1. Recent progress and applications of thermal lens spectrometry and photothermal beam deflection techniques in environmental sensingMladen Franko, Leja Goljat, Mingqiang Liu, Hanna Budasheva, Mojca Žorž, Dorota Korte, 2023, original scientific article Abstract: This paper presents recent development and applications of thermal lens microscopy (TLM) and beam deflection spectrometry (BDS) for the analysis of water samples and sea ice. Coupling of TLM detection to a microfluidic system for flow injection analysis (µFIA) enables the detection of microcystin-LR in waters with a four samples/min throughput (in triplicate injections) and provides an LOD of 0.08 µg/L which is 12-times lower than the MCL for microcystin-LR in water. µFIA-TLM was also applied for the determination of total Fe and Fe(II) in 3 µL samples of synthetic cloudwater.
The LODs were found to be 100 nM for Fe(II) and 70 nM for total Fe. The application of µFIA-TLM for the determination of ammonium in water resulted in an LOD of 2.3 µM for injection of a 5 µL sample and TLM detection in a 100 µm deep microfluidic channel. For the determination of iron
species in sea ice, the BDS was coupled to a diffusive gradient in the thin film technique (DGT). The 2D distribution of Fe(II) and total Fe on DGT gels provided by the BDS (LOD of 50 nM) reflected the distribution of Fe species in sea ice put in contact with DGT gels. Keywords: thermal lens microscopy, beam deflection spectrometry, microfluidic system, microcystin-LR detection, iron species determination, ammonium detection Published in RUNG: 03.01.2023; Views: 2644; Downloads: 36 Full text (2,90 MB) This document has many files! More... |
2. Correlation between FeCl2 electrolyte conductivity and electrolysis efficiencyUroš Luin, Matjaž Valant, Iztok Arčon, 2022, published scientific conference contribution abstract Abstract: The electrolysis efficiency is an important aspect of the Power-to-Solid energy storage technology (EST) based
on the iron chloride electrochemical cycle [1]. This cycle employs an aqueous FeCl2 catholyte solution for the
electro-reduction of iron. The metal iron deposits on the cathode. The energy is stored as a difference in the
redox potential of iron species. Hydrogen, as an energy carrier, is released on demand over a fully controlled
hydrogen evolution reaction between metallic Fe0 and HCl (aq) [1]. Due to these characteristics, the cycle is
suitable for long-term high-capacity and high-power energy storage. In a previous work [2] we revealed that
the electrolyte conductivity linearly increases with temperature. Contrary, the correlation between the
electrolyte concentration and efficiency is not so straightforward. Unexpectedly small efficiency variations were
found between 1 and 2.5 mol dm-3 FeCl2 (aq) followed by an abrupt efficiency drop at higher concentrations.
To explain the behavior of the observed trends and elucidate the role of FeCl2 (aq) complex ionic species we
performed in situ X-ray absorption studies. We made a dedicated experimental setup, consisting of a tubular
oven and PMMA liquid absorption cell, and performed the measurements at the DESY synchrotron P65
beamline. The XAS investigation covered XANES and EXAFS analyses of FeCl2 (aq) at different
concentrations (1 - 4 molL-1) and temperatures (25 - 80 °C). We found that at low temperature and low FeCl2
concentration the octahedral first coordination sphere around Fe is occupied by one Cl ion at a distance of 2.33
(±0.02) Å and five water molecules at a distance of 2.095 (±0.005) Å [3]. The structure of the ionic complex
gradually changes with an increase in temperature and/or concentration. The apical water molecule is
substituted by a chlorine ion to yield a neutral Fe[Cl2(H2O)4]0. The transition from the single charged
Fe[Cl(H2O)5]+ to the neutral Fe[Cl2(H2O)4]0 causes a significant drop in the solution conductivity, which well
correlates with the existing conductivity models [3].
[1] M. Valant, “Procedure for electric energy storage in solid matter. United States Patent and
Trademark Office. Patent No. US20200308715,” Patent No. US20200308715, 2021.
[2] U. Luin and M. Valant, “Electrolysis energy efficiency of highly concentrated FeCl2 solutions
for power-to-solid energy storage technology,” J. Solid State Electrochem., vol. 26, no. 4, pp.
929–938, Apr. 2022, doi: 10.1007/S10008-022-05132-Y.
[3] U. Luin, I. Arčon, and M. Valant, “Structure and Population of Complex Ionic Species in
FeCl2 Aqueous Solution by X-ray Absorption Spectroscopy,” Molecules, vol. 27, no. 3, 2022,
doi: 10.3390/molecules27030642. Keywords: Iron chloride electrochemical cycle, Power-to-Solid energy storage, XANES, EXAFS, electrical
conductivity, electrolyte complex ionic species structure and population Published in RUNG: 26.09.2022; Views: 2719; Downloads: 0 (1 vote) This document has many files! More... |
3. NONDESTRUCTIVE THERMAL, OPTICAL, CHEMICAL AND STRUCTURAL CHARACTERIZATION OF ADVANCED MATERIALS BY OPTOTHERMAL TECHNIQUESHanna Budasheva, doctoral dissertation Abstract: Advanced materials are promising ones in application in fields where it is necessary to decrease energy consumption and ensure better performance at a lower cost. They are materials, which have enhanced properties compared to conventional materials in the field of their applications.1 The huge group of them contributes significantly to every aspect of our lives. Among them, chosen for the present study, are resins for passive sampling of iron species in natural water and sediments, anticorrosive coatings, and multilayered polysaccharide aerogels for medical applications.
The composition and structure of each material determine its chemical, mechanical and physical properties, consequently their performance.2 The ability to use advanced materials in areas where their impact will be significant is largely dependent on the ability to precisely determine their characteristics to identify their properties that are either unique or has a better value. Therefore, the development of new methods or improvement of already known ones will make a great contribution to the development of the fields of application of the selected materials.
The present study is focused on the examination of the chosen materials by determining their optical, chemical, thermal and structural properties for applying them further in the desired applications. To provide the needed characterization, optothermal techniques such as optothermal beam deflection spectrometry (BDS) and thermal lens spectrometry (TLS) are developed and applied.
This dissertation is composed of the following chapters: introduction, theoretical background, optothermal techniques, research goal, part I (gels for passive sampling of iron species in natural water and sediments), part II (anticorrosive coatings), part II (polysaccharide aerogels), references. The core of this dissertation is presented in chapters 5 to 7. Each of the chapters separately covers the information about a selected group of advanced materials, including the sections describing sample preparation, developing the required characterization method, results, and conclusion. The connection link of these chapters is the study of the diffusion process of iron into different types of binding gels in passive samplers; external composites through the anticorrosive layers; drugs into the surrounding during the drug delivery process.
In Part I, the BDS method for the study was chosen, it was optimized, and a detailed protocol was developed for the determination of iron in passive sampler gels. The iron residues in the initial solutions were checked by a suitably tuned TLS method. The developed technique was applied to get the iron species distribution in the gel samples deposited in the sediments in the Vrtojbica River. The method was applied to the gels applied on ice from Antarctica in order to obtain the iron species distribution on its surface as well. The obtained results were validated using the TLS, UV-Vis and ICP-MS methods. The chapter contains the analysis of the Fe diffusion depth into the resin sampler, which is presented for the first time. The information is obtained by using the mathematical model and applying it to the obtained practical results by frequency scanning of the gels. The crucial information about the thermal properties of their layers containing Fe-ions from the fitting procedure was extracted. On the basis of these results, information about the diffusion depth of Fe inside the gels was obtained, which has not been previously described in the literature.
In Part II, the porosity in the anticorrosion coatings on the basis of their thermal parameters was determined. For the first time, the opened porosity was extracted from the total one. The analysis of Si/Zr-based hybrid sol-gel coatings has shown that the addition of cerium salts into the sol-gel matrix produces changes in its physical, chemical and corrosion properties. And it was found that the sample with the biggest amount of incorporated zirconium and loaded with cerium has the lowest values of porosity and, hence, the best barrier properties of the coating. The obtained thermal parameters of the Si/Zr-based hybrid sol-gel coatings by BDS were validated by the use of the photothermal radiometry method. On the other hand, the analysis of siloxane methacrylate coating has shown that the sol-gel hybrid methodology offers an important route for modification of thermal properties by a combination of inorganic to organic contents where the former than as an integral part of the coating network affects the thermal properties without the need for introducing fillers or nanoparticles.
In Part III, the multilayered structure of the samples, containing hyaluronic acid, amoxicillin and fucoidan layers deposited on stainless support has been analyzed by the use of the BDS technique. The thermal parameters of each layer were determined, as well as their thickness. The results revealed the diffusion between neighboring layers and followed changes in the properties of the whole sample, which is reflected in its thermal properties. Such data for multilayered materials, which potentially can be used for drug delivery systems, are presented for the first time.
Presented results indicated the ability of the BDS system for the chemical characterisation of the solid materials, the detection of their thermal parameters; investigation of total, opened and closed porosity; determining the thickness of layers in multilayered structures. The TLS method served as the validating one for the purpose of getting comprehensive information in liquid samples about their chemical composition. In summary, this dissertation explores alternative ways to apply optothermal methods to various areas of advanced materials to characterize them in order to improve their initial properties. Keywords: optothermal beam deflection spectrometry, thermal lens spectrometry, diffusive gradients in thin films, iron species, anticorrosive layers, porosity, polysaccharide aerogels, multilayered structures Published in RUNG: 29.08.2022; Views: 3608; Downloads: 65 Full text (5,46 MB) |
4. Towards a novel method for iron species determination in Antarctic sea iceHanna Budasheva, Arne Bratkič, Dorota Korte, Mladen Franko, 2021, published scientific conference contribution abstract Abstract: Sea-ice borne iron has been found to be an important factor controlling Southern Ocean phytoplankton growth [1]. Knowing the amount and chemical speciation of its labile fraction in sea ice would advance our understanding of the involved processes. Unfortunately, it is rather difficult to perform their measurement because of limited access to the Antarctic. Thus there is a strong need for the development of a quick, simple and reliable technique for determination of iron and its speciation in sea-ice that ensures also low enough limits of detection. Recently, diffusive gradients in thin films (DGT) have been widely used as passive samplers for collecting time-averaged data on the concentrations of transition metals in different media [2]. DGTs are further coupled to an analytical technique that in case of detecting metals in passive sampler films primarily requires their extraction [3], which may potentially lead to changes of the metal specification. In the present study, the beam deflection spectrometry (BDS) is coupled to DGT and used to determine the average concentration of iron in the sea ice samples collected at the Davis Station in the Antarctic. Such a combined technique has been already successfully applied for detecting labile iron species in freshwater sediments [4]. The obtained BDS data were validated by thermal lens spectrometry (TLS) and UV-Vis spectrophotometry (SPEC). The distribution of iron species over a given ice surface area using the DGT-BDS technique revealed total iron concentrations in the range of 0.6 – 5.3 μgL-1, whereas the Fe2+ content was found to be in the range of 0.1 – 1.5 μgL-1. The range taking into account all of the measurement points (5×4), the precision of a single measured point is 0.2 μgL-1. The calculated 24 h-average concentration of total Fe labile species in the ice by using BDS is 2.3 ± 0.5 μgL-1, which coincides with data obtained by SPEC (2.5 ± 0.4 μgL-1) and TLS (2.39 ± 0.02 μgL-1). Our results indicate that it is possible to develop a robust, contamination-resilient detection method for measuring the labile iron species concentration in the sea ice. In opposite to TLS and SPEC, BDS-DGT provides reliable information not only about the speciation of iron but also about their distribution on the ice surface. Keywords: beam deflection spectrometry, diffusive gradients, thin films, iron species, photothermal techniques, Antarctic sea ice Published in RUNG: 30.11.2021; Views: 3444; Downloads: 0 This document has many files! More... |
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6. Developing DGT technique for determination of iron redox species by photothermal beam deflection spectrometryHanna Budasheva, Arne Bratkič, Chang Zhou, Dorota Korte, Yue Gao, Mladen Franko, Bruno Delille, 2019, published scientific conference contribution abstract Keywords: Diffusive Gradients in Thin Films, Beam Deflection Spectrometry, iron redox species Published in RUNG: 25.09.2019; Views: 4459; Downloads: 0 This document has many files! More... |
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8. Determination of bioavailable Fe redox fractions of sediment pore waters by DGT passive sampling and BDS detectionHanna Budasheva, Dorota Korte, Arne Bratkič, Mladen Franko, 2019, published scientific conference contribution abstract Abstract: The bioavailability and toxicity of contaminants in sediments to benthic organisms depend on the speciation of the contaminant [1]. The level of iron supply to sediments creates contrasting chemical pathways, each producing distinctive mineral assemblag- es. Reliable measurement of Fe redox species (Fe2+ and Fe3+) in sediments is essential for studies of pollutants or trace-element cycling. This is, however, a difficult task, because the distribution of chemical species often changes during sampling and storage.
In this work the Diffusive Gradients in Thin-films technique (DGT) is investigated as a passive sampling approach used in combination with photothermal beam deflection spectroscopy (BDS) as a detection method for determination of labile Fe-redox species in sediments and natural waters. DGT offers the advantage of pre-concentration of labile (i.e. bioavailable) Fe species from the total dissolved Fe pool in sediment pore waters [2]. The advantage of using BDS [3-4] is also in avoiding contamination by using additional steps as extraction or pre-concentration. Furthermore, combined DGT-BDS provides 2D information about distribution of Fe2+ and the total Fe content in the resin hydrogels [5].
The goal of this research is to show the repeatability of this technique for determining trace amounts of Fe redox species in environmental samples. Keywords: beam deflection spectrometry, diffusive gradients in thin-films, iron species Published in RUNG: 16.07.2019; Views: 4327; Downloads: 0 This document has many files! More... |
9. Determination of Dissolved Iron Redox Species in Freshwater Sediment using DGT Technique Coupled to BDSHanna Budasheva, Aleksander Kravos, Dorota Korte, Arne Bratkič, Yue Gao, Mladen Franko, 2019, original scientific article Abstract: In this work we have developed a novel method for determination of iron redox species by the use of diffusive gradients in thin-film (DGT) technique coupled to photothermal beam deflection spectroscopy (BDS). The combination of both methods achieved low limit of detection (LOD) of 0.14 μM for Fe (II) ions. The total Fe concentration determined in the Vrtojbica river sediment (Slovenia, Rožna Dolina, 5000 Nova Gorica) was 49.3 μgL–1. The Fe (II) and Fe (III) concentra- tion amounted to 12.8 μgL–1 and 39.9 μgL–1, respectively. Such an approach opens new opportunities for monitoring the content of iron species in natural waters and sediments and provides highly sensitive chemical analysis and an accurate qualitative and quantitative characteristic of the materials under study. Keywords: Beam deflection spectroscopy, diffusive gradients in thin-film technique, iron redox species, photothermal techniques, sediment Published in RUNG: 26.02.2019; Views: 4647; Downloads: 117 Full text (452,58 KB) |
10. Optimization of DGT technique for determination of iron species in natural water and sediments by photothermal beam deflection spectroscopyHanna Budasheva, Arne Bratkič, Dorota Korte, Mladen Franko, 2018, published scientific conference contribution abstract Keywords: beam deflection spectroscopy, diffusive gradients in thin-film technique, iron redox species, photothermal techniques, natural water, sediments Published in RUNG: 23.11.2018; Views: 4716; Downloads: 0 This document has many files! More... |