Analytical Assessments of Gallstones and Urinary Stones: A Comprehensive Review of the Development from Laser to LIBS

Abstract

Laser-induced breakdown spectroscopy (LIBS) is a sensitive optical technique capable of fast multi-elemental analysis of various kinds of materials (solid, liquids, and gases) and its applications are growing rapidly and continue to extend to include a broad variety of biological materials. Its application is suited particularly for urinary stones and gallstones bulk analysis and microanalysis because investigation of the spatial distribution of matrix and trace elements can help to explain their emergence and growth. Therefore, we review the application of LIBS for the analysis of different kinds of gallstones and urinary stones. In brief, we also describe the history, fundamentals, advantages, and disadvantages of LIBS and its potential for spectrochemical analysis of gallstones and kidney stones. We also emphasize the applications of different kinds of lasers in urology, particularly the laser ablation of gallstones and urinary stones and its recent progress. We also summarize and compare the analytical figures of merits of analytical techniques that are commonly used to characterize and/or analyze stones.     

High resolution scanning microanalysis on material surfaces using UV femtosecond laser induced breakdown spectroscopy

Femtosecond lasers together with high resolution optics have given us the ability to achieve submicron ablation spots which can play an important role in specific micromachining applications. Light emitted from the plasma at the sample surface created by a focused femtosecond laser pulse can also be used in laser induced breakdown spectroscopy (LIBS) and allows us to characterize the chemical composition of the target surface with micron-level lateral resolution. The spatial resolution using LIBS has often been defined by measuring the FWHM of the crater size. In this report, we study the application of femtosecond 266 nm laser pulses with very low energies of 10׳s of nanojoules. We have investigated spatial resolution using the detection of thin strips of chromium on silicon substrates and compared the actual width of the chromium versus the experimentally obtained width using LIBS detection. The variation of signal levels for low pulse energies is investigated on chromium surfaces. A spatial resolution of ~1 μm was obtained for detection of chromium from the emission.     

In-Situ Monitoring of Chromium Uptake in Different Parts of the Wheat Seedling (Triticum aestivum) using Laser-Induced Breakdown Spectroscopy

The present work is a methodological study to investigate the effect of chromium (VI) stress on wheat seedlings. Point detection capability of laser-induced breakdown spectroscopy (LIBS) was utilized for the monitoring of in-situ chromium uptake in wheat (Triticum aestivum) seedlings. Chromium accumulation and its effects on other elements in wheat seedling were investigated by comparing the intensities of spectral lines of chromium and other minerals present in the LIBS spectra. In-situ LIBS spectra of the different parts of the wheat seedlings were recorded by directly focusing the laser beam on the surface of root, stem, and leaf of the seedlings grown with and without chromium-containing solutions. The spectra obtained from the different parts (root, stem, and leaf) of the wheat plant were analyzed to determine the distribution pattern/accumulation of chromium. Effect of the chromium uptake on the distribution pattern of other elements like calcium (Ca), magnesium (Mg), sodium (Na), and potassium (K) was also investigated. It was observed that chromium concentrations in plant organs decreased in the following order: roots > leaves > stems.     

Nuclear level densities in <Superscript>47</Superscript>V, <Superscript>48</Superscript>V, <Superscript>49</Superscript>V, <Superscript>53</Superscript>Mn,and <Superscript>54</Superscript>Mn from neutron evaporation spectra

The spectra of neutrons from the (p, n) reactions on ⁴⁷Ti, ⁴⁸Ti, ⁴⁹Ti, ⁵³Cr, and ⁵⁴Cr nuclei were measured in the proton-energy range 7–11 MeV. The measurements were performed with the aid of a fast-neutron spectrometer by the time-of-flight method over the base of the EGP-15 tandem accelerator of the Institute for Physics and Power Engineering (IPPE, Obninsk). Owing to a high resolution and a high stability of the time-of-flight spectrometer used, low-lying discrete levels could be identified reliably along with a continuum section of neutron spectra. An analysis of measured data was performed within the statistical equilibrium and preequilibrium models of nuclear reactions. The relevant calculations were performed by using the exact formalism of Hauser-Feshbach statistical theory supplemented with the generalized model of a superfluid nucleus, the back-shifted Fermi gas model, and the Gilbert-Cameron composite formula for the nuclear level density. The nuclear level densities for ⁴⁷V, ⁴⁸V, ⁴⁹V, ⁵³Mn, and ⁵⁴Mn were determined along with their energy dependences and model parameters. The results are discussed together with available experimental data and recommendations of model systematics.     

Application of laser-induced breakdown spectroscopy in carbon sequestration research and development

The success of carbon capture and storage (CCS) programme relies on the long-term isolation of CO₂ from the atmosphere. Therefore, technologies concomitant to physical storage of CO₂ such as reliable measurement, monitoring, and verification (MMV) techniques are needed to ensure that the integrity of the storage site is maintained. We propose the use of laser-induced breakdown spectroscopy (LIBS) analytical technique to detect carbon dioxide leaks to aid in the successful application of CCS. LIBS has a real-time monitoring capability and can be reliably used for the elemental and isotopic analysis of solid, liquid, and gas samples. The flexibility of probe design and use of fibre optics make it a suitable technique for real time measurements in harsh conditions and at hard-to-reach places. Proposed monitoring with LIBS includes terrestrial soil samples, water samples from monitoring wells or from different formations, air samples from monitoring wells or suspected leakage areas. This work details the laboratory scale experiments to measure carbon contents in rock, soil, aqueous, and air samples. The potential of the technology for measurements in high pressure high-temperature conditions will also be discussed.     

RECENT DEVELOPMENTS IN INSTRUMENTATION FOR LASER INDUCED BREAKDOWN SPECTROSCOPY

ABSTRACT

This review describes, in detail, the most recent developments in instrumentation for laser induced breakdown spectroscopy (LIBS). The paper focuses on various laser systems, including excimer, CO₂, and Nd: YAG and their performance in LIBS. The coupling of fiber-optics to LIBS and development of portable LIBS systems and their performance is presented. New approaches such as dual pulse operation, multi-fiber, resonant ablation, and combination with laser induced fluorescence are further described. Finally the use of the Echelle spectrometer in which it has been combined with various charge coupled devices.     

Resonance assignment of<Superscript>13</Superscript>C−<Superscript>15</Superscript>N-labeled snake neurotoxin II from<Emphasis Type="Italic">Naja oxiana</Emphasis>

Neurotoxin II fromNaja oxiana venom is a short-chain snake curaremimetic neurotoxin containing four disulfide bonds. We obtained¹³C-¹⁵N-labeled neurotoxin II to study its internal dynamics and surface properties with atomic resolution. The recombinant protein has the native spatial structure and is biologically active. The nearly complete assignment of¹H,¹³C and¹⁵N resonances for neurotoxin II was obtained by heteronuclear triple-resonance nuclear magnetic resonance spectroscopy. Analysis of the secondary chemical shifts of the¹H^α,¹³C^α,¹³C^β and¹³CO nuclei reveal their strong correlation with the protein secondary structure.     

Laser ablation of powdered samples and analysis by means of laser-induced breakdown spectroscopy

The presented work proves the capacities of laser-induced breakdown spectroscopy (LIBS) as a fast, universal, and versatile technique for analysis of complex materials as ceramics. This paper reports on the analysis of ceramic raw materials (brick clays and kaolin) submitted to laser ablation in the form of pressed pellets. Spectrographic study was provided by standard single-pulse LIBS technique and orthogonal reheating double-pulse LIBS. It was found that both methods are comparable in terms of analytical performance, if adequate experimental parameters and signal detection systems are used.     

Assessment of LIBS for Spectrochemical Analysis: A Review

Abstract

This review assesses the applications of laser-induced breakdown spectroscopy (LIBS) for the analysis of a variety of samples, including biomaterials (teeth, nail, hair, gallstones, and kidney stones, etc.), food materials (fruits and vegetables, milk, salt, nutritional supplements, etc.), medicinal plants, industrial waste, liquid samples, etc. In addition, for the first time the identification of cholesterol and pigment stones was performed on the basis of atomic lines of different elements and molecular bands of C₂ molecules present in the LIBS spectra of gallstones. Chemometric techniques such as principal component analysis (PCA) was also applied to LIBS data for rapid identification/classification of different gallstone samples. LIBS analysis of toxic/heavy elements present in vegetables (spinach, tomato) and rice is also presented in this review. It was observed that vegetables grown near industrial areas are rich in several toxic metals like Pb and Cr. The wastewater samples from different industries were also analyzed by recording their spectra using a liquid jet. These results clearly demonstrate the ability of LIBS technique as an instant monitoring device to detect heavy metals present in liquid samples. Finally, this review shows that LIBS is a versatile analytical technique with unlimited applications.     

激光烧蚀-电感耦合等离子体质谱技术在材料表面微区分析领域的应用进展

激光烧蚀-电感耦合等离子体质谱(LA-ICP-MS)技术不仅可以对导体及非导体进行元素的成分含量分析,而且还可进行元素分布及涂层深度表面微区分析,故在元素分析领域引起广泛的关注。主要介绍了LA-ICP-MS的仪器装置及其表面微区分析理论,同时对LA-ICP-MS在钢铁、有色金属及半导体等材料科学领域中的元素分布及涂层深度表面微区分析应用进展情况进行回顾,与SEM/EDS(扫描电子显微镜/能谱仪)、EPMA(电子探针微区分析)、AES(俄歇电子能谱)等传统经典的表面分析方法的比较,LA-ICP-MS具有无需或很少样品制备、空间分辨率可调、多元素同时分析及灵敏度高等优点,目前LA-ICP-MS已成为这些经典表面微区分析工具强有力的补充。随着LA-ICP-MS分析技术进一步的发展与成熟,相信不久的将来越来越多的元素分析工作者会使用这一强有力的分析工具,它像LIBS(激光诱导击穿光谱)一样,将会成为元素分析领域非常耀眼的一颗新星。     

Spectroscopic analysis using a hybrid LIBS-Raman system

A novel setup, combining two spectroscopic techniques, laser induced breakdown spectroscopy (LIBS) and Raman spectroscopy in a hybrid unit, is described. The work presented herein is part of a broader project that aims to demonstrate the applicability of the hybrid LIBS-Raman unit as an analytical tool for the investigation of samples and objects of cultural heritage. The system utilizes a nanosecond pulsed Nd:YAG laser (532 nm) for both LIBS and Raman analysis. In the Raman mode, a low intensity beam from the laser probes the sample surface and the scattering signal is collected into a grating spectrograph coupled to an intensified charge-coupled device (ICCD) detector, which records the Raman spectrum. In the LIBS mode a single high intensity pulse from the laser irradiates the sample surface and the time- and spectrally-resolved emission from the resulting laser ablation plume yields the LIBS spectrum. The use of a non-gated CCD detector was found to produce similar quality data (in terms of S/N ratio and fluorescence background) in the Raman mode, while in the LIBS mode spectral features were clearly broader but did not prevent identification of prominent atomic emission lines. Several model pigment samples were examined and the data obtained show the ability of the hybrid unit to record both Raman and LIBS spectra from the same point on the sample, a clear advantage over the use of different analytical setups. PACS 39.30.+w; 82.80.Dx; 82.80.Gk; 52.38.Mf     

Nuclear level densities in <Superscript>208</Superscript>Bi and <Superscript>209</Superscript>Po from the neutron spectra in the (<Emphasis Type="Italic">p,n</Emphasis>) reactions on <Superscript>208</Superscript>Pb and <Superscript>209</Superscript>Bi nuclei

The spectra of neutrons from the (p, n) reactions on the ²⁰⁸Pb and ²⁰⁹Bi nuclei were measured in the proton-energy range 8–11 MeV. These measurements were performed by using a time-of-flight spectrometer of fast neutrons on the basis of the pulsed tandem accelerator EGP-15 of the Institute of Physics and Power Engineering (Obninsk, Russian Federation). A high resolution and stability of the time-of-flight spectrometermade it possible to identify reliably low-lying discrete levels alongwith the continuum section of the neutron spectra. The measured data were analyzed on the basis of the statistical equilibrium and preequilibrium models of nuclear reactions. The respective calculations were performed by using the precise formalism of Hauser-Feshbach statistical theory together with the generalizedmodel of a superfluid nucleus and the back-shifted Fermi gas model for the nuclear-level density. The nuclear-level densities in ²⁰⁸Bi and ²⁰⁹Po were determined along with their energy dependences and model parameters. Our results are discussed together with available experimental data and recommendations of model systematics.     

Analysis of Ti in textile stippled by TiO<Subscript>2</Subscript> nanoparticle sol using double-pulse LIBS and ED XRF spectrometry

Double-pulse LIBS and ED XRF usabilities for quantitative analysis of Ti in samples of cotton, wool, and viscose fabrics were compared to each other. The analyzed samples were prepared by stippling a particular fabric with TiO₂ nanoparticle sol (particle size 100 nm). Both spectrometers were calibrated with the aid of the same sets of authentic fabric samples previously analyzed by ICP OES after the microwave digestion. Average values of the Ti concentration calculated from five repeated measurements of the same sample obtained by LIBS and ED XRF were comparable for all types of the tested materials (100∙(C_Ti-LIBS/C_{Ti-ED XRF})) ≅ 96–109%), but the precision of analysis expressed as RSD (relative standard deviation) was usually better for ED XRF (RSD_LIBS from 9 to 25%, RSD_{ED XRF} from 3 to 17%). Poor RSD values of LIBS measurements were observed mainly in the case of samples with lower areal weights. Limits of detection calculated as a triple standard deviation of five repeated measurements of Ti in a sample with the low concentration of the analyte were comparable for both methods (LOD_LIBS = from 15 to 97, and LOD_{ED XRF} = from 21 to 64, all in mg/kg).     

Fast X‐ray microfluorescence imaging with submicrometer‐resolution integrating a Maia detector at beamline P06 at PETRA III

The high brilliance of third‐generation synchrotron sources increases the demand for faster detectors to utilize the available flux. The Maia detector is an advanced imaging scheme for energy‐dispersive detection realising dwell times per image‐pixel as low as 50 µs and count rates higher than 10 × 10⁶ s^?1. In this article the integration of such a Maia detector in the Microprobe setup of beamline P06 at the storage ring PETRA III at the Deutsches Elektronen‐Synchrotron (DESY) in Hamburg, Germany, is described. The analytical performance of the complete system in terms of rate‐dependent energy resolution, scanning‐speed‐dependent spatial resolution and lower limits of detection is characterized. The potential of the Maia‐based setup is demonstrated by key applications from materials science and chemistry, as well as environmental science with geological applications and biological questions that have been investigated at the P06 beamline.     

Effect of high doses of N<Superscript>+</Superscript>, N<Superscript>+</Superscript> + Ni<Superscript>+</Superscript>, and Mo<Superscript>+</Superscript> + W<Superscript>+</Superscript> ions on the physicomechanical properties of TiNi

The surface layer of an equiatomic TiNi alloy, which exhibits the shape memory effect in the martensitic state, is modified with high-dose implantation of 65-keV N⁺ ions (the implantation dose is varied from 10¹⁷ to 10¹⁸ ions/cm²). TiNi samples are implanted by N⁺, Ni⁺-N⁺, and Mo⁺-W⁺ ions at a dose of 10¹⁷–10¹⁸ cm⁻² and studied by Rutherford backscattering, scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction (glancing geometry), and by measuring the nanohardness and the elastic modulus. A Ni⁺ concentration peak is detected between two maxima in the depth profile of the N⁺ ion concentration. X-ray diffraction (glancing geometry) of TiNi samples implanted by Ni⁺ and N⁺ ions shows the formation of the TiNi (B2), TiN, and Ni₃N phases. In the initial state, the elastic modulus of the samples is E = 56 GPa at a hardness of H = 2.13 ± 0.30 GPa (at a depth of 150 nm). After double implantation by Ni⁺-N⁺ and W⁺-Mo⁺ ions, the hardness of the TiNi samples is ∼2.78 ± 0.95 GPa at a depth of 150 nm and 4.95 ± 2.25 GPa at a depth of 50 nm; the elastic modulus is 59 GPa. Annealing of the samples at 550°C leads to an increase in the hardness to 4.44 ± 1.45 GPa and a sharp increase in the elastic modulus to 236 ± 39 GPa. A correlation between the elemental composition, microstructure, shape memory effect, and mechanical properties of the near-surface layer in TiNi is found.     

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.     

<Superscript>57</Superscript>Fe NMR study of multiferroic BiFeO<Subscript>3</Subscript>

The effects of the ⁵⁷Fe isotope content and high-frequency magnetic field amplitude h ₁ on the shape of the NMR spectrum of multiferroic BiFeO₃ at T = 4.2 K are studied by pulsed nuclear magnetic resonance. The NMR spectrum shape and transverse relaxation time T ₂ are found to depend strongly on the ⁵⁷Fe isotope content and h ₁ in multiferroic BiFeO₃ in the presence of a spatial spin-modulated structure of a cycloid type. In a sample with a high ⁵⁷Fe isotope content, the Suhl-Nakamura interaction contributes substantially to T ₂. When these dynamic effects are taken into account for analysis of the NMR spectrum shape, an undisturbed (without an anharmonicity effect) spatial spin-modulated structure of a cycloid type is shown to exist in BiFeO₃.     

Plasma property effects on spectral line broadening in double-pulse laser-induced breakdown spectroscopy

Double-pulse Laser-Induced Breakdown Spectroscopy (LIBS) in an orthogonal configuration was used to investigate plasma temperature and electron density effects on Mg II emission spectral line broadening. The experiments were carried out with two Nd:YAG lasers, one operating at 355 nm for ablation and the other one at 1064 nm for plasma reheating in air at atmospheric pressure. Temporally resolved plasma temperature and electron density were measured at various delay times. Data in this study show prolonged emission of Mg II (280.27 nm) as well as enhancement of the signal intensity when using double-pulse excitation compared to the single-pulse case. An enhancement of ～8× was attained with a delay between the laser pulses equal to 1 μs. The enhancement was accompanied by higher plasma temperature and increased electron density. The double-pulse LIBS configuration provides energy to sustain the plasma emission at a period in time when the linewidth is minimum, thereby improving the analytical capabilities of low spectral resolution instrumentation typically used in LIBS system.     

Spectroscopy of laser-produced plasmas: Setting up of high-performance laser-induced breakdown spectroscopy system

It is a well-known fact that laser-induced breakdown spectroscopy (LIBS) has emerged as one of the best analytical techniques for multi-elemental compositional analysis of samples. We report assembling and optimization of LIBS set up using high resolution and broad-range echelle spectrograph coupled to an intensified charge coupled device (ICCD) to detect and quantify trace elements in environmental and clinical samples. Effects of variations of experimental parameters on spectroscopy signals of copper and brass are reported. Preliminary results of some plasma diagnostic calculations using recorded time-resolved optical emission signals are also reported for brass samples.     

激光诱导击穿光谱在材料表面分析领域中的应用进展

激光诱导击穿光谱作为表面分析工具是近十年发展起来的,对表面分析基础理论、仪器装置及其在材料科学领域中的应用进行详细的综述。重点阐述了激光诱导击穿光谱在国内外冶金、半导体、电子等材料科学领域中的元素分布分析及镀层分析应用进展,指出激光束单个脉冲能量、环境气体及气压、激光束能量分布等参数对分辨率的影响,同时指出在兼顾灵敏度的前提下提高分辨率的途径。与传统经典表面分析工具相比较具有扫描面积大、分析速度快及样品导电与否均可分析等优点,成为传统表面分析工具的有力补充。