Evaluation of pore-fracture microstructure of gypsum rock fragments using micro-CT.

This study utilized X-ray micro-computed tomography (micro-CT) to investigate weathered gypsum rocks which can or do serve as a rock substrate for endolithic organisms, focusing on their internal pore-fracture microstructure, estimating porosity, and quantitative comparison between various samples. Examining sections and reconstructed 3D models provides a more detailed insight into the overall structural conditions within rock fragments and the interconnectivity in pore networks, surpassing the limitations of analyzing individual 2D images. Results revealed diverse gypsum forms, cavities, fractures, and secondary features influenced by weathering. Using deep learning segmentation based on the U-Net models within the Dragonfly software enabled to identify and visualize the porous systems and determinate void space which was used to calculate porosity. This approach allowed to describe what type of microstructures and cavities is responsible for the porous spaces in different gypsum samples. A set of quantitative analysis of the detected void and modeled networks provided a needed information about the development of the pore system, connectivity, and pore size distribution. Comparison with mercury intrusion porosimetry showed that both methods consider different populations of pores. In our case, micro-CT typically detects larger pores (> 10 µm) which is related to the effective resolution of the scanned images. Still, micro-CT demonstrated to be an efficient tool in examining the internal microstructures of weathered gypsum rocks, with promising implications particularly in geobiology and microbiology for the characterization of lithic habitats.

Gypsum endolithic phototrophs under moderate climate (Southern Sicily): their diversity and pigment composition.

In this study, we used microscopic, spectroscopic, and molecular analysis to characterize endolithic colonization in gypsum (selenites and white crystalline gypsum) from several sites in Sicily. Our results showed that the dominant microorganisms in these environments are cyanobacteria, including: Chroococcidiopsis sp., Gloeocapsopsis pleurocapsoides, Gloeocapsa compacta, and Nostoc sp., as well as orange pigmented green microalgae from the Stephanospherinia clade. Single cell and filament sequencing coupled with 16S rRNA amplicon metagenomic profiling provided new insights into the phylogenetic and taxonomic diversity of the endolithic cyanobacteria. These organisms form differently pigmented zones within the gypsum. Our metagenomic profiling also showed differences in the taxonomic composition of endoliths in different gypsum varieties. Raman spectroscopy revealed that carotenoids were the most common pigments present in the samples. Other pigments such as gloeocapsin and scytonemin were also detected in the near-surface areas, suggesting that they play a significant role in the biology of endoliths in this environment. These pigments can be used as biomarkers for basic taxonomic identification, especially in case of cyanobacteria. The findings of this study provide new insights into the diversity and distribution of phototrophic microorganisms and their pigments in gypsum in Southern Sicily. Furthemore, this study highlights the complex nature of endolithic ecosystems and the effects of gypsum varieties on these communities, providing additional information on the general bioreceptivity of these environments.

Scytonin in gypsum endolithic colonisation: First Raman spectroscopic detection of a new spectral biosignature for terrestrial astrobiological analogues and for exobiological mission database extension.

Microbial colonisations of gypsum from Eastern Poland (Badenian, Middle Miocene age) were investigated by Raman microspectrometry with a rarely used excitation 445 nm excitation. Zones of microbial colonisation in selenitic gypsum endolithic outcrops comprise algae and cyanobacteria, which commonly contain the photosynthetic and protective pigments carotenoids, scytonemin and gloeocapsin. Diagnostic bands differing from those of scytonemin have been identified in black colonies in gypsum outcrops at Chotel Czierwony (Poland). Raman spectral signatures of scytonin are reported here for the first time in two endolithic specimens identified by the band wavenumbers predicted from DFT calculations. The strong or medium strong intensity Raman bands observed at 1603, 1585, 1559, 1435, and 1424 cm-1. Other weaker bands were located at 1676 (sh), 1660 (sh), 1649, 1399, 1362, 1342, 1320, 1294, 1272, 1259, and 1052 cm-1. The first observation of the Raman spectrum of scytonin in the cyanobacterial colonisation of gypsum facilitates the inclusion of this new biomolecular signature in the library of unique Raman spectra of biological pigments invaluable for detection of traces of life in frame of the planetary missions.

Critical evaluation of portable Raman spectrometers: From rock outcrops and planetary analogs to cultural heritage - A review.

This review focuses on the progress made and recent developments regarding the use of portable Raman spectrometric devices in the geosciences as well as with scientific testing of objects of cultural heritage. By utilizing different types of Raman spectrometric devices - from the modular; through systems operating with optical heads mounted via optical fibers; to the compact, lightweight, and handheld - are herein described and critically evaluated. The wide range of applications under indoor and closed environments (museums, collections, religious buildings, etc.) are reviewed, and the more commonly used for characterization of art in the broadest sense, as well as fully outdoor investigations (e.g., on rocky outcrops; of the minerals, microbiological colonization, etc.), and including extreme Earth environments and projects with exo-planetary research potential. The rapid acquisition of relevant spectroscopic data and the non-destructiveness of the analyses and diagnostics are greatly appreciated by art historians and conservators on the one hand, as well as by mineralogists, geoscientists, microbiologists on the other. The various environments investigated and the broad range of compounds that can be detected by obtaining their Raman spectra have demonstrated the vast potential of portable, and especially handheld, Raman spectrometer devices for on-site applications.

Fast outdoor screening and discrimination of carotenoids of halophilic microorganisms using miniaturized Raman spectrometers.

Eight miniaturized Raman spectrometers were used to perform a fast outdoor screening and discrimination of carotenoids of a series of halophilic and non-halophilic microorganisms on a set of eight lyophilized samples, each containing high concentrations of a specific dominant carotenoid pigment. Raman spectra were acquired using different excitations (532, 785, sequentially shifted excitation of 785 and 853, and 1064 nm), based on the model of each Raman spectrometer, in order to ascertain the feasibility of individual wavelengths. The wavenumber positions of diagnostic Raman bands of carotenoids were observed for the different carotenoid species. Characteristic carotenoid Raman bands of the pigment bacterioruberin were reported (using the 532 nm excitation) at 1504-1509 cm-1, salinixanthin at 1510-1513 cm-1, spirilloxanthin at 1509-1513 cm-1, decaprenoxanthin at 1519 cm-1, ß-carotene at 1526 cm-1, and sarcinaxanthin at 1526-1528 cm-1. A 532 nm excitation consistently provided best results due to the significant resonance signal enhancement (both quantitative and qualitative carotenoid detection). Good results were also obtained using the sequentially shifted excitation combining two lasers in the near infrared spectral region, and similarly good results were acquired using a standard 1064 nm excitation. The least suitable was a 785 nm excitation, with the carotenoid Raman signal almost always weaker compared to major fluorescence signal arising from other types of pigments or biomolecules in the samples. A thorough light shielding was essential in order to acquire good quality data. This study shows that miniaturized Raman spectrometers, some even equipped with longer wavelength excitation, are able to detect different carotenoid pigments under non-laboratory conditions in a fast way, and discriminate between them, to a certain degree. The implications of this type of research are especially useful in astrobiology, where the searching, detection and discrimination of biomarkers such as carotenoids is receiving significant attention.

Evaluation of handheld and portable Raman spectrometers with different laser excitation wavelengths for the detection and characterization of organic minerals.

Organic minerals occur rather rarely in some types of peat bogs, sedimentary geological environments, and hydrothermal veins. Commonly, calcium oxalates are produced by several plants, terpenoids are often associated with conifers. Because of the organic precursor, these minerals, from the smallest group of the mineralogical system, are sometimes considered as biomarkers. Potential detection of these compounds has high relevance in the fields of exobiology or geobiology. Here we show the potential of four portable Raman spectrometers, using different excitation wavelengths and technologies (operating at 532, 785, and 1064nm together with an advanced spectrometer using the sequentially shifted excitation (SSE) technology), for the rapid and non-destructive identification of these phases. For the organic minerals investigated here, the most intense Raman bands are generally detected at the expected wavenumber positions ±1-4cm-1 in the region 100-2000cm-1 in the spectra obtained from all spectrometers. Additionally, two spectrometers (the 532nm instrument and the SSE) are capable of detecting Raman bands in the higher wavenumber shift region of 2000-3500cm-1, allowing the more detailed characterization and differentiation of the related phases. From this work, and on the basis of the experimental data obtained, it is clear that the longer laser excitation wavelengths are more preferable for organic minerals identification due to the better mitigation of fluorescence emission. In contrast, the Raman spectrometer equipped with the shortest excitation wavelength (532nm) gives a significantly higher spectral resolution and a more detailed discrimination of the Raman bands, provided that the conditions of general lower level of fluorescence emission are met. The results presented in the current study complement the knowledge on minerals and biomarkers of relevance for Martian environments which have been measured with mobile Raman spectrometers. The outcome creates a solid base towards the use of lightweight mobile Raman systems that can be used outdoors and on terrestrial outcrops. Moreover, these results and conclusions are of use for the further development of dedicated spectrometers destined for the instrumental suites on planetary rovers, in the frame of the forthcoming exobiology focused missions to Mars to be launched by NASA and ESA.

Detection of carotenoids of halophilic prokaryotes in solid inclusions inside laboratory-grown chloride and sulfate crystals using a portable Raman spectrometer: applications for Mars exploration.

Inclusions in evaporitic minerals sometimes contain remnants of microorganisms or biomarkers, which can be considered as traces of life. Raman spectroscopy with resonance enhancement is one of the best analytical methods to search for such biomarkers in places of interest for astrobiology, including the surface and near subsurface of planet Mars. Portable Raman spectrometers are used as training tools for detection of biomarkers. Investigations of the limits and challenges of detecting biomolecules in crystals using Raman spectroscopy is important because natural occurrences often involve mineral assemblages as well as their fluid and solid inclusions. A portable Raman spectrometer with 532 nm excitation was used for detection of carotenoid biomarkers: salinixanthin of Salinibacter ruber (Bacteroidetes) and α-bacterioruberin of Halorubrum sodomense (Halobacteria) in laboratory-grown artificial inclusions in compound crystals of several chlorides and sulfates, simulating entrapment of microorganisms in evaporitic minerals. Crystals of halite (NaCl), sylvite (KCl), arcanite (K2SO4) and tschermigite ((NH4)Al(SO4)2·12H2O) were grown from synthetic solutions that contained microorganisms. A second crystalline layer of NaCl or K2SO4 was grown subsequently so that primary crystals containing microorganisms are considered as solid inclusions. A portable Raman spectrometer with resonance enabling excitation detected signals of both carotenoid pigments. Correct positions of diagnostic Raman bands corresponding to the specific carotenoids were recorded.

Comparison of Miniaturized Raman Spectrometers for Discrimination of Carotenoids of Halophilic Microorganisms.

We present a comparison of the performance of four miniature portable Raman spectrometers for the discrimination of carotenoids in samples of carotene-producing microorganisms. Two spectrometers using a green laser allowing to obtain Resonance Raman (or pre-Resonance Raman) signals, one instrument with a 785 nm laser, and a recently developed Portable Sequentially Shifted Excitation Raman spectrometer (PSSERS) were used for identifying major pigments of different halophilic (genera Halobacterium, Halorubrum, Haloarcula, Salinibacter, Ectothiorhodospira, Dunaliella) and non-halophilic microorganisms (Micrococcus luteus, Corynebacterium glutamicum). Using all the tested instruments including the PSSERS, strong carotenoids signals corresponding to the stretching vibrations in the polyene chain and in-plane rocking modes of the attached CH3 groups were found at the correct positions. Raman spectra of carotenoids can be obtained from different types of microbiological samples (wet pellets, lyophilized culture biomass and pigment extracts in organic solvents), and can be collected fast and without time-consuming procedures.

Analyzing carotenoids of snow algae by Raman microspectroscopy and high-performance liquid chromatography.

We tested the potential of Raman microspectroscopy to determine carotenoid pigments - both primary (lutein, beta-carotene) and secondary (astaxanthin) carotenoids - in the different species and life-cycle stages of snow algae from the order Chlamydomonadales (Chlorophyta). We compared the performance of Raman spectrometry to a reference method of biological pigment analysis, high-performance liquid chromatography (HPLC). The three main carotenoid Raman bands of the astaxanthin-rich red cysts were located at 1520, 1156 and 1006 cm-1. The shifts (orange aplanozygotes and green motile cells with flagella) in the position of the ν1(CC) Raman band of the polyenic chain is consistent with the expected changes in the ratios of the various carotenoid pigments. Flagellated green cells commonly contain lutein as a major carotenoid, together with minor amounts of ß­carotene and varying amounts of antheraxanthin, violaxanthin and neoxanthin. Aplanozygotes contain mixtures of both primary and secondary carotenoids. In most cases, the ν1(CC) band is an overlapping set of bands, which is due to the signal of all carotenoid pigments in the sample, and a deconvolution along with the band position shifts (mainly ν1) could be used to characterize the mixture of carotenoids. However, the ability of Raman spectroscopy to discriminate between structurally slightly differing carotenoid pigments or several carotenoids in an admixture in an unknown biological system remains limited.

Using a portable Raman spectrometer to detect carotenoids of halophilic prokaryotes in synthetic inclusions in NaCl, KCl, and sulfates.

Cell suspensions of the haloarchaea Halorubrum sodomense and Halobacterium salinarum and the extremely halophilic bacterium Salinibacter ruber (Bacteroidetes) in saturated solutions of chlorides and sulfates (NaCl, KCl, MgSO4·7H2O, K2SO4, and (NH4)Al(SO4)2·12H2O) were left to evaporate to produce micrometric inclusions in laboratory-grown crystals. Raman spectra of these pinkish inclusions were obtained using a handheld Raman spectrometer with green excitation (532 nm). This portable instrument does not include any microscopic tool. Acceptable Raman spectra of carotenoids were obtained in the range of 200-4000 cm-1. This detection achievement was related to the mode of illumination and collection of scattered light as well as due to resonance Raman enhancement of carotenoid signals under green excitation. The position of diagnostic Raman carotenoid bands corresponds well to those specific carotenoids produced by a given halophile. To our best knowledge, this is the first study of carotenoids included in the laboratory in crystalline chlorides and sulfates, using a miniature portable Raman spectrometer. Graphical abstract ᅟ.

Effects of nicotine on the biosynthesis of carotenoids in halophilic Archaea (class Halobacteria): an HPLC and Raman spectroscopy study.

Nicotine has a profound influence on the carotenoid metabolism in halophilic Archaea of the class Halobacteria. In a study of Halobacterium salinarum, Haloarcula marismortui and Halorubrum sodomense, using different analytical techniques to monitor the production of different carotenoids as a function of the presence of nicotine, we showed that the formation of α-bacterioruberin was inhibited in all. In Hbt. salinarum, addition of nicotine led to a significant change in the color of the culture due to the accumulation of lycopene, in addition to the formation of bisanhydrobacterioruberin which does not differ in color from α-bacterioruberin. Very little or no lycopene was formed in Har. marismortui and in Hrr. sodomense; instead bisanhydrobacterioruberin was the only major carotenoid found in nicotine-amended cultures. The findings are discussed in the framework of the recently elucidated biochemical pathway for the formation of the different carotenoid pigments encountered in the Halobacteria.

Unleaded gasoline as a significant source of Pb emissions in the Subarctic.

After the phasing out of leaded gasoline, Pb emissions to the atmosphere dramatically decreased, and other sources became more significant. The contribution of unleaded gasoline has not been sufficiently recognized; therefore, we evaluated the impact of Pb from unleaded gasoline in a relatively pristine area in Subarctic NE Norway. The influence of different endmembers (Ni slag and concentrate from the Nikel smelter in Russia, PM10 filters, and traffic) on the overall Pb emissions was determined using various environmental samples (snow, lichens, and topsoils) and Pb isotope tracing. We found a strong relationship between Pb in snow and the Ni smelter. However, lichen samples and most of the topsoils were contaminated by Pb originating from the current use of unleaded gasoline originating from Russia. Historical leaded and recent unleaded gasoline are fully distinguishable using Pb isotopes, as unleaded gasoline is characterized by a low radiogenic composition (206Pb/207Pb = 1.098 and 208Pb/206Pb = 2.060) and remains an unneglectable source of Pb in the region.

Stable isotope tracing of Ni and Cu pollution in North-East Norway: Potentials and drawbacks.

The use of Ni and Cu isotopes for tracing contamination sources in the environment remains a challenging task due to the limited information about the influence of various biogeochemical processes influencing stable isotope fractionation. This work focuses on a relatively simple system in north-east Norway with two possible endmembers (smelter-bedrock) and various environmental samples (snow, soil, lichens, PM10). In general, the whole area is enriched in heavy Ni and Cu isotopes highlighting the impact of the smelting activity. However, the environmental samples exhibit a large range of δ60Ni (-0.01 ± 0.03‰ to 1.71 ± 0.02‰) and δ65Cu (-0.06 ± 0.06‰ to -3.94 ± 0.3‰) values which exceeds the range of δ60Ni and δ65Cu values determined in the smelter, i.e. in feeding material and slag (δ60Ni from 0.56 ± 0.06‰ to 1.00 ± 0.06‰ and δ65Cu from -1.67 ± 0.04‰ to -1.68 ± 0.15‰). The shift toward heavier Ni and Cu δ values was the most significant in organic rich topsoil samples in the case of Ni (δ60Ni up to 1.71 ± 0.02‰) and in lichens and snow in the case of Cu (δ65Cu up to -0.06 ± 0.06‰ and -0.24 ± 0.04‰, respectively). These data suggest an important biological and biochemical fractionation (microorganisms and/or metal uptake by higher plants, organo-complexation etc.) of Ni and Cu isotopes, which should be quantified separately for each process and taken into account when using the stable isotopes for tracing contamination in the environment.

Accurate Differentiation of Carotenoid Pigments Using Flight Representative Raman Spectrometers.

Raman spectrometers will be utilized on two Mars rover missions, ExoMars and Mars 2020, in the near future, to search for evidence of life and habitable geological niches on Mars. Carotenoid pigments are recognized target biomarkers, and as they are highly active in Raman spectroscopy, they can be readily used to characterize the capabilities of space representative instrumentation. As part of the preparatory work being performed for the ExoMars mission, a gypsum crust colonized by microorganisms was interrogated with commercial portable Raman instruments and a flight representative Raman laser spectrometer. Four separate layers, each exhibiting different coloration resulting from specific halophilic microorganism activities within the gypsum crust, were studied by using two excitation wavelengths: 532 and 785 nm. Raman or fluorescence data were readily obtained during the present study. Gypsum, the main constituent of the crust, was detected with both excitation wavelengths, while the resonance Raman signal associated with carotenoid pigments was only detected with a 532 nm excitation wavelength. The fluorescence originating from bacteriochlorophyll a was found to overwhelm the Raman signal for the layer colonized by sulfur bacteria when interrogated with a 785 nm excitation wavelength. Finally, it was demonstrated that portable instruments and the prototype were capable of detecting a statistically significant difference in band positions of carotenoid signals between the sample layers. Key Words: Gypsum-Raman spectrometers-Carotenoids-ExoMars-Mars exploration-Band position shift. Astrobiology 17, 351-362.

Colonization of Snow by Microorganisms as Revealed Using Miniature Raman Spectrometers-Possibilities for Detecting Carotenoids of Psychrophiles on Mars?

We tested the potential of a miniaturized Raman spectrometer for use in field detection of snow algae pigments. A miniature Raman spectrometer, equipped with an excitation laser at 532 nm, allowed for the detection of carotenoids in cells of Chloromonas nivalis and Chlamydomonas nivalis at different stages of their life cycle. Astaxanthin, the major photoprotective pigment, was detected in algal blooms originating in snows at two alpine European sites that differed in altitude (Krkonose Mts., Czech Republic, 1502 m a.s.l., and Ötztal Alps, Austria, 2790 m a.s.l.). Comparison is made with a common microalga exclusively producing astaxanthin (Haematococcus pluvialis). The handheld Raman spectrometer is a useful tool for fast and direct field estimations of the presence of carotenoids (mainly astaxanthin) within blooms of snow algae. Application of miniature Raman instruments as well as flight prototypes in areas where microbes are surviving under extreme conditions is an important stage in preparation for successful deployment of this kind of instrumentation in the framework of forthcoming astrobiological missions to Mars. Key Words: Snow algae-Chloromonas nivalis-Chlamydomonas nivalis-On-site field detection-Raman spectroscopy-Astaxanthin. Astrobiology 16, 913-924.

The Ring Monstrance from the Loreto treasury in Prague: handheld Raman spectrometer for identification of gemstones.

A miniature lightweight portable Raman spectrometer and a palm-sized device allow for fast and unambiguous detection of common gemstones mounted in complex jewels. Here, complex religious artefacts and the Ring Monstrance from the Loreto treasury (Prague, Czech Republic; eighteenth century) were investigated. These discriminations are based on the very good correspondence of the wavenumbers of the strongest Raman bands of the minerals. Very short laser illumination times and efficient collection of scattered light were sufficient to obtain strong diagnostic Raman signals. The following minerals were documented: quartz and its varieties, beryl varieties (emerald), corundum varieties (sapphire), garnets (almandine, grossular), diamond as well as aragonite in pearls. Miniature Raman spectrometers can be recommended for common gemmological work as well as for mineralogical investigations of jewels and cultural heritage objects whenever the antiquities cannot be transported to a laboratory.This article is part of the themed issue 'Raman spectroscopy in art and archaeology'.

Raman Investigation of Precious Jewelry Collections Preserved in Paolo Orsi Regional Museum (Siracusa, Sicily) Using Portable Equipment.

This work is a part of a large scientific project aimed at highlighting the potential of portable Raman equipment in characterizing jewelry materials preserved in museums, carried out in collaboration with gemologists and archeologists. In detail, we report the results of a measurement campaign performed for the study of gems and jewels preserved in the well-known Medagliere section at the Paolo Orsi Regional Museum of Siracusa (Sicily). The studied materials consist of exquisite examples of engraved loose gems and really rare examples of Hellenistic-Roman jewels, mainly coming from relevant Sicilian archaeological sites. Portable Raman measurements have been carried out using two instruments equipped with different excitation wavelengths. The obtained results have allowed for a complete characterization of the studied gemological materials, also suggesting sometimes misclassification for some valuable objects and gems.

Mobility and attenuation of arsenic in sulfide-rich mining wastes from the Czech Republic.

The mineralogical composition of mining wastes deposited in countless dumps around the world is the key factor that controls retention and release of pollutants. Here we report a multi-method data set combining mineralogical (X-ray diffraction, electron microprobe and Raman microspectrometry) and geochemical (sequential extraction and pore water analysis) methods to resolve As mobility in two 50-years-old mining waste dumps. Originally, all of the As in the mining wastes selected for the study was present as arsenopyrite and with time it has been replaced by secondary As phases. At Jedová jáma mining area, the most of As precipitated as X-ray amorphous ferric arsenate (HFA). Arsenic is also accumulated in the scorodite and Fe (hydr)oxide (with up to 3.2wt.% As2O5) that is particularly represented by hematite. Mining wastes at Dlouhá Ves contain only trace amount of scorodite. Arsenic is primarily bound to Pb-jarosite and Fe (hydr)oxides (especially goethite) with up to 1.6 and 1.8wt.% As2O5, respectively. The pore water collected after rainfall events indicated high concentrations of As (~4600µg·L(-1)) at Jedová jáma, whereas aqueous As at Dlouhá Ves was negligible (up to 1.5µg·L(-1)). Highly mobile As at Jedová jáma is attributed to the dissolution of HFA and simultaneous precipitation of Fe (hydr)oxides under mildly acidic conditions (pH~4.4); immobile As at Dlouhá Ves is due to the efficient adsorption on the Fe (hydr)oxides and hydroxosulfates under acidic pH of ~2.8. Taken together, As mobility in the ferric arsenates-containing mining wastes may significantly vary. These wastes must be kept under acidic conditions or with high aqueous Fe(III) concentrations to prevent the release of As from incongruent dissolution of ferric arsenates.

Sustainable Soil Washing: Shredded Card Filtration of Potentially Toxic Elements after Leaching from Soil Using Organic Acid Solutions.

Shredded card (SC) was assessed for use as a sorbent of potentially toxic elements (PTE) carried from contaminated soil in various leachates (oxalic acid, formic acid, CaCl2, water). We further assessed SC for retention of PTE, using acidified water (pH 3.4). Vertical columns and a peristaltic pump were used to leach PTE from soils (O and A/B horizons) before passing through SC. Sorption onto SC was studied by comparing leachates, and by monitoring total PTE contents on SC before and after leaching. SC buffers against acidic soil conditions that promote metals solubility; considerable increases in solution pH (+4.49) were observed. Greatest differences in solution PTE content after leaching with/without SC occurred for Pb. In oxalic acid, As, Cd, Pb showed a high level of sorption (25, 15, and 58x more of the respective PTE in leachates without SC). In formic acid, Pb sorption was highly efficient (219x more Pb in leachate without SC). In water, only Pb showed high sorption (191x more Pb in leachate without SC). In desorption experiments, release of PTE from SC varied according to the source of PTE (organic/mineral soil), and type of solvent used. Arsenic was the PTE most readily leached in desorption experiments. Low As sorption from water was followed by fast release (70% As released from SC). A high rate of Cd sorption from organic acid solutions was followed by strong retention (~12% Cd desorption). SC also retained Pb after sorption from water, with subsequent losses of ≤8.5% of total bound Pb. The proposed use of this material is for the filtration of PTE from extract solution following soil washing. Low-molecular-mass organic acids offer a less destructive, biodegradable alternative to strong inorganic acids for soil washing.

Raman spectroscopic identification of arsenate minerals in situ at outcrops with handheld (532 nm, 785 nm) instruments.

Minerals are traditionally identified under field conditions by experienced mineralogists observing the basic physical properties of the samples. Under laboratory conditions, a plethora of techniques are commonly used for identification of the geological phases based on their structural and spectroscopic parameters. In this area, Raman spectrometry has become a useful tool to complement the more widely applied XRD. Today, however, there is an acute need for a technique for unambiguous in situ identification of minerals, within the geological as well as planetary/exobiology realms. With the potential for miniaturization, Raman spectroscopy can be viewed as a practical technique to achieve these goals. Here, for the first time, the successful application of handheld Raman spectrometers is demonstrated to detect and discriminate arsenic phases in the form of earthy aggregates. The Raman spectroscopic analyses of arsenate minerals were performed in situ using two handheld instruments, using 532 and 785 nm excitation. Bukovskýite, kankite, parascorodite, and scorodite were identified from Kank near Kutná Hora, CZE; kankite, scorodite, and zýkaite were identified at the Lehnschafter gallery in an old silver mine at Mikulov near Teplice, Bohemian Massif, CZE.