Article
Spectroscopy
T. F. Akhmetzhanov, A. N. Drozdova, A. M. Popov
Summary: The Mn/Fe ratio in ferromanganese nodules was determined using calibration-free laser-induced breakdown spectroscopy. The analysis relied on plasma parameters and analytical line intensities of manganese and iron. The ability to determine the Mn/Fe ratio in nodules of different geographic origins was demonstrated, with high accuracy and correlation to inductively coupled plasma atomic emission spectrometry.
JOURNAL OF APPLIED SPECTROSCOPY
(2022)
Article
Geochemistry & Geophysics
Chengshuai Liu, Michael S. Massey, Drew E. Latta, Yafei Xia, Fangbai Li, Ting Gao, Jian Hua
Summary: This study elucidates the reaction processes of aqueous Fe(II) with ferromanganese nodules and discusses its impact on the exchange of Fe atoms and the formation of magnetite in the nodules. The observed Fe(II)-induced recrystallization of nodules is expected to play a significant role in influencing the geochemical behavior of elements in nodule-enriched soils.
Article
Chemistry, Analytical
Andrey M. Popov, Timur F. Akhmetzhanov, Sergey M. Zaytsev, Anastasiya N. Drozdova, Ildar A. Kalko, Timur A. Labutin
Summary: This study investigates the application of laser-induced breakdown spectroscopy (LIBS) in oceanography. By using a prototype mobile setup with a portable laser and different detection systems, accurate determination of metal elements in marine ferromanganese nodules from the Kara Sea is achieved. The results show that LIBS has great potential for rapid onboard analysis, especially for the determination of calcium, strontium, and titanium, which offers more accurate results compared to energy-dispersive X-ray fluorescence (EDXRF).
JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY
(2022)
Review
Chemistry, Analytical
Zhenlin Hu, Deng Zhang, Weiliang Wang, Feng Chen, Yubin Xu, Junfei Nie, Yanwu Chu, Lianbo Guo
Summary: Calibration-free LIBS (CF-LIBS) is an important element quantitative analysis method without standards, with advantages such as real-time, in-situ, on-site, single-point, and multi-elemental analysis. This review summarizes the development of CF-LIBS and discusses modified methods, variants, and applications in various fields.
TRAC-TRENDS IN ANALYTICAL CHEMISTRY
(2022)
Article
Chemistry, Physical
Yiping Su, Yangke Long, Shiyin Zhao, Pengju Wang, Feng Xie, Junyi Huang, Bing Han, Zuotai Zhang, Bo-Ping Zhang
Summary: A novel porous ferromanganese oxides (FeMnOx) nanocubes were prepared through a successive codeposition-calcination method and further synthesized by a hydrogenation process. The FeMnOx showed outstanding catalytic activity in the Fenton-like degradation of Rhodamine B and other dyes in the presence of peroxymonosulfate (PMS). The optimized sample exhibited high degradation efficiency and strong stability, suggesting its potential in the field of decolorization.
APPLIED SURFACE SCIENCE
(2023)
Article
Geochemistry & Geophysics
Chao Li, Weiyu Song, Zhenjun Sun, Wei Huang, Gang Hu, Xiaojun Yuan, Shuh-Ji Kao
Summary: Due to the complexity and poor crystallization of ferromanganese nodules, the variability of micro-layers in nodules and the accumulation of various elements during their growth have not been well studied. In this study, we used electron microprobe analyses, backscattered electron imaging, and high-resolution X-ray elemental intensity mapping to examine the spatial distributions of elements in cross-sections of nodules from the Northwestern Pacific Ocean. Our findings reveal significant selective enrichment of metal elements similar to typical hydrogenetic and diagenetic nodules. Additionally, we observed that Fe-Mn oxyhydroxide acts as a diluter during nodule growth, and suboxic conditions lead to the release of Mn, Ni, and Co, with remaining Fe oxyhydroxide reacting with surrounding sediment to form Si-rich layers. These insights contribute to a better understanding of the growth processes and chemical heterogeneity of ferromanganese nodules.
Article
Crystallography
Haipeng Chen, Lihua Gao, Wenlong Zhan, Zhijun He, Junhong Zhang
Summary: The molecular interaction volume model (MIVM), developed by Tao, is a fluid-based model derived from statistical thermodynamics and fluid phase equilibria. It has been successfully applied to predict the activity of each element in Mn-based alloys, particularly in Mn-C, Mn-Fe, and Mn-Fe-C systems. The MIVM accurately calculates the binary parameters between metals (Fe, Mn) and nonmetal (C) in Mn-Fe-C alloys, demonstrating a strong interaction between Fe and Mn. This model is reliable, convenient, and economical, as it effectively explains experimental phenomena in the Mn-Fe-C ternary system.
Article
Environmental Sciences
Guang Yang, Guanyu Chen, Zixuan Cai, Xiangqian Quan, Yang Zhu
Summary: A laser-induced breakdown spectroscopy (LIBS) optical system was designed and built to meet the requirements of near-in situ chemical component detection of deep-ocean mineral resources on ocean-going survey ships. Hyperspectral data of Fe-Mn crusts were obtained through the LIBS system during a deep-sea exploration mission. The LIBS instrument can potentially provide a fast, convenient, accurate, and economical detection method for deep-ocean resource exploration.
FRONTIERS IN MARINE SCIENCE
(2023)
Article
Spectroscopy
Paulino Ribeiro Villas-Boas, Luis Carlos Leva Borduchi
Summary: In this study, a statistical LOD definition is proposed for calibration-free LIBS based on emitter density, plasma parameters, and measurement uncertainties. The LOD is determined through the propagation of uncertainties applied to CF-LIBS calculations and is shown to depend on plasma temperature and emission line properties. The proposed expression provides a sound and thorough LOD definition for LIBS quantitative analyses, and it was validated using carbon and calcium analysis in sodium chloride samples.
SPECTROCHIMICA ACTA PART B-ATOMIC SPECTROSCOPY
(2023)
Article
Chemistry, Analytical
Aya Taleb, Vincent Motto-Ros, Mauro J. Carru, Emanuel Axente, Valentin Craciun, Frederic Pelascini, Jorg Hermann
Summary: A method is proposed to quantify measurement errors caused by self-absorption based on spectral radiance calculation; Line-integrated intensity measurements enable accurate analysis, affected by the spectral shape and intensity measurement method.
ANALYTICA CHIMICA ACTA
(2021)
Article
Multidisciplinary Sciences
Saju Varghese, Rajani P. Ramesh, Rachna Pillai, Sethu Rose Joseph, B. Gopakumar, Resmi Sathikumar, Rajesh Kumar Joshi, Priyanka Dey Guha, R. Manoj, M. Nagasundaram
Summary: The study reveals that the concentration and sources of Platinum Group Elements (PGE) in hydrogenous ferromanganese crusts and nodules in the Andaman Sea are influenced by various processes, with Ruthenium, Iridium, and Platinum possibly originating from ophiolites.
Article
Chemistry, Analytical
Igor B. Gornushkin, Tobias Voelker
Summary: The study investigates the application of the Monte Carlo algorithm in calibration-free LIBS, using a simulated spectrum similar to a metallurgical slag sample. By iterating plasma parameters until the cost function reaches its minimum, the algorithm accurately reads the concentrations of species. The algorithm is parallelized on a GPU to reduce computation time and exhibits high accuracy.
Article
Physics, Multidisciplinary
Zongyu Hou, Weilun Gu, Tianqi Li, Zhe Wang, Liang Li, Xiang Yu, Yecai Zhang, Zijun Liu
Summary: This study clarified the reason for the unsatisfactory quantification performance of CF method in LIBS with non-gated detectors, and proposed a new time-integration calibration-free (TICF) model, which improved the accuracy of elemental concentration measurement.
FRONTIERS OF PHYSICS
(2022)
Article
Environmental Sciences
Zhao Wang, Yubo Wen, Wenxian Gou, Junfeng Ji, Wei Li
Summary: Zn isotope has the potential to be used as an environmental tracer, and this study focuses on its system in terrestrial Fe/Mn nodules. The isotopic compositions of Zn in the nodules are analyzed, revealing their sources and behaviors. The study also characterizes the Zn speciation in the nodules using synchrotron-based methods. The findings provide important insights into the Zn isotope compositions in terrestrial soil Fe/Mn nodules and their implications for environmental tracing.
SCIENCE OF THE TOTAL ENVIRONMENT
(2023)
Article
Optics
Siyu Zhang, Zhenlin Hu, Zhifang Zhao, Feng Chen, Yun Tang, Ziqian Sheng, Deng Zhang, Zhanjie Zhang, Honglin Jin, Huangsheng Pu, Lianbo Guo
Summary: Human biomarkers such as hair and nails provide a continuous record of element concentration indicating nutritional status and metabolic changes. CF-LIBS assisted with the standard reference line method can be used to quantify the content ratio of elements in hair and nails, with relative errors less than 10% compared to ICPOES. This method shows promise as a tool for biomedicine.
Article
Spectroscopy
Aleksandr S. Zakuskin, Timur A. Labutin
Summary: Knowledge of electron temperature and electron number density in laser-induced plasma is crucial for both fundamental and applied research. This paper evaluates the possibility of using wavelet denoising to preprocess Thomson scattering spectra and proposes a robust approach for plasma diagnostics. The results show that wavelet denoising outperforms FFT filtration and provides high-quality results even under low signal-to-noise ratio. The combination of wavelet denoising and nomograms approach is considered to be the most reliable way for plasma diagnostics.
SPECTROCHIMICA ACTA PART B-ATOMIC SPECTROSCOPY
(2022)
Article
Environmental Sciences
Anastasia N. Drozdova, Ivan N. Krylov, Andrey A. Nedospasov, Elena G. Arashkevich, Timur A. Labutin
Summary: The East Siberian Sea is an area with high biogeochemical activity, characterized by unique dissolved organic carbon behavior and spectral distribution. Compared to the Laptev Sea, the shelf waters of the East Siberian Sea contain higher levels of protein-like and marine humic-like fluorescent substances.
FRONTIERS IN MARINE SCIENCE
(2022)
Article
Spectroscopy
T. F. Akhmetzhanov, A. N. Drozdova, A. M. Popov
Summary: The Mn/Fe ratio in ferromanganese nodules was determined using calibration-free laser-induced breakdown spectroscopy. The analysis relied on plasma parameters and analytical line intensities of manganese and iron. The ability to determine the Mn/Fe ratio in nodules of different geographic origins was demonstrated, with high accuracy and correlation to inductively coupled plasma atomic emission spectrometry.
JOURNAL OF APPLIED SPECTROSCOPY
(2022)
Article
Chemistry, Analytical
Nikolai I. Sushkov, Gabor Galbacs, Patrick Janovszky, Nikolay V. Lobus, Timur A. Labutin
Summary: This study investigates the identification methods of zooplankton species through spectroscopic analysis and computer vision techniques. The results show that spectroscopic data is more useful than photo analysis, with the best performance achieved by the combined LIBS + Raman dataset. In addition, methods like principal component analysis can effectively distinguish zooplankton species.
Article
Astronomy & Astrophysics
A. S. Zakuskin, B. G. Beglaryan, T. A. Labutin
Summary: We studied Fe and FeO emission in laser-induced plasma under reduced pressure to find the conditions matching bolide wake plasma.
ASTRONOMY & ASTROPHYSICS
(2023)
Article
Spectroscopy
A. S. Zakuskin, B. G. Beglaryan, T. A. Labutin
Summary: A scheme for the CaO molecular fluorescence was proposed and implemented, which involved transitions between the B-1 Pi and X-1 Sigma(+) electronic states. Two molecular bands were observed in the fluorescence spectra at 408.43 nm and 421 nm, with the latter being assigned to the (0, 3) transition. Selective excitation of rotational states was demonstrated, showing a shift in the fluorescence intensity maximum within the vibrational band. The proposed scheme was then used to spatially resolve the distribution of calcium oxide molecules in the laser-induced plasma.
JOURNAL OF APPLIED SPECTROSCOPY
(2023)
Article
Spectroscopy
Ivan N. Krylov, Timur A. Labutin
Summary: Interpolation of scattering areas in fluorescence spectroscopy and data modelling is commonly achieved using row-by-row interpolation, which can lead to artifacts. In this study, we proposed a penalty matrix construction method for Whittaker smoothing, which reduced the number of parameters and improved signal reconstruction. We compared Whittaker smoothing with other interpolation methods and found that it had better signal reconstruction and interpretable parameters.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2023)
Article
Spectroscopy
I. N. Krylov, I. V. Seliverstova, T. A. Labutin
Summary: The PARAFAC canonical tensor decomposition is commonly used to recover fluorophore groups in dissolved organic matter in natural waters. However, fitting the PARAFAC model is time-consuming, especially for validation. Various strategies were explored to accelerate the PARAFAC fitting to EEM of sea waters. Optimization of a large set of hyperparameters did not significantly speed up the process, but optimizing one variable once for several iterations proved effective. The line-search strategy with extrapolation step achieved the maximum acceleration of 2.3 times, despite collinear sequential steps at certain stages of the algorithm.
JOURNAL OF APPLIED SPECTROSCOPY
(2023)
Article
Engineering, Marine
Sergey A. Mosharov, Elena I. Druzhkova, Andrey F. Sazhin, Pavel V. Khlebopashev, Anastasia N. Drozdova, Nikolay A. Belyaev, Andrey I. Azovsky
Summary: Knowledge of the structure and productivity of Arctic marine planktonic algae communities is crucial to understanding potential changes in the pelagic ecosystem in the Kara Sea under climate change. This study found that species diversity, phytoplankton abundance, and algal production were highest at the beginning of summer during ice melting. The study was conducted in the southwestern Kara Sea and estuarine zone of the Ob and Yenisei rivers from June 29 to July 15, 2018. Factors such as silicate content and salinity were found to influence phytoplankton abundance and productivity.
JOURNAL OF MARINE SCIENCE AND ENGINEERING
(2023)
Article
Chemistry, Analytical
Zhang Qi, Timur Akhmetzhanov, Arina Pavlova, Evgeny Smirnov
Summary: In this study, a highly efficient Raman-enhancing structure was developed by depositing core-shell nanoparticles consisting of a gold core and a thin inert SiO2 shell. The prepared substrate exhibited uniform spatial distribution of hotspots and excellent Raman enhancement, allowing for sensitive detection of malachite green dye and bovine serum albumin. These findings highlight the potential of these substrates for various applications in biomedical research and clinical diagnosis.
Article
Chemistry, Analytical
Timur F. Akhmetzhanov, Timur A. Labutin, Dmitry M. Korshunov, Alexey A. Samsonov, Andrey M. Popov
Summary: In this study, a handheld LIBS analyzer was used to quantitatively determine cerium and lanthanum in ores enriched with rare earth elements. Design of Experiment based on Latin Hypercube Sampling was employed to construct an artificial calibration set. The study showed that cerium could be accurately quantified, but lanthanum determination was affected by matrix effects. Using OREAS samples as calibration sets was suggested to optimize the online in-field monitoring of the mining process.
JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY
(2023)
Article
Optics
B. G. Beglaryan, A. S. Zakuskin, T. A. Labutin
Summary: The optimum parameters for studying the distribution of calcium atoms in low-pressure laser-induced plasma have been determined. A nonresonant fluorescence scheme based on transitions between the 4s4p-4p2 states has been proposed and implemented for the first time. The use of pure calcium carbonate as a target for fluorescence observation and the neglect of spontaneous emission contribute to a substantial enhancement of the fluorescence signal under optimum conditions. Temperature has been shown to have a low impact on the excitation of fluorescence, allowing for spatial measurements of the lateral distribution of calcium atoms in plasma.
OPTICS AND SPECTROSCOPY
(2022)
Article
Chemistry, Analytical
Andrey M. Popov, Timur F. Akhmetzhanov, Sergey M. Zaytsev, Anastasiya N. Drozdova, Ildar A. Kalko, Timur A. Labutin
Summary: This study investigates the application of laser-induced breakdown spectroscopy (LIBS) in oceanography. By using a prototype mobile setup with a portable laser and different detection systems, accurate determination of metal elements in marine ferromanganese nodules from the Kara Sea is achieved. The results show that LIBS has great potential for rapid onboard analysis, especially for the determination of calcium, strontium, and titanium, which offers more accurate results compared to energy-dispersive X-ray fluorescence (EDXRF).
JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY
(2022)
Article
Chemistry, Analytical
Nikolai I. Sushkov, Gabor Galbacs, Krisztian Fintor, Nikolay V. Lobus, Timur A. Labutin
Summary: This study used modern analytical techniques and chemometric techniques to analyze zooplankton organisms that accumulate lithium. The study found correlations between the elemental and molecular composition of zooplankton. By using different algorithms to process the spectra data, the study revealed correlations between lithium and potassium, carotenoids, and tryptophan. The combination of laser-induced breakdown spectroscopy and Raman spectroscopy, followed by appropriate mathematical treatment, is a convenient tool for comprehensive studies of environmental objects.
