基于颜色计算和原位成分分析对紫色玉髓颜色成因的探究

产于印度尼西亚的紫色葡萄状玉髓,具有特殊的球粒状外观和浓郁的紫罗兰体色,其双面抛光片在反射光照射下为紫色,透射光下则为棕黄色,且颜色浓集于球粒中心。为探究其颜色成因,进行了偏光显微镜和扫描电子显微镜结构观察,显微紫外-可见光谱,热处理以及LA-ICP-MS原位成分分析。玉髓具有纤维状核心--粗粒石英外壳的特殊结构,粗粒石英外壳粒度500 μm左右,隐晶质部分则主要由粒度小于1 μm的形状不规则的SiO₂颗粒组成。紫外-可见光谱显示紫色主要来源于540 nm左右的吸收峰,而黄色则由于谱线“左倾”产生的近紫外区及蓝光区强烈吸收所致。紫外-可见光谱使用塞尔迈耶尔方程修正表面反射误差、减去无吸收波段强度矫正仪器误差,并用最小二乘平滑扣除基线得到540 nm吸收峰的强度信息。计算玉髓在反射光下的紫色调及透射光下的黄色调的L*a*b*值和E*值定量表征颜色。热处理实验中,玉髓的紫色调在350 ℃左右开始褪去,紫外-可见光谱390和540 nm吸收峰消失,反射光和透射光下颜色差异减小,都呈现黄色调。随温度升高至400 ℃后,棕色调加深,出现478 nm左右的吸收峰。热处理过程中谱线吸收强度升高,“左倾”加剧,峰位“红移”。该现象与铁/二氧化硅纳米粒子（Fe/SiO₂ NPs）生长过程中的谱形变化相似,有可能与玉髓内部与Fe有关的微细结构或包裹体在热处理过程中的变化有关。颜色参数结合原位成分分析,将数据采用标准分数（Z-score）归一化处理,比对紫色调的E*值与540 nm吸收峰强度及元素含量之间的关系,发现540 nm吸收峰强度可很好的反映紫色的浓集程度,但紫色调与过渡金属元素含量的线性相关性却并不显著,黄色调的E*值则与Fe元素含量具有近似的负相关性。Fe并不以杂质矿物的形式存在,元素含量这一因素也并不能完全决定玉髓的颜色,可能还受到Fe在玉髓中的存在形式,内部微细结构或包裹体等因素的影响。     

Mineralogical Characterization of the Polychrome in Cultural Heritage Artifacts (Antiquity to Date) from Southern Spain Using Micro-Raman Spectroscopy and Complementary Techniques

This work reports on the use of micro-Raman spectroscopy for the characterization of materials used for producing the polychrome in cultural heritage artifacts from southern Spain. The micro-Raman technique was applied for the characterization of several types of artworks or for cross-sections from these works, which were produced along different historical epochs. This technique was demonstrated to be valuable for the characterization of compounds, which were all detected within the artworks studied. The identification of all of these compounds by micro-Raman was confirmed by other complementary techniques, such as micro-X-ray diffraction and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy.     

二氧化碲(TeO2)晶体的Raman光谱研究

利用激光显微高温Raman光谱仪 ,测定了TeO2 晶体的常温Raman光谱及高温熔体法生长TeO2 晶体固 液边界层的高温Raman光谱。通过分析 ,指认了TeO2 晶体的常温Raman谱图 2 0 0～ 80 0cm- 1 谱峰的振动模式 ,解析了高温Raman谱图各谱峰的展宽、频移 ,提出了熔体可能的结构基团 ,从而为研究功能性晶体材料生长机理提供了一定依据。     

晚清彩瓷釉料的拉曼光谱研究

本文利用便携式拉曼光谱仪并结合显微拉曼光谱仪对几件清末彩瓷的拉曼光谱进行了研究。根据谱峰分析, 这几件晚清彩瓷中暗红色釉料均为Fe2O3; 浅红色和绿色彩釉的主要原料是碱式碳酸铜, 是由于工艺不同而导致铜化合物显色不同; 青黄色颜料的主要原料则是复合铅锡锑黄釉料。     

Maximum permissible noise levels at the workplace in the EEC,Spain, Portugal and Turkey (as at 1981)

The aim of this paper is to update a survey made in 1975 on scientific standards and legislation for the protection of workers from hazardous levels of noise in the workplace.This paper covers the present ten member states of the EEC and the prospective member states of Spain, Portugal and Turkey.     

Study on the contamination by transuranides of pulmonata gastropoda collected in Palomares (Spain)

A study on the contamination levels and distribution of plutonium in gastropods collected in Palomares (south-east Spain) has been performed. This region is partially contaminated with actinides following the nuclear accident occurred in 1966. The existence of plutonium in gastropods (Helix albicans and Theba pisana) along with their great gastronomic interest in the area reinforces the concern in studying the incorporation of these radioelements into a trophic level of the alimentary chain.In this work, plutonium concentration levels have been determined in the excrements, washing waters, flesh and shell of different types of gastropods collected in the Palomares most contaminated area. Plutonium analyses have been carried out following normalized procedures for the determination of this radionuclide.The results show the distribution of plutonium in washing and boiling water, excrements, soft tissues and shell of the snails. In addition, it has been estimated that the consumption of one kilogram of snails collected in the most contaminated area of Palomares could contribute up to 1/3 of the effective dose (due to ingestion) to the inhabitants of the area.     

Study on the contamination by transuranides of pulmonata gastropoda collected in palomares (Spain)

A study on the contamination levels and distribution of plutonium in gastropods collected in Palomares (south-east Spain) has been performed. This region is partially contaminated with actinides following the nuclear accident occurred in 1966. The existence of plutonium in gastropods (Helix albicans and Theba pisana) along with their great gastronomic interest in the area reinforces the concern in studying the incorporation of these radioelements into a trophic level of the alimentary chain. In this work, plutonium concentration levels have been determined in the excrements, washing waters, flesh and shell of different types of gastropods collected in the Palomares most contaminated area. Plutonium analyses have been carried out following normalized procedures for the determination of this radionuclide. The results show the distribution of plutonium in washing and boiling water, excrements, soft tissues and shell of the snails. In addition, it has been estimated that the consumption of one kilogram of snails collected in the most contaminated area of Palomares could contribute up to 1/3 of the effective dose (due to ingestion) to the inhabitants of the area.     

Investigation of environmental pollution effects on stone monuments in the case of Santa Maria La Blanca, Seville (Spain)

The aim of the study was to characterize specimens submitted to the effects of weathering in an urban atmosphere. Samples investigated were stones covered by crusts and deposits of thickness ranging from micrometers to millimetres due to traffic pollutants and mineral dust. The pieces were collected in the Church of Santa Maria La Blanca in Seville (South Spain). In the Historical Centre of this city, the traffic is the main source of sulphur oxides.     

Investigation of scaling properties in monthly streamflow and Standardized Streamflow Index (SSI) time series in the Ebro basin (Spain)

Scaling behaviors in monthly streamflow and Standardized Streamflow Index (SSI) of 11 gauging stations in Ebro basin (Spain) were analyzed: four located in the mainstream and seven in tributaries. The time span is from 1950 to 2005. The methods used are the power spectrum and the detrended fluctuation analysis. All the streamflows are signaled by the presence of the yearly oscillation, which also plays the role of crossover between two regions: for frequencies smaller than the yearly cycle (or timescales higher than 1 year) the dynamics is approximately random, while for frequencies higher than the yearly frequency (or timescales smaller than 1 year) the dynamics is persistently correlated. The SSI shows approximately similar characteristics, although the annual oscillation is not evidenced. Except for a few peculiar features, the power spectrum and the detrended fluctuation analysis (DFA) have shown similar results for all the streamflow and SSI time series, indicating a universal scaling behavior over the Ebro basin.     

Cathodoluminescence Spectral Characteristics of Quartz and Feldspars in Unaltered and Hydrothermally Altered Volcanic Rocks (Almeria,Spain)

The volcanic rocks of the Cabo de Gata region have been transformed by hydrothermal alteration, forming in some areas, highly silicified and feldspatized rocks. Various samples from outcrops of unaltered and hydrothermally altered volcanic rocks were studied by conventional transmitted-light microscopy to determine their genesis (magmatic, inherited or neoformed) and scanning electron microscope cathodoluminescence to define their spectral features. The magmatic quartz shows emission bands at 400, 440, and 480nm., and these bands disappear or decrease in the secondary hydrothermal quartz, characterized also by an intense emission band at around 570–580 nm, and another around 460 nm. The inherited magmatic plagioclase and neoformed anorthoclase have some similar emission bands and their genesis is not marked by cathodoluminescence features. The magmatic K-feldspars (sanidine), have emission bands at around 425, 440, and 490 nm, constituting a strong blue emission (420–500 nm). This emission is weaker in the neoformed K-feldspars that, however, have a strong emission band at around 570 nm. These data show that some cathodoluminescence spectral characteristic can be used to determine the petrogenesis of rock.     

Contribution of collagen stable isotope biogeochemistry to the paleobiology of extinct endemic vertebrates from Tenerife (Canary Islands,Spain)

The paleodiet and paleoenvironmental context of two extinct species from Tenerife island, one giant rat Canariomys bravoi and one giant lizard Gallotia goliath, have been investigated using carbon and nitrogen isotopic compositions of fossil bone collagen. Preliminary to this study, a calibration of the isotopic variations of bone collagen from modern Rat Rattus rattus, Rabbit Oryctolagus cuniculus and Lizard Gallotia galotti relative to environmental conditions on Tenerife Islands has been attempted. No clear relationship could be found between collagen δ¹³C and δ¹⁵N values and aridity; the only relevant factors seem to be seashore proximity for rat, and the relative amount of C₃ and CAM plants. It seems that anthropic activities have interfered with the expected relationships between collagen isotopic compositions and environmental conditions. Most fossil specimens yielded well preserved collagen. The isotopic composition of giant rat and giant lizard collagen suggest a purely C₃ environment, possibly more humid than today on Tenerife. Large ranges of nitrogen isotopic compositions, especially within giant rats, may be due to local environmental conditions. Further work is needed in order to provide more valuable paleobiological information in order to better understand the role of environmental factors in the evolution and extinction of insular endemic species on Tenerife.     

Contribution of collagen stable isotope biogeochemistry to the paleobiology of extinct endemic vertebrates from Tenerife (Canary Islands, Spain)

The paleodiet and paleoenvironmental context of two extinct species from Tenerife island, one giant rat Canariomys bravoi and one giant lizard Gallotia goliath, have been investigated using carbon and nitrogen isotopic compositions of fossil bone collagen. Preliminary to this study, a calibration of the isotopic variations of bone collagen from modern Rat Rattus rattus, Rabbit Oryctolagus cuniculus and Lizard Gallotia galotti relative to environmental conditions on Tenerife Islands has been attempted. No clear relationship could be found between collagen delta13C and delta15N values and aridity; the only relevant factors seem to be seashore proximity for rat, and the relative amount of C3 and CAM plants. It seems that anthropic activities have interfered with the expected relationships between collagen isotopic compositions and environmental conditions. Most fossil specimens yielded well preserved collagen. The isotopic composition of giant rat and giant lizard collagen suggest a purely C3 environment, possibly more humid than today on Tenerife. Large ranges of nitrogen isotopic compositions, especially within giant rats, may be due to local environmental conditions. Further work is needed in order to provide more valuable paleobiological information in order to better understand the role of environmental factors in the evolution and extinction of insular endemic species on Tenerife.     

XANES speciation of mercury in three mining districts – Almadén,Asturias (Spain), Idria (Slovenia)

The mobility, bioavailability and toxicity of mercury in the environment strongly depend on the chemical species in which it is present in soil, sediments, water or air. In mining districts, differences in mobility and bioavailability of mercury mainly arise from the different type of mineralization and ore processing. In this work, synchrotron‐based X‐ray absorption near‐edge spectroscopy (XANES) has been taken advantage of to study the speciation of mercury in geological samples from three of the largest European mercury mining districts: Almadén (Spain), Idria (Slovenia) and Asturias (Spain). XANES has been complemented with a single extraction protocol for the determination of Hg mobility. Ore, calcines, dump material, soil, sediment and suspended particles from the three sites have been considered in the study. In the three sites, rather insoluble sulfide compounds (cinnabar and metacinnabar) were found to predominate. Minor amounts of more soluble mercury compounds (chlorides and sulfates) were also identified in some samples. Single extraction procedures have put forward a strong dependence of the mobility with the concentration of chlorides and sulfates. Differences in efficiency of roasting furnaces from the three sites have been found.     

μ‐Raman spectroscopy of prehistoric paintings from the Abrigo Remacha rock shelter (Villaseca,Segovia, Spain)

The composition of the materials present in prehistoric paintings discovered on the walls of the Abrigo Remacha rock shelter (Villaseca, Segovia, Spain) has been characterised by micro‐Raman spectroscopy. In addition, scanning electron microscopy and energy dispersive X‐ray microanalysis have been used as auxiliary techniques. The results show that haematite (α‐Fe₂O₃) is the main component of the red pigment. Amorphous carbon and paracoquimbite (Fe₂(SO₄)₃.9H₂O) have been detected in the bluish black pigment used in a significant bi‐colour pictograph. This is the first time that this mineral has been discovered in a prehistoric painting. Accretions of whewellite and weddellite form crusts covering most of the painting panel. Different carbonates are the main components of the rocky substrate. The detection of gypsum on the surface of the panel is associated to the flaking process that is affecting the painting panel. Copyright © 2013 John Wiley & Sons, Ltd.     

Radon levels in the volcanic region of La Garrotxa, Spain

A preliminary survey in the city of Olot, the main town of the volcanic region of La Garrotxa, showed that dwellings built on volcanic formations present higher indoor radon levels than dwellings on non-volcanic materials. The soil of the area is not especially rich in radium. However, some of the volcanic materials present very high permeability and therefore radon entering the houses might have travelled over long distances. In this paper we present indoor radon values measured in a larger survey carried out during April–July 2004. The influence of the volcanic materials found in the preliminary survey has been confirmed. The results obtained suggest the possibility that radon comes from the degassification of mantle through active faults. The values obtained in working places do not constitute a relevant radiological risk for workers.     

Determination of the recharge area and salinization degree of karst springs in the Lamas Basin (Turkey)

The Lamas Basin is an area covering approximately 4,400 km(2) situated on the eastern Mediterranean coast of Turkey covered with highly karstified limestone and dolomitic limestone from the Miocene and Mesozoic age, respectively. Owing to the area's low karstification basement, groundwater in the karst aquifer circulates deep from the surface towards the springs along the coast as well as to the submarine springs. This study aims working out the salinization level and recharge characteristics of the Lamas Basin using environmental isotopes techniques. In the study, the data collected previously to discover, in general terms, the groundwater characteristics within the area are reanalyzed to fulfil the purpose of the study. In conclusion, it is found that the down gradient karst springs discharging along the Mediterranean coast mostly contain groundwater contributions from higher altitudes with depleted delta(18)O and delta(2)H compositions. The delta(18)O-altitude effect was determined as approximately-0.12 per thousand/100 m which may indicate sea-spray intrusion towards inland. As a result, the salinization level of coastal springs changes ranging between 1.2 % and 17.0 %. Owing to the seawater encroachment, Ca-HCO(3) water type changes to Na-HCO(3) or Na-Cl water by the cation exchange during the dry period. As the unique freshwater potential extends along the coastal area, the groundwater production should be exploited in a way that seawater encroachment is kept at minimum.     

An authentication case study: Antonio Palomino versus Vicente Guillo paintings in the vaulted ceiling of the Sant Joan del Mercat church (Valencia,Spain)

In 1695, the Valencian artist Vicente Guillo was engaged in painting the vault of the Sant Joan del Mercat church in Valencia, Spain. After preliminary work was carried out, his contract was cancelled. In 1697, Antonio Palomino, renowned for the publication of his technical treatise entitled El Museo Pictorio y Escala Optica, was finally selected as the painter in charge of decorating the vaulted ceiling of Sant Joan del Mercat. This paper reports an analytical study focused on the characterisation and discrimination of the palette and painting procedures used by Palomino and Guillo in the frescoes of Sant Joan del Mercat. For this purpose, Raman spectroscopy combined with light microscopy, scanning electron microscopy–X‐ray microanalysis, voltammetry of microparticles, X‐ray diffraction, Fourier transform infrared spectroscopy and gas chromatography–mass spectrometry has been employed. The use of gypsum as stucco material for the ground layers contrasts with the recommendations made by Palomino in his treatise about the convenience of using slaked lime‐sand mortars according to traditional fresco recipes. Although lead‐based pigments were not traditionally recommended for frescoes because of their empirically known alterations when subjected to strong alkaline fresco medium, both Guillo and Palomino used them. Palomino, probably supported by his personal experience as a painter, recommended and used Naples yellow, which has been found in a good state of preservation. In contrast, white lead areas found on Guillo's paintings have transformed into lead oxides. Other pigments found in the vaulted ceiling such as smalt, goethite, haematite, azurite and malachite have also undergone substantial changes because of the extreme temperature conditions to which they were subjected in the church. Copyright © 2012 John Wiley & Sons, Ltd.     

Weathering of gilding decorations investigated by SR: development and distribution of calcium oxalates in the case of Sant Benet de Bages (Barcelona,Spain)

In this paper seventeenth century gilded paintings from the crypt of Sant Benet de Bages, a medieval monastery in the Catalonia region of Spain, near Barcelona, have been studied. Cross sections from two different gilded decorations were studied by means of optical microscopy and electron microscopy and EDS to determine the statigraphy and elemental composition, and by means of FTIR coupled to a microscope to determine the binding media associated to each layer. These preliminary results demonstrated that gilded decorations were made by the application of a gold foil on a mordant substrate on a gypsum base, while the mouldings of the vaults seem to be gilded on a bol with a glaze on top of the gold leaf. It is interesting to notice that the first remained unaltered, while the gilded vault mouldings look almost black, due to the darkening of the organic material. To elucidate the causes involved in the darkening of the sample from the vaults a set of synchrotron μXRD and μFTIR experiments have been carried out on these samples at the ESRF (ID18F and ID21, respectively). High brightness and small spot working conditions revealed the development and distribution of calcium oxalates in the binding media, which seem to be responsible for the darkening. Results point out the fact that weddellite (CaC₂O₄·2H₂O) is the phase formed in those layers where organic material has also been identified or at least it would be supposed to be by bibliographic sources and not necessarily those superficial as it would have been suggested due to the similarities with patinas formation. PACS 78.30-j; 68.37.Hk; 61.10.Nz