激光诱导击穿光谱分析法及其在彩绘文物分析与表征中的应用

激光诱导击穿光谱分析法是基于激光辐射与物质相互作用产生等离子体而进行实时、快速测定、表征的一种光谱分析新方法。其具有高灵敏度、高分辨率,分析速度快,样品用量少,无需样品预处理,一次光谱可测定多种元素组分等特点,且可在非破坏和非接触的条件下进行在线和实时分析测定,已广泛应用于材料、生物、环境、冶金、医学和文物等领域的测量和表征研究。本文从激光诱导击穿光谱分析法的基本原理、仪器装置及其在彩绘文物研究中的应用和进展进行了综述。     

A COMBINED MULTI‐ANALYTICAL APPROACH FOR THE STUDY OF ROMAN GLASS FROM SOUTH‐WEST IBERIA: SYNCHROTRON μ‐XRF,EXTERNAL‐PIXE/PIGE AND BSEM–EDS

An integrated, multi‐analytical approach combining the high sensitivity of SR‐μXRF, the light element capability of PIXE/PIGE under a helium flux and the spatial resolution of BSEM + EDS was used to characterize chemical composition and corrosion of glass samples (first to fourth centuries ad ) from an important, but scarcely investigated, Roman region of south‐west Iberia (southern Portugal). The geochemical trends and associations of major, minor and trace elements were investigated to shed light on production techniques, the provenance of raw materials and decay mechanisms. The results, while confirming a production technique common to Roman glasses throughout the Empire—that is, a silica‐soda‐lime low‐Mg, low‐K composition, with glass additives as colouring and/or decolouring agents (Fe, Cu, Mn, Sb)—show at one site high Zr–Ti contents, suggesting a more precise dating for these glasses to the second half of the fourth century. The Ti–Fe–Zr–Nb geochemical correlations in the pristine glass indicate the presence of minerals such as ilmenite, zircon, Ti‐rich Fe oxides and columbite in the sands used as raw materials for the glass former: these minerals are typical of granitic‐type source rocks. The unusually high K content in the corrosion layers is consistent with burial conditions in K‐rich soils derived from the alteration of 2:1 clays in K‐bearing rock sequences.     

Chemical Weathering of Detrital Sediments in the Taklamakan Desert,Northwestern China

Based on the analysis of major‐element compositions of detrital sediments from the Taklamakan Desert of northwestern China, this paper aims to study chemical weathering in a hyper‐arid desert environment. The major‐element compositions are basically similar to the Upper Continental Crust but show a clear enrichment of CaO and depletion of Na₂O and K₂O, indicating the enrichment of carbonates and the decomposition of sodium and potassium silicates. The indexes of chemical alteration are relatively low and correlate negatively with the content of Na₂O, implying that the degree of chemical weathering is weak and mainly controlled by the weathering of sodium feldspars. An A‐CN‐K model demonstrates that the detrital sediments from the Taklamakan Desert have a high homogeneity in the trend of chemical weathering. They are weathered less than sands and soil in many other Chinese deserts, and also less than similar detrital sediments in many other countries. This evidence suggests a low degree of mineralogical maturity in the Taklamakan Desert. The aeolian sediments of different ages have similar indexes of chemical weathering, suggesting that the degree of chemical weathering was consistent in the Taklamakan Desert throughout the period of aeolian deposition. The low degree of chemical weathering is caused principally by extreme aridity, rapid rejuvenation of detrital sediments associated with strong aeolian processes, and an intensive input of fluvial deposits, as well as a lack of vegetation. Due to the high concentration of erodible minerals, the desert is quite vulnerable to soil erosion and land degradation.     

EVALUATION OF THE ANALYTICAL POTENTIAL OF LASER‐INDUCED BREAKDOWN SPECTROMETRY (LIBS) FOR THE ANALYSIS OF HISTORICAL GLASSES*

The novel and—for archaeometrical applications—still rarely used Laser‐Induced Breakdown Spectrometry (LIBS) was tested on various standard glasses for its spectrometric performance. LIBS is an almost non‐destructive method based on the time‐resolved detection of optical emission following direct laser ablation. A frequency‐quadrupoled Nd:YAG laser at 266 nm was found to cause a hardly visible crater of c. 200 µm in diameter. The application of an innovative high‐resolution Echelle spectrograph allows the fast and simultaneous determination of up to 90 elements in the spectral range from 200 to 780 nm, with a resolution of 10–30 pm under ambient conditions. In principle, LIBS has a high analytical potential for archaeometry; in particular, for the determination of light elements (Li, Be, B and others). Because the measurement parameters (laser energy, delay time and number of pulses) do not independently influence the emission signal, their optimization proved to be complex and is rather a compromise for the range of elements. The effects of sample distance, surface roughness and the accumulation of depth profiles were studied. Problems arose for the determination of sodium and potassium in higher contents due to self‐absorption effects. Quantification tests using a silicon line as internal standard yielded a precision range between 3% and 20% relative, but in general no satisfying accuracy for a number of elements. However, these problems might be overcome in the near future by improved spectrometer set‐ups and matrix correction approaches.     

A laboratory cave for the study of wall degradation in rock art caves: an implementation in the Vézère area

The aim of this proposal is to present an original approach to the study and preservation of rock art caves. A multidisciplinary study of cave wall alteration will be performed to understand the impact of environmental context on the evolution of wall surfaces. The approach involves the choice of a cave with characteristics similar to painted caves in the studied area (Vézère Valley in Dordogne, France): e.g., cave wall alteration, lithology, morphology, etc. This selected cave is intended to become a laboratory cave, monitored for the acquisition of chemical, physical and biological environmental data on bedrock, air and fluids along with their characteristics. A cave without art or archaeological interest has been chosen specifically to conduct experiments, to make in situ analysis and to obtain samples. The results are to be completed by specific observations in several other caves and compiled in a database.     

秦俑陶片的偏光显微分析研究

为了预防性保护和修复秦俑,必须掌握秦俑残片显微结构及其烧制环境、破损方式,从而为改善秦俑修复工艺、筛选修复材料提供基础,运用偏光显微镜对秦兵马俑残片中的一些矿物质(石英、长石、云母等)颗粒的分布形态和含量来分析陶土的成分结构、制作工艺、烧成气氛及原料来源等信息。结果表明,秦俑陶片主要成分为少量砂屑及大量粘土,而粘土为岩土矿风化的产物,秦俑残片裂痕较多的部位风化、酥粉痕迹明显。秦俑制作工艺以模为主,模、塑结合,并在粘土中添加了细砂,多于还原气氛中烧制而成。     

Hydrothermal control on organic matter alteration and illite precipitation, Mt Isa Basin, Australia

Abundant illite precipitation in Proterozoic rocks from Northern Lawn Hill Platform, Mt Isa Basin, Australia, occurred in organic matter‐rich black shales rather than in sandstones, siltstones and organic matter‐poor shales. Sandstones and siltstones acted as impermeable rocks, as early diagenetic quartz and carbonate minerals reduced the porosity–permeability. Scanning and transmission electron microscopy (SEM and TEM) studies indicate a relation between creation of microporosity–permeability and organic matter alteration, suitable for subsequent mineral precipitation. K–Ar data indicate that organic matter alteration and the subsequent illite precipitation within the organic matter occurred during the regional hydrothermal event at 1172 ± 50 (2σ) Ma. Hot circulating fluids are considered to be responsible for organic matter alteration, migration and removal of volatile hydrocarbon, and consequently porosity–permeability creation. Those rocks lacking sufficient porosity–permeability, such as sandstones, siltstones and organic matter poor shales, may not have been affected by fluid movement. In hydrothermal systems, shales and mudstones may not be impermeable as usually assumed because of hydrocarbons being rapidly removed by fluid, even with relatively low total organic carbon.     

Source of ore fluids at the Kalahari Goldridge deposit, Kraaipan greenstone belt, South Africa: evidence from Sr, C and O isotope signatures in carbonates

The Kalahari Goldridge deposit is located in the Archaean Kraaipan greenstone belt in the north-west province of South Africa. Gold mineralization in this deposit is hosted within banded iron formation which is flanked by a mafic schist in the footwall and clastic metasedimentary units in the hanging wall. Data from carbonate minerals from mineralized veins and bulk rock from the A and D zone ore bodies have helped to define the ultimate origin of the ore-forming fluids and their migration history. Carbon isotope ratios of carbonates from both the A and D zone ore bodies have tight clustering from −7.6 to −5.3‰ that indicates a unique origin for the ore-forming fluids associated with the mineralization at Kalahari Goldridge. The δ¹⁸O values of the carbonates have been influenced by temperature gradients and variable degrees of fluid–rock interaction promoting oxygen isotope exchange between ore fluid and host rocks. Minimum ⁸⁷Sr/⁸⁶Sr ratio values of 0.70354 in mineralized veins are most consistent with ore-forming fluids being relatively pristine with a mantle origin. Strontium and the corresponding ore-forming fluids were most likely derived from mantle-derived magmatic rocks probably represented by the meta-basaltic rocks that underlie the ferruginous package in the Kraaipan greenstone belt. Strontium isotopic composition of vein carbonates show considerable variation in ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.70354 to 0.73914. This is consistent with an ore fluid composition that has been modified by the addition of radiogenic Sr possibly during passage of fluid through siliciclastic country rock concomitant with the observed hydrothermal alteration.     

Diffusion and kinetic control of weathering layer development

The formation of porous weathering rinds (layers of chemical alteration) on the exterior of rocks is a consequence of dissolution and precipitation of minerals occurring at the mineral–fluid interface within the pores. The speed at which the developed rind advances is controlled by both kinetic reaction rates and the transport of reaction products away from the pore spaces into the outside fluid. We show, using both reaction‐diffusion theory and numerics, that under diffusion limitations, the weathering rate depends on the size and curvature of the sample. This leads to a relationship between rind thickness, δ, and age, t. As the rind thickens, the result in three dimensions differs substantially from the one‐dimensional result of . We describe the conditions under which the one‐dimensional and diffusion‐limited approximations apply and how they evolve as the rock weathers. Under chemical kinetic limitations, the rind advances at a constant rate, dδ/dt = v. We defend the application of a spherical approximation to irregular non‐spherical rocks and apply our results to field observations reported in the literature to show consistency with established methods. Finally, we argue that the variability in size, as well as in mineralogy, over ensembles of grains contributes to heterogeneous weathering rates. We demonstrate that this heterogeneity can contribute to the aging, or gradual decrease with time, of weathering rates previously observed in laboratory and field measurements.     

An experimental and modeling study of Na-rich hydrothermal alteration

Sodic alteration assemblages including clinoptilolite, mordenite, analcime and Na‐montmorillonite were locally observed in sediments in the eastern part of the Hachimantai geothermal region, northeast Japan. This study investigated the mechanisms of sodic enrichment in the sediments during alteration. Kinetic results for water/rock interaction experiments are reported here. Batch‐type experiments were conducted at 150–250°C under saturated vapor pressure. Pyroclastic rocks dissolved incongruently in these experiments, and the solubility and dissolution rates among elements varied as follows: the apparent steady‐state concentrations of major elements are Si > Na ? K > Ca > Al and the order of the dissolution rates is Si > Al > Na ? K > Ca. Na had the highest steady‐state concentration and fastest dissolution rate of the alkali and alkali earth metal ions. Based on surface analysis of plagioclase, dissolution was effected via a reaction layer of Na‐montmorillonite on the mineral surface. Additionally, a reaction model constructed based on the experimentally observed reaction mechanism quantitatively explains the dissolution behavior. These results show that Na‐montmorillonite can be precipitated by pyroclastic rock/meteoric water interactions without seawater involvement: the Na is derived from the host rocks.     

贺兰口岩画附近典型危岩体稳定性分析

通过前期现场调查,分析了贺兰口岩画的主要病害,提出岩画附近的危岩体是其中威胁较大的一类地质病害。根据现场勘察将贺兰口岩画附近不同状态的危岩体分为坠落式、滑塌式和倾倒式三类失稳模式。经过室内试验得到了岩石矿物组成、密度、气孔率、吸水率、单轴抗压强度等物理性质,并且利用Hoek-Brown准则、贯通率法以及岩石表面回弹值估算了危岩体与主控结构面的强度参数,例如单轴抗拉和抗压强度、变形模量、内摩擦角和黏聚力,然后利用不同失稳模式的计算方法进行稳定性分析。结果表明部分危岩体处于不稳定状态中,需要进行加固。     

Monitoring fluid chemistry in iron oxide–copper–gold‐related metasomatic processes,eastern Mt Isa Block,Australia

Most researchers in the Proterozoic eastern Mt Isa Block, NW Queensland, Australia, favour magmatic fluid and salt sources for sodic‐(calcic) alteration and iron oxide–copper–gold mineralization. Here we compare spatial, mineralogic and stable isotope data from regional alteration assemblages with magmatic and magmatic‐hydrothermal interface rocks in order to track chemical and isotopic variations in fluid composition away from inferred fluid sources. Tightly clustered δ¹⁸O values for magnetite, quartz, feldspar and actinolite for igneous‐hosted samples reflect high temperature equilibration in the magmatic‐hydrothermal environment. In contrast, these minerals record predominantly higher δ¹⁸O values in regional alteration and Cu–Au mineralization. This dichotomy reflects partial equilibration with isotopically heavier wallrocks and slightly lower temperatures. Increases in Si concentrations of metasomatic amphiboles relative to igneous amphiboles in part reflect cooling of metasomatic fluids away from igneous rocks. Variations in X_Mg for metasomatic amphiboles indicate local wallrock controls on amphibole chemistry, while variations in X_Cl/X_OH ratios for amphiboles (at constant X_Mg) indicate variable aH₂O/aHCl ratios for metasomatic fluids. Biotite geochemistry also reflects cooling and both increases and decreases in aH₂O/aHCl for fluids away from plutonic rocks. Decreased aH₂O/aHCl ratios for metasomatic fluids reflect in part scavenging of chlorine out of meta‐evaporite sequences, although this process requires already saline fluids. Local increases in aH₂O/aHCl ratios, as well as local decreases in δ¹⁸O values for some minerals (most notably haematite and epithermal‐textured quartz), may indicate ingress of low salinity, low δ¹⁸O fluids of possible meteoric origin late in the hydrothermal history of the region. Taken together, our observations are most consistent with predominantly magmatic sources for metasomatic fluids in the eastern Mt Isa Block, but record chemical and isotopic variations along fluid flow paths that may be important in explaining some of the diversity in alteration and mineralization styles in the district.     

云冈石窟盐类析出物与石雕表面风化破坏形式的关系研究

云冈石窟盐害机理研究对于治理策略选择具有重要意义,为探析云冈石窟风化砂岩破坏形式与岩面伴生盐类析出物的关系,本工作采用XRD法进行了矿物组成的半定量测试,采用酸碱中和法进行了CO₂含量测定,另外采用XRD进行了盐类矿物和硅酸盐矿物定性鉴定,试图探析云冈石窟风化砂岩破坏形式与岩面伴生盐类析出物的关系。结果显示:云冈石窟岩面片状风化与砂岩碳酸盐含量高有关,而粉状风化与岩石中石膏含量高有关,不同盐类结晶析出与洞窟环境有关,这些研究结果对云冈石窟风化病害治理有借鉴意义。     

Decreasing CO2 partial pressure triggered Mg–Fe–Ca carbonate formation in ancient Martian crust preserved in the ALH84001 Meteorite

We retrace hydrogeochemical processes leading to the formation of Mg–Fe–Ca carbonate concretions (first distinct carbonate population, FDCP) in Martian meteorite ALH84001 by generic hydrogeochemical equilibrium and mass transfer modeling. Our simple conceptual models assume isochemical equilibration of orthopyroxenite minerals with pure water at varying water‐to‐rock ratios, temperatures and CO₂ partial pressures. Modeled scenarios include CO₂ partial pressures ranging from 10.1325 to 0.0001 MPa at water‐to‐rock ratios between 4380 and 43.8 mol mol^?1 and different temperatures (278, 303 and 348 K) and enable the precipitation of Mg–Fe–Ca solid solution carbonate. Modeled range and trend of carbonate compositional variation from magnesio‐siderite (core) to magnesite (rim), and the precipitation of amorphous SiO₂ and magnetite coupled to magnesite‐rich carbonate are similar to measured compositional variation. The results of this study suggest that the early Martian subsurface had been exposed to a dynamic gas pressure regime with decreasing CO₂ partial pressure at low temperatures (approximately 1.0133 to 0.0001 MPa at 278 K or 6 to 0.0001 MPa at 303 K). Moderate water‐to‐rock ratios of ca. 438 mol mol^?1 and isochemical weathering of orthopyroxenite are additional key prerequisites for the formation of secondary phase assemblages similar to ALH84001’s ‘FDCP’. Outbursts of water and CO_2(g) from confined ground water in fractured orthopyroxenite rocks below an unstable CO₂ hydrate‐containing cryosphere provide adequate environments on the early Martian surface.     

四川摩崖造像岩石的工程物理特性

在自然力的影响下摩崖造像所产生的风化、剥蚀、开裂等种种病害,是与其岩石本体的理化性质有着密切关系.因此,进行摩崖造像保护工程的前期,做好对岩石的工程物理特性调研是非常必要的.为此,根据摩崖造像的分布,经代表性选点、取样并测试.结果表明,四川地区摩崖造像的岩石本体均为砂岩,存在明显软化现象,试验数据有明显的规律性,且各项指标间的相关性较好.其成果为今后保护工程的顺利开展奠定了初步基础.     

水硬石灰作为贺兰口岩画加固材料的耐候性能研究

为了研究水硬性石灰在贺兰口地区的稳定性,以贺兰口岩石为试验对象,在实验室里分别用水硬性石灰和环氧树脂加固试块,并且做了耐冻融、耐热、耐高低温交变等一系列的耐候性能对比试验。结果表明,水硬性石灰与环氧树脂相比有较好的耐热性能;在冻融环境中,水硬石灰没有环氧树脂性能稳定,容易产生脱落现象。     

Weathering of rock art at two sites in the KwaZulu-Natal Drakensberg,southern Africa

Sediments of the Karoo Basin in southern Africa represent one of the world's finest laboratories for investigating sandstone weathering. The natural breakdown of these sandstones, most notably in the Clarens Formation, is destroying much of the indigenous rock art heritage that exists there. In an attempt to elucidate the operative weathering processes, a range of micro-climatic, rock temperature, rock moisture, rock chemistry, and rock property data have been monitored over a 15 year period at two sites in the KwaZulu-Natal Drakensberg. Results suggest that rock moisture regimes and to a lesser extent, rock thermal regimes exert the most damaging influence on San paintings. It is argued that granular disintegration and the enlargement of existing sandstone pores and bedding planes close to the rock surface, facilitate an increasingly dynamic moisture regime, which leads to an accelerating rate of weathering. Recent technological advances in data collection suggest that a re-evaluation of environmental controls may be necessary before weathering, at a scale appropriate to the deterioration of rock art, can be fully understood. The continued existence of indigenous rock art in southern Africa depends on investigations aimed at the development of techniques for its preservation.     

Tectonic evolution of a Paleozoic thrust fault influences the hydrogeology of a fractured rock aquifer,northeastern Appalachian foreland

In polyorogenic regions, the superposition of structures during a protracted tectonic history produces complex fractured bedrock aquifers. Thrust‐faulted regions, in particular, have complicated permeability patterns that affect groundwater flow paths, quantity, and quality. In the Appalachian foreland of northwestern Vermont, numerous bedrock wells that are spatially related to the Paleozoic Hinesburg thrust have elevated naturally occurring radioactivity and/or low yields. The association of groundwater quality and quantity issues with this thrust was a unique opportunity to investigate its structural and hydrogeologic framework. The Hinesburg thrust juxtaposed metamorphic rocks of the hanging wall with sedimentary rocks of the footwall during the Ordovician. It was then deformed by two orthogonal Devonian fold sets and was fractured during the Cretaceous. Median well yields in the hanging wall aquifer are significantly lower than those of the footwall aquifer, consistent with the respective permeability contrast between metamorphic and carbonate rocks. For wells drilled through the Hinesburg thrust, those completed closest (vertically) to the thrust have the highest median yields, whereas others completed farther below have yields in the footwall range. The geochemical signature of the hanging wall and footwall aquifers correlates with their whole‐rock geochemistry. The hanging wall aquifer is enriched in alpha radiation, Na+K‐Cl, Ba, and Sr, whereas the footwall aquifer is enriched in Ca‐Mg‐HCO₃ and alkalinity. Wells that penetrated the Hinesburg thrust generally have hanging wall geochemical signatures. A simple hydrogeologic model for the permeability evolution of the Hinesburg thrust involves the ductile emplacement of a low‐K hanging wall onto a high‐K footwall, with subsequent modification by fractures.     

The inclusion record of fluid evolution,crack healing and trapping from a heterogeneous system during rapid cooling of pegmatitic veins (Dronning Maud Land; Antarctica)

Granitoid (pegmatite and aplite) veins in metamorphic rocks and intrusive syenites of central Dronning Maud Land, Antarctica, are flanked by conspicuous light‐coloured alteration halos, which represent the damage zone of fracture propagation. The damage zone is characterized by a high density of sealed or healed microcracks, about 1 order of magnitude above background. Fluid inclusions along healed microcracks in quartz of both pegmatite and alteration halos are inspected by optical and scanning electron microscopy, and their composition is analysed by microthermometry and quadrupole mass spectrometry. The similar inclusion record in the granitoid vein and in the damaged host rock indicates the derivation of the fluids from the hydrous melt phase. The aqueous inclusions bear abundant daughter crystals, mainly silicates, and may represent a hydrous melt. The volatile composition is variable in the system H₂O–CO₂, with mostly subordinate amounts of N₂. Phase separation with partitioning of CO₂ into the fluid phase coexisting with the hydrous melt, and possibly immiscibility in the subsolidus range, govern fluid evolution during cooling. The variable CO₂/N₂ ratio suggests mixing with fluids from an external source in the host rock and vigorous circulation at an early stage of high transient permeability. Experiments have shown that healing of microcracks at high temperatures is a matter of hours to weeks, hence similar in time scale to the cooling of the cm‐ to dm‐thick granitoid veins. In this case, rapid cooling and concomitant crack healing in a system undergoing phase separation causes a broad compositional variability of the inclusions due to necking down, and the underpressure developing in closed compartments precludes a meaningful thermobarometric interpretation.