电感耦合等离子体发射光谱法测定铝土矿中镓——酸溶和碱熔预处理方法比较

研究了盐酸-硝酸-氢氟酸-高氯酸酸溶和氢氧化钠碱熔两种测定铝土矿石样品中镓的前处理方法,利用电感耦合等离子体发射光谱法(ICP-AES)进行测定。对熔矿试剂及条件、分析谱线的选择和元素的干扰进行了讨论,采用不同含量的铝土矿石国家标准物质样品进行了条件实验。分析结果表明:采用盐酸-硝酸-氢氟酸-高氯酸溶解样品,会导致铝土矿石样品溶解不完全,得到的数据失真;而采用氢氧化钠碱熔法处理铝土矿石样品后,用ICP-AES法测定,镓的测定值准确度高,方法检出限为0.15μg/g,相对标准偏差(RSD,n=11)为2.51%～5.97%,回收率为94.8%～108.2%。该方法灵敏度高,精密度好,分析时间短,易于流程操作。方法经国家一级标准物质分析验证,测定结果与标准值相符,特别适用于铝土矿石样品中镓的测定。     

Effet de l'agrégation sur le transport de la kaolinite recouverte d'acide humique à travers un sable de quartz d'origine naturelleAggregation effect on the transport of humic-coated kaolinite colloids through a natural quartz sand

To evaluate the risk of contaminant transport by mobile colloids, it is necessary to understand how colloids and associated pollutants behave during their migration through uncontaminated soil or groundwater. In this study, we investigated the influence of aggregation induced by Ca²⁺ and trace metals (Pb²⁺, Cu²⁺) concentrations on the transport of humic-coated kaolinite colloids through a natural quartz sand at pH=4. Adsorbed divalent cations reduce the colloids surface charge and thereby induce aggregation and deposition in porous media. To cite this article: R. Ait Akbour et al., C. R. Geoscience 334 (2002) 981–985.     

模拟酸雨对东北地区农作物生长、生理及品质的影响

通过模拟试验,研究不同pH模拟酸雨胁迫对农作物(小白菜)生长、生理及品质的影响,量化不同pH酸雨对小白菜的影响程度。试验结果表明:小白菜植株受害与pH密切相关,酸性越强,胁迫影响越显著,受害程度越重。随着酸雨酸性增强,小白菜生长受抑,生物量、株高等明显降低,食部鲜质量、干质量受影响程度比根部鲜质量、干质量大。在酸雨胁迫下,小白菜游离氨基酸总量、可溶性糖、可溶性蛋白质和维生素C含量均出现不同程度的降低,且酸性越强,受影响幅度越大,弱酸条件下可在一定程度上促进营养物质的合成。酸雨可抑制叶绿素类与类胡萝卜素合成,影响光合作用,最终导致产量降低、品质下降。     

苹果酸对含铊黄铁矿的淋滤实验研究

在２５￣５５℃低温条件下研究了苹果酸对广东云浮含铊黄铁矿的准动态淋滤,模拟考察了Ｔ１、Ｃｄ和Ｐｂ三种有毒元素随矿山开采和环境介质等因素作用而进入环境的情况。结果表明,云浮矿中Ｔ１的含量大大超过地壳背景值,越细的料级中含量越高。从淋滤结果可以推测,在矿山开采过程中,在环境介质的淋滤作用下,Ｔ１进入环境的速率远比Ｃｄ和Ｐｂ快。在介质浓度、作用时间和温度等影响淋滤结果诸因素中,温度的影响尤为明显。     

Effects of the peat acid digestion protocol on geochemically and morphologically diverse tephra deposits

Tephra shards for electron probe microanalysis are most efficiently extracted from peat using acid digestion, which removes organic material that hinders density separation methods. However, strong acids are known to alter glass chemical compositions, and several studies have examined how acid digestion affects rhyolitic volcanic glass. The focus on rhyolitic tephra in these studies leaves considerable uncertainty, as the dissolution rates of natural glasses (including tephra) are determined by the chemical composition and surface area/volume ratio, both of which vary in tephra deposits. Here, we use duplicate samples of basaltic, trachydacitic and rhyolitic tephra to examine physical and geochemical alteration following acid digestion. Scanning electron microscope imagery reveals no discernible degradation of glass surfaces, and electron probe microanalysis results from duplicate samples are statistically indistinguishable. These findings suggest the acid digestion protocol for organic peats does not significantly alter glass geochemistry regardless of shard morphologies or geochemical compositions.     

考虑非达西效应的酸蚀裂缝流场数值模拟

酸压改造后的酸蚀裂缝是储层流体的主要流动通道,研究流体在酸蚀裂缝中的流动规律是十分必要的。本文介绍了目前裂隙流动研究中的4种常用控制方程及各自的适用条件,确定了Navier-Stokes方程为酸蚀裂缝流场数值模拟的控制方程。为了分析酸蚀裂缝流场分布规律以及非达西效应对裂缝导流能力的影响,利用逆向工程技术对两种不同刻蚀形态的酸蚀岩样壁面进行了实体重构,并采用有限元数值模拟方法进行了不同流量下的酸蚀裂缝流动试验。结果表明：酸刻蚀形态和裂缝接触关系对流场分布的影响较大。隙宽分布平滑的均匀刻蚀裂缝,其流态稳定、曲折度低,但由于裂缝开度较窄且比表面较高,边界层效应明显,流体流动时产生的黏滞阻力较高;沟槽裂缝曲面粗糙,隙宽分布复杂,流体流动时流态不稳定,曲折度高,在高流量下会产生明显的涡流流动,增大惯性阻力。裂缝通道存在缩颈现象会引起流体绕流和多次加减速,产生额外的压力损耗。随着模拟流量的增大,压降与流量会逐渐偏离线性关系而呈现出非达西流动现象。酸蚀裂缝壁面越粗糙,产生非达西效应时的临界流量和临界雷诺数就越小,在相同流量下非达西效应就越强烈,导流能力下降速率更快。     

海洋粘土沉积物的组成及其增白试验

为了海洋粘土的开发应用,利用FTIR和XRD衍射对其进行了矿物成分分析。结果表明,海洋粘土样品中粘土矿物含量较高,其主要矿物组成为伊/蒙混层和伊利石并含有少量其它矿物,同时证实样品中有磁铁矿和赤铁矿存在。粘土沉积物的化学成分分析显示,粘土中Fe2O3质量分数较高,约为7%。采用酸溶氢气还原法对东太平洋的粘土样品进行了化学增白试验,并探讨了酸种类及其浓度、药剂用量、反应时间、煅烧温度等因素对除铁增白效果的影响,优选出最佳除铁增白方案,使海洋粘土的白度由原来的23.8%提高到73.1%。另外,对增白前后样品的粒度、比表面积和分散性的测试表明,在增白的同时样品的活性也得到了提高。     

动能歧视模式ICP-MS测定地球化学样品中14种痕量元素

应用传统ICP-MS法测定勘查地球化学样品中Ag、Cd等痕量元素,基体效应和多原子离子干扰严重,准确测定的难度较大。本文基于当前ICP-MS消除干扰技术,分析了ICP-MS标准模式(STD)及动能歧视模式(KED)测定地球化学样品中Ag、Cd等14种痕量元素的有效性,通过比较这两种模式的测定效果,在此基础上确定了各元素的有效测定模式。结果表明:在KED模式下,基体元素如Zr、Nb氧化物的产率降低,基本上消除了Zr、Nb氧化物对痕量元素Ag、Cd的多原子离子干扰。KED模式提高了信噪比,降低了方法检出限,如Ag、Cd的检出限分别为0. 004mg/kg、0. 005mg/kg,其他12种元素的检出限也低于多目标地球化学调查76种元素分析方案中的检出限。测定痕量元素的准确度显著优于STD模式。实验中采用简单的硝酸-氢氟酸-高氯酸消解样品,残渣用王水复溶,结合KED模式下优选出干扰较小的同位素作为测定同位素,以Rh作为内标校正仪器产生的信号漂移,将样品溶液稀释至1000倍,基体效应降低至最小。本方法经国家一级标准物质的验证,测定结果与认定值相符,可为勘查地球化学提供高质量数据。     

CdTe量子点荧光猝灭法测定赤泥中痕量镍

Cd Te量子点具有荧光强度高和稳定性好的优点,应用Cd Te量子点荧光猝灭法分析基体复杂的样品,需要有效分离对测定干扰的金属元素和高效富集待测元素。本文以巯基乙酸(TGA)作稳定剂,采用水相合成法制备了巯基乙酸修饰的Cd Te量子点,基于镍离子在p H=10.0硼砂缓冲溶液中对Cd Te量子点的荧光具有较强猝灭作用,建立了一种测定赤泥中痕量镍的荧光光度方法。荧光猝灭反应的最佳实验条件为:Cd Te量子点的浓度3.0×10-4mol/L,反应温度为室温,反应时间10 min,在此条件下镍离子浓度在2.0×10-7~7.8×10-5mol/L范围内与Cd Te量子点的相对荧光强度呈良好的线性关系;方法检出限为1.5×10-7mol/L。本方法针对Fe3+、Co2+、Cu2+等主要基体金属元素允许量低的问题,采用25%的2-羟基-4-仲辛氧基二苯甲酮肟(N530)磺化煤油萃取回收滤液中的Ni2+,镍回收率达到99%以上;赤泥中痕量镍的测定结果与催化光度法相符,加标回收率为98.3%-104.2%。     

Humic Ion-Binding Model VI: An Improved Description of the Interactions of Protons and Metal Ions with Humic Substances

Humic Ion-Binding Model VI, a discrete site/electrostatic model of the interactions of protons and metals with fulvic and humic acids, is applied to 19 sets of published data for proton binding, and 110 sets for metal binding. Proton binding is described with a site density, two median intrinsic equilibrium constants, two parameters defining the spread of equilibrium constants around the medians, and an electrostatic constant. Intrinsic equilibrium constants for metal binding are defined by two median constants, log K_MA and log K_MB, which refer to carboxyl and weaker-acid sites respectively, together with a parameter, LK₁, defining the spreads of values around the medians. A further parameter, LK₂, takes account of small numbers of strong binding sites. By considering results from many data sets, a universal average value of LK₁ is obtained, and a correlation established between log K_MB and log K_MA. In addition, a relation between LK₂ and the equilibrium constant for metal-NH₃ complexation is tentatively suggested. As a result, metal-binding data can be fitted by the adjustment of a single parameter, log K_MA. Values of log K_MA are derived for 22 metal species. Model VI accounts for competition and ionic strength effects, and for proton-metal exchange.