Study of thermally immobilized Cu in analogue minerals of contaminated soils

Thermal immobilization of copper contaminants in soil analogue minerals, quartz and kaolin, at low temperatures such as 300 degrees C is studied to corroborate its technical feasibility as a method for soil remediation. We use a synchrotron-based, X-ray absorption spectroscopy (XAS) technique to study the speciation of and the local structure around copper in the soil analogues that are thermally treated at 300-900 degrees C for 1 h. The toxicity characteristic leaching procedure (TCLP) method is employed to investigate the leaching behavior of copper compounds. CuO, being predominately transformed from Cu(OH)2 with a lesser amount from Cu(NO3)2 by 1-h heat application at 300-900 degrees C, is identified by the spectroscopy of X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) as the key species that is leaching-resistant due to its low solubility and its chemisorption onto the soil analogue minerals. Fourier transform of EXAFS spectrum of the Cu-doped kaolin heated at 900 degrees C for 1 h indicates that the intensity of Cu-Cu peaks (2.50 and 5.48 A, both without phase shift correction) is either relatively smaller or disappearing as compared with that of kaolin samples heated at 300 and 500 degrees C. The EXAFS analysis suggests that the Cu solid phase in the 900 degrees C kaolin sample is different from the lower temperature samples, the 900 degrees C SiO2 sample, and the Cu standards. The leaching studies also support the formation of a less soluble phase in the 900 degrees C kaolin sample. An increase of heating temperature, in the range of 105-900 degrees C, reduces the Cu leaching percentage; this reduction trend is more marked for Cu-doped kaolin than for Cu-doped SiO2.     

Surface complexation of copper(II) on soil particles: EPR and XAFS studies

The interactions of transition metals with natural systems play an important role in the mobility and the bioavailability of these metals in soils. In this study, the adsorption of copper(II) onto natural soil particles was studied as a function of pH and metal concentration. The retention capacity of soil particles was determined at pH 6.2 to be equal to 6.7 mg of copper/g of solid. The Langmuir and Freundlich isotherm equations were then used to describe the partitioning behavior of the system at different pH values. A combination of EPR, extended X-ray absorption fine structure (EXAFS), and X-ray absorption near-edge structure (XANES) spectroscopies was used to probe the Cu atomic environment at the soil particles/aqueous interface. The spectroscopic study revealed that copper(II) ions are held in inner-sphere surface complexes. It also revealed that Cu was in an octahedral coordination with first-shell oxygen atoms. A weak tetragonal distortion was pointed out due to the Jahn-Teller effect, with a mean Cu-Oequatorial bond distance of 1.96 A and a Cu-Oaxial bond distance of 2.06 A. A detailed analysis of the spectroscopic data suggested that Cu(II) was bonded to organic matter coated onto the mineral fraction of soil particles.     

Spectroscopic study of copper(II)--wheat straw cell wall residue surface complexes

The sorption of copper(II) by wheat straw cell wall residue (CWR) was studied and revealed a relatively stable surface complexation on the acid sites of the substrate (carboxylic and phenolic moieties). The copper binding capacity at pH = 5.75 and ionic strength of 0.1 M was evaluated at 63 micromol x g(-1) CWR. The Langmuir and Freundlich isotherm equations were then used to describe the partitioning behavior for the system at different pH values. Batch experiments have been achieved in the presence of calcium in order to mimic the calcareous soil of the Champagne region. A competitive effect on copper complexation has been shown, which is presumably due to the calcium ability to form outer-sphere complexes far less stable than copper(II) ones. Electron spin resonance and X-ray absorption spectroscopy were combined to obtain information on the geometry and structure of Cu bound to CWR. At least two different binding sites for Cu2+ were found to take place in CWR. From ESR parameters, we deduced that copper(II) ions, when complexed with CWR, are coordinated in a square-planar arrangement with four oxygen-containing groups. EXAFS and XANES experiments revealed that Cu(II) is surrounded by four oxygen atoms, with an average Cu-O equatorial distance equal to 1.94 A.     

微波消解-连续光源原子吸收法快速顺序测定枸杞果中的6种金属元素

建立一种微波消解-连续光源原子吸收法快速测定枸杞果中金属元素的新方法。通过微波消解快速处理样品,用连续光源原子吸收法同时顺序测定枸杞果中的铁、锌、铜、锰、镉、铅6种金属元素,并对仪器使用条件、金属元素含量、精密度、检出限、回收率等进行研究。结果表明：方法检出限为0.006070～0.04975μg/L,RSD为1.5%～5.0%,回收率为86.68%～111.7%。该法用于枸杞中6种金属元素的同时顺序测定,具有快速、简便、成本低廉等特点,分析结果令人满意。     

X-ray spectroscopic studies of the high temperature reduction of Cu(II)O by 2-chlorophenol on a simulated fly ash surface

The reaction of 2-chlorophenol on Cu(II)O at 375 degrees C is studied using X-ray absorption near edge structure (XANES) spectroscopy. A mixture of copper(II) oxide and silica is prepared to serve as a surrogate for fly ash in combustion systems. 2-Chlorophenol is utilized as a model precursor for formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F). The Cu K-edge spectra shiftto lower binding energy, reflecting the reduction of the copper. The substrate is found to form a mixture of Cu(II), Cu(I), and Cu(O), with the dominant species being Cu(I). The data are fitted well with a first-order reaction scheme, with a time constant at 375 degrees C of 76 s. This is the first application of XANES spectroscopy for studying the kinetics and mechanism of heterogeneous reactions relevant to combustion processes, and the results demonstrate the utility and desirability of such X-ray spectroscopic studies.     

EXAFS analysis of arsenite adsorption onto two-line ferrihydrite, hematite, goethite, and lepidocrocite

The modes of As(III) sorption onto two-line ferrihydrite (Fh), hematite (Hm), goethite (Gt), and lepidocrocite (Lp) have been investigated under anoxic condition using X-ray absorption spectroscopy (XAS). X-ray absorption near-edge structure spectroscopy (XANES) indicates that the absence of oxygen minimized As(III) oxidation due to Fenton reactions. Extended X-ray absorption fine structure spectroscopy (EXAFS) indicates thatAs(III)forms similar inner-sphere surface complexes on two-line ferrihydrite and hematite that differ from those formed on goethite and lepidocrocite. At high surface coverage, the dominant complex types on Fh and Hm are bidentate mononuclear edge-sharing (2E) and bidentate binuclear corner-sharing (2C), with As-Fe distances of 2.90 +/- 0.05 and 3.35 +/- 0.05 A, respectively. The same surface complexes are observed for ferrihydrite at low surface coverage. In contrast, As(III) forms dominantly bidentate binuclear corner-sharing (2C) sorption complexes on Gt and Lp [d(As-Fe) = 3.3-3.4 A], with a minor amount of monodentate mononuclear corner-sharing (1V) complexes [d(As-Fe) = 3.5-3.6 A]. Bidentate mononuclear edge-sharing (2E) complexes are virtually absent in Gt and Lp at the high surface coverages that were investigated in the present study. These results are compared with available literature data and discussed in terms of the reactivity of iron(III) (oxyhydr)oxide surface sites.     

Extraction of nanosize copper pollutants with an ionic liquid

Speciation and possible reaction paths of nanosize copper pollutants extracted with a RTIL (room-temperature ionic liquid ([C4mim][PF6], 1-butyl-3-methylimidazolium hexafluorophosphate)) have been studied in the present work. Experimentally, in a very short contact time (2 min), 80-95% of nanosize CuO as well as other forms of copper (such as nanosize Cu, Cu2+, or Cu(II)(ads) (in the channels of MCM-41)) in the samples could be extracted into the RTIL. The main copper species extracted in the RTIL as observed by XANES (X-ray absorption near edge structure) were Cu(II). Existence of Cu-N bondings with coordination numbers (CNs) of 3-4 for copper extracted in the RTIL was found by EXAFS (extended X-ray absorption fine structural) spectroscopy. Interestingly, chelation of Cu(II) with 1-methylimidazole (MIm) in the RTIL during extraction was also observed by 1H NMR (nuclear magnetic resonance). At least two possible reaction paths for the rapid extraction of nanosize copper pollutants with the RTIL might occur: (1) an enhanced dissolution of nanosize CuO (to form Cu2+) and (2) formation of [Cu(MIm)4(H2O)2]2+ that acted as a carrier of copper into the RTIL matrix.     

Microprobe techniques for speciation analysis and geochemical characterization of mine environments: the mercury district of Almadén in Spain

Metallurgic calcines with very high mercury and methylmercury content from the Almadén mining district were analyzed by synchrotron-based microprobe techniques. Information about mercury speciation was obtained by micro-EXAFS (microscopic extended X-ray absorption fine structure) spectroscopy, whereas elemental associations were evaluated by micro-XRF (microscopic X-ray fluorescence analysis) mapping. Complementary characterization methodologies, including X-ray diffraction (XRD), inductively coupled plasma-optical spectroscopy (ICP-OES), as well as a sequential extraction scheme (SES), were used to predict the potential availability of mercury. Analysis of total metal content revealed extremely high concentrations of mercury and iron (between 7 and 35 and 65-70 g kg(-1), respectively) and high zinc concentrations (2.2-2.5 g kg(-1)), whereas other metals such as copper, nickel, and lead were found at low concentration levels (30-300 mg kg(-1)). Micro-EXAFS results indicate that cinnabar (HgS(red)) is one of the main species within the studied mercury-rich particles (5-89% of total mercury content), together with more soluble mercury compounds such as Hg3(SO4)02 (schuetteite) and HgO (5-55% of total mercury content). Additionally, element-specific micro-XRF maps of selected mercury-rich particles in the studied samples revealed an evident correlation among Hg-Pb-Ni (and S), indicating a possible geochemical linkage of these elements. Correlations were also found among Fe-Mn and Hg, which have been attributed to sorption of mercury onto oxyhydroxides of Fe and Mn. This finding was supported by results from a sequential extraction scheme, where a significant     

Determination of Cd,Co, Cu,Fe, Pb,Mn, Ni and Zn in diets: Development of a method

A method useful for the determination of cadmium, cobalt, copper, iron, lead, manganese, nickel and zinc in diets is described. Organic matter is destroyed applying a wet procedure, and element content is measured by flame atomic absorption spectroscopy (FAAS) in the case of copper, iron, manganese, nickel and zinc, and by graphite furnace (GF-AAS) in the case of cadmium, cobalt and lead. The matrix interference study is carried out. Values found for linearity, detection and quantitation limits as well as accuracy show that the described method is useful to determine the elements taken into account at usual levels in diets.     

Determination of Cd, Co, Cu, Fe, Pb, Mn, Ni and Zn in diets: development of a method.

A method useful for the determination of cadmium, cobalt, copper, iron, lead, manganese, nickel and zinc in diets is described. Organic matter is destroyed applying a wet procedure, and element content is measured by flame atomic absorption spectroscopy (FAAS) in the case of copper, iron, manganese, nickel and zinc, and by graphite furnace (GF-AAS) in the case of cadmium, cobalt and lead. The matrix interference study is carried out. Values found for linearity, detection and quantitation limits as well as accuracy show that the described method is useful to determine the elements taken into account at usual levels in diets.     

废弃羽毛的结构特征及其吸声性能

为对废弃羽毛资源进行合理化利用,借助多功能纤维投影仪、扫描电子显微镜、傅里叶变换红外光谱仪和X射线衍射仪分析了羽毛的大分子结构、聚集态结构及其形态结构,探究了羽毛结构与其吸声性能之间的关系。采用声阻抗传递函数法对羽毛及其他几种可用于吸声领域的纤维集合体进行吸声性能测试及对比。结果表明:几种纤维集合体吸声性能排序为废弃羽毛、木棉纤维、羊毛、大麻纤维、涤纶;在整个测试频率范围内废弃羽毛的吸声性能随纤维集合体密度的增加而提高,且纤维集合体最大吸声系数对应的吸声频率随纤维集合体密度的增加逐渐降低;废弃羽毛纤维具有优良的吸声性能,在吸声领域具有很高的应用价值。     

Studies on the static and dynamic properties of different types of polyester industrial yarns

Four major types of polyester industrial yarns, viz. high tenacity (HT), high modulus low shrinkage (HMLS), low shrinkage (LS) and super low shrinkage (SLS) polyester yarns, were studied for their static and dynamic properties. An attempt has been made to establish a linkage between static and dynamic properties of these yarns with its structure and with its end applications. HMLS and HT polyester yarns have lower tan δ and work loss, which are the desired characteristics required for its end applications which include tire and conveyer belt. Higher overall orientation and higher fraction of tie molecules helped to achieve these properties in HT and HMLS polyester yarns. LS and SLS polyester yarns are mostly used for static applications. Low thermal shrinkage is the key requirement for the downstream processes of these yarns. Lower amorphous orientation in these two yarns is primarily responsible for achieving very low thermal shrinkage. A good co-relation has been established between the peak temperature of work loss (in slow speed hysteresis test) and the peak temperature of tan δ (in high-speed dynamic test).     

胶原蛋白-壳聚糖-聚乙烯吡咯烷酮共混膜的结构及性能

利用溶液共混法成功制备了新型生物膜材料--胶原蛋白-壳聚糖-聚乙烯吡咯烷酮共混膜,通过红外光谱、X-射线衍射和透光率测试表征了共混膜的结构,同时测定了共混膜的力学性能,考察了溶液pH值对共混膜吸水率的影响.结果表明共混膜中胶原蛋白、壳聚糖和聚乙烯吡咯烷酮三者具有较强的相互作用和良好的相容性.共混膜具有良好的力学性能,一定pH敏感性,作为一种潜在的生物材料可望在生物医学领域得到应用.     

Structure–property relationship of different types of polyester industrial yarns

Four major types of polyester industrial yarns (1000 Denier) which are used commercially were studied for their key structural parameters. An attempt has been made to establish a relationship between morphology and properties of these yarns. High tenacity (HT) polyester yarn has the highest birefringence, amorphous orientation, and long period but is relatively less crystalline. High shrinkage characteristic of HT polyester yarn can be accounted for its higher amorphous orientation. High modulus low shrinkage (HMLS) polyester yarn has higher crystallinity and crystal size compared to HT yarn. Fraction of tie molecules of these yarns has been calculated and found that low shrinkage (LS) and super low shrinkage (SLS) yarns have lesser tie molecules. These LS and SLS yarns are tailor-made to achieve lower shrinkage and at the same time maintaining a good level of tenacity. This is achieved with lower amorphous orientation in the final drawn yarn structure. Amorphous orientation was found to have stronger influence than any other structural parameter on the key yarn properties like modulus, tenacity, elongation, and shrinkage.     

Toxic trace metals in food. II. A comparative study of the levels of toxic trace metals in wine by differential pulse anodic stripping voltammetry and electrothermal atomic absorption spectrometry.

A new high-performance analytical procedure for the determination of the toxic trace metals cadmium, lead and copper in wines by differential pulse anodic-stripping voltammetry (DPASV) subsequent to UV irradiation of the sample is compared with the hitherto more common application of electrothermal atomic absorption spectrometry (AAS). In this manner also mutually the accuracy attainable with both alternatives has been established. The particularly favourable potentialities of the new voltammetric approach for toxic metal control of wines are demonstrated by the investigation of a typical selection of 36 wines from recent vintages and common vine types of the German and some European wine cultivating regions.     

同位镀汞阳极溶出伏安法测定牛奶中镉、铅、铜

建立阳极溶出伏安法同时快速测定牛奶中的镉、铅和铜元素的方法。利用同位镀汞阳极溶出伏安法对 牛奶样品中镉、铅和铜元素含量进行同时测定,并对测试条件进行优化。镉、铅和铜元素峰电位分别为－0.70、 －0.52、－0.08 V;线性范围分别为0.1～40、1～80、0.5～100 μg/L;检测限为0.06、0.3、0.1 μg/L。采用该方法测 定了牛奶样品中的镉、铅和铜含量,加标回收率分别为99.57%、101.3%、98.00%,相对标准偏差（n=5）分别为 4.0%、2.9%、2.7%,将测定结果与原子吸收光谱法检测结果对比,两者无显著性差异(P＞0.05）。结果表明该方法 快速、简单、准确,可用于牛奶中镉、铅和铜元素的同时检测。     

Interfacial interactions between Np(V) and manganese oxide minerals manganite and hausmannite

Manganese oxides, present as minor phases in the vadose zone, have been previously shown to sequester large quantities of plutonium under environmental conditions. We are now continuing these studies with Np(V). Sorption onto manganite (MnOOH) and hausmannite (Mn3O4) at solid-to-solution ratios of 2.5-3.3 mg/mL has been studied as a function of neptunium concentration and pH. The sorption of Np increased as a function of pH for both minerals, attaining a maximum at neutral pH, and then decreased with increasing alkalinity. X-ray absorption fine structure spectroscopy (XAFS), taken at the Np L(III)-edge, has been used to determine the oxidation state of the sorbed Np. Our experimental results indicate reduction of the Np(V) because of interaction with the X-ray beam. These findings significantly impact the interpretation of results reported elsewhere on Np(V) investigated though the use of high-intensity X-ray beams.     

某口服液对染铅小鼠体内铅、铜、锌含量的影响

为观察以金属硫蛋白为主要成分的某口服液对小鼠体内铅、锌、铜含量的影响 ,小鼠自由饮用Pb2 浓度为 5 46 2mg L的水溶液 ,低、中、高剂量组分别灌胃给予 1 6 7、3 34、10 0mL kgBW 受试液 ,模型对照组给予去离子水灌胃 ,阴性对照组饮用、灌胃均给予去离子水。连续 30d后 ,采血 ,取肝、脑、肾、股骨 ,用火焰原子吸收分光光度法测定铅、锌、铜含量。 3个剂量组与模型组小鼠铅摄入剂量大致相当 ,但全血铅水平显著低于模型组 ,10 0mL kgBW 剂量还使肝组织铅含量显著降低 ,使股骨铜含量显著升高 ,对小鼠全血和其它组织内锌、铜含量无不良影响。     

电位溶出法同时测定茶叶中的铅、铜

目前测定食品中铅、铜常用原子吸收法.本文提出用电位溶出法同时测定茶叶中的铅、铜.该方法仪器设备简单,容易普及推广,它通过电积富集,把低浓度的离子富集,提高了灵敏度.样品经过湿法消化,适当稀释可直接测定,本法可同时测定茶叶中的铅、铜含量,方法简单、快速、灵敏度高、重现性好,具有很好的实用性.     

Test method for lead in metal utensils for food contact use

We compared test methods for measurement of lead in metal utensils using flame-atomic absorption spectroscopy (AAS), graphite furnace-AAS (GFAA), inductively coupled plasma atomic emission spectrometry (ICP) and X-ray fluorescence analysis (XRF). The procedure for preparation of the test solution was improved. A 100 mg of sample was dissolved in 2.5 mL of HCl and HNO(3) (3 : 1) mixture (in the case of titanium sample, dissolved in HCl). Stock solution was prepared by diluting to 50 mL with water. The test solution was prepared by diluting with 0.1 mol/L HNO(3). The recoveries of lead added to various kinds of metal reagent at the level of 0.1% were 90-118%. When standard materials which contained lead at the level of 0.0098-0.11% were measured, the measured values were in close agreement with the standard values. These procedures are applicable to aluminum, iron, stainless steel, copper, tin and titanium products. The AAS method, GFAA method and ICP method were suitable as the lead test methods. Moreover, the XRF method was useful as a screening method or a simple determination method. The ICP method was used to determine the lead contents in 22 kinds of commercial metal utensils, and 0.011-0.040% of lead were detected in 6 samples.