A new approach to study the mobility of metals and metalloids in sediments using sequential extraction

Cilj ove doktorske disertacije je određivanje sadržaja metala i metaloida u uzorcima sedimenata i muljeva iz otpadnog kanala industrijske zone Pančeva i okoline, ustanovljavanje njihovih asocijacija sa različitim supstratima, procena potencijalne mobilnosti ispitivanih elemenata u uslovima koji vladaju u ispitivanoj sredini, kao i identifikacija eventualnog antropogenog zagađenja, korišćenjem metode standardizovane sekvencijalne ekstracije. Primenjene su tri tehnike ekstrahovanja za prva tri koraka standardizovane BCR sekvencijalne ekstrakcije i to: mućkanje uzoraka na rotacionoj mućkalici u trajanju od šesnaest sati u okviru konvencionalne sekvencijalne ekstrakcije (KSE); dvominutno izlaganje uzoraka mikrotalasima snage 90 W u okviru mikrotalasne sekvencijalne ekstrakcije (MTSE); i tridesetominutno izlaganje uzoraka ultrazvučnim talasima u okviru ultrazvučne sekvencijalne ekstrakcije (UZSE). Četvrti korak u primeni sve tri tehnike je bio isti, kuvanje uzoraka sa carskom vodom na vodenom kupatilu. Tačnost i preciznost sve tri primenjene tehnike ekstrahovanja je utvrđen pomoću referentnog materijala, BCR 701. Pored sekvencijalne ekstrakcije, uzorci su rastvarani u mikrotalasnom digestoru pomoću carske vode i carske vode sa HF. Nakon svih primenjenih ekstrakcionih koraka, u rastvorima je određivan sadržaj Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Si, Sn, Sr, V, Ti, Zn, As, Se i Hg metodom induktivno spregnute plazme sa optičkom emisionom spektrometrijom (ICP/OES). Računanjem osnovnih (baseline) geohemijskih koncentracija i primenom multivarijantnih statističkih metoda, određeni su antropogeno poreklo elemenata i/ili kvantifikovan njihov antropogeni udeo, kao mogući izvori zagađivanja na ovim lokalitetu. Poređenje rezultata ekstrakcije sertifikovanog materijala, dobijenih različitim tehnikama, pokazalo je da je KSE najpreciznija metoda dok se primenom ultrazvučne sekvencijalne ekstrakcija (UZSE) dobijaju zadovoljavajuće tačnosti za polovinu sertifikovanih metala u prvom i trećem koraku BCR ekstrakcije, za razliku od MTSE koja daje najnepreciznije rezultate. Na osnovu procentualne zastupljenosti ekstrahovanih koncentracija elemenata nakon prve faze BCR ekstrakcije, može se konstatovati da, na osnovu ekstrahovanih koncentracija Cd, Cu i Zn uzorci sedimenata uzeti sa lokaliteta Dekantera imaju povišen i visok rizik po životnu sredinu, dok, na osnovu koncentracija esktrahovanih Ba, Cd, Cu, Zn i Se, sedimenti sa lokaliteta Elektrolize imaju nizak i srednji rizik po životnu sredinu...The goal of this dissertation is to determine the c ontent of heavy metals and metalloids, in sediments and mud samples from the waste canals of the industrial zone of Pan č evo and its surroundings, to establish their associations with different substrates, the evaluation examined the potential mobility of elements in the condition s prevailing in the environment of investigated study, and the identification of possible anthropog enic pollution using the method of standardized sequential extraction. We used three t echniques to extract the first three steps of the standardized BCR sequential extraction as follows: sample agitation on a rotary shaker for a period of sixteen hours in the conventional sequent ial extraction (CSE), two-minute exposure of microwaves under 90 W in the microwave sequential e xtraction (MWSE), and thirty-minute exposure of ultrasound waves in the ultrasonic sequ ential extraction (USSE). The fourth step for all three techniques was the same, digestion of sam ples with aqua regia on a water bath. Accuracy and precision of the three extraction tech niques were determined with the reference material, BCR 701. In addition to sequential extrac tion, samples were digested in a microwave digestor with aqua regia and aqua regia with HF. In extracts, the content of Al, Ba, Ca, C d, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Si, Sn, Sr, V, T i, Zn, As, Se and Hg were determined by inductively coupled plasma with optical emission sp ectrometry (ICP/OES). After chemical analysis of sediments and mud samples, based on the calculation of basic ( baseline ) geochemical concentrations and application of multivariate stat istical methods, we defined anthropogenic origin of elements and quantify their anthropogenic share, as well as the possible sources of contamination at investigated sites. Comparing the results of the extraction of certified material, obtained by different techniques, showed that the m ost accurate technique is CSE, while after the ultrasonic extraction (USSE) satisfactory accuracy were obtained for half of certified metals in the first and third step of BCR extraction, unlike MWSE which gives less accurate results. Based on the percentage of the extracted elements c oncentrations after the first phase of the BCR extraction, it can be concluded that based on the e xtracted concentrations of Cd, Cu and Zn, sediment samples taken from the site Decanter are h aving an increased and a high risk to the environment, while sediments from Electrolysis are having a low to medium risk based on concentrations of Ba, Cd, Cu, Zn..

Supplementary data for article: Relić, D.; Đorđević, D. S.; Popović, A. R. Assessment of the Pseudo Total Metal Content in Alluvial Sediments from Danube River, Serbia. Environmental Earth Sciences 2011, 63 (6), 1303–1317. https://doi.org/10.1007/s12665-010-0802-1

Supplementary material for: [https://doi.org/10.1007/s12665-010-0802-1]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/1170

Ranking and similarity of conventional, microwave and ultrasound element sequential extraction methods

This study aims to compare three extraction techniques of four sequential element extraction steps from soil and sediment samples that were taken from the location of the Pancevo petrochemical industry (Serbia). Elements were extracted using three different techniques: conventional, microwave and ultrasound extraction. A novel procedure sum of the ranking differences (SRD) - was able to rank the techniques and elements, to see whether this method is a suitable tool to reveal the similarities and dissimilarities in element extraction techniques, provided that a proper ranking reference is available. The concentrations of the following elements Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Si, Sn, Sr, V and Zn were determined through ICP OES. The different efficiencies and recovery values of element concentrations using each of the three extraction techniques were examined by the CRM BCR-701. By using SRD, we obtained a better separation between the different extraction techniques and steps when we rank their differences among the samples while lower separation was obtained according to analysed elements. Appling this method for ordering the elements could be useful for three purposes: (i) to find possible associations among the elements; (ii) to find possible elements that have outlier concentrations or (iii) detect differences in geochemical origin or behaviour of elements. Cross-validation of the SRD values in combination with cluster and principal component analysis revealed the same groups of extraction steps and techniques.The peer-reviewed version: [http://cer.ihtm.bg.ac.rs/handle/123456789/2934

Removal of heavy metals from aqueous media by sunflower husk: A comparative study of biosorption efficiency by using ICP-OES and LIBS

Presented research aimed to develop an alternative approach for the estimation of biosorption capability of sunflower husk. The acid-pretreated sunflower biomass was characterized by scanning electron microscopy combined with energy dispersive X-Ray spectroscopy (SEM-EDX) analysis and Fourier transform infrared (FTIR) spectroscopy. Biosorption efficiency has been evaluated using inductively coupled plasma optical emission spectroscopy (ICP-OES) and laser-induced breakdown spectroscopy (LIBS). The adsorption capacity of the adsorbent was determined as the function of the pH of the solution, the initial concentration of heavy metal solutions, and contact time. The optimal conditions were achieved after 15 min of contact at pH 6, while the percentage of the removal was from 80.0–98.7 %, depending on the element. The results obtained from the kinetic and isotherm studies show that maximum adsorption of ions was quickly reached and followed the pseudo-second-order kinetic model. Real samples were tested and obtained Ni values by LIBS method were 3100±200 and 1240±100 mg kg-1, while estimated values by the ICP-OES were 2995±20 and 1130±10 mg kg-1, respectively. The obtained results prove that LIBS method can be used as a “green alternative” for the evaluation of biosorption efficiency

Supplementary material for the article: Relić, D.; Héberger, K.; Sakan, S.; Škrbić, B.; Popović, A.; Đorđević, D. Ranking and Similarity of Conventional, Microwave and Ultrasound Element Sequential Extraction Methods. Chemosphere 2018, 198, 103–110. https://doi.org/10.1016/j.chemosphere.2017.12.200

Supplementary material for: [https://doi.org/10.1016/j.chemosphere.2017.12.200]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2109]Related to accepted version: [http://cherry.chem.bg.ac.rs/handle/123456789/3250

Supplementary data for article: Sakan, S.; Dević, G.; Relić, D.; Anđelković, I.; Sakan, N.; Đorđević, D. Risk Assessment of Trace Element Contamination in River Sediments in Serbia Using Pollution Indices and Statistical Methods: A Pilot Study. Environmental Earth Sciences 2015, 73 (10), 6625–6638. https://doi.org/10.1007/s12665-014-3886-1

Supplementary material for: [https://doi.org/10.1007/s12665-014-3886-1]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/1701

Supplementary data for the article: Milićević, T.; Urošević, M. A.; Relić, D.; Vuković, G.; Škrivanj, S.; Popović, A. Bioavailability of Potentially Toxic Elements in Soil–Grapevine (Leaf, Skin, Pulp and Seed) System and Environmental and Health Risk Assessment. Science of the Total Environment 2018, 626, 528–545. https://doi.org/10.1016/j.scitotenv.2018.01.094

Supplementary material for: [https://doi.org/10.1016/j.scitotenv.2018.01.094]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2114

Supplementary data for article: Pantelić, M. M.; Zagorac, D. Č. D.; Ćirić, I. Ž.; Pergal, M. V.; Relić, D. J.; Todić, S. R.; Natić, M. M. Phenolic Profiles, Antioxidant Activity and Minerals in Leaves of Different Grapevine Varieties Grown in Serbia. Journal of Food Composition and Analysis 2017, 62, 76–83. https://doi.org/10.1016/j.jfca.2017.05.002

Supplementary material for: [https://doi.org/10.1016/j.jfca.2017.05.002]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2505]Related to accepted version: [http://cherry.chem.bg.ac.rs/handle/123456789/3063

Problemi u životnoj sredini i po zdravlje prouzrokovani proizvodnjom energije u Srbiji

Still, now the main energy production in Serbia (70%) is from low-caloric lignite of Kolubara and Kostolac basins which contain harmful elements: As, Be, Co, Mo, Mn, Ni, Pb, Se, Sb, V, U, Th, Ra, Rn etc. Six Serbian CFPPs generate about 6,000,000 t/year of ash enriched by toxic elements which are being deposited on fertile arable land and emitted in ambient air. About 1600 hectares of fertile soil is permanently contaminated with toxic elements from ash disposals endangering surface and underground waters. An increased carcinogenic risk was observed due to arsenic in ambient air, contained in the respiratory particles of the finest fraction. CFPPs are identified as their emission sources. In recent years, small hydropower plants have been installed on last mountains clean rivers in Serbia based on decades old echnical projects and old water data, which do not include the climate change factors. Our research has shown the consequence on Vlasina River, making it the swamp quality water and enhanced erosion processes. Particularly dangerous in mountainous areas is of landslides and torrential floods induced by enormous precipitation due to climate change. Problems of the water supply of Vlasotince municipality are already evident. Serbia has many other possibilities for clean and low carbon energy production: 1) biogas production from biomass with which Serbia is globally one of the richest countries, 2) in summer period Serbia is country with Mediterranean climate and solar energy is easy to use, 3) Serbia is rich with underground geothermal waters that are not used for domestic and public heating, 4) energy production from methane from farms and waste disposal, 5) wind energy etc. The most important approach must be towards energy efficiency in the public and domestic sector and to prosumers concept. With this approach, Serbia does not need any CFPPs and especially small hydro power plants.International scientific conference Environmental impact of illegal construction, poor planning and design IMPEDE 2019, 10 – 11 October 2019, Belgrade, Serbi

Supplementary data for the article: Milićević, T.; Relić, D.; Urošević, M. A.; Vuković, G.; Škrivanj, S.; Samson, R.; Popović, A. Integrated Approach to Environmental Pollution Investigation – Spatial and Temporal Patterns of Potentially Toxic Elements and Magnetic Particles in Vineyard through the Entire Grapevine Season. Ecotoxicology and Environmental Safety 2018, 163, 245–254. https://doi.org/10.1016/j.ecoenv.2018.07.078

Supplementary material for: [https://doi.org/10.1016/j.ecoenv.2018.07.078]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2210