Development and optimization of methods of analysis of metals in plant materials using wavelength dispersive X-ray fluorescence spectrometry (WD-XRF) and comparison with other spectrometry techniques

Спектрометријске технике које се конвенционално користе (ICP-OES, ICP-MS) за анализу биљака обично подразумевају захтевну процедуру припреме која укључује коришћење агресивних и токсичних хемикалија за минерализацију што узрокује повећану потребу за развијањем техника директне анализе. Основни циљ ове дисертације је био развијање методе за анализу елемената у биљном материјалу употребом целулозе као универзалног матрикса за производњу синтетичких стандарда за калибрацију. У оквиру ове дисертације оптимизовани су аналитички параметри WD-XRF спектрометра за анализу 20 елемената (Na, Mg, Al, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Sr, Ag, Cd, In, Tl, Pb и Bi) и развијене су три методе анализе, које се примењују у зависности од начина припреме пелета биљног узорка за XRF анализу. Метода „Целулоза“ (Ц) се примењује за анализу пелета сачињених само од биљног материјала, метода „Целулоза са воском“ (ЦВ) за анализу пелета од биљног материјала са додатком воска (везивног средства) и метода „Танак слој“ (ТС) за анализу мале количине узорка. Испитани су основни параметри валидације развијених метода: осетљивост, линеарност, лимит детекције, лимит квантификације, прецизност (поновљивост и унутарлабораторијска репродуктивност) и тачност. Осим развијених метода, испитивање тачности је проширено на безстандрадну методу анализе UniQuant (УК). Како би се сагледао потенцијал УК методе и добио оптималан пелет, испитан је утицај промене параметара припреме биљног узорка на безстандардну методу. У последњем делу дисертације упоређени су резултати добијени WD-XRF техником (емпиријском калибрацијом и безстандардном методом) и конвенционално коришћеним техникама (ICP-MS, ICP-OES и INAA). У ту сврху, свим поменутим техникама је анализирано укупно 49 узорака четири врсте четинара (Pinus nigra, Abies alba, Taxus baccata и Larix decidua).Conventionally used spectrometric techniques for plant analysis (ICP-OES, ICP-MS) usually involve demanding sample preparation procedure that requires the usage of aggressive and toxic chemicals for mineralization, which increases the need for the development of direct analysis techniques. The main goal of this dissertation was development of a method for analysis of elements in plant samples using cellulose as a universal matrix for the production of synthetic calibration standards. WD-XRF spectrometer analytical parameters for analysis of 20 elements (Na, Mg, Al, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Sr, Ag, Cd, In, Tl, Pb, and Bi) have been optimized within this dissertation. Moreover, three methods of analysis have been developed, which are applied depending on the method of preparation of the plant sample pellet for XRF analysis. Method “Pure Cellulose” is applicable for the analysis of pellets made solely from plant material, method “Cellulose with wax” for the analysis of pellets made from the plant material and wax (binder), and method “Thin layer” for the analysis of small amounts of sample. The basic validation parameters of the developed methods were examined: sensitivity, linearity, limit of detection, limit of quantification, precision (repeatability and intralaboratory reproducibility), and accuracy. In addition to the developed methods, the accuracy examination has been extended to a UniQuant standardless method of analysis. In order to assess the potential of the UniQuant method and obtain the optimal pellet, the influence of variation of sample preparation parameters on the standardless method was examined. In the last part of the dissertation, the results obtained using WD-XRF technique (empirical calibration and standardless methods) and conventionally used techniques (ICP-MS, ICP-OES и INAA) were compared. For that purpose, a total of 49 samples of four types of conifer needles were analyzed using all investigated techniques (Pinus nigra, Abies alba, Taxus baccata и Larix decidua)

Development and optimization of methods of analysis of metals in plant materials using wavelength dispersive X-ray fluorescence spectrometry (WD-XRF) and comparison with other spectrometry techniques

Спектрометријске технике које се конвенционално користе (ICP-OES, ICP-MS) за анализу биљака обично подразумевају захтевну процедуру припреме која укључује коришћење агресивних и токсичних хемикалија за минерализацију што узрокује повећану потребу за развијањем техника директне анализе. Основни циљ ове дисертације је био развијање методе за анализу елемената у биљном материјалу употребом целулозе као универзалног матрикса за производњу синтетичких стандарда за калибрацију. У оквиру ове дисертације оптимизовани су аналитички параметри WD-XRF спектрометра за анализу 20 елемената (Na, Mg, Al, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Sr, Ag, Cd, In, Tl, Pb и Bi) и развијене су три методе анализе, које се примењују у зависности од начина припреме пелета биљног узорка за XRF анализу. Метода „Целулоза“ (Ц) се примењује за анализу пелета сачињених само од биљног материјала, метода „Целулоза са воском“ (ЦВ) за анализу пелета од биљног материјала са додатком воска (везивног средства) и метода „Танак слој“ (ТС) за анализу мале количине узорка.Испитани су основни параметри валидације развијених метода: осетљивост, линеарност, лимит детекције, лимит квантификације, прецизност (поновљивост и унутарлабораторијска репродуктивност) и тачност. Осим развијених метода, испитивање тачности је проширено на безстандрадну методу анализе UniQuant (УК). Како би се сагледао потенцијал УК методе и добио оптималан пелет, испитан је утицај промене параметара припреме биљног узорка на безстандардну методу.У последњем делу дисертације упоређени су резултати добијени WD-XRF техником (емпиријском калибрацијом и безстандардном методом) и конвенционално коришћеним техникама (ICP-MS, ICP-OES и INAA). У ту сврху, свим поменутим техникама је анализирано укупно 49 узорака четири врсте четинара (Pinus nigra, Abies alba, Taxus baccata и Larix decidua).Conventionally used spectrometric techniques for plant analysis (ICP-OES, ICP-MS) usually involve demanding sample preparation procedure that requires the usage of aggressive and toxic chemicals for mineralization, which increases the need for the development of direct analysis techniques. The main goal of this dissertation was development of a method for analysis of elements in plant samples using cellulose as a universal matrix for the production of synthetic calibration standards. WD-XRF spectrometer analytical parameters for analysis of 20 elements (Na, Mg, Al, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Sr, Ag, Cd, In, Tl, Pb, and Bi) have been optimized within this dissertation. Moreover, three methods of analysis have been developed, which are applied depending on the method of preparation of the plant sample pellet for XRF analysis. Method “Pure Cellulose” is applicable for the analysis of pellets made solely from plant material, method “Cellulose with wax” for the analysis of pellets made from the plant material and wax (binder), and method “Thin layer” for the analysis of small amounts of sample.The basic validation parameters of the developed methods were examined: sensitivity, linearity, limit of detection, limit of quantification, precision (repeatability and intralaboratory reproducibility), and accuracy. In addition to the developed methods, the accuracy examination has been extended to a UniQuant standardless method of analysis. In order to assess the potential of the UniQuant method and obtain the optimal pellet, the influence of variation of sample preparation parameters on the standardless method was examined.In the last part of the dissertation, the results obtained using WD-XRF technique (empirical calibration and standardless methods) and conventionally used techniques (ICP-MS, ICP-OES и INAA) were compared. For that purpose, a total of 49 samples of four types of conifer needles were analyzed using all investigated techniques (Pinus nigra, Abies alba, Taxus baccata и Larix decidua)

Supplementary data for the article: Orlić, J.; Gržetić, I.; Ilijević, K. Effect of Sample Preparation Procedure on Standardless Wavelength Dispersive X-Ray Fluorescence Analysis of Plant Samples. Spectrochimica Acta Part B: Atomic Spectroscopy 2021, 184, 106258. https://doi.org/10.1016/j.sab.2021.106258.

Supplementary material for: [https://doi.org/10.1016/j.sab.2021.106258]Related to published version: [https://cherry.chem.bg.ac.rs/handle/123456789/4618

Konstrukcija i empirijska provera testa homofobije

The paper presents development and empirical evaluation of the Homophobia scale (H25). The Homophobia scale consists of 25 items with a five-point Likert type scale. The sample of 476 subjects participated in the research. The results shown good psychometric properties of the H25 (KMO = .99, α = .97). Factor analysis revealed two highly correlated underlying dimensions of homophobia, which can be interpreted as 'homosexuality as a threat to a society' and 'homosexuality as a threat to me'. Convergent and predictive validities of the scale were also demonstrated. The H25 correlated with alternative measures of homophobia (feeling thermometer and connotative differential) as well as with discriminatory attitudes toward homosexuals. Additionally, homophobia was related to gender, political orientation, religiousness, contact with homosexuals and basic personality traits (i.e., Openness and Conscientiousness). In conclusion, the H25 proves to be a reliable and valid measure of homophobia in heterosexuals, which can be used for both research and practical purposes.U ovom radu predstavljena je konstrukcija i evaluacija Testa homofobije koji u sadržinskom smislu objedinjuje dosadašnja znanja i ideje o prirodi ovog fenomena. Test homofobije (H25) sastoji se od 25 stavki u formi tvrdnji kojima je pridružena petostepena skala Likertovog tipa. Na uzorku od 476 ispitanika proverene su psihometrijske karakteristike testa i njegova faktorska struktura. U celini test pokazuje dobre psihometrijske karakteristike (KMO = .99, α = .97). Faktorskom analizom ekstrahovana su dva visoko korelirana faktora, koja su interpretirana kao 'homoseksualnost kao pretnja za društvo' i 'homoseksualnost kao pretnja za mene'. Takođe, test je pokazao zadovoljavajuću konvergentnu validnost spram dve alternativne mere homofobije, kao i visoku predikciju diskriminatornih stavova prema osobama homoseksualne orijentacije. Dodatno, pokazano je da homofobija, merena konstruisanim instrumentom, ima veći broj socio-demografskih i personalnih korelata. Homofobiji su sklonije osobe muškog pola, religiozne osobe, osobe konzervativne političke orijentacije, zatim osobe koje imaju manje kontakta sa homoseksualnom populacijom, i osobe nižih skorova na dimeziji Otvorenosti, a viših na dimenziji Savesnosti. U celini, konstruisani instrument predstavlja pouzdanu i validnu meru heteroseksualnog stava prema homoseksualnoj populaciji, te predstavlja ekonomičan instrument pogodan za primenu, kako u istraživačke tako i u praktične svrhe

Early-Middle Miocene paleoenvironmental and paleoclimate changes in the Toplica Basin (Serbia) inferred from plant biomarkers, biochemical and elemental geochemical proxies

The study investigates the influence of alluvial-lacustrine processes and paleoclimate variations on the distribution of terpenoids and unsubstituted Polycyclic Aromatic Hydrocarbons (PAHs). The XRF, ICP-MS, Rock-Eval, and organic geochemical analyses were employed to investigate thirty Lower and Middle Miocene sedimentary samples from the Prebreza and Čučale formations, collected from boreholes BL3 and BL5, situated in the central part of the Toplica Basin (Serbia). The development of the studied basin part was influenced by alluvial-lacustrine processes, which affected the type of organic matter (OM) and the paleoenvironment. Sandy silt and gravel layers in the profile of the BL3 borehole indicate the contribution of thicker clasts brought by rivers. In the BL5 borehole, there are fine-grained intrabasinal lacustrine sediments in the lower part, and swamp sediments in the upper part. The lowest total organic carbon (TOC) content is in alluvial sediments of BL3 and some lacustrine sediments of BL5. Based on Hydrogen Index (HI) and C/N ratio, various mixtures of terrigenous and algal organic matter are present in the sediments, while an increase in the proportion of terrestrial organic matter with higher HI (Type II kerogen) is recorded in upper parts of both boreholes, which may be related to paleoclimatic changes. Based on Tmax, the OM is immature and/or in the initial stage of maturity. The presence of plant terpenoids and unsubstituted PAHs, which reflected paleoflora and paleoclimate changes, was associated with the suggestion of predominating Type III kerogen in the studied sediments. Various factors influenced the application of gymnosperms/angiosperms parameters. For instance, the progressive aromatization of triterpenoids occurred in the BL5, whereas the process was hindered in the upper part of the BL3, probably as a result of high sedimentation rates. Based on C-value, Sr/Cu, and Rb/Sr ratios, during the deposition of the Lower and Middle Miocene formations of Čučale and Prebreza, a warm and humid climate prevailed, reflecting the Middle Miocene Climatic Optimum (MMCO). The production of unsubstituted PAHs in the studied samples probably relates to paleo-wildfires, anoxic conditions, or the presence of specific biomass precursors

Supplementary data for the article: Kašanin-Grubin, M.; Štrbac, S.; Antonijević, S.; Djogo Mračević, S.; Randjelović, D.; Orlić, J.; Šajnović, A. Future Environmental Challenges of the Urban Protected Area Great War Island (Belgrade, Serbia) Based on Valuation of the Pollution Status and Ecosystem Services. Journal of Environmental Management 2019, 251. https://doi.org/10.1016/j.jenvman.2019.109574

Supplementary material for: [https://doi.org/10.1016/j.jenvman.2019.109574]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/3510

Comparison of non-destructive techniques and conventionally used spectrometric techniques for determination of elements in plant samples (coniferous leaves)

Conventionally used spectrometric techniques of inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma optical emission spectrometry (ICP-MS) usually involve time-consuming sample preparation procedure of a sample dissolution which requires the usage of aggressive and toxic chemicals. The need for suitable and sustainable analytical methods for direct multi-elemental analysis of plant samples has been increased in recent years. Spectrometric techniques for direct sample analysis, instrumental neutron activation analysis (INAA) and X-ray fluorescence (XRF) have been applied in environmental studies and various fields of screening tests. Nevertheless, these techniques are not commonly used for plant sample analysis and their performances need to be evaluated. This research aimed to assess how reliable non-destructive techniques are in the determination of elements in plants compared to conventionally used spectrometric techniques. A total of 49 plant samples of four conifer species (Pinus nigra, Abies alba, Taxus baccata and Larix decidua) were measured using two conventionally applied (ICP-MS, ICP-OES) and two non-destructive techniques (wavelength dispersive XRF (WD-XRF), INAA). The comparison was performed by investigation of relative ratios of concentrations and by correlation analysis. Moreover, precision of the techniques was examined and compared. The quality control included analysis of NIST pine needles certified reference material (1575a) using all examined techniques. Our results suggest that additional analytical and quality control steps are necessary for reaching the highest accuracy of multi-elemental analysis

Supplementary data for the article: Kašanin-Grubin, M.; Štrbac, S.; Antonijević, S.; Djogo Mračević, S.; Randjelović, D.; Orlić, J.; Šajnović, A. Future Environmental Challenges of the Urban Protected Area Great War Island (Belgrade, Serbia) Based on Valuation of the Pollution Status and Ecosystem Services. Journal of Environmental Management 2019, 251. https://doi.org/10.1016/j.jenvman.2019.109574

Supplementary material for: [https://doi.org/10.1016/j.jenvman.2019.109574]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/3510

Safe trapping of Cs radionuclides in sintered matrix of zeolites

Cesium aluminosilicate phases are of the great interest as possible host for Cs immobilization in radioactive waste management. The possibility to use zeolite as a host material for radioactive Cs immobilization was investigated. Cs-exchanged forms of clinoptilolite and 13X which were prepared by ion-exchange treatment were compacted. The powders compacts of exchanged zeolites were thermally treated at 1200 °C. The XRD analysis showed that Cs was successfully immobilized after heat treatment by formation of stable cesium-aluminosilicate ceramic forms. Thermal and mechanical properties of the sintered samples were investigated. From the perspective of these characteristics, Cs-exchanged zeolite (clinoptilolite and 13 X) can be considered as a potential material for safe waste disposal

Optimization of the plant sample preparation procedure for metal analysis using Wavelength Dispersive X-Ray Spectroscopy (WDXRF)

Plants are known as good biomonitors in contaminated areas due to their tendency to accumulate toxic metals. Methods based on direct solid sample analysis are more favourable because they avoid utilization of aggressive and toxic agents, which is in line with green chemistry principles [1]. Besides nondestructiveness, X-ray fluorescence spectroscopy (XRF) is suitable for plant analysis because it offers wide linearity range (from ppm level to 100 %) and possibility of analysis of almost whole PSE (from Be to Am) [2]. Plant sample preparation procedure for WDXRF analysis includes grinding and drying at 60 C. After obtaining a homogeneous mixture, the plant sample is mixed with a certain amount of binder (Hoechst wax C micropowder) and pressed in a hydraulic press (Retsch PP 25) in order to obtain stable pellet (32 mm diameter). The plants are mostly made of light elements (O, N and C) which are transparent for X-rays. During analysis of elements with a higher atomic number, Xrays penetrate quite deep into the sample. It is important to establish the minimum thickness of the pellet that will provide reliable results during determination of the heavier elements in the plant matrix. Samples are measured under conditions of high vacuum and slightly elevated temperature, and for that reason herbal matrix is prone to physical changes after analysis. It is important to determine ideal ratio between mass of the sample and the binder that will provide a stable pellet without affecting determination of elements which are present in low concentrations. During this study, two types of plant samples were analysed: fir and pine needles. Samples were collected in 2017 during autumn. The influence of pellet mass (thickness) on elements concentration was examined by measuring pellets prepared from 1, 2, 3, 4 or 5 g of plans material. By preparing pellets with: 0, 5, 10, 15, 20 and 25 % of wax, the influence of binder ratio was examined. Analysis was performed on ARL™ PERFORM’X Sequential Wavelength Dispersive XRay Fluorescence Spectrometer (Thermo Fisher Scientific, Switzerland) combined with ARL software program UniQuant [3]. In both types of plant samples the following elements were determined: Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, Mn, Fe, Ni, Zn, Sr and Zr. Both fir and pine needles show similar trends. As quantity of binder increases, the concentration of Ca and K increases, because wax as binder can contain small quantities of those elements. Repeatability of elements that were found in higher concentrations (Mg, Al, Si, P, S, Cl, K and Ca) is high, while repeatability for low concentration elements (Ti, Fe, Ni, Zn, Sr) decreases as percent of binder increases. Reason for that phenomenon is that dilution with wax is affecting elements in low concentration more than high concentration elements. For light elements results show small impact of pellet mass on the measurements because observed X-rays have low penetration depth. Elements with higher Z number are usually present in smaller concentrations in plants and such measurements are less precise, especially when the smaller pellet mass is analyzed. We can say that UniQuant, as standardless method of analysis, which uses the advanced Fundamental parameters Algorithms for data processing, is well adjusted and able to deal with analysis of different sample masses. When physical properties of pellets are investigated, addition of 20% of wax provides the most stabile pellets with flattest surface. For adequate pellet stability, recommend mass of pellets should be 4 g, but it has been shown that 3 g is acceptable in the case of a small sample quantity. In case when we have less than 3 g, it is recommended to carefully place sample as thin layer on the top of 3 g of boric acid inert carrier.The conference was organized by the Institute of Chemistry of Clermont-Ferrand (ICCF) from the Clermont Auvergne University / CNRS / Sigma-Clermont, on behalf of the Association of Chemistry and the Environment (ACE).Book of Abstract