铋和二氧化锰共沉淀分离-火焰原子吸收光谱法测定铅锭中铋

铅锭样品经硝酸(1+3)溶解,分别用氨水和硝酸(1+3)调节溶液的pH值约为3.1,加入10mL 100g/L硝酸锰溶液,于70℃的温度下,在0.47~0.70mol/L硝酸中加入10mL10g/L高锰酸钾溶液并不断搅拌,利用二氧化锰与铋共沉淀的特性实现了铋与基体铅的分离,将过滤所得沉淀用盐酸双氧水混合酸(49+2)溶解,以10%~25%(V/V)盐酸为测定溶液介质,选择223.1nm为测定波长,建立了火焰原子吸收光谱法(FAAS)测定铅锭样品中铋的方法。在选定的仪器条件下,铋在0.50~5.00μg/mL范围内和其对应的吸光度呈良好的线性关系,相关系数r=0.999 8,铋的方法检出限为0.002 8μg/mL。干扰试验表明,铅锭中分离后余下的铅及其他元素不干扰对铋的测定。将实验方法应用于4个质量分数为0.000 39%~0.062%的铅锭标准样品中铋的测定,结果与认定值基本一致,相对标准偏差(RSD,n=11)在0.67%~8.1%之间,加标回收率为98%~102%。     

Membrane Behavior of Compacted Clay Liners

The containment function of clay barriers used for waste containment applications (e.g., landfills) can be enhanced if such clays exhibit membrane behavior or the ability to restrict the migration of solutes (e.g., contaminants). In this regard, compacted specimens of a locally available natural clay known as Nelson Farm Clay (NFC), as well as NFC amended with 5% (dry weight) sodium bentonite, were evaluated for hydraulic conductivity, k, and the potential for membrane behavior. The membrane efficiencies of specimens of both soils compacted such that k was less than 10?7?cm/s were measured by establishing steady salt (KCl) concentration differences, ?ΔCo, ranging from 3.9 to 47 mM across the specimens in a flexible-wall cell under closed-system boundary conditions. The measured membrane efficiency for the unamended NFC was negligible (i.e., ≤ 1.4%), even though the k was suitably low (i.e., k<10?7?cm/s). In contrast, compacted specimens of the bentonite amended NFC exhibited not only lower k but also significant membrane behavior, with membrane efficiencies as high as 97.3% for ?ΔCo of 3.9-mM KCl. The results suggest that natural clays typically suitable for use as compacted clay liners (CCLs) are not likely to behave as semipermeable membranes unless the clay is amended with bentonite or the clay is inherently rich in high swelling clay minerals (e.g., sodium smectite). The potential benefit resulting from membrane behavior in a CCL constructed with the bentonite amended NFC is illustrated analytically in terms of liquid flux.     

Centrifuge Permeameter for Unsaturated Soils. II: Measurement of the Hydraulic Characteristics of an Unsaturated Clay

This paper presents the hydraulic characteristics of an unsaturated, compacted clay, including its soil-water retention curve (SWRC) and hydraulic conductivity function (K function), determined using a new centrifuge permeameter developed at the University of Texas at Austin. A companion paper describes the apparatus, its instrumentation layout, and data reduction procedures. Three approaches are evaluated in this study to define the SWRC and K function of the compacted clay under both drying and wetting paths, by varying the inflow rate, the g level, or both. For imposed inflow rates ranging from 20 to 0.1 mL/h and g levels ranging from 10 to 100 g, the measured matric suction ranged from 5 to 70 kPa, the average volumetric water content ranged from 23 to 33%, and the hydraulic conductivity ranged from 2×10?7 to 8×10?11?m/s. The SWRCs and K functions obtained using the three different testing approaches were very consistent, and yielded suitable information for direct determination of the hydraulic characteristics. The approaches differed in the time required to complete a testing stage and in the range of measured hydraulic conductivity values. The g level had a negligible effect on the measured hydraulic characteristics of the compacted clay. The SWRCs and K functions defined using the centrifuge permeameter are consistent with those obtained using pressure chamber and column infiltration tests. The K functions defined using the centrifuge permeameter follow the same shape as those obtained from predictive relationships, although the measured and predicted K functions differ by two orders of magnitude at the lower end of the volumetric water content range.     

Sepiolite as an Alternative Liner Material in Municipal Solid Waste Landfills

Compacted clay has traditionally been used as a lining material in municipal solid waste landfills. However, natural clays may not always provide good contaminant sorption properties. One alternative material that is abundant in some parts of Europe and Turkey as well as Western United States is sepiolite. A laboratory study was undertaken to investigate the feasibility of sepiolite as a liner material. Two clays, one rich in sepiolite and the other one rich in kaolinite mineral, as well as their mixtures were subjected to geomechanical, hydraulic, and environmental tests. The same soils were also subjected to strength and hydraulic conductivity tests after a series of freeze and thaw cycles. The results of the study indicated that relatively high hydraulic conductivity and shrinkage capacity of sepiolite necessitates addition of kaolinite before being used as a landfill material. The valence of the salt solutions affected the swell and hydraulic conductivity characteristics of the clays tested. Retardation factors for sepiolite for metal solutions are 1.2–2.2 times higher than those calculated for the clay that is rich in kaolinite, and the inorganic contaminant adsorption capacity of the clay can be improved by addition of sepiolite. The results indicated that the clay mixtures utilized in this study provide good geomechanical, hydraulic, and metal adsorption properties which may justify their potential use as a liner material in solid waste landfills.     

Extraction of rare earth elements from a South American ionic clay

Ionic clays,formed by the natural weathering of REE-bearing minerals and the adsorption of the resulting liberated REE ions onto the clay surface,are an important resource for critical rare earth elements(REEs).Here,a two-step desorption process using ammonium sulfate with active pH adjustment using sulfuric acid was developed to extract REEs from a South American clay.The desorption process was optimized using response surface methodology approach and the optimum operating conditions were deter...     

Shear Behavior of Compacted Rubber Fiber-Clay Composite in Drained and Undrained Loading

The ductility, toughness, and resistance to tensile cracking of clays can be improved with the inclusion of short fibers. Tire buffings are derived from the tire retread process and because of their elongated shape, may be used as fiber inclusions. The objective of this study was to evaluate the drained and undrained shear strength of mixtures of clay and tire buffings. Mixtures of silty low plasticity kaolinitic clay and 10% by dry weight of tire buffings were compacted at both Standard and Modified compaction energy. Consolidated-drained and consolidated-undrained triaxial tests were run at confining stresses ranging from 50?to?300?kPa. Preshear and postshear permeability tests were conducted. Results showed that the peak strength of the composite is comparable to or greater than that of clay alone when tested at confining stresses below 200–300?kPa. Above this threshold, the presence of inclusions tends to degrade the strength of the clay. Changes in permeability were not significant.     

Experimental Study of Wellbore Instability in Clays

This paper presents the results of an extensive program of laboratory model wellbore tests that have been performed to study wellbore instability in saturated clays. The tests were conducted on resedimented Boston blue clay (RBBC) anisotropically consolidated to vertical effective stresses up to 10?MPa by using two custom-built thick-walled cylinder (TWC) devices with outer diameters Do = 7.6 and 15.2?cm. The experimental program investigated the effects of specimen geometry, mode of loading, strain rate, consolidation stress level, and overconsolidation ratio (OCR) on deformations of the model wellbore measured during undrained shearing. Results indicate that for normally consolidated clays most of the change in cavity pressure occurs at volumetric strains less than 5% after which the borehole becomes unstable. Increases in outer diameter and strain rate led to a reduction in the minimum borehole pressure. Stress-strain properties were interpreted by using an analysis procedure originally developed for undrained plane strain expansion of hollow cylinders. The backfigured undrained strength ratios from these analyses for normally consolidated specimens range from su/σvc′ = 0.19–0.22. Overconsolidation greatly improves the stability of the borehole, and interpreted undrained strength ratios from the TWC tests are consistent with well-known power law functions previously developed for elemental shear tests.     

Design of Foundations on Sensitive Champlain Clay Subjected to Cyclic Loading

Sensitive clay subjected to cyclic loading may experience gradual loss of its shear strength, which may lead to liquefaction. Foundations built on this clay would suffer extensive settlement and significant loss of bearing capacity or perhaps catastrophic failure. This paper presents an experimental investigation on sensitive (Champlain) clay obtained from the city of Rigaud, Quebec (Canada). Consolidation tests, static and cyclic undrained and drained triaxial tests were performed on representative samples of this clay. The objective of this investigation was to examine the influence of the physical and mechanical parameters, which govern the shear strength of sensitive clay subjected to cyclic loading. Based on the results of the present investigation and those available in the literature, it can be reported herein that the undrained response is the most critical for these foundations; furthermore, the preconsolidation pressure is considered as an important parameter in establishing the shear strength of sensitive clay. A design procedure is developed to determine the safe zone for the undrained and drained responses, within which a combination of the cyclic deviator stress and the number of cycles for a given soil/loading/site conditions can achieve a quasielastic resilient state without reaching failure. The proposed design procedure is applicable to all regions around the world, where sensitive clays can be found. Furthermore, this procedure can be adopted to examine the conditions of existing foundations built on sensitive clay at any time during its lifespan.     

Ceria-Modified Clay Supported Palladium Catalysts for Complete Oxidation of Volatile Organic Compounds

Ceria- and alumina-pillared interlayered clays were synthesized in the presence of PEO surfactant by using laponite clay as raw material.And the synthesized pillared clays were used as supports to load palladium catalysts for complete oxidation of benzene.Nitrogen adsorption/desorption experiments reveal that the pillared clays have higher tests show that ceria pillar exhibited promoting effect on the activity of the palladium catalysts, and ceria-pillared clay supported palladium catalyst catalyzed the complete oxidation of benzene at less than 250 ℃.The calcination temperature affects the activity of the catalysts significantly, and it is found that the optimal calcination temperature are 600 and 400 ℃ for ceria- and alumina-pillared clay supported palladium catalysts, respectively.     

Elastic Anisotropic Viscoplastic Modeling of the Strain-Rate-Dependent Stress–Strain Behavior of K0-Consolidated Natural Marine Clays in Triaxial Shear Tests

This paper presents a new three-dimensional (3D) anisotropic elastic viscoplastic (EVP) model for the time-dependent stress–strain behavior of K0-consolidated marine clays. A nonlinear creep function with a limit for the creep volumetric strain under an isotropic or odometer K0-consolidated stressing condition and a nonsymmetrical elliptical loading locus are incorporated in the 3D anisotropic EVP model. An α-line defines the inclination of the nonsymmetrical elliptical loading locus in the p′-q plane and is commonly used for natural soils. All model parameters are determined from the results of one set of consolidated undrained compression tests and an isotropic consolidation/creep test. With the parameters determined, the 3D anisotropic EVP model is used to simulate the behavior of K0-consolidation tests and the strain-rate-dependent stress–strain behaviors of the K0-consolidated triaxial compression and extension tests on natural Hong Kong marine deposit clay specimens. These triaxial K0-consolidated specimens were sheared at step-changed axial strain rates from +2?to?+0.2, +20, ?2 (unloading) and +2%/h (reloading) for compression tests; or from ?2?to??0.2, ?20, +2 (unloading), and ?2%/h (reloading) for extension tests, all in an undrained condition. The simulation results of all these tests are compared with the test results. The validation and limitations of the model are then evaluated and discussed.     

Removal of Lead from Contaminated Water and Clay Soil Using a Biosurfactant

Lead removal from water and contaminated soils was investigated using biosurfactant, anionic, and nonionic surfactants in continuously stirred batch reactors. Lead-contaminated water up to 100?mg/L and clay soil up to 3,000?mg/kg were used in this investigation. The surfactant concentration up to 10 critical micelle concentration was used. The speciation of lead into the micelles was quantified and the lead removal efficiency depended on the level of contamination, surfactant type, and concentration. Of the surfactants used, biosurfactant (produced from used vegetable oil) had the best removal efficiency (75%) at a lead contamination of 100?mg/L in water at pH of over 12. The Fourier-transformed infrared spectroscopy study showed that the carboxyl group in the biosurfactant was effective in removing the lead from the solution. Langmuir and Freundlich relationships were used to represent the micelle partitioning of lead in the surfactant solutions. Desorption of lead from contaminated kaolinite clay was represented using linear isotherms. The biosurfactant solution had a higher micelle partitioning for the lead from contaminated water and desorbing the lead from the contaminated soil compared to the other chemical surfactants.     

电感耦合等离子体原子发射光谱法测定锰铁合金、锰硅合金和金属锰中8种微量元素

锰铁合金、锰硅合金、金属锰中铅、砷、钛、铜、镍、钙、镁、铝的含量决定了产品质量,以往常采用化学法或原子吸收光谱法进行测定,但存在准确度较差或测定速度不能满足要求等问题。为了实现上述元素的准确、快速测定,建立了采用电感耦合等离子体原子发射光谱法(ICP-AES)测定锰铁合金、锰硅合金和金属锰中微量铅、砷、钛、铜、镍、钙、镁、铝的方法。实验以硝酸、盐酸、氢氟酸、高氯酸分解样品,并使硅与氢氟酸反应生成四氟化硅挥发除去,试液中剩余共存元素主要有铁、锰等。实验结果表明,铁不干扰测定,通过在标准溶液系列中进行锰基体匹配消除锰基体效应的影响。以2mL高氯酸和6mL盐酸混合酸(8%)作为分析介质,可以达到最佳分析效果。在各元素校准曲线线性范围内,线性相关系数在0.9992~0.9999之间;方法中各元素的检出限在0.0001~0.0040μg/mL。实验方法用于测定锰铁合金、锰硅合金、金属锰中铅、砷、钛、铜、镍、钙、镁、铝,结果的相对标准偏差(RSD,n=11)在2.2%~9.4%;回收率在95%~105%;选择7个实验室进行了验证试验,各实验室间结果基本一致;按照实验方法测定了4个标准样品(材字-32、YSB C 28618、YSB C 26605)中铅、砷、钛、铜、镍、钙、镁、铝,结果与认定值相吻合。     

Lactate Transport in Soil by DC Fields

Electrokinetic injection of lactate, a negatively charged biodegradable organic, in homogeneous soils is evaluated. Net lactate migration rate on the order of 5?cm2/V?day is measured in sand from cathode towards the anode. The ionic injection in sand was dependent on current density; however, the increase in electric current did not result in an equivalent increase in lactate transport due to development of an appreciable electroosmotic (EO) flow from the anode to the cathode. While high EO flow (ke on the order 10?6 to 10?5?cm2/V?s) occurred in clay samples, ion migration from cathode to anode is the dominant transport process under relatively high current density (5.3?A/m2 in this study) and can be used as an effective transport mechanism for negatively charged additives. An effective lactate reactive transport rate of more than 3?cm/d (under 1?V/cm) can be achieved in clays, which is at least two orders of magnitude greater than hydraulic injection under unit hydraulic gradient. Even though lactate concentrations in the clay were below 10% of the boundary value due to biological transformation, these concentrations (few 100?s?mg/L) are high enough to maintain microbial activities capable of degrading organic contaminants. At the same time, control experiments showed that, while lactate adsorption was negligible, hydraulic injection under a unit gradient was ineffective because of the low hydraulic conductivity of clay and the biodegradation of lactate.     

Predicting Solute Flux through a Clay Membrane Barrier

Measured solute flux breakthrough curves (FBCs) from column tests performed on a semipermeable clay membrane subjected to KCl solutions are compared with predicted FBCs using independently measured flow and transport properties. The predicted FBCs are based on three scenarios: (1) Advective–dispersive transport that neglects membrane behavior; (2) advective–dispersive transport that accounts for the concentration dependency of the effective salt-diffusion coefficient (Ds?) resulting from membrane behavior, referred to as partially coupled transport; and (3) fully coupled transport that includes both the explicit coupling terms (e.g., hyperfiltration, chemico-osmosis) associated with clay membrane behavior and the concentration dependency of Ds?. The FBCs predicted by fully coupled transport agree best with the measured FBCs. However, for the diffusion-controlled conditions of the column tests, the steady-state solute fluxes predicted by partially coupled transport are only 23–69% higher than the measured steady-state fluxes. The results imply that the advective–dispersive transport theory can be used to provide reasonably accurate, albeit somewhat conservative, estimates of steady-state solute flux through clays that behave as semipermeable membranes, provided diffusion is a significant, if not dominant, solute transport process and the concentration dependency of Ds? are taken into account.     

熔融制样-X射线荧光光谱法测定锰铁和金属锰中锰硅磷

为了解决锰铁、金属锰等合金试样玻璃熔融制片时侵蚀铂黄坩埚的难题,实验采用四硼酸锂-碳酸锂混合熔剂、五氧化二钒氧化剂在石墨垫底瓷坩埚中高温预氧化熔融,有效避免了熔融制样过程中铂金坩埚腐蚀的问题,建立了X射线荧光光谱法(XRF)测定锰铁、金属锰中锰、硅、磷的分析方法。讨论了预氧化熔融的熔剂体系及氧化方法、试样与熔剂的稀释比,结果表明,试样与四硼酸锂-碳酸锂混合熔剂以1∶45的稀释比、以0.5mL200g/L溴化锂溶液为脱模剂,在1120℃熔融制得的玻璃片均匀、透亮、无气泡,符合测定要求。精密度和正确度试验结果显示,各元素测定结果的相对标准偏差(RSD,n=10)在0.10%~0.96%之间,结果与锰铁标准物质、金属锰内控标样认定值(参考值)相符,完全满足常规分析要求。     

基于场放大进样-电动反平衡扫集的毛细管电泳富集分离系统的研究及其在铁矿石检测中的应用

利用EDTA作为捕获载体,结合场放大进样技术,建立了一种基于场放大进样-电动反平衡扫集在线双重富集的毛细管电泳富集分离新体系并用于铁矿石中锰、铬、铅、铜、镍和钴6种重金属元素的检测。金属离子首先通过场放大进样堆积在水塞与高电导缓冲溶液的界面上,然后被迎面而来的带负电荷的EDTA捕获,样品区带被进一步压缩,实现信号的双重放大。通过控制电渗流使金属-EDTA螯合物处于准静止状态,实现大体积进样及检测信号的高度放大。通过15 kV电动进样50 min双重富集后,灵敏度比常规毛细管电泳提高了1.2×10⁴～8.5×10⁴倍,铁矿石中6种重金属离子的检出限为0.06~0.32 μg/L。用建立的方法测定铁矿石中锰、铬、铅、铜、镍和钴,测定值与ICP-MS法测定值之间的相对误差在5.3%～11.5%之间。     

离子交换分离-电感耦合等离子体原子发射光谱法测定锰矿中铊

锰矿用盐酸、硝酸、氢氟酸和高氯酸溶解,以氢氧化钠溶液调整试液酸度至pH 1.7～2.0,用溴水氧化Tl 为Tl,过D401离子交换树脂柱,经0.015 mol/L硝酸淋洗后,用2 mL 3 g/L亚硫酸溶液还原柱上的Tl为Tl,再用0.015 mol/L硝酸洗出Tl,选择Tl 190.857 nm为分析谱线,电感耦合等离子体原子发射光谱法(ICP-AES)测定分离后溶液中的铊。方法中铊的检出限为1 ng/mL,测定下限为0.8 μg/g。干扰试验结果表明,测定0.1 μg/mL铊,不大于50 μg/mL铁、2 μg/mL锰、10 μg/mL铝、镉、铬、镍、铅、锌不干扰。一般锰矿样品按实验方法分离和测定,铁、锰、铝、镉、铬、镍、铅、锌不影响铊的测定。按照实验方法测定锰矿样品中的铊,测定结果的相对标准偏差(RSD,n=8)在1.6%～11%之间,加标回收率为90%～108%。     

Impaired cortisol binding to glucocorticoid receptors in hypertensive patients

We compared glucocorticoid receptor binding characteristics and glucocorticoid responsiveness of human mononuclear leukocytes (HML) from hypertensive patients and matched normotensive volunteers. We also considered associations of these variables with plasma renin activity, aldosterone, cortisol, corticotropin, and electrolyte concentrations. We calculated binding affinity (Kd; nmol/L) and capacity (Bmax; sites/cell) for dexamethasone and cortisol from homologous and heterologous competition curves for specific [3H]dexamethasone binding sites on HML isolated from the blood of normotensive volunteers and subjects with essential hypertension. Glucocorticoid responsiveness of HML was evaluated as IC50 values (nmol/L) for dexamethasone and cortisol for the inhibition of lysozyme release. We measured plasma hormones by radioimmunoassay. Kd values (mean+/-SE) for cortisol in HML of hypertensive patients were higher than in control subjects (24.6+/-2.4 versus 17.5+/-1.7 nmol/L, P<.04). Binding capacity (4978+/-391 versus 4131+/-321 sites/cell), Kd values for dexamethasone (6.7+/-0.5 versus 5.7+/-0.3 nmol/L), and IC50 values for dexamethasone (3.4+/-0.3 versus 3.1+/-0.2 nmol/L) and cortisol (12.2+/-1.6 versus 9.5+/-0.3 nmol/L) were not significantly different. Patients with renin values less than 0.13 ng angiotensin I/L per second were markedly less sensitive to cortisol than those with higher values. Both Kd (30.3+/-2.5 versus 19.2+/-2.4 nmol/L) and IC50 values (15.5+/-1.8 versus 8.9+/-1.2 nmol/L) for cortisol were significantly higher in patients with lower renin values (P<.03). Other variables, including plasma hormone and electrolyte values and binding characteristics for dexamethasone, were not different. These data suggest that cortisol binding to glucocorticoid receptor is slightly impaired in patients with essential hypertension. In vivo, this could lead to inappropriate binding of cortisol to mineralocorticoid receptors. Hence, decreased sensitivity to cortisol is associated with renin suppression. This hypothesis is supported by evidence of hypertension and low renin activity, which others have described in patients with primary glucocorticoid resistance due to mutations of the glucocorticoid receptor.     

Influence of Strength Anisotropy on Piezocone Resistance in Clay

Since different undrained shear strengths may be obtained from different laboratory or field tests, different cone factors are needed to calculate the undrained shear strengths from the results of a piezocone test in clay. Based on the anisotropic undrained shear strength criterion, a set of cone factors for calculating undrained shear strength is proposed in this paper. These cone factors are interrelated with each other in terms of the strength anisotropy ratio of the clay. The suitability of the proposed cone factors has been verified using the test results generated from different tests and from clays with different origins. By comparing with the cone factor for isotropic clay, it was found that the effect of strength anisotropy on the cone factor is not always significant. In fact, the effect of strength anisotropy becomes significant only in lightly overconsolidated to normally consolidated clay with moderate to high strength anisotropy. Furthermore, the maximum difference in cone factor is not expected to exceed 20% with or without taking into account the strength anisotropy of clay.     

Analysis of Factors Influencing Soil Classification Using Normalized Piezocone Tip Resistance and Pore Pressure Parameters

This paper discusses the development of a framework for classifying soil using normalized piezocone test (CPTU) data from the corrected tip resistance (qt) and penetration pore-water pressure at the shoulder (u2). Parametric studies for normalized cone tip resistance (Q = qcnet/σv0′) and normalized excess pressures (Δu2/σv0′) as a function of overconsolidation ratio (OCR = σvy′/σv0′) during undrained penetration are combined with piezocone data from clay sites, as well as results from relatively uniform thick deposits of sands, silts, and varietal clays from around the globe. The study focuses on separating the influence of yield stress ratio from that of partial consolidation on normalized CPTU parameters, which both tend to increase Q and decrease the pore pressure parameter (Bq = Δu2/qcnet). The resulting recommended classification chart is significantly different from existing charts, and implies that assessment of data in Q–Δu2/σv0′ space is superior to Q–Bq space when evaluating piezocone data for a range of soil types. Still, there are zones of overlap for silty soils and heavily overconsolidated clays, thus requiring that supplementary information to Q and Δu2/σv0′ be obtained in unfamiliar geologies, including variable rate penetration tests, dissipation tests, CPT friction ratio, or soil sampling.