Apatite and Portland/apatite composite cements obtained using a hydrothermal method for retaining heavy metals

Apatite and Portland/apatite composite cements containing steelwork dusts have been prepared using a low temperature hydrothermal method (200 degrees C, 48h). The produced solids were characterized by means of XRD, IR, and SEM-EDX, and the remaining liquid was analyzed by ICP. The results clearly show the capability of these cements to inertise the heavy metals contained in steelwork dusts, that is Fe, Pb, Mo, Cr, Mn, Ni, and Zn. In the case of apatitic cements, Fe, Mg, Cr, Mn, and Pb coming from steel dust replaced Ca in the divalent cation position of the apatite structure, while Si and Mo replaced P in tetrahedral position. The average crystal size of the apatite-containing dust is smaller than in pure apatite synthesized using the same procedure, which is related to the magnesium content of the dust, since magnesium seems to inhibit the crystal growth. XRD diagrams of composite cements show only peaks corresponding to phases observed in the single cements, and in that no new phases are found. However, EDX analysis reveals the introduction of cations coming from Portland cement into the apatite structure. From the results of water analysis it could be concluded that the capability of retention is higher in composite matrices than in the pure apatite one. In conclusion, the obtained data allow stating that the proposed method, the hydrothermal synthesis of steelwork dust containing cement, is a reliable one for immobilization of toxic residues containing heavy leachable cations.     

Determination of the major,minor, and trace element mass fractions in Iranian cement by INAA and WDXRF

The elemental composition of three different Iranian cement samples was determined by instrumental neutron activation analysis with the aim of quality control. The mass fractions for 4 major (Ca, Si, Fe, Al) and the 21 minor and trace elements (Mg, V, Mn, Na, As, La, Sb, Sm, U, Ba, Ce, Co, Cr, Eu, Hf, Sc, Sr, Th, Zn, S, K) were determined. X-ray fluorescence analysis was also used. The results obtained by both methods for Na, Mg, Fe, Ca, and Al are in good agreement. On the whole, the Iranian cement quality is quite acceptable according to national and international standards.     

Contamination assessment of copper, lead, zinc, manganese and nickel in street dust of Baoji, NW China

Street dusts collected from Baoji, NW China were analyzed for Cu, Pb, Zn, Mn and Ni by using PANalytical PW-2403 wavelength dispersive X-ray fluorescence spectrometry and assessed the contamination level of heavy metals on the basis of geoaccumulation index (I(geo)), enrichment factor (EF), pollution index (PI) and integrated pollution index (IPI). The results indicate that, in comparison with Chinese soil, street dusts in Baoji have elevated metal concentrations as a whole. The concentrations of heavy metals investigated in this paper are compared with the reported data of other cities. The calculated results of I(geo) and EF of heavy metals reveal the order of I(geo) and EF are Pb>Zn>Cu>Ni>Mn. The high I(geo) and EF for Pb, Zn and Cu in street dusts indicate that there is a considerable Pb, Zn and Cu pollution, which mainly originate from traffic and industry activities. The I(geo) and EF of Mn and Ni are low and the assessment results indicate an absence of distinct Mn and Ni pollution in street dusts. The assessment results of PI also support Pb, Zn and Cu in street dusts presented serious pollution, and IPI indicates heavy metals of street dust polluted seriously.     

杭州市大气悬浮颗粒PM_(2.5)污染状况及化学组成特征分析

为了解杭州市大气悬浮颗粒物PM2.5污染状况及化学组成特征,2006年在杭州市内布设2个监测点位,按季节进行采样,并对悬浮颗粒物PM2.5中20种元素进行定量研究。结果表明:杭州市区大气中悬浮颗粒物PM2.5的年均质量浓度值为77.5μg/m3,其中S、Si、Ca、K等元素年平均质量浓度大于1.0μg/m3。元素Si、Al、Fe、Mg、V、K、Na、Ti、Mn、Ca、P、Cr、Ni主要来源于地壳,而元素Cl、Cu、Zn、Pb、As、Br、S、Se等主要来源于人为排放源。     

Integrated hydrometallurgical process for production of zinc from electric arc furnace dust in alkaline medium

In this study, a novel and integrated hydrometallurgical process for the production of zinc powder from electric arc furnace (EAF) dust in alkaline medium is reported. The dust is firstly hydrolysed in water, and then fused in caustic soda at 350°C for 1 h, followed by leaching in alkaline solution in which both zinc and lead are effectively extracted. Zinc powder is then produced by electrowinning from the leach solution after the lead is selectively removed by precipitation using sodium sulphide as precipitant. The EAF dust tested contained 25% Zn, 1.8% Pb and 33% Fe. It was found that 38% of zinc and 68% of lead could be extracted from the dust when leached directly in caustic soda solution. Leaching of zinc increased to 80% when dust was directly fused with caustic soda followed by alkaline leaching. However, the leaching further increased to 95% when the dust was hydrolysed first with water before fusion. Zinc powder with a purity of 99.95% was then produced by electrowinning from the lead depleted solution. Stainless electrodes were used as both anode and cathode.     

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.     

Effect of NaOH on the vitrification process of waste Ni-Cr sludge

This study investigated the effect of NaOH on the vitrification of electroplating sludge. Ni, the major metal in the electroplating sludge, is the target for recovery in the vitrification. Sludge and encapsulation materials (dolomite, limestone, and cullet) were mixed and various amounts of NaOH were added to serve as a glass modifier and a flux. A vitrification process at 1450 °C separated the molten specimens into slag and ingot. The composition, crystalline characteristics, and leaching characteristics of samples were measured. The results indicate that the recovery of Ni is optimal with a 10% NaOH mass ratio; the recoveries of Fe, Cr, Zn, Cu, and Mn all exhibited similar trends. The results of the toxicity characteristic leaching procedure (TCLP) show that leaching characteristics of the slag meet the requirements of regulation in Taiwan. In addition, a semi-quantitative X-ray diffraction analysis revealed that the main crystalline phase of slag changed from Ca(3)(Si(3)O(9)) to Na(4)Ca(4)(Si(6)O(18)) with a NaOH mass ratio of over 15%, because the Ca(2+) ions were replaced with Na(+) ions during the vitrification process. Na(4)Ca(4)(Si(6)O(18)), a complex mineral which hinders the mobility of metals, accounts for the decrease of metal recovery.     

Recycling of an electric arc furnace flue dust to obtain high grade ZnO

The production of steel in electric arc furnace (EAF) generates a by-product called EAF dusts. These steelmaking flue dusts are classified in most industrialized countries as hazardous residues because the heavy metals contained in them, tend to leach under slightly acidic rainfall conditions. However, and at the same time they contain zinc species which can be used as a source to obtain valuable by-products. The present investigation shows results on the processing of an EAF flue dust using ammonium carbonate solutions. Once zinc is dissolved: ZnO + 4NH3 + H2O --> Zn(NH3)4(2+) + 2OH- with other impurities (i.e. cadmium and copper), these are eliminated from the zinc solution via cementation with metallic zinc. The purified zinc solution was evaporated (distilled) until precipitation of a zinc carbonate species, which then was calcined to yield a zinc oxide of a high grade. For the unattacked dust residue from the leaching operation, mainly composed of zinc ferrite, several options can be considered: back-recycling to the furnace, further treatment by sodium hydroxide processing or a more safely dumping due to its relatively inertness.     

A crystal phase study of zinc hydroxide chloride in electric-arc-furnace dust

Chemical analysis shows that electric-arc-furnace (EAF) dust obtained from 13 steelmaking factories in Taiwan is composed chiefly of Fe (15–37%), Zn (7–28%) and Mn (1.55–3.99%) and that the mineral composition is mainly (Mn, Zn) Fe₂O₄, ZnO and ZnCl₂·4Zn(OH)₂·H₂O. It was also found that EAF dust exists as irregular agglomerates from 3 to 20 m in size and are made up of much smaller round particles from 0.3 to 1 m in size. ZnCl₂ gas in the dust condenses after passing through the EAF gas-cooler system binding small particles of Mn-Zn ferrite together. The agglutinative substance was identified as being ZnCl₂·4Zn(OH)₂·H₂O possibly arising from the interaction between ZnCl₂ and ZnO adhering to the Mn-Zn ferrite particles; a conjecture supported by the fact that EAF dust dissolves easily in hydrochloricacid solution leaving only loosely aggregated Mn-Zn ferrite material.     

Preparation of magnetic and bioactive calcium zinc iron silicon oxide composite for hyperthermia treatment of bone cancer and repair of bone defects

In this paper, a calcium zinc iron silicon oxide composite (CZIS) was prepared using the sol-gel method. X-ray diffraction (XRD) was then employed to test the CZIS composite. The results from the test showed that the CZIS had three prominent crystalline phases: Ca(2)Fe(1.7)Zn(0.15)Si(0.15)O(5), Ca(2)SiO(4), and ZnFe(2)O(4). Calorimetric measurements were then performed using a magnetic induction furnace. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) analysis were conducted to confirm the growth of a precipitated hydroxyapatite phase after immersion in simulated body fluid (SBF). Cell culture experiments were also carried out, showing that the CZIS composite more visibly promoted osteoblast proliferation than ZnFe(2)O(4) glass ceramic and HA, and osteoblasts adhered and spread well on the surfaces of composite samples.     

Multivariate analysis of selected metals in tannery effluents and related soil

Effluent and relevant soil samples from 38 tanning units housed in Kasur, Pakistan, were obtained for metal analysis by flame atomic absorption spectrophotometric method. The levels of 12 metals, Na, Ca, K, Mg, Fe, Mn, Cr, Co, Cd, Ni, Pb and Zn were determined in the two media. The data were evaluated towards metal distribution and metal-to-metal correlations. The study evidenced enhanced levels of Cr (391, 16.7 mg/L) and Na (25,519, 9369 mg/L) in tannery effluents and relevant soil samples, respectively. The effluent versus soil trace metal content relationship confirmed that the effluent Cr was strongly correlated with soil Cr. For metal source identification the techniques of principal component analysis, and cluster analysis were applied. The principal component analysis yielded two factors for effluents: factor 1 (49.6% variance) showed significant loading for Ca, Fe, Mn, Cr, Cd, Ni, Pb and Zn, referring to a tanning related source for these metals, and factor 2 (12.6% variance) with higher loadings of Na, K, Mg and Co, was associated with the processes during the skin/hide treatment. Similarly, two factors with a cumulative variance of 34.8% were obtained for soil samples: factor 1 manifested the contribution from Mg, Mn, Co, Cd, Ni and Pb, which though soil-based is basically effluent-derived, while factor 2 was found associated with Na, K, Ca, Cr and Zn which referred to a tannery-based source. The dendograms obtained from cluster analysis, also support the observed results. The study exhibits a gross pollution of soils with Cr at levels far exceeding the stipulated safe limit laid down for tannery effluents.     

北京地区冬季气溶胶分级化学成分及来源分析

在北京城区进行冬季大气气溶胶采样,样品采用PIXE方法进行分析,得到大气气溶胶中20种元素的质量浓度。结果表明:元素Mg、Fe、Si这3种元素均呈粗粒模态单峰型分布,且峰值出现在2～4μm,表明它们来自土壤尘;S、Cl、K等3种元素谱分布呈细粒单峰型分布,峰值都出现在0.25～0.5μm范围内,表明这3种元素主要来自燃煤;Cu、Zn、As、Br、Pb等5种元素谱分布呈双峰型谱分布;Ni、Cu、Zn、As、Se、Br、Pb等元素的粗、细模态的富集因子都较大,尤其是细粒模态,表明这些元素更容易在细粒模态上富集,进一步说明这些元素主要来自人为污染源。因子分析结果表明:土壤尘、煤烟尘、工业源和汽车尾气排放源对北京冬季气溶胶有主要贡献。     

On the distribution and bonding environment of Zn and Fe in glasses containing electric arc furnace dust: a mu-XAFS and mu-XRF study

We apply synchrotron radiation assisted X-ray fluorescence (SR-XRF), SR-XRF mapping as well as micro- and conventional X-ray absorption fine structure (mu-XAFS and XAFS) spectroscopies in order to study the bonding environment of Fe and Zn in vitrified samples that contain electric arc furnace dust from metal processing industries. The samples are studied in the as-cast state as well as after annealing at 900 degrees C. The SR-XRF results demonstrate that annealing does not induce any significant changes in the distribution of either Fe or Zn, in both the as-cast and annealed glasses. The mu-XAFS spectra recorded at the Fe-K and Zn-K edges reveal that the structural role of both Fe and Zn remains unaffected by the annealing procedure. More specifically, Fe forms both FeO(6) and FeO(4) polyhedra, i.e. acts as an intermediate oxide while Zn occupies tetrahedral sites.     

Crystallization kinetics of magnetic glass–ceramics prepared by the processing of waste materials

The objective of the present investigation was to study the feasibility of conversion of an intimate mixture of blast furnace slag and blast furnace flue dust generated by a single industrial company into magnetic glass–ceramic product. Blast furnace slag (BFS) and blast furnace flue dust (BFD) are generated at a rate of 300,000 and 30,000 tons/year, respectively, from iron and steel factory. The crystallization mechanisms of a composition containing BFS and BFD in a 50/50 proportion were investigated by differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The crystallization temperature was found to vary from 900 to 1100 °C and two phases appeared in the crystallized samples: pyroxene Ca(Mg, Fe, Al)(Si, Al)₂O₆ and magnetite/maghemite. Heating rate and particle sizes effects on crystal growth of powdered samples were studied by DTA. The apparent activation energy of crystal growth using the particle size 180–315 μm was determined to be 355 and 329 kJ/mol for the first and second peak, respectively. The presence of sharp and broad crystallization peaks indicate simultaneous surface and internal crystallization mechanism. Good wear resistance and chemical durability particularly in alkaline environment, combine with good hardness and magnetic properties make this glass–ceramic material potentially useful for various industrial applications.     

Determination of various impurities in synthetic diamond powder

Impurities in industrial synthetic diamond powder samples were analyzed by X-ray diffraction (XRD) and Flame Atomic Absorption Spectrometry (FAAS). Specimen for FAAS is required in solution form. Diamonds are chemically inert to most acids and alkalies. Carbon was removed as CO₂ on heating and estimated gravimetrically. The remaining residue was fused with di-lithium tetraborate and dissolved in nitric acid. Impurities such as Si, Al, Fe, Ca, Mg, W, Na, Co and Ni were then determined by FAAS. Crystalline phases of major impurities were identified by XRD.     

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.     

Sol-gel制备PLCT薄膜的结晶特性与电畴结构研究

运用sol-gel技术制备了(Pb,La,Ca)TiO3(简写为PLCT)铁电薄膜;利用XRD、SEM、AFM和EDAX分析了PLCT薄膜的结构、表面形貌和组分。XRD衍射结果表明,PLCT薄膜呈钙钛矿结构。随着退火时间的增加,PLCT薄膜的XRD衍射峰的强度也随之增加。SEM、AFM分析表明,PLCT铁电薄膜表面平整、致密、无裂缝。EDAX分析表明,PLCT薄膜的实际组分十分接近设计组分。利用PFM分析了PLCT薄膜的电畴结构,发现随着退火时间的增加,PLCT薄膜的电畴由细小圆点状逐渐增大并形成片状电畴。     

亚洲沙尘影响台湾期间大气悬浮微粒之粒径大小及化学组成变化趋势

旨在针对2002年3￣4月亚洲沙尘影响台湾期间,探讨位于台湾海峡中间澎湖群岛之大气悬浮微粒物化特征变化情形。本研究在澎湖群岛的小门村设置悬浮微粒采样站,借以采集近海面之大气悬浮微粒。由悬浮微粒浓度变化情情得知,2002年3￣4月共有3次亚洲沙尘暴抵达澎湖群岛,其粒径分布很明显地由双峰分布(bi-modaldistribution)转变为以粗微粒(coarseparticle)为主之单峰分布(singlemodaldistribution)。此外,悬浮微粒中水溶性离子成分之粒径分布亦随亚洲沙尘之抵达而呈明显变化,其中Cl-和Na+之变化趋势具有一致性,显示海盐之影响颇为重要;NH4+、Ca2+和SO42-均由细微粒(fineparticle)转变为粗微粒,显示(NH4)2SO4或CaSO4应为亚洲沙尘之特征指纹;NO3-主要来自当地污染(localemission),故其分布并无明显变化;Mg2+虽维持以粗微粒为主之单峰分布,但其浓度却增加约2倍左右。上述研究结果显示,当亚洲沙尘抵达台湾地区,不仅悬浮微粒之粒径大小改变,就连化学组成亦出现明显变化。     

Distribution, correlation and risk assessment of selected metals in urban soils from Islamabad, Pakistan

Urban soil samples were analyzed for Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Pb, Sr and Zn by atomic absorption spectrophotometric method. Multivariate statistical approach was used to study the apportionment of selected metals in the soil samples during summer and winter. The degree of contamination along with the geoaccumulation index, enrichment factor and contamination factor was also evaluated. In water-extract of the soil samples, relatively higher levels were noted for Na, Ca, K, Fe, Mg, and Pb with average concentrations of 56.38, 33.82, 12.53, 7.127, 5.994, and 1.045 mg/kg during summer, while the mean metal levels during winter were 76.45, 38.05, 3.928, 0.627, 8.726, and 0.878 mg/kg, respectively. In case of acid-extract of the soils, Ca, Fe, Mg, Na, K, Mn and Sr were found at 27,531, 12,784, 2769, 999.9, 737.9, 393.5, and 115.1 mg/kg, during summer and 23,386, 3958, 3206, 254.6, 1511, 453.6, and 53.30 mg/kg, during winter, respectively. Most of the metals showed random distribution with diverse correlations in both seasons. Principal component analysis and cluster analysis revealed significant anthropogenic intrusions of Cd, Pb, Co, Cr, Cu, Li, Zn and Na in the soils. Geoaccumulation indices and contamination factors indicated moderate to heavy contamination for Pb and Cd in the soils, while enrichment factor exhibited significant enrichment (EF > 5) of Cd, Pb, Ca, Co, Li, Mn and Zn by anthropogenic activities. Overall, on the average basis, considerable degree of contamination (C_deg > 16) was observed in both seasons, although it was higher in winter. Present metal levels were also compared with those reported from other areas around the world.     

Analysis of mosses along Sarp-Samsun highway in Turkey

The elemental analysis of mosses along Sarp-Samsun highway in Turkey was determined using energy dispersive X-ray fluorescence method. A radioisotope excited X-ray fluorescence analysis using the method of multiple standard additions is applied for the elemental analysis of mosses. An annular 50 mCi (241)Am radioactive source and annular 50 mCi (55)Fe radioactive source were used for excitation of characteristic K X-rays. An Si(Li) detector which has a 147 eV full width at half maximum for 5.9 keV photons was used for intensity measurements. A qualitative analysis of spectral peaks showed that the samples contained phosphates, potassium, calcium, titanium, iron, strontium, tin and barium. Since this study is the elemental analysis along the highway, one can expect to detect Pb. Due to the detection limit of EDXRF, elements were analyzed with Atomic Absorption Spectroscopy (AAS) for Pb. Evaluation of these elements with their potential hazards for ecology and human is briefly discussed.