A planetary environment and analysis chamber (PEACh) for coordinated Raman–LIBS–IR measurements under planetary surface environmental conditions

A planetary environment and analysis chamber (PEACh) has been developed at Washington University in St. Louis, in order to perform in situ multiple spectroscopic measurements on geological samples under relevant planetary environmental conditions and to support future planetary missions, with particular interest on Mars. The pressure in the chamber can range from ambient to 3 × 10⁻² mbar. The simulated atmospheric composition and pressure are regulated via a combination of needle and ball valves connecting the chamber with containers filled with premixed gas. The temperature of the samples can be controlled in a range from ambient to − 100 °C. The in situ analytical techniques implemented (and to be implemented) are laser Raman spectroscopy, laser‐induced breakdown spectroscopy (LIBS), near‐IR reflectance spectroscopy, mid‐IR attenuated total reflectance spectroscopy, and microscopic imaging. The coordinated spectroscopic sensing on the same geological sample under well‐controlled atmospheric conditions in the PEACh establishes a way to link the results from the laboratory experiments to the spectral data obtained by landed and orbital planetary exploration missions, which will facilitate understanding the surface processes by which mineral phases occur and their association with atmospheric changes. Copyright © 2011 John Wiley & Sons, Ltd.     

Raman spectra of organic acids obtained using a portable instrument at −5 °C in a mountain area at 2000 m above sea level

Well‐resolved Raman spectra of organic acids were obtained with 785 nm excitation using a portable Raman instrument (Ahura First Defender XL) under low temperature −5 °C atmospheric conditions at an altitude of 2000 m (Axamer Lizum, Innental, Austria). The portable Raman spectrometer tested in this setting permits fast and unambiguous detection of solid forms of these organic acids (formic, acetic, valeric, hexanoic, heptanoic, isophthalic, ascorbic and mellitic) under field conditions. This demonstrates the possibility to use a miniaturized Raman spectrometer as a key instrument for investigating the presence of organic compounds and biomolecules under low temperature conditions. These results are important for future missions focusing not only on Mars, where Raman spectroscopy will be a key non‐destructive analytical tool for the in situ identification of organic compounds relevant to life detection on planetary surfaces or near sub‐surfaces. Copyright © 2009 John Wiley & Sons, Ltd.     

拉曼-荧光联合光谱水下原位探测技术研究

深海热液环境中存在着巨大的化学和热梯度,快速剧烈的混合和生物过程产生了多种多样的矿物过程,并培养了大量的化学合成微生物。激光拉曼光谱非常适合于深海热液环境矿物过程的探测,然而要对矿物与微生物作用过程进行研究,还需要与荧光光谱技术进行联合,针对此需求开展了原理验证实验研究。在实验室搭建了一套拉曼-荧光联合光谱探测桌面系统,利用一台双波长激光器同时作为拉曼光谱和荧光光谱的激发光源,其中拉曼光谱采用532 nm波长,荧光光谱采用266 nm波长,双波长激光器发出的光束经分光镜分为两路,经过后向散射光路收集的两路信号分别进入两个小型光纤光谱仪进行分光探测,拉曼光谱采用QE65000光谱仪,荧光光谱采用USB2000光谱仪,通过软件可以方便的分别设置两个光谱仪的参数。利用搭建的实验系统对海水和拟菱形藻样品进行探测,分别获得了海水样品的SO2-₄拉曼光谱和可溶性有机物(CDOM)荧光光谱,拟菱形藻样品的类胡萝卜素拉曼光谱和类蛋白、叶绿素等荧光光谱,实验结果证明了研制小型拉曼-荧光联合光谱探测装置的可行性,并为发展原位联合光谱探测装置提供了技术参考。     

In situ detection of cocaine hydrochloride in clothing impregnated with the drug using benchtop and portable Raman spectroscopy

This study describes the application of benchtop and portable Raman spectroscopy for the in situ detection of cocaine hydrochloride in clothing impregnated with the drug. Raman spectra were obtained from a set of undyed natural and synthetic fibres and dyed textiles impregnated with the drug. The spectra were collected using three Raman spectrometers: one benchtop dispersive spectrometer coupled to a fibre‐optic probe and two portable spectrometers. Despite the presence of some spectral bands arising from the natural and synthetic polymer and dyed textiles, the drug could be identified by its characteristic Raman bands. High‐quality spectra of the drug could be acquired in situ within seconds and without any sample preparation or alteration of the evidential material. A field‐portable Raman spectrometer is a reliable technique that can be used by emergency response teams to rapidly identify unknown samples. Copyright © 2009 John Wiley & Sons, Ltd.     

Analysis of the chromite inclusions found in nephrite minerals obtained from different deposits using SEM‐EDS and LRS

Scanning electron microscopy with energy dispersive spectrometer (SEM‐EDS) and laser Raman spectroscopy (LRS) were used to analyse the chromite inclusions found in four samples of the mineral nephrite that were obtained from Taiwan (one), Manasi in China (two) and New Zealand (one). The chromite inclusions found in sample HL‐1 (Taiwan) contain low contents of Mg and Al, as well as a characteristically high Zn content. The most significant finding, however, was that HL‐1 could also be distinguished from the other samples by the lower wavenumbers of the positions of the peaks that belong to the A_1g, F_2g⁽¹⁾ and E_g modes. Compared to the difference in compositions, the difference in the positions of the peaks in the Raman spectra of the chromite inclusions, as revealed by LRS, can more easily be used to distinguish between samples of nephrite that have been obtained from different deposits, and in particular to identify the provenance of the raw material used in ancient nephrite artefacts, in view of the fact that LRS is non‐destructive and easy to apply. Copyright © 2011 John Wiley & Sons, Ltd.     

Application of the backscatter fundamental parameter method for in situ element determination using a portable energy‐dispersive x‐ray fluorescence spectrometer

The backscatter fundamental parameter (BFP) algorithm was adapted and modified for the use with a portable energy‐dispersive x‐ray fluorescence (EDXRF) spectrometer system. The method utilizes coherently and incoherently scattered peaks of primary radiation to estimate the ‘dark matrix’ of the analysed sample. A so‐called ‘full fundamental parameter’ model was implemented in the algorithm, allowing a simple calibration of the method using only one standard sample. To improve the accuracy of the method, the differential mass scattering cross‐sections were used. The algorithm also takes into account the secondary excitation effects. The method was applied to element determinations in various matrices with minimum sample preparation. It was tested in the laboratory with homogeneous samples prepared from standard reference materials and was also successfully applied to in situ element determinations in soil. The analyses were performed using a portable XRF spectrometer equipped with a ¹⁰⁹Cd radioisotope source and an Si‐PIN photodiode detector. The BFP algorithm was found to perform well for the analysis of loose powder samples containing an unknown fraction of ‘dark matrix,’ and therefore it is regarded as suitable for in situ element determinations. Copyright © 2003 John Wiley & Sons, Ltd.     

Extraterrestrial Mössbauer spectrometry

We describe a combined backscatter Mössbauer spectrometer and X-ray fluorescence analyzer (BaMS/XRF) instrument suitable for planetary missions to the surfaces of Mars (MESUR Program), the Moon, asteroids, or other solid solar-system objects. The BaMS/XRF instrument is designed to be capable of concurrent analysis of a sample for its elemental abundances (XRF) and for the mineralogy of its iron-bearing phases (BaMS) without any sample preparation.     

Raman spectra of nitrogen‐containing organic compounds obtained using a portable instrument at −15 °C at 2860 m above sea level

Well‐resolved Raman spectra of samples of nitrogen‐containing compounds were detected using a portable Raman instrument (Ahura First Defender XL) outdoors at a low ambient temperature of −15 °C and at an altitude of 2860 m (Pitztall, Austria). The portable Raman spectrometer tested here is equipped with a 785‐nm diode laser and a fixed frontal probe. Solid form of formamide, urea, 3‐methylpyridine, aniline, indene, 1‐(2‐aminoethyl)piperazine, indoline and benzofuran were detected unambiguously under high‐mountain field conditions. The main Raman features (strong, medium and partially weak bands) were observed at the correct wavenumber positions (with a spectral resolution 7–10 cm⁻¹) in the wavenumber range 200–1600 cm⁻¹. The results obtained demonstrate the possibility of employing a miniaturised Raman spectrometer as a key instrument for investigating the presence of nitrogen‐containing organic compounds and biomolecules outdoors under low temperature conditions. Within the payload designed by European Space Agency (ESA) and National Aeronautics and Space Administration (NASA) for future missions, focussing not only on Mars, Raman spectroscopy represents an important instrumentation for the detection of organic nitrogen‐containing compounds relevant to life detection on planetary surfaces or near sub‐surfaces. Copyright © 2009 John Wiley & Sons, Ltd.     

Integration of correlative Raman microscopy in a dualbeam FIB SEM

We present an integrated confocal Raman microscope in a focused ion beam scanning electron microscope (FIB SEM). The integrated system enables correlative Raman and electron microscopic analysis combined with focused ion beam sample modification on the same sample location. This provides new opportunities, for example the combination of nanometer resolution with Raman advances the analysis of sub‐diffraction‐sized particles. Further direct Raman analysis of FIB engineered samples enables in situ investigation of sample changes. The Raman microscope is an add‐on module to the electron microscope. The optical objective is brought into the sample chamber, and the laser source, and spectrometer are placed in a module attached onto and outside the chamber. We demonstrate the integrated Raman FIB SEM function with several experiments. First, correlative Raman and electron microscopy is used for the investigation of (sub‐)micrometer‐sized crystals. Different crystals are identified with Raman, and in combination with SEM the spectral information is combined with structurally visible polymorphs and particle sizes. Analysis of sample changes made with the ion beam is performed on (1) structures milled in a silicon substrate and (2) after milling with the FIB on an organic polymer. Experiments demonstrate the new capabilities of an integrated correlative Raman–FIB–SEM. Copyright © 2016 John Wiley & Sons, Ltd.     

The first in situ Raman spectroscopic study of San rock art in South Africa: procedures and preliminary results

Southern Africa has a rich heritage of hunter‐gatherer, herder and farmer rock art traditions made by using both painted and engraved techniques. Until now, there have been only a handful of studies on the chemical analysis of the paint, as all previous types of analysis required the removal of pigment samples from the sites a practice which has been avoided. Raman spectroscopy is an ideal techniques to analyse the paint non‐destructively and also offers the possibility of in situ work with portable instruments. This article describes the procedures and reports the preliminary results of the first in situ Raman spectroscopic study of rock art in South Africa (also a first worldwide), where we, first, evaluate the capability of a Raman portable instrument in very difficult conditions, second, analyse the paints in order to contribute to a better knowledge of the technology used and, third, evaluate the possible contribution of in situ analyses in conservation studies. The paintings from two different rock art sites were studied. The instrument proved to be highly suitable for in situ analyses in physically very challenging conditions. Most of the pigments and alteration products previously detected under laboratory conditions were identified, thereby giving information on both the pigments and conservation state of the paintings. A layered structure of alteration products and pigment was identified in situ for the first time by controlling the laser power, thereby obtaining the same results as in mapping experiments of cross sections of paint. Copyright © 2010 John Wiley & Sons, Ltd.     

马达加斯加玛瑙的光谱学特征研究

玛瑙在世界各地分布广泛,有关玛瑙矿物学和光谱学特征的研究颇丰,但对产自马达加斯加安楚希希市和马哈赞加省的玛瑙的光谱学和产地特征研究甚少。采用正交偏光显微镜、红外光谱和拉曼光谱仪对5块来自安楚希希市和马哈赞加省具有纹带结构的玛瑙样品进行光谱学特征分析。结果表明：这两个产地玛瑙的主要矿物成分一致,均为α-石英和斜硅石。来自马哈赞加省的样品靠近中心的白色、红色部分斜硅石的特征拉曼峰（501cm-1）缺失,根据前人研究发现是与玛瑙内部的结构水之间发生脱水反应形成中性水分子,而这些中性水分子与斜硅石反应生成了石英颗粒有关。然而两产地玛瑙的致色矿物不同,马哈赞加省玛瑙棕色和红色部分具有222, 294, 410以及1 316 cm-1的特征拉曼位移峰,与赤铁矿的拉曼特征峰相符,确定这部分的致色矿物是赤铁矿,而安楚希希市玛瑙黄色部分只具有400和1 160 cm-1的特征峰,与六方纤铁矿的拉曼特征峰相符,因此此部分的致色矿物是六方纤铁矿（δ-FeOOH）。部分来自安楚希希市的玛瑙具有少量的杂质矿物,通过拉曼测试发现杂质矿物的成分也是六方纤铁矿（δ-FeOOH）和α-石英。结合六方纤铁矿的特性推测来自安楚希希市的四块样品是处于低温（<80 ℃）、Fe2+含量很少（β<0.03）且空气不流通的偏酸性的环境当中形成的。红外光谱测试发现两个产地的玛瑙均有液态水（3 400 cm-1左右）和结构水（3 750～3 500 cm-1）的红外特征峰,安楚希希市的结构水红外特征峰位于3 740 cm-1处,可推测该结构水位于结构缺陷处。结合马达加斯加玛瑙的光谱学特征和纹带结构的讨论,对推测马达加斯加玛瑙的形成机制有着重要的意义;并且六方纤铁矿（δ-FeOOH）可以作为区别于其他产地的标型矿物,具有产地特征意义;同时为研究马达加斯加玛瑙形成的地质环境提供了数据支持。     

Combined Laser-Induced Breakdown with Raman Spectroscopy: Historical Technology Development and Recent Applications

Abstract: A modern trend in the development of laser-based analytical instruments is to integrate more functions in a single device, which could supply complementary information and improve the capability to identify different components. This review presents historical development of the combined analysis by laser-induced breakdown spectroscopy (LIBS) and Raman Spectroscopy, which briefly describes basic instrumental principles and technological aspects of the hyphenated technique, as well as the requirements in the design of interactive instruments, including laser systems, optical systems for laser beam delivery, emission collection devices, and spectrum measurement systems. Various configurations of the combined instrumentation have been designed and used depending on the different applications, such as pigment analysis in the cultural heritage field, detection of explosives, analysis of geological samples, and applications in future planetary missions. In addition, the feasibility, applicability, and prospective aspects of the hybrid technology are discussed in detail.     

2D Raman spectroscopy study of dolomite and cyanobacterial extracellular polymeric substances from Khor Al‐Adaid sabkha (Qatar)

Dolomite precipitation, limited at low temperature, appears to be impacted by microbial extracellular polymeric substances (EPS). The presence of dolomites has been reported in the extreme environments of Arabian Gulf sabkhas. Many of these sites are characterized by extensive growth of cyanobacterial mats that are recognized as key producers of EPS. However, no information has been gathered on the cyanobacterial EPS involvement in dolomite precipitation. The objective of this study was to obtain in situ information on the spatial distribution of cyanobacterial EPS and dolomite in Khor Al‐Adaid sabkha (Qatar) sediments by chemical mapping. For this purpose, in situ 2D Raman spectroscopy and atomic force microscopy were applied. Additionally, samples were analyzed with scanning electron microscopy and X‐ray diffraction. Raman fingerprints of dolomite (300, 725, and 1098 cm⁻¹), cyanobacteria, and their EPS (1000, 1130, 1148, and 1508 cm⁻¹) were observed widely distributed in the top 2 cm of the sabkhas sediments. 2D chemical imaging of sediment layers characterized minerals and organic matter of microbial origins at high spatial resolution. Raman mapping indicated small dolomite clusters (<2 µm) embedded in a dense cyanobacterial EPS matrix. The spatial distribution showed that small dolomite clusters are closely associated with cyanobacterial EPS and organic carbon. Our results prove that cyanobacterial molecules are closely related to dolomite in the sabkhas sediments. This study demonstrated that Raman mapping is a robust and sensitive technique for acquisition of in situ information on cell–mineral interactions. Copyright © 2013 John Wiley & Sons, Ltd.     

A large‐solid‐angle X‐ray Raman scattering spectrometer at ID20 of the European Synchrotron Radiation Facility

An end‐station for X‐ray Raman scattering spectroscopy at beamline ID20 of the European Synchrotron Radiation Facility is described. This end‐station is dedicated to the study of shallow core electronic excitations using non‐resonant inelastic X‐ray scattering. The spectrometer has 72 spherically bent analyzer crystals arranged in six modular groups of 12 analyzer crystals each for a combined maximum flexibility and large solid angle of detection. Each of the six analyzer modules houses one pixelated area detector allowing for X‐ray Raman scattering based imaging and efficient separation of the desired signal from the sample and spurious scattering from the often used complicated sample environments. This new end‐station provides an unprecedented instrument for X‐ray Raman scattering, which is a spectroscopic tool of great interest for the study of low‐energy X‐ray absorption spectra in materials under in situ conditions, such as in operando batteries and fuel cells, in situ catalytic reactions, and extreme pressure and temperature conditions.     

An original approach for Raman spectroscopy analysis of radioactive materials and its application to americium‐containing samples

An approach for Raman measurements of highly radioactive samples is presented here. The innovative part of this approach lies in the fact that no single part of the Raman equipment is in direct contact with the radioactive sample, as the sample is sealed in an alpha‐tight capsule. Raman analysis is effectively performed through the optical‐grade quartz window closing the capsule. This allows performing micro‐Raman measurements on radioactive samples with no limitations on the laser source wavelength, polarisation mode, spectrometer mode and microscope mode (provided the focal length of the microscope objective is greater than the thickness of the quartz window and with sub mg samples). Some example results are shown and discussed. In particular, some spectral features of americium‐containing oxide nuclear fuel specimens are presented. Raman spectra clearly reveal in these specimens the presence of abundant oxygen defects induced in the fcc fluorite lattice by trivalent americium. In order to complete the analysis the Raman spectrum of pure americium dioxide was also measured with a lower energy excitation source compared with previous research. The current results seem to be consistent with the possible occurrence of a photolysis process induced by the Raman laser, resulting in the formation of hyperstoichiometric americium sesquioxide Am₂O_{3 + z}. Such a photolytic process is deemed to be unavoidable when visible lasers are used as excitation sources for the Raman analysis of americium dioxide. © 2015 The Authors Journal of Raman Spectroscopy Published by John Wiley & Sons, Ltd.     

用于远程探测的空间外差拉曼光谱技术研究

空间外差拉曼光谱技术是一种新型拉曼光谱探测技术,具有光通量大、高分辨率、无移动部件等技术优势,非常适用于行星探测任务中,对行星表面的矿物及有机物进行分析,探寻可能存在的生命标志物。作者将这一技术运用于远程拉曼光谱探测中,对远程空间外差拉曼光谱仪的光谱分辨率、光谱范围及信噪比等主要特性进行了分析与实验验证。文章对远程空间外差拉曼光谱探测的基本原理进行了简述,设计搭建了一套实验平台,并进行了定标,验证了其性能参数。在此基础上,获取了10 m处部分无机固体样品、有机样品及天然矿物的拉曼散射信号,对系统信噪比进行了估计。由于装调精度不高、光学器件缺陷等原因,系统远非理想。但测试结果表明,对于大部分样品的主要拉曼散射峰,系统信噪比优于5,基本可以满足清楚分辨典型拉曼谱峰的要求,依然可以证明这一技术的可行性。空间外差拉曼光谱技术可以弥补色散型光栅光谱仪与傅里叶变换型光栅光谱仪的主要技术缺陷,在行星表面物质探测与分析领域具有较大的应用前景。作者对于这一技术的研究一定程度上证明了空间外差拉曼光谱技术在远程探测方面的潜力,可为远程空间外差拉曼光谱仪的工程实现提供参考。     

FTIR和Raman用于盐酸曲马多的结构分析

采用AVATAR 360型傅里叶变换红外光谱仪和RM-1000型激光共聚焦拉曼光谱仪测定盐酸曲马多的红外光谱和拉曼光谱。拉曼光谱和红外光谱中均显示出了盐酸曲马多的特征峰,都能够用于其结构鉴别。采用红外、拉曼光谱这两种方法互相印证,互相补充,可增强鉴定的准确性、可靠性。     

Time resolved Raman spectroscopy for depth analysis of multi‐layered mineral samples

Time resolved Raman spectroscopy (TRRS) can provide subsurface information from multi‐layered samples of transparent and translucent evaporative and silicate minerals up to several centimetres thick. Depth information was obtained using 3‐ps pulsed laser excitation at 720 nm and a gated intensified charge‐coupled device detector with stepwise increasing delay times. Blocks of different minerals were used as first, second or third layers, and Raman spectra from deeper layers could be detected through 10 mm of translucent calcite and up to 40 mm of transparent halite crystals. Measurements by conventional confocal Raman, as well as spatially offset Raman spectroscopy were also successful in distinguishing different mineral layers. This study establishes the great potential for the use of Raman spectroscopy in future planetary exploration, where TRRS could be used as a non‐invasive tool for profiling the (sub‐)surface at millimetre‐depth resolution. Copyright © 2013 John Wiley & Sons, Ltd.     

Application of monitoring methodology in carbon complex contained solution using surface-enhanced Raman spectroscopy (SERS)

Raman spectroscopy is employed to obtain information that cannot be obtained using other technologies, using inelastic scattering. The development of laser technology enables Raman spectroscopy to overcome its limits and succeed in various fields. For example, compared with other analysis methods that use light, it does not require a sample preparation or long measuring time—thus, it is a great breakthrough for in situ process applications. Also, it is difficult to analyze functional groups that are combined and the influence on the reaction is analyzed during the reaction in chemical solutions. Therefore, Raman spectroscopy provides an analytic method and assists in every step to increase the accuracy of the chemical process. Lately, developed surface-enhanced Raman spectroscopy (SERS) are used in precise analyzing methods. High-resolution SERS needs a specific substrate to satisfy each purpose. Raman spectroscopy is now advanced to be more a powerful analytic tool, combined with surface-enhancing technology, atomic force microscopy (AFM), and other technology.     

二元混合溶液闪点行为的激光拉曼光谱研究

本文以乙醇-甲酰胺,乙腈-甲酰胺,乙醇-环己酮,乙腈-环己酮四种混合溶液为研究对象,采用激光拉曼光谱对四种溶液体系的闪点行为进行讨论和研究。通过测定四种溶液体系的拉曼光谱和闪点,结合溶液拉曼光谱的特征峰强度比和拉曼位移的变化,探索四种溶液闪点的变化规律。试验结果表明,随着溶液浓度的增大,溶质的拉曼特征峰强线性增加,混合溶液的闪点降低。采用三次多项式分别对四种溶液体系的闪点与拉曼特征峰、溶液浓度的关系进行拟合,拟合结果良好。混合溶液的闪点随拉曼特征峰强比、溶液浓度的变化趋势相同。该试验方法将有助于从分子结构角度分析混合溶液的闪点变化规律,同时该方法可用于混合溶液闪点的实时在线检测。