LIBS analysis of geomaterials: Geochemical fingerprinting for the rapid analysis and discrimination of minerals

Laser-induced breakdown spectroscopy (LIBS) is a simple atomic emission spectroscopy technique capable of real-time, essentially non-destructive determination of the elemental composition of any substance (solid, liquid, or gas). LIBS, which is presently undergoing rapid research and development as a technology for geochemical analysis, has attractive potential as a field tool for rapid man-portable and/or stand-off chemical analysis. In LIBS, a pulsed laser beam is focused such that energy absorption produces a high-temperature microplasma at the sample surface resulting in the dissociation and ionization of small amounts of material, with both continuum and atomic/ionic emission generated by the plasma during cooling. A broadband spectrometer-detector is used to spectrally and temporally resolve the light from the plasma and record the intensity of elemental emission lines. Because the technique is simultaneously sensitive to all elements, a single laser shot can be used to track the spectral intensity of specific elements or record the broadband LIBS emission spectra, which are unique chemical ‘fingerprints’ of a material. In this study, a broad spectrum of geological materials was analyzed using a commercial bench-top LIBS system with broadband detection from ∼200 to 965 nm, with multiple single-shot spectra acquired. The subsequent use of statistical signal processing approaches to rapidly identify and classify samples highlights the potential of LIBS for ‘geochemical fingerprinting’ in a variety of geochemical, mineralogical, and environmental applications that would benefit from either real-time or in-field chemical analysis.     

Diagenetic and other highly mineralized waters in the Polish Carpathians

Highly mineralized waters of different chemical types and origin occur in the flysch formations and their bedrocks in the western part of the Polish Carpathians. The marine sedimentation water of the flysch formations is not preserved, as the most mineralized and the heaviest isotopic values of flysch waters are characterized by δ¹⁸O and δ²H values in the ranges of 5–7‰ and −(20–30)‰, respectively. Their origin is related to the dehydration of clay minerals during burial diagenesis, with molecules of marine water completely removed by molecules of released bound water. They are relatively enriched in Na⁺ in respect to the marine water, supposedly due to the release of Na⁺ during the illitization of smectites and preferable incorporation of other cations from the primary brine into newly formed minerals. In some parts of younger formations, i.e. in the Badenian sediments, brines occur with isotopic composition close to SMOW and Cl⁻ contents greatly exceeding the typical marine value of about 19.6 g/L, supposedly due to ultrafiltration. Most probably, the marine water of the flysch formations was similarly enriched chemically in its initial burial stages. Final Cl⁻ contents in diagenetic waters depend on different Cl⁻ contents in the primary brines and on relationships between diagenetic and further ultrafiltration processes. In some areas, diagenetic waters migrate to the surface along fault zones and mix with young local meteoric waters becoming diluted, with the isotope composition scattering along typical mixing lines. In areas with independent CO₂ flow from great depths, they form chloride CO₂-rich waters. Common CO₂-rich waters are formed in areas without near-surface occurrences of diagenetic waters. They change from the HCO₃–Ca type for modern waters to HCO₃–Mg–Ca, HCO₃–Na–Ca and other types with elevated TDS, Mg²⁺ and/or Na⁻ contents for old waters reaching even those of glacial age. Bedrocks of the flysch are represented by Mesozoic and Paleozoic mudstones, sandstones and carbonates, and in some areas by Badenian sediments. Brines of the Mesozoic and Paleozoic bedrocks are usually significantly enriched in Ca²⁺ and Mg²⁺ in comparison with the Badenian brines. By analogy to the deepest brines in the adjacent Upper Silesian Coal Basin, they are supposed to originate from paleometeoric waters of a hot climate.     

Mathematical modeling and practical verification of groundwater and contaminant transport in a chosen natural aquifer

The paper addresses the 2D mathematical equation of conservative contaminant transport in an aquifer for chosen contaminants. The contaminants (chlorides and sulfates) are subject to instantaneous reversible part of sorption process. The term of instantaneous reversible sorption in the presented equation has been described by the non-linear Freundlich adsorption isotherm, widely applied in practice in relation to static processes (for local equilibrium). The numerical solution (using the finite difference method) has been based on the previously calculated values of longitudinal and transverse dispersion coefficients and the non-linear adsorption parameters for the chosen contaminants. Based on this model, the values of chloride and sulfate concentration isolines have been calculated and compared with the measured maximal concentrations in the chosen natural aquifer (installed piezometers). Additionally, the values of chloride concentrations have been calculated taking into account the influence of radioactive decay term, using the numerical value of the firstorder decay rate constant for an adopted theoretical radionuclide.     

Airborne Fungal Spores of Subalpine Zone of the Karkonosze and Izerskie Mountains （Poland）

The incidence of the airborne fungal spores was determined in the air of subalpine zone of the Karkonosze Mountains and of the Izerskie Mountains in the borderland between Poland and the Czech Republic. The experiment was conducted in 2011 and 2012 at three to four week intervals from May to October. Air samples were taken from three locations in the Karkonosze Mts. and one from the Izerskie Mts. To examine the air, the Air Ideal 3P sampler and acidified PDA medium were used. The results show that Cladosporium cladosporioides was the most abundant spore type in all the sampling locations （up to 30%）, followed by Alternaria alternata （16%-20%）, Fusarium （up to 10%） and Sclerotinia sclerotiorium （up to 6%）. The lower spore counts were recorded in May samples, compared to the other months. In this case the snow cover, that was still present in the area at the beginning of May, may be the reason for the lower, compared to June, July and August samplings, CFU （Colony Forming Unit） counts in that month.. The influx of air masses from SE, S and SW sectors in the area under study may affect dissemination of the plant-pathogenic fungi from the Czech Republic and from the South of Europe in general.     

Attenuation and Shock Waves in Linear Hereditary Viscoelastic Media; Strick–Mainardi,Jeffreys–Lomnitz–Strick and Andrade Creep Compliances

Dispersion, attenuation and wavefronts in a class of linear viscoelastic media proposed by Strick and Mainardi (Geophys J R Astr Soc 69:415–429, 1982) and a related class of models due to Lomnitz, Jeffreys and Strick are studied by a new method due to the author. Unlike the previously studied explicit models of relaxation modulus or creep compliance, these two classes support propagation of discontinuities. Due to an extension made by Strick, either of these two classes of models comprise both viscoelastic solids and fluids. We also discuss the Andrade viscoelastic media. The Andrade media do not support discontinuity waves and exhibit the pedestal effect.     

Erroneous GNSS Strain Rate Patterns and their Application to Investigate the Tectonic Credibility of GNSS Velocities

The paper concerns investigation of the credibility of tectonic interpretation of GNSS strain rates. The analysis was focused on stable regions, where the crustal deformations are small and the reliability of GNSS velocities is questionable. We are showing how the unreliable motion of stations affects calculated strains around them. We expressed distribution of local principal strains by a sinusoidal function and used them to investigate the significance of strain distortion. Then we used this method to investigate real motions of GNSS stations. As a test object we used Polish GNSS stations belonging to the ASG-EUPOS network. Station velocities were estimated on the basis of the 4.5 years of observations. The results let us identify stations that disturb the obtained local GNSS strain rate field. After verification and exclusion of some stations, the new GNSS strains show a much greater internal compatibility and also better fit to the directions of lithosphere stresses.