The origin of calcium oxalates on historical buildings,monuments and natural outcrops

Calcium oxalates (whewellite and weddellite) occur widely in nature. They usually form a patina on the marbles and limestones of monuments, historical buildings and artifacts, as well as natural outcrops. Whewellite and weddellite are produced by a pervasive transformation of the calcium carbonate, occurring in the presence of lichens (or more rarely of other microorganisms such as blue algae and fungi) which provide the oxalic acid required to precipitate the calcium in the form of oxalates.In the past, when the quality of the atmosphere was more suitable for lichen support, the formation of oxalate patinae was a widespread weathering phenomenon in urban areas. Today, in highly polluted sites, weddellite and whewellite are found only as a testimony to such a past transformation.The limited thickness of the oxalate patina must be related to the shallow penetration of the fungi hypae into the rock. Because of this, the phenomenon of oxalate formation: (1) has been first observed on monuments, where superficial weathering processes are better studied; and (ii) has been found on the vertical surfaces of monuments where this phenomenon is not masked by other weathering processes, as usually occurs on natural outcrops.Finally, regarding the oxalates present on monuments, such as the so-called “scialbatura” of Roman imperial marble: their origin has been widely reported in the literature as being due to protective treatments. Our experimental results firmly exclude this.     

Chemical composition and origin of black patinas on granite

Black patinas from the surfaces of granite outcrops (including some with engravings) and granite buildings were analysed. Rock samples were also taken from areas of the same surfaces where there were no black patinas. The constituent elements of the granite rocks, elements of essentially biological origin (C, N, H) and other minor elements, including some typical from pollution, were all determined. The ratios between the concentrations of each element in the patinas and in the corresponding rock samples without patina were calculated in order to determine which elements form the patinas. The data were then examined by hierarchical cluster analysis and principal components analysis to establish the factors that determine the differences between samples. It was found that the elements that differentiate the patinas from the samples of rock without patina are those unrelated to granite, which indicates that, at least from a geochemical point of view, the rocky substrate does not affect patina formation. In all patinas analysed, the concentrations of carbon were higher than in the corresponding samples without patina; there were also relatively higher concentrations of sulphur, phosphorus, chlorine, calcium, etc. in some patinas, depending on the situation of the outcrop or monument.     

高温下大理岩受压破坏的细观结构分析

探究高温对岩石的作用机制,对于解决高温岩石工程问题具有重要意义。利用日本日立公司制造S–3000 N扫描电子显微镜对在20 ℃,200 ℃,400 ℃,600 ℃,800 ℃高温作用下以及经历400 ℃,600 ℃和800 ℃高温作用冷却后受单轴压缩破坏的徐州大理岩进行表面元素分布测定、表面形貌观察和超微结构分析,以期在细观层次上对大理岩的受压变形、强度及破坏特性等做出机制性的解释。研究结果表明：常温下徐州大理岩的颗粒较为粗大,为典型解理开裂且部分颗粒内及颗粒间存在裂纹,温度升高至800 ℃时,岩样端口表面碎裂明显、颗粒变小且形态较为规整、部分区域内存在细长裂纹;高温下和高温后受压破坏的大理岩细观结构差异较大;800 ℃之前大理岩总体的质量百分比没有明显变化,温度达到800 ℃时大理岩各元素的质量百分比发生较大的变化,Ca元素的质量百分比急剧下降而Si元素的质量百分比迅速上升,说明其结构可能发生由晶态向非晶态的相转变,致使大理岩的力学指标骤降。     

骨料界面特性对混凝土力学性能的影响

采用计算机断层扫描成像(CT)技术、扫描电镜(SEM)、X射线能谱仪(EDS)、显微硬度(MH)等各种微细观测试手段对砂岩、锈染砂岩、锈面砂岩、板岩及大理岩骨料界面特性开展了试验研究,分析了以上几种骨料的界面特性对混凝土力学性能的影响机理.研究表明：不同骨料界面区微结构相差很大,不同骨料的化学成分和矿物组成影响了界面区水化产物的数量、形态、尺寸和生长发育特性;骨料的界面区显微硬度与界面区钙硅比有良好的对应关系,钙硅比越大则界面显微硬度越低;大理岩混凝土的起裂强度明显低于砂岩、板岩和锈染砂岩混凝土,且相同荷载条件下,大理岩混凝土的裂纹面积远高于其他骨料混凝土.     

Changes in the engineering properties of marble in fire-exposed columns

Two marble columns in the bottom floor of a school building were exposed to intensive heat in the fire, and were subject of a debate about their load-carrying capacity following the event. After their removal from their original spots, series of tests on column samples were carried out to investigate variations in their engineering characteristics due to fire hazard. The temperature at the surface of the marble columns hit by the flames directly during the fire was estimated to be on the order of 500 °C using an empirically established relationship between porosity and temperature on intact marble core samples. Results of mechanical tests indicated that marble columns were still holding a significant load-carrying capacity despite 23% loss of strength at fire temperature. The spallings at the corners of the blocks forced the board of education to give the decision of replacing the gray marble columns with steel members. Occurrence of these spallings is attributed to stress concentrations and widening of micro fractures. Based on the results of mechanical, physical and chemical tests, a methodology to assess influence of fire hazard on marble and similar geological materials was developed.     

单轴拉伸作用下层状岩石表面裂纹的形成模式及其机制研究

 层状岩石的表面裂纹发端于表面自由边界,而后向着层与层之间的交界面扩展,最后止于交界面或沿着交界面继续扩展。为更深入地理解这一表面裂纹扩展现象的机制,采用数值模拟方法,再现微裂纹从萌生、扩展、贯通、成核、填充到饱和的全过程,以及层间剥离现象。首先以表面预制裂纹的模型为例,对其进行单轴拉伸加载,发现不同预制裂纹间距的情况下两裂纹间的应力分布不同,这将直接影响到新裂纹的产生模式,即裂纹是插入到表层(与已有裂纹平行),还是不再有新裂纹插入(裂纹饱和),而是产生层间剥离,或已有裂纹向下扩展,导致模型破坏。其次,对比分析模型均质和非均质情况下不同裂纹间距时的应力分布,结果表明非均质材料情况下产生相同间距的裂纹所需的荷载较均质材料情况下更小,裂纹饱和对应的裂纹间距与层厚比值的临界值基本一致。最后,提取等间距裂纹形成过程中若干具有代表性的截面应力,通过分析其应力转化机制,解释裂纹饱和现象的力学机制。数值计算得到的应变与裂纹间距之间的关系拟合结果良好。研究结果还表明：产生层间开裂的裂纹间距比没有层间开裂的裂纹间距大。通过对层间的应力传递过程随着裂纹间距变化规律的探讨,研究此过程的应力传递模式。     

Restaurierung antiker Tempel: Experimentelle Untersuchungen zum Ausziehverhalten von Verankerungen im Marmor

Restoration of antique temples: Experimental investigations on the pull‐out behaviour of anchors in marble. In restoration works of antique Greek temples individual marble blocks are connected together to form a single element, e.g. an architrave. Due to the demand of reversibility of the intervention, this is done in the Acropolis of Athens by means of titanium threaded bars that are inserted in the marble, in predrilled holes filled with cement mortar. This way of restoration corresponds to a partial rehabilitation of the architraves. This paper presents experimental investigations on the pull‐out behaviour of such anchors. The tests are performed in specially designed equipment. Failure takes place for all tests in the interface between the mortar and the marble. It has been shown that the form of the thread influences considerably the carrying capacity. Possible limit states are introduced.     

掺纳米SiO2与掺硅粉的水泥硬化浆体的性能比较

作者应用XRD物相分析净浆稠度与凝结时间和硬化浆体强度试验，对掺纳米SiO2与掺硅粉的水泥硬化浆体的性能进行了比较性研究。研究得到：与掺硅粉的水泥浆体相比，掺纳米SiO2的浆体具有流动性变小和凝结时间缩短的现象，掺入纳米SiO2能显著地提高水泥硬化浆体的早期强度，能更有效更迅速地吸收界面上富集的氢氧化钙，能更有效更大幅度地降低界面氢氧化的取向程度。这些结果均有利于界面结构的改善和界面物理力学性能的提高。     

Performance analysis of solar still with different energy-absorbing materials

Solar still is a simple device which can convert available waste or brackish water into potable fresh water by utilising solar energy. In the present research work, an attempt has been made to store excess heat energy in solar stills during the daytime for the continuation of the process at late evening and night hours for increment distillate output. To investigate the effect of energy storage materials on the productivity under the same climatic conditions, three same-size single-basin single-slope solar stills with an area of 1?m² made of fibre reinforced plastic (FRP) sheet were tested with 0.04?m layer of water level to investigate effects on solar still. Different energy storage materials like marble pieces and sandstones were used for easy availability and lower price. It has been found that sand stones are more productive compared with marble pieces and without materials inside solar still.     

河南省卢氏县橡子庙沟铁矿床特征及成因研究

河南省卢氏县橡子庙沟铁矿床地处北秦岭加里东褶皱系多金属成矿带,通过地表工程和中深部钻探工程,控制主矿体9条矿脉。矿体多呈似层状产出,矿体与围岩产状基本一致,层控作用明显。与成矿关系密切的为二郎坪群火神庙组地层,在变细碧岩与大理岩的接触带是最有利的成矿部位,矿区内断裂构造的多期次活动对矿液的运移和富集起到了重要作用,汤河岩体及张家庄岩体为本区多金属成矿提供了丰富的成矿物质和成矿热液。结合区域地质背景、矿床地质特征及区内矿物岩石学特征,认为矿床成因与海相火山—侵入活动有关,为海相火山岩型铁矿床。     

Protective patinas applied on stony façades of historical buildings in the past

The ochre patina that covers the limestone façades of Palacio de Nuevo Baztán is composed of calcite, clay minerals, gypsum, quartz, potassium feldspar, alongside traces of calcium oxalates, calcium phosphates, iron oxides and hydroxides. It is a polistratified film, rich in Ca, Si, Al and P, as well as Mg, K, Fe and Cl. Results obtained indicate that the origin of the patina lies in a treatment applied on the stone in the past, consisting of a mixture of lime, gypsum, milk-derived compounds and inorganic earth pigments. This film has protected the stone on which it was applied, and should be preserved in any further stages of intervention on the stone façades.     

Investigation of meso-failure behaviors of Jinping marble using SEM with bending loading system

In this study, the meso-failure mechanism and fracture surface of Jinping marble were investigated by means of scanning electron microscope(SEM) with bending loading system and laser-scanner equipment. The Yantang and Baishan marbles specimens from Jinping II hydropower station were used. Test results show that the fracture toughness and mechanical behaviors of Yantang marble were basically higher than those of Baishan marble. This is mainly due to the fact that Baishan marble contains a large percentage of dolomite and minor mica. Crack propagation path and fracture morphology indicated that the direction of tensile stress has a significant effect on the mechanical behaviors and fracture toughness of Baishan marble. For Yantang and Baishan marbles, a large number of microcracks around the main crack tip were observed when the direction of tensile stress was parallel to the bedding plane.Conversely, few microcracks occurred when the direction of tensile stress was perpendicular to the bedding plane. The presence of a large number of microcracks at the main crack tip decreased the global fracture toughness of marble. The results of three-point bending tests showed that the average bearing capacity of intact marble is 3.4 times the notched marble, but the ductility property of the defective marble after peak load is better than that of the intact marble. Hence, large deformation may be generated before failure of intact marbles at Jinping II hydropower station. The fractal dimension of fracture surface was also calculated by the cube covering method. Observational result showed that the largest fractal dimension of Yantang marble is captured when the direction of tensile stress is parallel to the bedding plane. However, the fractal dimension of fracture surface of Yantang and Baishan marbles with tensile stress vertical to the bedding plane is relatively small. The fractal dimension can also be used to characterize the roughness of fracture surface of rock materials.     

锦屏层状大理岩断裂机制的细观试验研究

 锦屏地下深埋岩石处于高应力状态,地下洞室开挖后围岩变形破坏所引起的工程问题十分突出。结合取自锦屏二级交通辅助洞的层状盐塘组大理岩及均质的白山组大理岩,利用扫描电镜高温疲劳试验系统,对层状盐塘组大理岩进行不同作用方向下的三点弯曲试验,并和均质的白山组大理岩试件进行对比分析研究层状大理岩不同层理方向的细观断裂机制及其与特征参数间的关系,同时,研究层理与主应力方向的关系对洞室围岩破坏机制的影响。结果表明：围岩层状特性是由于白云石及方解石矿物条带状分布所致;作用力方向对层状围岩的断裂机制有着决定性的影响,均质白山组大理岩试件细观断裂机制为沿晶断裂,作用力方向垂直盐塘组大理岩层理时为穿晶断裂与沿晶断裂的耦合作用模式,作用力方向平行层理时则以沿矿物条带间的沿晶断裂机制为主;断裂机制的不同使得宏观上的强度参数呈规律性差异,盐塘组平行层理试件与白山组试件的峰值荷载分别为盐塘组垂直层理的58%,44%,峰值断裂能分别为42%,29%;作为断裂机制外在宏观表现的3组试件断面形貌具有自相似分形特征。     

Effects of powder concentration and type of resin on the performance of marble composite structures

In this work, we will expose the behaviour of a composite structure reinforced with marble powder. The attention was focused on the effects produced on the physical and mechanical properties due to different kinds of matrix (epoxy and polyester resins) and filler amounts (60%, 70%, 80%). Rheological, static flexural and Izod impact tests have been carried out. An experiment designed was defined for the mechanical tests, in order to quantify the effects of both the resin and the marble percentage on the material properties, as well as to identify a possible correlation between these factors. Moreover, water absorption and stain resistance have been evaluated to study the surface properties of the panels.     

含预制裂隙大理岩SHPB动态力学破坏特性试验研究

为了研究端部裂隙形态对岩石动态力学特性以及裂纹扩展的影响,利用50 mm×50 mm圆柱形大理岩加工含不同裂隙倾角的试样,在50 mm杆径分离式霍普金森压杆(SHPB)试验平台上进行冲击加载试验,并使用高速摄影仪实时记录裂纹扩展以及动态破坏全过程。研究表明,大理岩的动态抗压强度、峰值应变、动态弹性模量等力学参数随预制裂隙倾角增大整体呈先减小后增大的趋势;裂纹大多是从裂隙尖端或附近起裂,起裂裂纹为II型剪切裂纹或I–II型复合裂纹(拉剪复合裂纹),起裂角和起裂应力随着预制裂隙角度的增大分别呈M和W型变化,完整和90°裂隙试样最终呈劈裂拉伸破坏,45°裂隙试样呈拉剪复合型破坏,30°和60°裂隙试样呈剪切破坏,存在一个临界角度,临界角两侧裂纹扩展特性表现出较好的对称性;随着预制裂隙角度的增大,岩石的能量吸收率先增大后减小,当端部裂隙与端面成适当角度,会使能量吸收率最大,可以有效提高破岩效率。     

深圳光汇油库边坡稳定性分析及工程治理

 针对深圳光汇油库边坡由于连续强降雨导致的滑坡,分析该滑坡形成的原因和工程治理方案。现场勘查结果表明,滑动面处于顺坡向陡倾角的强～中风化接触面上,在强降雨条件下,部分下渗的降雨在岩土分界面上汇流,渗流强度加大,黏性颗粒大量流蚀,致使黏聚力值急剧下降,削弱岩土体的整体强度并导致滑坡的产生。根据该边坡的滑坡体结构特征反算滑动面的强度指标,结果表明黏聚力在饱水状态后的大幅度衰减与预先的分析是吻合的。在保持岩土参数不变的情况下,讨论软弱面坡度变化对稳定性的影响规律,认为二者之间并非呈单调变化的关系。考虑到坡脚的大型油罐和坡顶高压电塔的破坏后果很严重,采用抗滑桩加锚索的分级支护体系并基于计算分析确定支护参数。监测结果证明在后续强降雨条件下变形稳定,治理效果良好。上述分析和治理方法为类似强降雨条件下高危边坡的工程治理提供参考经验。     

Effects of microfissures on the engineering properties of the marble at Wadi Lisb,Saudi Arabia

The marble at Wadi Lisb was investigated in detail in order to assess its engineering properties and to examine the effect of the microfissures on these properties. The marble is white with some dark bands containing the microfissures and parallel to the regional foliation direction. The samples that are cut parallel to these dark bands have better physical and mechanical properties than those cut perpendicular to them. The general effect of the microfissures on Wadi Lisb marble is similar to their effect on Al Madrakah marble indicating a regional phenomenon. During the quarrying operation, it is recommended to take the direction of the microfissures in consideration and to correct for any deviation during the slapping process.     

Geochemical changes in sulfidic mine tailings stored under a shallow water cover

The objective of this study was to assess the effectiveness of an engineered shallow water cover in reducing the oxidation of sulfidic mine tailings and thus preventing the development of acid rock drainage. Fresh tailings were submerged under a 0.3-m water cover in experimental field cells. From 1996 to 1998, we followed the chemistry of the interstitial water near the tailings-overlying water interface using in situ dialysis, and determined pH and dissolved oxygen (DO) profiles across the tailing water interface using micro-electrodes. Penetration of DO into the tailings was limited to <7 mm, even in the presence of DO produced by benthic periphyton. Anoxia in the tailings was further demonstrated by the appearance of dissolved sigmaH2S, Fe and Mn in pore water at depths -1.5 cm below the interface. However, there was clear evidence of surface oxidation of the mine tailings at the mm scale (i.e., DO depletion, coupled with localized increases in [H+] and [SO4(2-)]). Mobilization of Cd and Zn from this surface layer was indicated by the presence of sub-surface peaks in the concentrations of these two metals in the tailings interstitial water and by a change in their solid phase partitioning from refractory to more labile fractions. In contrast, mobilization of Cu from tailings was less evident. Unlike previous reports, which suggested that submerged tailings were effectively inert, our results show alteration of the superficial layer over time.     

Origin of the pozzolanic effect of rice husks

Rice husk ash has been used in many countries as a low cost concrete admixture because of its role as a filler and a pozzolan. A study is made of an ash produced in Senegal to establish the existence and origin of silica. Two calcinated rice husk ashes were studied. X-Ray diffraction analysis revealed the presence of quartz whose origin may be attributed to contamination and/or re-crystallisation of silica in the calcination. Amorphous silica was detected by scanning electron microscopy and microanalysis, its presence is concentrated on the interior and exterior surfaces of the uncalcinated husk which may promote a pozzolanic action on the surface of the husk and therefore enable its use in lightweight concrete.     

Adhesion processes and formation of a sludge in granular layers of the medium of contact filters

The paper introduces a modern dynamic model of the process of contact regent clarification of aqueous suspensions in a granular filtering layer. It has been found that the intermittent mode of introducing the solutions of a coagulant and a flocculant before the granular layer at certain time intervals and doses makes it possible to increase the total surface between the intergranular space compared with the initial one 1.1–1.2 times. Due to the enhancement of adhesion forces at the interface and strength properties of the sludge the specific sludge capacity of the filtering layer increases. The obtained data is a framework for designing radial high-capacity filters with relatively small (up to 30–40 cm) layers o the filter medium.