炼锌固体废渣中重金属(Pb、Zn)的存在状态及环境影响

利用XRD、TEM/EDS和连续提取实验研究了土法炼锌固体废渣中重金属的矿物学特征及不同粒度中重金属的相态分布特征。与通常发现的重金属一般富集在小粒径废渣中的情况不同,本工作所研究的废渣样品中大粒径废渣与细粒径废渣相似,甚至有更高的金属含量。化学形态研究表明,冶炼过程形成的矿物(或玻璃质)集合体和堆积后的风化过程形成的次生矿物是废渣中重金属存在的主要化学相。同时发现Pb的残渣态很少(0.39%～15.75%),而Zn的残渣态较高(14.3%～46.2%),这可能与冶炼工艺所形成较多Zn的硅酸盐矿物有关。尽管可交换态Pb、Zn在不同相态中的相对比例非常小(Pb0.03%～1.30%;Zn0.03%～3.30%),但其绝对含量却比一般土壤或沉积物要高(Pb1.5～385μg/g;Zn3～590μg/g)。由于重金属可交换态有比其他化学相态更高的活动性和生物可利用性,因此,对环境有较大的潜在影响。废渣样品的微束分析表明,Pb在废渣中见有金属Pb存在形式或呈纳米金属Pb颗粒包裹于其他矿物或铁合金及熔球集合体中。同时不排除有Pb的碳酸盐矿物存在的可能。而以硅锌矿Zn2(SiO4)、锰硅锌矿(Zn,Mn)2犤SiO4犦和纤维状的丝锌铝石Zn8Al4犤(OH)8(SiO4)5犦·7H2O等矿物形式存在以及Fe、Mn等的铝硅酸盐形式存在的Zn,可能是导致Zn的残渣态较高的原因。与连续提     

Mineralogy of metallic phases in sulphide mattes from primary lead smelting

The mattes resulting from lead smelting have been studied in order to determine the distribution of heavy metals and metalloids in primary phases. The chemical analysis (EPMA) revealed the presence of various metals (Pb, Sb, Cu), sulphides (galena, wurtzite, pyrrhotite, bornite, digenite, cubanite), arsenides (koutekite, löllingite) and other complex intermetallic compounds. Extreme saturation of the initial matte melt in heavy metals and metalloids as well as a relatively rapid cooling regime are responsible for numerous elemental substitutions in the crystal structures of all the involved phases. To cite this article: V. Ettler, Z. Johan, C. R. Geoscience 335 (2003).     

Natural alteration products of sulphide mattes from primary lead smelting

The natural alteration products developed on mattes from lead metallurgy were determined: oxides and hydroxides (HFO, Cu(OH)₂), sulphates (thenardite, gypsum), hydroxysulphates (jarosite, beaverite, brochantite) and carbonates (cerussite, malachite, NaOH·2 PbCO₃). The large range of stability of newly formed phases confirms a significant variety of E_h–pH conditions of natural weathering of matte. Jarosite is stable at pH<3, but some hydroxides and carbonates typically form in neutral and alkaline environments. Consequently, the best dumping conditions for metallurgical mattes are difficult to determine. Such materials can have severe environmental effects and should be dumped in controlled waste-disposal sites. To cite this article: V. Ettler et al., C. R. Geoscience 335 (2003).     

X射线荧光光谱-X射线衍射-红外光谱联用技术鉴别锰矿与锰冶炼渣

鉴别锰矿与锰冶炼渣对于锰矿进口贸易和环境保护具有重要意义,由于锰冶炼渣与一些锰矿具有相似的元素组成,都含有锰和硅铝镁钙等杂质元素,仅从元素含量的高低无法准确将其鉴别。本文按国别收集我国主要进口锰矿及不同工艺的主要锰冶炼渣作为研究样品,应用X射线荧光光谱、X射线衍射及傅里叶变换红外光谱技术相结合,建立了锰矿与锰冶炼渣的鉴别方法。在元素组成上,锰冶炼渣的硅含量较高,水淬渣和空气冷却渣的钙含量较高。在物相上,锰矿的特征物相包括软锰矿、氧化锰、方锰矿、菱锰矿等;而锰冶炼渣因为经过冶炼的过程存在硅酸铁、锰橄榄石等特征峰,从而对样品属性进行鉴别。红外光谱显示,锰矿在600~400 cm~(-1)范围内有两个强吸收带,并单独或者同时在1420 cm~(-1)处有特征吸收峰;而锰冶炼渣在960 cm~(-1)左右有宽强吸收峰。本法建立了锰矿的物相谱图库及锰冶炼渣的物相特征,并充分利用红外光谱技术作了有力佐证,确定了锰矿及其冶炼渣的主要区别点。     

河西走廊4200年以来青铜冶炼的元素地球化学记录

金属的使用与冶炼是人类社会发展过程中一项革命性事件。河西走廊地区全新世条湖湖相沉积元素地球化学记录显示,10500-9500cal aBP和8000-7200cal aBP时段Cu、Pb、Zn、Ni元素含量高值区,分别对应了早全新世增温期冰川融水量增加和全新世适宜期季风降水的增强。Cu、As、Pb、Zn、Ni含量在4200-3700cal aBP时段出现最高峰值,另外Cu、Pb、Zn、Ni4种元素在3000-2700和2100-1900cal aBP时段出现较高峰值。4200-3700cal aBP时段元素异常记录了我国西北地区最早的青铜冶炼,As元素是这一时期青铜合金的主要成份。另外,西周时期(3000-2700cal aBP)和汉代(2100-1900cal aBP)Cu、Pb、Zn、Ni元素峰值,可能是先民青铜冶炼的结果。元素地球化学记录不仅可以判定早期青铜冶炼的起迄时间,也提供了甄别不同时代青铜合金元素组成变化的信息。     

钢铁厂附近树木年轮的磁学性质及其环境意义

通过磁学手段以树木年轮为研究对象,通过多参数磁学研究探讨钢铁厂周围环境污染的历史.研究表明:钢铁厂附近树木年轮样品中磁性矿物为准单畴(其中颗粒偏向于多畴)的磁铁矿,磁性矿物形状各异,粒径大小不一;样品中磁铁矿的含量随年份的不同差异很大;通过树木不同方向上磁性参数尤其是饱和等温剩磁(SIRM)值的差异以及扫描电镜(SEM)和X射线能谱(EDX)分析,发现树木木质部中的磁性颗粒来自于树皮,即大气中颗粒被树皮和树叶表面吸附后,在树木的生长季节通过树皮进入形成层的木质部细胞,然后通过木质化作用被固定在当年生长的树木木质部木材中;另外,朝向钢铁厂方向的树干年轮钻芯样品SIRM值与对应年份钢铁厂年生产量之间高度相关,磁性颗粒在年轮之间不存在横向迁移,树干年轮钻芯的磁性参数(SIRM和部分磁滞参数)可指示该区大气环境污染的历史;污染树木钻芯样品的SIRM随时间的变化曲线说明该研究区大气污染日益严重.     

沟锰矿石火法选矿(富锰渣法)的可能性

富锰渣法的基本原理是根据各种元素在冶炼过程中还原温度的不同,使各种有益、有害组份相对分离富集,但该方法对矿石的成份有一定要求,硐沟锰矿石为低磷,高铁、锰、银共生矿石。经过计算可知,矿石的物质组份适合火法选矿,矿石可选性良好。     

Heavy Metal Distribution in Soils near the Almalyk Mining and Smelting Industrial Area,Uzbekistan

Abstract: The present study demonstrates distribution and chemical forms of heavy metals in soils of the Almalyk mining and smelting industrial area along five transects. The study area is located in Almalyk, Uzbekistan, where the intensification of industrial enterprises negatively impacts the environment. The distribution of 17 heavy metals (Cu, Zn, Pb, Sc, V, Cr, Co, Ni, Ga, Rb, Sr, Y, Zr, Nb, Ba, Th, and U) were studied in 21 sampling locations (21×3=63 soil samples) along five radial transects with a total length of 60?km downwind deposition gradient. Soil samples were collected from the upper layer (0–10?cm) at 4–6?km intervals. As a result of X-ray fluorescence spectrometry analyses by using X-ray fluorescence spectroscopy (XRF, Philips Analytical Ink, USA ), a significant decrease in heavy metal (Cu, Zn, Pb) deposition was found going from the source in a downwind direction. Soil samples taken from the first location (near the pollution sources) showed higher concentrations of Cu, Zn and Pb, and lower concentrations with increasing distance from the source. Obtained data showed different impact of pollution sources to heavy metal deposition and distribution in soils. The Almalyk mining and smelting complex is the major source of Pb, Zn and Cu enrichment in soils. Distribution of other trace elements does not exceed background content and suggests lithogenic background. This allowed us to divide these elements into two groups: (1) technogenic (Cu, Zn and Pb); and (2) lithogenic (Sc, V, Cr, Co, Ni, Ga, Rb, Sr, Y, Zr, Nb, Ba, Th and U) origins.     

Exposure of smelting workers to mercury vapor with indigenous method for mercury smelting in Wuchuan areas, Guizhou Province, China

Small-scale mercury smelting activities with indigenous method are always extensive in the Wuchuan area, northeastern Guizhou Province, China. Because of the simple processes without any environmental protection, a large amount of mercury vapor released to the ambient air during the processing of cinnabar roasting. So the health of the workers may be negatively affected through inhalation of the mercury-polluted air. Mercury, creatinine and β2-MG contents in urine among the workers in the study areas and the residents in the control site （Changshun County） were determined to discuss the health impact of mercury vapor exposure to the workers in the study areas. Health examinations also were carded out to identify clinical symptoms of mercury poisoning for the smelting workers. Results indicated that the geometric mean value of urinary mercury for the smelting workers was g/g Cr μg/g Cr （N=22）, significantly higher than 1.24 μg/g （N=54） for residents in the control site. β2-MG as a renal biomarker can be used to study human nephrotoxicity at an early stage and it is most useful to define effects for assessing re-absorption function to indicate tubular injury. The results showed a serious adverse effect on renal system for the smelting workers due to mercury exposure. Several workers have already manifested some clinical symptoms of lightly chronic mercury poisoning and the symptoms include finger and eyelid lightly tremor, gingivitis and blue mercury line in mouth. The study illuminated that the workers in gaged in indigenous mercury smelting in the Wuchuan area were seriously exposed to mercury vapor,     

Mineralogy, geochemistry and release of heavy metals in wastes from indigenous zinc smelting in Northwest Guizhou

Environmental impact resulting from mining activities is serious and ubiquitous all over the world, and it has become one of the important aspects in environmental geochemistry. The environment was seriously damaged by wastes from historical zinc smelting in Northwest Guizhou. The geochemical distributions of Pb and Zn in the different grain-size fractions of wastes indicate that the coarser particles show similar or even higher heavy metal concentrations than finer ones in the samples, although the concentrations of heavy metals tend generally to increase as the size fractions get finer. The heavy metal contents are very high, with maximum values of 31631, 57178, 2367 and 311.5 mg/kg for Pb, Zn, Cu and Cd, respectively. It is also shown that the residual fraction of Pb is less than that of Zn, accounting for 0.39%-15.75% and 14.3%-46.2%, respectively, of the total, and this is likely relative to Zn-silicate minerals formed from smelting. Although the relative partitioning of Pb and Zn is very low （0.03%- 1.3.% for Pb; 0.03% -3.3% for Zn）, the exchangeable fraction of the waste contains large amounts of heavy metals （1.5%-385 μg/g for Pb; 3-590 μg/g for Zn）. Heavy metals in exchangeable forms have the highest solubility to give the highest potential bioavailability in contrast to other chemical forms. Mineralogical study indicates that the wastes were found to be highly heterogeneous materials, dominated by quartz, feldspar, carbonatite, iron or/and aluminum vitric compounds and a few secondary mineral phases, and their contents vary with the type of smelting wastes. The secondary minerals formed from smelting and sequentially weathering are the major chemical phase for heavy metals. Complex composition of many phases and substitution of elements suggested that many of the phases were found to be non-stoichiometric compounds. Pb was found to be the main Pb phase in the wastes by precipitation or/and adsorption.