A new FEBIAD-type ion source for use at the reactor-based ISOL facility TRISTAN

To use a FEBIAD-type ion source at a reactor-based on-line isotope separator facility, several modifications are desirable. Since more beam time is usually available at a reactor than at an accelerator, most of the changes to the ion source were those that make it possible to extend the source lifetime. The modifications described in this paper make it possible to operate a FEBIAD ion source for 1500 continuous hours without a failure. Beams of Zn, Ga, Ge, Br, Kr, Rb, Ag, Cd, In, Sn, Sb, Te, I, Xe, and Cs were obtained from the source and yields are presented for some of these elements. The effect of target outgassing on the operating conditions of the source are discussed and a Penning-ionization mode of operation is postulated.     

Long-term leaching from MSWI air-pollution-control residues: leaching characterization and modeling

Long-term leaching of Ca, Fe, Mg, K, Na, S, Al, As, Ba, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Zn, Mo, Sb, Si, Sn, Sr, Ti, V, P, Cl, and dissolved organic carbon from two different municipal solid waste incineration (MSWI) air-pollution-control residues was monitored during 24 months of column percolation experiments; liquid-to-solid (L/S) ratios of 200-250L/kg corresponding to more than 10,000 years in a conventional landfill were reached. Less than 2% of the initially present As, Cu, Pb, Zn, Cr, and Sb had leached during the course of the experiments. Concentrations of Cd, Fe, Mg, Hg, Mn, Ni, Co, Sn, Ti, and P were generally bellow 1microg/L; overall less than 1% of their mass leached. Column leaching data were further used in a two-step geochemical modeling in PHREEQC in order to (i) identify solubility controlling minerals and (ii) evaluate their interactions in a water-percolated column system over L/S of 250L/kg. Adequate predictions of pH, alkalinity, and the leaching of Ca, S, Al, Si, Ba, and Zn were obtained in a simultaneous calculation. Also, it was suggested that removal of Ca and S together with depletion of several minerals apparently caused dissolution of ettringite-like phases. In turn, significant increase in leaching of oxyanions (especially Sb and Cr) was observed at late stage of leaching experiments.     

The role of iron in hexavalent chromium reduction by municipal landfill leachate

The function of iron (ferric (Fe(III)) and ferrous (Fe(II))) in the hexavalent chromium (Cr(VI)) reduction mechanism by bacteria in municipal landfill leachate (MLL) was assessed. Evidence of an "electron shuttle" mechanism was observed, whereby the Cr(VI) was reduced to trivalent chromium (Cr(III)) by Fe(II) with the resulting Fe(III) bacterially re-reduced to Fe(II). Typically, investigations on this electron shuttle mechanism have been performed in an artificial medium. As MLL comprises an elaborate mixture of bacteria, humic materials and organic and inorganic species, additional complexities were evident within the cycle in this study. Bioavailability of the Fe(III) for bacterial reduction, availability of bacterially produced Fe(II) for chemical Cr(VI) reduction and hydrolysis of Fe(II) and Fe(III) become prevalent during each phase of the shuttle cycle when MLL is present. Each of these factors contributes to the overall rate of bacterial Cr(VI) reduction in this media. This work highlights the need to consider local environmental conditions when assessing the bacterial reduction of Cr(VI).     

Trace elements partitioning during co-firing biomass with lignite in a pilot-scale fluidized bed combustor

This study describes the partitioning of 18 trace elements (As, Ba, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, P, Pb, Sb, Se, Sn, Tl, V, Zn) and 9 major and minor elements (Al, Ca, Fe, K, Mg, Na, S, Si, Ti) during co-firing of olive residue, hazelnut shell and cotton residue with high sulfur and ash content lignite in 0.3 MW(t) Middle East Technical University (METU) Atmospheric Bubbling Fluidized Bed Combustor (ABFBC) test rig with limestone addition. Concentrations of trace elements in coal, biomass, limestone, bottom ash, cyclone ash and filter ash were determined by inductively coupled plasma optical emission and mass spectroscopy (ICP-OES and ICP-MS). Partitioning of major and minor elements are influenced by the ash split between the bottom ash and fly ash and that the major proportion of most of the trace elements (As, Ba, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Tl, V and Zn) are recovered in fly ash when firing lignite only. Co-firing lignite with biomass enhances partitioning of these elements to fly ash. Co-firing also shifts the partitioning of Cd, P, Sb and Sn from bottom to fly ash.     

Determination of various constituent elements of polyethylene terephthalate bottles used for beverages in Japan

Polyethylene terephthalate (PET) bottles are some of the most commonly used containers for beverages. During the manufacturing process of PET resin in Japan, metallic catalysts such as Sb and Ge are widely used, with other metals or metallic compounds also being employed to improve the quality of PET bottles. However, few reports into the contents of such elements exist. Thus, we herein report the concentrations of 34 elements (ie, Li, B, Na, Mg, Al, P, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Zr, Mo, Ag, Cd, Sn, Sb, Cs, Ba, W, Pb, and U) in 16 samples of unused virgin PET bottles for beverages. The measurement was performed by inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS), and these bottles were found to contain five main elements (ie, <0.5- to 50-mg/kg Ge, <1- to 26-mg/kg Ti, <0.1- to 279-mg/kg Sb, <10- to 48-mg/kg P, and <0.5- to 53-mg/kg Co) that were used as polymerisation catalysts, stabilisers, oxidation catalysts, and bluing agents. Furthermore, when these residual element concentrations in 21 commercial mineral-water PET bottles were determined, there was no significant difference from unused bottles.     

空心阴极光谱法分析铁镍基高温合金杂质

采用ＨＣＤ－Ⅰ型空心阴极光源作为发射光谱的激发光源,以一套Ｋ３镍合金基标准做工艺曲线来分析铁镍基高温合金中的微量杂质元素砷,磅、锑、铅、锡、铊和银。该方法简便快速,并上有较低的检出限,较好的准确度和精密度。     

Investigation of the transport and fate of Pb, Cd, Cr(VI) and As(V) in soil zones derived from moderately contaminated farmland in Northeast, China

Some farmland in Shenyang had been irrigated with industrial wastewater since 1962. Although wastewater irrigation was ceased in 1992, soil had been heavily polluted by heavy metals, especially by Cd. For better understanding processes of soil-heavy metal interactions, in particular, the mobility and retention mechanism of heavy metal in soil, a study on the transport and fate of heavy metals in soil zones from Shenyang suburb was carried out by column leaching tests in laboratory. Breakthrough curves of Pb, Cd, Cr(VI) and As(V) fitted by Thomas model and Yoon–Nelson model. The results of fitted breakthrough curves showed that transport rates of the four heavy metals in the soil zones followed the order: Cr(VI) > As(V) > Cd > Pb, which indicated that Cr(VI) was much more mobile, and Pb was comparatively unmovable. Cr in effluents and As were almost entirely Cr(VI) and As(V), respectively, and no Cr(III) and As(III) was ever detected during the leaching tests. The contents of Pb, Cd, Cr and As in leached soils decreased in the order of Pb > Cd > Cr > As, which suggested that adsorption ability of soil to Pb was greatest and to As was least. The methods of selective sequential extraction and solvent extraction were used to determine the fractions of Pb, Cd, Cr, As and the valent states of Cr, As [Cr(VI) or Cr(III), As(V) or As(III)] in original soils and in leached soils. After leaching tests, the relative and absolute concentrations of exchangeable, carbonate, Fe–Mn oxide and organic fraction of each element were all increased, which enhanced the potential mobility and risk of Pb, Cd, Cr and As to soil/groundwater system. The relative concentrations of Cr(III) and As(III) in different depth of the soil zones after leaching tests were increased by about 6.0% and 5.6%, respectively. Cr(III) and As(III) tended to be adsorbed by soils, which reduced the mobility of them into groundwater.     

Vapor generation by UV irradiation for sample introduction with atomic spectrometry

Volatile species of the conventional hydride-forming elements (As, Bi, Sb, Se, Sn, Pb, Cd, Te), Hg, transition metals (Ni, Co, Cu, Fe), noble metals (Ag, Au, Rh, Pd, Pt), and nonmetals (I, S) were generated following UV irradiation of their aqueous solutions to which low molecular weight carboxylic acids (formic, acetic, propionic) had been added. Free radicals arising from photodissociation of the latter provide a new and useful alternative to the common methods of chemical/electrochemical vapor generation techniques for the determination of these analytes by atomic spectrometry. Quantitative estimates of the efficiencies of these generation processes were not undertaken, although calculated signal-to-background ratios (>1500 for 5 ng/mL As, Sb, Bi, Se, and Te; 20 for 10 ng/mL Sn, Cu, Rh, Au, Pd, Pt, and Cd; 2400 for 1 ng/mL Hg; and 1000 for Co using ICP-TOF-MS detection) do provide clear evidence of the efficacy of this approach for sample introduction. In the case of Ni and Se, the tetracarbonyl and alkylated selenium compounds have been identified, respectively.     

The comprehensive investigation on removal mechanism of Cr(VI) by humic acid-Fe(II) system structured on V,Ti-bearing magnetite surface

The Cr(VI) could be adsorbed and reduced by the humic acid (HA)-Fe(II) system structured on the V, Ti-magnetite (VTM) surface. The Cr(VI) removal process included adsorption and reduction stages. First, the Cr(VI) was adsorbed on the VTM-HA surface via the ionic bonds between the Ti atoms of VTM core and the O atoms of the HCrO₄^?. The adsorption of Cr(VI) is uniform, monolayer, and controlled by Cr(VI) diffusion. Subsequently, the adsorbed Cr(VI) was reduced by the HA-Fe(II) system on the VTM-HA surface. During the Cr(VI) reduction process, the HA and Fe(II) have a synergistic effect. The Cr(VI) was reduced to the Cr(III) by the HA and Fe(II). Meanwhile, the HA could also reduce Fe(III) to Fe(II), making Fe(II) continue to participate in the Cr(VI) reduction. The olefin, hydroxyl, and aldehyde groups of HA were the primary electron donors during the Cr(VI) reduction. The Fe(II) acted as an electron bridge, transferring the electron from HA to Cr(VI). The reduced Cr(III) was deposited on the VTM-HA surface via the complexation with the carboxyl and hydroxyl groups of HA. The results demonstrated that the Cr(VI) could be adsorbed, reduced and complexed by the HA-Fe(II) system on the VTM-HA surface synchronously.     

Chemical vapor generation atomic spectrometry using amineboranes and cyanotrihydroborate(III) reagents

Amineboranes of the type L-BH3 (L = NH3; tert-BuNH2; Me2NH; Me3N) and sodium cyanotrihydroborate(III) (NaBH3CN) have been tested as derivatization reagents in the generation of volatile hydrides and elemental mercury following aqueous phase reaction with ionic species of Hg(II), As(III), As(V), Sb(V), Sb(III), Bi(III), Se(IV), Se(VI), Te(IV), and Te(VI). Continuous flow generation atomic absorption spectrometry coupled with a flameless quartz tube atomizer (T = 25 degrees C) and a miniature argon-hydrogen diffusion flame atomizer were employed for the detection of mercury vapors and volatile hydrides, respectively. All of the reductants were able to reduce Hg(II) to the elemental state, giving sensitivities comparable to NaBH4 reduction. Under reaction conditions giving maximum sensitivity for hydride generation with NaBH4, only some amineboranes are able to produce volatile hydrides from all the elements. No evidence of hydride formation was observed from the Se(VI) and Te(VI). In general, the reducing power decreased in the order NaBH4 > H3N-BH3 > tert-BuNH2-BH3 > NaBH3CN > or = Me2HN-BH3 > Me3N-BH3. In comparison with THB, amineboranes and NaBH3CN allowed, in general, a better control of interference effects of Fe(III), Ni(II), Co(II), and Cu(II). Application to determination of mercury in certified reference material is reported. The most likely mechanism of reaction of borane complexes in chemical vapor generation is based on the direct action of hydrogen bound to boron.     

Grape waste as a biosorbent for removing Cr(VI) from aqueous solution

Grape waste generated in wine production is a cellulosic material rich in polyphenolic compounds which exhibits a high affinity for heavy metal ions. An adsorption gel was prepared from grape waste by cross-linking with concentrated sulfuric acid. It was characterized and utilized for the removal of Cr(VI) from synthetic aqueous solution. Adsorption tests were conducted in batch mode to study the effects of pH, contact time and adsorption isotherm of Cr(VI), which followed the Langmuir type adsorption and exhibited a maximum loading capacity of 1.91 mol/kg at pH 4. The adsorption of different metal ions like Cr(VI), Cr(III), Fe(III), Zn(II), Cd(II) and Pb(II) from aqueous solution at different pH values 1-5 has also been investigated. The cross-linked grape waste gel was found to selectively adsorb Cr(VI) over other metal ions tested. The results suggest that cross-linked grape waste gel has high possibility to be used as effective adsorbent for Cr(VI) removal.     

Partitioning behavior of trace elements during pilot-scale fluidized bed combustion of high ash content lignite

This study describes the partitioning of 20 trace elements (As, B, Ba, Cd, Co, Cr, Cu, Hg, Li, Mn, Mo, Ni, P, Pb, Sb, Se, Sn, Tl, V, Zn) and eight major and minor elements (Al, Ca, Fe, K, Mg, Na, Si, Ti) during the combustion of high ash content lignite. The experiments were carried out in the 0.3 MW(t) Middle East Technical University (METU) atmospheric bubbling fluidized bed combustor (ABFBC) test rig with and without limestone addition. Inert bed material utilized in the experiments was bed ash obtained previously from the combustion of the same lignite without limestone addition in the same test rig. Concentrations of trace elements in coal, limestone, bottom ash, cyclone ash and filter ash were determined by inductively coupled plasma optical emission spectroscopy (ICP-OES). Partitioning of major and minor elements are influenced by the ash split between the bottom ash and fly ash and that the major proportion of most of the trace elements (As, Ba, Cr, Hg, Li, Mo, Ni, Sn, V, Zn) are recovered in fly ash. Limestone addition shifts the partitioning of Ba, Cr, Mo, Ni, Sn, V, Zn from bottom ash to fly ash.     

Accompanying Elements in Sphalerite in Pyrometallurgical Process of Zinc and Lead Production

The primary raw materials used in the imperial smelting process (ISP) are Zn and Pb concentrates. Dust generated in the course of ISP is recycled. The identified sphalerite grains indicate the presence of Pb, Fe, Cd sulfides, Fe and Zn oxides, as well as accompanying elements (Ca, Mn, Cu, As, Se, Ag, Sn, and Sb). The tests performed have demonstrated the differentiation in the content of the accompanying elements in sphalerite present in both charge mixture as well as in dusts. This differentiation may be an indication of the migration of these element from sphalerite to the products or to waste during the process.     

Utilization of ICP/OES for the determination of trace metal binding to different humic fractions

In this study, the use of inductively coupled plasma/optical emission spectrometry (ICP/OES) to determine multi-metal binding to three biomasses, Sphagnum peat moss, humin and humic acids is reported. All the investigations were performed under part per billion (ppb) concentrations. Batch pH profile experiments were performed using multi-metal solutions of Cd(II), Cu(II), Pb(II), Ni(II), Cr(III) and Cr(VI). The results showed that at pH 2 and 3, the metal affinity of the three biomasses exposed to the multi-metal solution that included Cr(III) presented the following order: Cu(II), Pb(II)>Ni(II)>Cr(III)>Cd(II). On the other hand, when Cr(VI) was in the heavy metal mixture, Sphagnum peat moss and humin showed the following affinity: Cu(II), Pb(II)>Ni(II)>Cr(VI)>Cd(II); however, the affinity of the humic acids was: Cu(II)>Pb(II), Cr(VI)>Ni(II)>Cd(II). The results demonstrated that pH values of 4 and 5 were the most favorable for the heavy metal binding process. At pH 5, all the metals, except for Cr(VI), were bound between 90 and 100% to the three biomasses. However, the binding capacity of humic acids decreased at pH 6 in the presence of Cr(VI). The results showed that the ICP/OES permits the determination of heavy metal binding to organic matter at ppb concentration. These results will be very useful in understanding the role of humic substances in the fate and transport of heavy metals, and thus could provide information to develop new methodologies for the removal of low concentrations of toxic heavy metals from contaminated waters.     

一种新型改性PbTiO3压电陶瓷材料研究

研制了一种新型的添加Pb（Mn1／3Sb2／3）O3、碱土金属CaCO3、Bi2O3、NiO的改性钛酸铅压电陶瓷材料．该材料具有高压电活性、大压电各向异性、低介电常数及小的机械品质因素．实验确定其典型配方为Pb0．80Ca0．20［（Mn1／3Sb2／3）0．05Ti0．95］3＋0．5wt％NiO＋1wt％Bi2O3；在优化后的制备工艺条件下，其主要性能参数为：d33＝70×10-12C·N-1；Kt＝60．0；Hp≈0，Qm＝43，Nt＝2004Hz·m．     

A mechanism study of light-induced Cr(VI) reduction in an acidic solution

The mechanisms of photo-catalytic reduction of Cr(VI) were investigated in acidic solutions with and without Fe(III). In a system without Fe(III), no Cr(VI) reduction was observed in dark conditions; conversely, under light conditions, the reduction reaction rate increased to 0.011 and 0.020microM min(-1) at pH 2 and pH 1, respectively, indicating the occurrence of Cr(VI) photo-reduction. The Cr(VI) photo-reduction reaction was induced by the photolysis of water molecules, leading to O(2) production. Upon the addition of Fe(III), the photo-reduction rate of Cr(VI) was significantly enhanced due to the formation of Fe(II), which is the photolytic product of FeCl(2)(+) and the electron donor for Cr(VI) reduction. However, with the same concentration of FeCl complexes, a strong inhibition of Cr(VI) reduction at pH 2 was observed, compared with pH 1. A possible explanation is that FeOH(2+) becomes predominant with increasing pH and that its photolytic product, the OH free radical, is an oxidant for Fe(II) and Cr(III) and can compromise Cr(VI) reduction. The kinetic result of each photo-reduction reaction pathway shows zero-order kinetics, suggesting that the photolysis reaction of H(2)O or FeCl(2+) is the rate-determining step in each pathway. The results also show the potential of developing a homogeneous photo-catalytic method to treat Cr(VI)-containing water.     

Theoretical Migration Model for Micellar Capillary Electrophoresis and Its Application to the Separation of Anionic Metal Complexes of HEDTC and CDTA

A mathematical model relating the effective mobility of an analyte in micellar capillary electrophoresis (MCE) to the concentration of surfactant and organic modifier in the background electrolyte (BGE) was derived. Effective mobility is expressed in terms of the electrophoretic mobility of the analyte, the partition coefficient of the analyte into the micelle, and the influence of organic modifier on these two factors. The performance of the model was evaluated using Cd(II), Pb(II), Co(II), Ni(II), Bi(III), Cu(II), and Hg(II) complexes of bis(2-hydroxyethyl)dithiocarbamate, all of which carry a partial negative charge, and Cd(II), Pb(II), Co(II), Ni(II), Bi(III), Cu(II), Hg(II), Fe(III), Ag(I), Tl(I), and Mn(II) complexes of trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid, all of which are anionic having charges in the range -1 to -3. These analytes were separated in borate BGEs containing 10-50 mM sodium dodecyl sulfate and 0-20% (v/v) methanol. Nonlinear regression was used to derive parameters for the model from experimental data and these parameters were used to predict effective mobilities of the analytes. Predicted values of effective mobilties agreed with experimental values to within 3.1%. Values of parameters from the model equation are used to explain changes in separation selectivity observed at different BGE compositions and the model equation is shown to be applicable to computer-assisted optimization of the BGE composition, in MCE using a limited number of experiments.     

钎焊散热器用钎料的成份改进及性能

本文根据金属学原理及钎焊润湿性原理，以铅－锡钎料为基，以降低钎料熔点和增加其润湿性为目的，以Ａｇ、Ｈｇ、Ｃｄ、Ｓｂ、Ｂｉ为改善钎料工艺性能的添加元素，通过正交试验，提出了一种含锡量为１４％的新材料。这种新材料的工艺性能可与含锡４０％的铅－锡钎料相媲美。     

杭州市典型污水处理厂所产污泥重金属含量及资源化分析

以杭州市内4所典型城市污水处理公司产生的城市污泥为研究对象,对污泥中的重金属种类及含量进行了分析.结果表明,四种污泥中主要含Pb、Ni、Cr、Zn、Cu、Mn、Sn、Fe、Hg等重金属,且毒性较大的元素Hg、As和Pb的含量较高.四种污泥中Ni的含量均超出《城镇污水处理厂污染物排放标准》（GB18918--2002）中污泥农用标准限值（土壤pH＜6.5）.尤其是富阳污泥,其Pb、Hg和Cr的含量较高,且Pb及Hg的含量超出农用标准限值,污泥的资源化利用受限.除富阳污泥外,其他三种污泥可采用掺烧方式实现污泥的资源化利用.     

Influence of inorganic anion on Cr(VI) photo-reduction in the presence of ferric ion

Photo-reduction of Cr(VI) in a solution with single or multi-inorganic anions was evaluated. The results show that 38.5 microM Cr(VI) is photo-reduced in the presence of NO(3)(-) at pH 1. The photolysis of NO(3)(-), producing NO(2)(-) or H(2)O(2), may contribute to Cr(VI) reduction. The addition of 0.001-0.1 M chlorite to NO(3)(-) enhanced Cr(VI) photo-reduction when 35.8 microM Fe(III) was present. This enhancement was the combinative result of photolysis of NO(3)(-) and Fe-Cl complexes, leading to the formation of NO(2)(-) and Fe(II), respectively, for Cr(VI) reduction. On the contrary, a significant decrease in Cr(VI) photo-reduction was observed with the addition of PO(4)(3-) and SO(4)(2-). This decrease was due to their strong competition with Fe(III) from Cl(-), resulting in a marked decrease in the concentrations of Fe-Cl complexes. The results suggest that a direct irradiation of acidic wastewaters containing Cl(-), NO(3)(-), and Fe(III) is a feasible strategy for eliminating Cr(VI).