扩散,达到选择性提取的目的,建立了提取液中金的预富集及ICP-MS测定方法。实验确定的分析条件为:采用5g/L柠檬酸铵-2g/L硫脲-5g/L硫代硫酸钠为提取剂,提取时间24h,在酸性硫脲介质下用活性炭富集金,金吸附率可达89.6%～109.2%,灰化解吸温度为650～700℃。本方法检出限为0.05ng/g,相对标准偏差(RSD)为9.4%～10.2%,加标回收率为91.2%～93.4%。与已报道的硫酸铁-硫脲-硫代硫酸钠溶液提取再GFAAS测定的方法相比,本方法具有检出限低、测试线性范围宽、测试速度快的优势;应用于森林覆盖区黑龙江东安金矿区地球化学探测试验,金活动态异常与隐伏金矿位置一致。     

敞开酸溶-电感耦合等离子体发射光谱法测定石煤钒矿中钒铁铝磷

石煤钒矿资源的勘探、研究和利用均需对其成分进行准确的分析测试,其中钒、铁、铝、磷等主要成分的测定尚未建立标准方法,当前所用的分析测试方法各有不足。采用碱熔电感耦合等离子体发射光谱法(ICP-OES)测定石煤钒矿样品时,高浓度的可溶性盐会导致高背景,干扰测定。酸溶法可避免上述问题,但由于常规的氢氟酸-盐酸-硝酸-高氯酸四酸体系不能消除碳和有机质对样品的吸附和包裹,待测成分无法完全释放,需先将样品高温灼烧除碳,过程繁琐。本文采用少量硫酸加四酸的五酸体系处理样品,电热板加热,盐酸浸提,利用硫酸的强氧化性将样品中大量的碳氧化成二氧化碳,免却了灼烧除碳流程,消除了含碳物质对样品的吸附和包裹,显著增强了消解效果。由此建立了ICP-OES测定石煤钒中钒、铁、铝、磷的分析方法,在称样量为0.1g、浓硫酸加入量为0.30mL时,样品消解率达到99%以上。方法检出限为17~51mg/kg,相对标准偏差(RSD, n=11)在1.7%~5.1%之间;相对误差为-4.6%~2.7%。该方法背景低、测定结果准确,可满足石煤钒矿石样品的检测要求。     

NUMERICAL STUDY ON DOMINATING FACTOR AND KEY AREA OF EL NINO CYCLE FORMATION*

A coupled model,which is employed to study the dominating factor and key area of El Nino cycle formation,consists of a dynamical ocean model and a statistical atmospheric model.The coupled model with seasonal forcing successfully reproduces the El Nino event cycle which exhibits quasi-regular oscillations with a preferred period of about 4 years.The results show that the heat content(HC) is transported between the eastern and the western tropical Pacific areas.The spatial distribution of HC anomalies for four phases of the whole cycle clearly shows a possible formation mechanism of El Nino.Experiments further suggest that sea surface temperature in the tropical Pacific and HC in the central tropical Pacific are the most important factors and the central tropical Pacific is the most important area for determining formation of El Nino cycle.     

铜锡复合成矿研究进展与展望

铜与锡具有不同的地球化学性质,然而铜锡共生或复合成矿现象在世界主要铜、锡成矿带中比较常见,如中国的右江、南岭(湘南)、大兴安岭南段(内蒙东部)、葡萄牙伊比利亚、秘鲁安第斯、英格兰德文郡、德国厄尔士山、日本西南、俄罗斯远东、加拿大新不伦瑞克等成矿带均为铜锡复合矿床的集中产区。铜锡复合矿床主要为岩浆热液矿床,以矽卡岩型、脉状矿床为主,兼有火山热液沉积型、斑岩型及云英岩型等。铜矿体的主要矿石矿物为黄铜矿,兼有斑铜矿、黝铜矿、辉铜矿等;锡矿体的主要矿石矿物为锡石,兼有黝锡矿。铜锡复合矿床的成矿物质来源(尤其是铜、锡成矿元素的来源是否具有一致性)尚有不少争议,锡普遍被认为是岩浆来源,而铜的来源具有多样性。成矿流体演化过程中的氧化还原环境的改变及流体的混合是导致铜锡复合成矿的主要原因。目前对于铜锡复合成矿的研究,主要是从矿床的年代学、单矿物(黄铜矿、锡石)微量元素及传统同位素地球化学、流体包裹体等方面入手,但对厘定铜锡复合成矿过程的作用有限。铜锡复合矿床的成因及勘查模型的建立具有重要的理论价值及现实意义。本文提出未来研究可以从多种非传统稳定同位素(例如Cu、Sn、W、Zn同位素)的联合示踪探索、成...     

白云鄂博矿区土壤和植物中稀土元素的分布特征

白云鄂博矿区是稀土的主要产出地,在矿山开采和选炼等过程中,稀土元素通过迁移、富集等作用进入植物体,研究稀土元素的分布特征和迁移规律,可为白云鄂博矿体闭坑后的生物修复提供数据支持。本文设置了7个土壤采样点,采集铁花、沙蒿、沙打旺、沙朋、青蒿、小叶杨、猪毛菜七种植物,用电感耦合等离子体质谱法测定土壤和植物的根、茎、叶及整株的稀土含量,研究稀土元素在土壤和植物中的分布特征和迁移规律。统计分析结果表明:随着采样区与主矿区的距离增加,土壤样品中的稀土含量逐渐减少;在七种植物中,铁花的稀土含量最高,青蒿最低;对不同植物的整株稀土含量和各部位(根、茎、叶)稀土含量进行多元线性回归分析,叶(或花)的稀土含量在整珠植物中的占比最大。此外在不同季节,植物中的稀土含量基本保持不变,含量较高的稀土元素为Ce(0.0035%～0.020%)、La(0.0012%～0.011%)、Nd(0.0010%～0.0094%)和Pr(0.00036%～0.0046%),其中Ce最高。本研究提出:根据土壤样品中的稀土含量逐渐减少的特征,矿区周围土壤的稀土来源可能是矿石在采、选过程中的扩散造成的;根据植物富集稀土的能力,在矿山闭坑后,可种植富集稀土能力强的植物——铁花,进行矿山生物修复。     

Fully coupled hydraulic fracture simulation using the improved element partition method

The improved element partition method (IEPM) is a newly developed fracture simulation approach. IEPM allows a fracture to run across an element without introducing extra degrees of freedom. It can also simulate any number of fractures in a prescribed mesh without remeshing. In this study, the IEPM is extended to hydraulic fracture simulation. First, the seepage and volumetric storage matrix of a cracked element are derived using virtual nodes (the intersection points of a crack with element edges). Subsequently, the fully coupled hydromechanical equation is derived for this cracked element. To eliminate the extra degrees of freedom (virtual nodal quantities), the water pressure and displacement of the virtual nodes are associated with their adjacent nodes through least squares interpolation. Finally, the fully coupled equation in terms of nodal quantities is obtained. The verification cases validate the method. By using this method, the field-scale hydraulic fracturing process is well simulated. The proposed approach is simple and efficient for field-scale hydraulic fracture simulation.     

Multi-scale analysis on last millennium climate variations in Greenland by its ice core oxygen isotope

The empirical mode decomposition method is used for analyzing the paleoclimate proxy δ18O from Greenland GISP2 ice core.The results show that millennium climate change trends in Greenland record the Medieval Warm Period (MWP) from 860AD-1350AD lasting for about 490 years,and the Little Ice Age (LIA) from 1350AD-1920AD lasting about 570 years.During these events,sub cooling-warming variations occurred.Its multi-scale oscillations changed with quasi-period of 3-year,6.5-year,12-year,24-year,49-year,96-year,213-year and 468-year,and are not only affected by ENSO but also by solar activity.The oscillation of intrinsic mode function IMF7,IMF8 and their tendency obviously appear in 1350AD which is considered as the key stage of transformation between MWP and LIA.The results give more detailed changes and their stages of millennium climate change in high latitude areas of the Northern Hemisphere.     

A FINITE ELEMENT DOUBLE POROSITY MODEL FOR HETEROGENEOUS DEFORMABLE POROUS MEDIA

The mathematical base of the double porosity concept, consisting of the continuity and equilibrium equation respectively, is briefly reviewed. A quasi-steady-state transfer function, the so-called leakage term, is used. Important aspects of the developed code, based on the double porosity theory, are presented together with two hypothetical example problems. The resulting trend of the settlements are compared to those from previous work and was found to be significantly different. However, the implications are that the present study exhibits a more realistic prediction for the settlement.     

电感耦合等离子体质谱法同时测定地下水中硼溴碘

建立了电感耦合等离子体质谱法同时测定地下水中B、Br、I的方法。选定φ=2%(体积分数)的稀NH3.H2O介质消除碘的记忆效应。采用干扰较少的10B和79Br同位素。B、Br、I在0~10 000 ng/mL呈良好的线性关系。方法的检出限为10B 0.176 ng/mL,79Br 0.876ng/mL,127I 0.132 ng/mL;精密度(RSD,n=12)为10B 2.86%,79Br 3.36%,127I 2.69%;10B的阶梯加标回收率为94.6%~101.5%,79Br为98.3%~104.9%,127I为96.5%~102.0%。     

敞开酸溶和偏硼酸锂碱熔ICP-MS法测定多金属矿中的稀土元素及铌钽锆铪

用电感耦合等离子体质谱法(ICP-MS)测定地质样品中的稀土及难熔元素,混合酸敞开酸溶法和碱熔融法是两种主要的溶样方法。但地质样品组分复杂,元素之间存在相互共生的现象,对于特殊元素、特殊样品用传统酸溶法会造成部分元素消解不完全,使测定结果不准确;而碱熔法的操作过程繁琐,且溶液盐度高,易产生基体干扰和堵塞仪器进样系统。本文改进了传统四酸和五酸体系,采用氢氟酸-硝酸-硫酸敞开酸溶体系,用国家一级标准物质制作标准曲线测定15种稀土元素,方法准确度(ΔlgC)为0.001～0.027。同时改进了偏硼酸锂碱熔法,样品用偏硼酸锂碱熔提取,加入氢氧化钠调节溶液至碱性条件,所测元素与偏硼酸锂共沉淀后过滤分离熔剂,再用硝酸复溶测定15种稀土元素及铌钽锆铪。两种溶样方法的测定值与认定值的相对误差为1.09%～9.30%。将混合酸敞开酸溶法测定稀土元素、偏硼酸锂碱熔法测定铌钽锆铪的结果与其他实验室密闭酸溶法相比,两组数据的相对偏差为0.13%～15.32%。本实验表明,混合酸敞开酸溶法适用于测定地质样品中的稀土元素,偏硼酸锂碱熔法不仅适用于测定地质样品中的稀土元素及铌钽锆铪,也适用于测定如古老高压变质岩石及铝含量高的样品中的铌钽锆铪。