氯化钯作基体改进剂石墨炉原子吸收光谱法测定土壤中的铍

铍是一种对人体有害的金属元素,土壤中铍的测定目前尚无国家标准方法.本文采用盐酸-硝酸-氢氟酸体系微波消解、石墨炉原子吸收光谱法测定土壤样品中的铍,实验了钯、硝酸铝、硝酸镁、钙盐的增敏效果.结果表明,以氯化钯为基体改进剂,灰化温度和原子化温度分别提高到1100℃和2650℃,原子化峰形尖锐,背景吸收很小,提高了测定灵敏度;其他三种基体改进剂虽然也能提高测定灵敏度,但背景吸收较大.采用优化的实验条件,Fe、Mg、K、Na、Ca、Ti、Cu、Ba、Mn、Zn、Pb、Sr等共存元素对测定不产生干扰.铍的浓度在0 ～4.00 μg/L范围内线性良好,方法检出限为0.01 μg/g,精密度(RSD,n=6)为3.5％ ～6.7％,实际土壤样品的加标回收率为84.0％ ～ 113.0％,土壤国家标准物质的测定值在标准值的误差范围内.本法与萃取光度法、电感耦合等离子体发射光谱/质谱法相比,操作简便,分析成本较低.     

The chemical composition including the Rare Earth Elements of the three major glass types of Europe and the Orient used in late antiquity and the Middle Ages

Sets of 20 soda ash glasses, 16 soda lime glasses and 23 wood ash glasses mainly from excavations in Europe (additional soda ash glasses from Egypt) were analysed on 61 chemical elements. Average SiO₂ is about 62% in soda glasses and 50% in wood ash glasses. The three groups of glasses contain on average 13% Na₂O, 18% Na₂O and 13% K₂O as fluxes to lower the melting temperature of quartz at their production. The starting materials beside quartz were halophytic plant ash for soda ash glass, trona (Na₃H(CO₃)₂·2H₂O) and lime (clamshells) for soda lime glass and beech ash for wood ash glass. Each of the three major glass types contains specific Rare Earth Element (REE) concentrations mainly contained in quartz and its intergrown minerals. 50 Paleozoic and Mesozoic sandstones from Central Europe represent the quartz composition. The REE pattern of these glasses apparently indicates major compositional stages of the Continental Earth's Crust. The boron to lithium and sodium to potassium ratios as in seawater suggest reactions of materials for soda glass with seawater. Negative Ce anomalies in the three glasses are caused by reactions of quartz with seawater.     

泡沫塑料富集-电感耦合等离子体质谱法测定土壤中超痕量金铂钯

样品采用王水溶解,二氯化锡还原,泡沫塑料富集,用Re作内标,电感耦合等离子体质谱法同时测定土壤中超痕量金、铂、钯。在盐酸-二氯化锡体系中,盐酸酸度为15%,二氯化锡浓度为45 g/L,吸附时间30 min时吸附效果明显,吸附温度为25℃时吸附率相对稳定。方法检出限Au为0.21 ng/g,Pt为0.18 ng/g,Pd为0.16ng/g,方法加标回收率Au为91.3%~97.8%,Pt为92.0%~96.7%,Pd为96.0%~101.6%。该方法用于测定国家一级标准物质,线性范围宽、重现性好,结果准确可靠,样品处理简便、快速。     

硫氰酸盐比色法测定钨的改进

硫氰酸盐比色法测定钨是基于W5+与硫氰酸盐形成黄色络合物。为使钨完全还原为5价,通常单独使用三氯化钛或氯化亚锡作还原剂。此方法在应用过程中,由于Ti3+本身呈紫色,加多会掩盖络合物的黄色,加少则出现硫氰酸铁之红色丝状物影响比色的情况。通过大量的试验,采用氯化亚锡-三氯化钛作双还原剂,控制最佳酸度、温度和时间,从而获得稳定的络合物,提高了分析结果的稳定性。通过对国家一级标准物质进行分析验证,从而证实方法可行,能够保证样品的测试精密度和准确度。本方法尤其适用于低含量、大批量钨矿样品的测定。     

复方化学消毒剂中苯扎氯铵的高效液相色谱测定

建立了一种测定复方化学消毒剂中苯扎氯铵成分十二烷基二甲基苄基氯化铵、十四烷基二甲基苄基氯化铵和十六烷基二甲基苄基氯化铵的反相离子对高效液相色谱法。色谱柱为Platisil ODS(5μm,250 mm×4.6mm),流动相为甲醇-0.2 mol/L己烷磺酸钠(含1%三乙胺,V/V,用高氯酸调节至pH=6.0,体积比85∶15),紫外220 nm检测。用己烷磺酸钠作为离子对试剂,增强了苯扎氯铵成分的保留,三乙胺作为扫尾剂,通过抑制固定相表面残存的硅羟基对苯扎氯铵成分的吸附,减少了色谱峰拖尾。3种苯扎氯铵成分分离良好,标准曲线的线性范围分别为0.002～5 mg/mL、0.005～10 mg/mL和0.005～10 mg/mL,检测限分别为0.0005 mg/mL、0.001mg/mL和0.001 mg/mL。方法具有良好的准确度和精密度,在测定低浓度样品时优势明显。实际用于测定苯扎氯铵消毒液和医用消毒纸巾中3种苯扎氯铵成分的含量,回收率为99.3%～104.1%,日内和日间测定相对标准偏差(RSD)均小于2.0%。     

高温高压下流体中电解质活度系数的确定

高温高压下流体中电解质的活度系数在地球化学领域有着广泛的应用。本实验测量了100—500℃、0．11—12GPa下0．01mol／L KCl溶液的电导率,并利用Hueckel方程由实验确定的摩尔电导和极限摩尔电导计算出了KCl的平均摩尔活度系数。平均摩尔活度系数随温度升高而减小,随压力升高而增大,而在高温高压下随温度压力的升高几乎保持恒定。     

钾长石粉酸浸除铁废液资源化的实验研究

钾长石粉经过硫酸或盐酸酸浸除铁后, 废液中含有大量的金属离子和游离酸.对废硫酸进行循环利用实验, 钾长石粉铁的浸出率达到88.3%.对酸浸废液进行蒸发结晶, 分别制备得到了纯度为94.1%的绿钾铁矾和74%的三氯化铁.用硫酸酸浸废液蒸发结晶后, 铁的回收率为70.0%, 钾的回收率为96.5%, 整个工艺无需高温, 无需加压, 操作简单, 具有高效、低能耗、低污染的特点, 表明用本项技术处理酸浸废液行之有效.分析认为, 废液呈强酸性、溶液中存在大量Fe2+、碱金属离子含量偏低是蒸发结晶过程中形成绿钾铁矾而不是黄钾铁矾的主要原因.      

Lead and Aroclor 1254 disrupt reproductive neuroendocrine function in Atlantic croaker

We have previously shown that lead (lead chloride) and a polychlorinated biphenyl (PCB) mixture (Aroclor 1254) can alter hypothalamic serotonin (5-hydroxytryptamine, 5-HT) content, and pituitary gonadotropin II (GTH II) release in vitro, in the Atlantic croaker (Micropogonias undulatus). In the present study we investigated whether impairment of the hypothalamic 5-HT pathway involves alterations in tryptophan hydroxylase (TPH), the rate-limiting enzyme in 5-HT biosynthesis, or monoamine oxidase (MAO), the catabolic enzyme. Aroclor 1254 (1 mg/kg body wt. for 30 days) significantly inhibited hypothalamic TPH activity without altering MAO activity, and caused a significant decline in 5-HT content. On the other hand, lead exposure (15 mg/kg body wt. for 30 days) only induced a slight decrease in hypothalamic 5-HT content and TPH activity, and a minor increase in MAO activity. However, both Aroclor 1254 and lead significantly inhibited the GTH II response to stimulation by a luteinizing hormone-releasing hormone analog (LHRHa) in vivo and caused reduced gonadal growth. These results demonstrate that impairment of hypothalamic serotonin metabolism by Aroclor 1254 involves inhibition of 5-HT synthesis, whereas lead does not exert a profound influence on 5-HT metabolism. The decline in 5-HT availability due to reduced 5-HT synthesis in the PCB-exposed fish may result in disruption of the stimulatory 5-HT-GnRH pathway controlling GTH II secretion leading to impairment of gonadal growth.     

黄土碳酸盐碳同位素环境意义讨论

黄土碳酸盐碳同位素广泛应用于第四纪气候环境变化的研究中,以往研究中多利用钙结核、次生碳酸盐或成壤碳酸盐,认为其反映了C₄植物的丰度。黄土高原碳酸盐碳同位素表现为黄土层高,古土壤层中低,即黄土层中C₄植物丰度高于古土壤层。然而,这样的结果和黄土有机碳同位素得到的结果矛盾,有机碳同位素的结果表明温度对C₄植物的分布起到了决定性作用。由于有机碳同位素对植物类型的反映更为直接而可靠,因此碳酸盐碳同位素反映C₄植物丰度存在疑问。对黄土高原黄土碳酸盐碳同位素的系统概括后认为,第四纪期间黄土碳酸盐碳同位素与C₄植物有直接联系,但C₄植物丰度不是唯一决定性的因素,碳酸盐碳同位素的指示意义存在复杂性。在黄土高原地区,植被发育程度、与大气CO₂交换程度、植被本身的碳同位素值的变化以及原生碳酸盐的影响等因素都会对碳酸盐碳同位素产生影响。由黄土碳酸盐碳同位素的讨论可延伸到不同土壤碳酸盐碳同位素揭示的环境指示意义,不同的土壤环境,其气候条件、植被类型及发育程度...     

Modelling of chloride ingress into concrete through a single‐ion approach. Application to an idealized surface crack pattern

The paper examines ion (chloride) transport equations in porous media (concrete) integrated over a representative elementary volume, that is to say, averaging over the macroscopic level the phenomena that occur really at the pore scale. There are three basic variables to be used: chloride concentration, moisture and temperature. The diffusion process is examined, in addition to other phenomena such as convection (the motion of dissolved substances caused by flow of water in a pore solution of partially saturated media) or chloride binding (the capacity of free chloride of being chemically bound, particularly with C₃A to form Friedel salts). Contrary to other approaches, such effects are not considered by means of apparent diffusion coefficients but by developing the complete set of time‐dependent equations for both the chloride concentration within the pore solution and the moisture content within the pore space. Once the general model is described, the system of equations can be solved numerically by means of a two‐dimensional finite element formulation. The main objective is to reproduce results of experimental tests by means of a priori parameter estimation, according to the characteristics of materials and external environment conditions, thereby superseding the well‐known best fit a posteriori through Fick's second equation. While the introduction of hygrometric conditions and convection phenomena appears to be of high significance, other factors like temperature, surface concentration, chloride binding or equivalent hydration time are analysed too. The proposed model can reproduce bidimensional complex geometries, for example, cracked concrete cover, as well as variable surface condition. An application case is developed through a realistic model of the geometry of a crack. Copyright © 2014 John Wiley & Sons, Ltd.