Laser cleaning of historical limestone buildings in Bordeaux appraisal using cathodoluminescence and electron paramagnetic resonance

BACKGROUND: Most historical buildings in Bordeaux city are made of limestone. This yellowish-white rock is rather porous and highly sensitive to pollution. As a consequence of local weathering conditions, these buildings present a dark appearance due to the development of a superficial dark grey to black crust. METHODS: For the last decade, a campaign has been underway to clean these buildings. Eleven techniques of surface treatment have been used, including laser beam technology. As a contribution to the study of laser beam effects on stone buildings, two analytical methods have been used on clean versus unclean surfaces: Cathodoluminescence (CL) and Electron Paramagnetic Resonance (EPR), in addition to SEM-EDX and XRD. RESULTS: The black crust is composed of different types of particles: carbon porous micro-particles of industrial origin, atmospheric dust due to the erosion of soils and rocks, alumino-silicate particles from urban pollution; all these particles being cemented by gypsum. DISCUSSION: As far as heritage conservation is concerned, the laser surface treatment not only preserves the original patina of the stone, but also leaves surface smoothness unaltered. CONCLUSIONS AND PERSPECTIVES: CL and EPR data confirm that lasers--with highly controlled parameters--only get rid of the black crust and, thus, reveal the underneath layer, the so-called patina. This patina shows no luminescence, whereas the limestone on which it has grown shows a bright orange emission of CL. This indicates CL to be a fast and easy way to provide a high quality control for the restoration of polluted ancient stones.     

A study of heavy metal pollution of Asa River, Ilorin. nigeria; trace metal monitoring and geochemistry

Chemical and mineralogical characterization of sediments collected from seven different locations along Asa River in Ilorin, Nigeria have been carried out. The total concentration of Mn, Cr, Fe, Zn and Cu were monitored using Total Reflection X-ray Fluorescence (TXRF). The range of concentration of these metals were: Mn (179.9–469.4, Fe (1998.4–4420.4) Cr (3.0–11.3), Zn (26.6–147.6), Cu (1.9-13.3) mg kg⁻¹. The mineralogical composition was determined using X-ray diffraction (XRD) method and this was complemented with the Infrared Spectroscopy. It was found that the sediments of Asa River had predominantly quartz, and goethite was present in five of the seven locations. Chromite (FeCr₃O₄) and pyrite (FeS) were also identified at some locations along the River. Higher enrichment factors were calculated for Zn, Cr, Mn, and Fe in the sediment indicating anthropogenic source of contamination. Pyrite was prominent at a location receiving effluent from a detergent industry and near a refuse dumpsite.     

供水管网大口径管道管垢中污染物分布的径向差异

以管龄为11年的城市主供水管道上的DN300球墨铸铁管为研究对象,采用扫描电镜(SEM)、能谱分析(EDS)、晶体衍射结构分析(XRD)等手段对其径向不同位置的管垢进行了表征,并分析了其各类金属与有机污染物的分布差异.结果表明:管道下部的管垢总量高,平均粒径大.重金属在空间上的分布明显不同,铁、锰、锌、铅、铜和铬在上部的管垢中含量最高,而下部管垢中,铝的含量最高,该分布与管垢中其来源密切相关.管垢中累积了多种的有机污染物,除了微生物代谢形成的烃类物质之外,还累积了藻类的代谢产物及外源有机污染物,不同位置上出现的有机污染物类型也有所差异.该研究结果对将来饮用水管网生物化学安全的研究方法提出了更高的要求,并为管网的饮用水安全保障提供了理论依据.     

Quantitative and structural analyses of hazardous elements in Chinese medicines and herbs

Thirty samples of Chinese medicines and herbs were analyzed using instrumental neutron activation analysis (INAA) and X-ray diffraction (XRD) methods, mainly noting on the hazardous elements arsenic (As), mercury (Hg), chromium, antimony and cobalt. The three Niuhuang Jiedu Pian samples contained 8.6%, 8.3% and 2.2% As. Two out of four Liushen Wan samples contained approximately7% of both As and Hg. Despite being identically named, the other two Liushen Wan samples did not contain such high concentrations. Japanese Liushen Wan for children contained 1.2 ± 0.03% As and 31 ± 12 mg/kg Hg, whereas Liushen Wan for adults manufactured by another Japanese company contained 550 ± 22 mg/kg As and 1.2 ± 0.05 mg/kg Hg. All the chemical structural formulas of As and Hg in the high-concentration Niuhuang Jiedu Pian and Liushen Wan were realgar (As₄S₄), uzonite (As₄S₅) and cinnabar (HgS). Although the human body is generally not believed to absorb sulphides, continuous intake of these Chinese medicines is potentially no good because it is possible that some arsenic-sulfides will dissolve in gastric acid and then alter their chemical structures. Additionally, many herbs contained low concentrations of Hg, and their chemical structures were unknown.     

钙基吸附剂吸附氯化镉的微观形态及机理初探

在生活垃圾焚烧烟气模拟净化试验装置中,采用氯化镉(CdCl2)作为气态重金属发生源,模拟改性钙基吸附剂对重金属的动态吸附能力,并与活性炭进行对比.采用X-射线衍射和SEM-EDX(扫描电子显微镜-X射线能谱分析)方法,对吸附重金属前后的吸附剂样品的微观形态特征进行观察,并且对吸附机理进行研究.结果表明:改性吸附剂存在CaO/NaCI共晶体,具有发达的内孔结构,对气态CdCl2除了具有物理吸附作用以外,还存在化学扩散和吸附作用,且化学吸附是主要作用机制.     

爆炸冲击对高阶煤微晶结构的影响特征*

为探究爆炸冲击荷载对煤微晶结构的影响,以河南赵固二矿山西组二1煤层高阶无烟煤为研究对象,利用炸药对煤样进行爆炸冲击试验,通过改变炸药量控制冲击荷载的大小,并对冲击过后的煤样进行X射线衍射测试,分析在不同强度冲击荷载作用下煤样微晶结构的变化规律。研究结果表明:煤样的峰值应变随着冲击荷载的增大而升高;与原煤相比,受冲击荷载之后煤样XRD图谱的002峰与100峰均变的更高且陡,衍射峰位置向θ值大的一侧偏移;与原煤样相比,受冲击荷载之后煤体的微晶结构参数发生规律性变化,面层间距（d002）表现出减小的趋势,单元堆砌度（Lc）、单元延展度（La）以及（La/Lc）表现出增大的趋势;微晶结构变化快慢也呈现一定的规律性,随着煤样受到冲击荷载的增大,面层间距呈现减小的趋势;单元堆砌度与单元延展度呈现增加的趋势,前期增加缓慢,后期增加迅速;受冲击煤样的微晶结构更加有序,从微观结构上解释了冲击载荷对煤微晶结构的影响。     

Direct and indirect methods for chromium identification in industrial wastes

The examinations of selected wastes and stream sediments from the vicinity of a chemical plant by sequential extraction procedures and direct methods, SEM/EDX and XRD, were carried out in order to identify the different forms of chromium, particularly as they are released to potential mobility. The results show that the top and bottom waste samples contain 37,756 and 53,650 μg g¹ Cr, respectively, but about 7% and 2% of the total chromium type Cr(VI). The chemical extraction results show that the mobility of Cr in the upper part of the waste pile is significantly higher than in the bottom section; the exchangeable form of Cr accounts for 25% and < 1%, respectively, the last one irrespective of redox conditions. About 50% of Cr is associated with the reducible fraction of the top waste, and similar with the residual fraction in the bottom waste. Oxidation of the bottom waste shift some portion of Cr from residual to the moderately reducible fraction. The major Cr-forms in the river sediments are compounded with Fe-oxides. The < 2 μm size fraction of the selected sediment sample, particular enriched in chromium contained up to 73,000 μg g¹ Cr with about 95% of this in the moderately reducible fraction, predominantly bound with oxyhydroxides. SEM/EDX and XRD analysis of wastes and river sediment indicate that the main insoluble Cr-phase is ferroan — (Mg, Fe) (Cr, Al)²O⁴ which would be dissolved mainly in the residual fraction.     

不同浓度硒处理对彩叶草铅胁迫的EDXS和XRD分析

以彩叶草（ColeusblumeiBenth．）为材料,用营养液培养方法,研究了不同浓度硒（se）处理对浓度为1．0mmol·L-1Pb2＋胁迫下彩叶草根、叶的形貌变化及其组分形态等变化,从光谱学角度初步探讨了硒对重金属铅毒害的缓解机制。结果表明：铅胁迫下的彩叶草根系c、K、ca含量减少,O、Mg、Al、Si、Fe、Pb含量增加,叶片中的C、Mg、Al、si、K、Ca、Fe含量减少,O、Cl含量增加。铅胁迫下硒处理的彩叶草根元素种类及其元素含量均发生了明显变化;根中晶体情况及其晶相也发生了相应变化。     

磷对降低土壤中铅的生物有效性的X-衍射及电镜分析

通过盆栽实验,对不同磷化合物处理的铅污染土壤和植物分别进行X-衍射(XRD)、能谱扫描电镜(SEM-EDS)及能谱透射电镜(TEM-EDS)分析.结果显示,不同磷化合物处理土样的X-衍射图在0.288 nm、0.296 nm及0.321 nm处有明显衍射峰生成,以SSP5、HA5及HASSP2处理土样的X-衍射谱图中生成的衍射峰比较明显,而PR5处理的衍射峰相对较弱,其原因可能与磷矿粉的弱溶解特性有关.这显示了土壤经不同磷化合物处理后,土壤中新生成了较多的磷酸铅及Ca-Pb磷酸铅盐的沉淀,不同程度地降低了土壤中铅的迁移和转化特性.对植株根系的SEM分析结果表明,土壤中加入不同的磷化合物处理后,磷酸铅类化合物在植株根表细胞有明显的晶体沉淀物.对植物根细胞的透射电镜分析结果发现,在不同磷处理土壤中,铅以不同的磷酸盐化合物的形式沉淀在植物的细胞壁及细胞间隙,从而有效地阻止了铅离子向原生质细胞及植物中柱内的迁移,不同程度地降低了污染土壤中铅的蓄积毒性.