Project title: Simultaneous elemental microanalytical method for environment and food control using passive sampling coupled with miniaturized instrumentation based on plasma microtorch optical emission spectrometry

Acronym: MULTIPASS

Contract no: 733PED / 27.06.2022

Contracting Authority: Executive Agency for Higher Education, Research, Development and Innovation Funding (UEFISCDI), P2 – Increasing the competitiveness of the Romanian economy through RDI

Abstract

The project aims to develop and validate new highly-sensitive microanalytical methods without matrix effects to determine Hg, Pb, Cd, As, Sb, Cu and Zn of interest for environmental and food quality control using passive preconcentration by gradient diffusion in thin layer (DGT) and detection by optical emission spectrometry in capacitively coupled plasma microtorch (DGT-SSETV-μCCP-OES). The starting level of the project is TRL3 through the existence of the miniaturized spectrometric experimental model and the TRL4 level is reached by validation of the methods applied to environmental and food samples. The duration of the project is 24 months, in two stages, and is carried out in partnership by Research Institute for Analytical Instrumentation Cluj-Napoca (CO-ICIA), Babes-Bolyai University Cluj-Napoca (P1-UBB) and Technical University Cluj-Napoca (P2-UTCN). The first stage is intended to increase the technological maturity of the SSETV-μCCP-OES system at TRL4 by in-situ and ex-situ DGT preconcentration. The preconcentration and spectral detection will be optimized in such a way as to develop simultaneous multielemental methods. Analytical performances will be compared with traditional methods based on inductively coupled plasma optical emission spectrometry, graphite furnace atomic absorption and thermal desorption atomic absorption spectrometry. The second stage is dedicated to the development and validation of DGT-SSETV-μCCP-OES microanalytical methods compared to traditional methods and European Commission requirements for official control laboratories. The analytical capability will be presented to potential users through a practical demonstration. The standard operating procedures will be implemented in the CO-ICIA and P1-UBB laboratories. The results will be disseminated through 4 articles in WoS journals and participation in conferences (4 national and 6 international). An application for a national patent will be considered.

Project objective

The main objective of the MULTIPASS project is to develop new microanalytical methods as TRL4 for the simultaneous determination of priority hazardous elements (Pb, Cd, Hg) and other elements (As, Sb, Se, Cu, Zn) in environment and food microsamples using a fully miniaturized laboratory experimental model based on direct liquid microsampling SSETV-μCCP-OES in tandem with DGT device for in-situ and ex-situ preconcentration and analyte separation.

Estimated results

  • Testing and optimization report on the working conditions for in-situ and ex-situ preconcentration of Hg, Pb, Cd, As, Sb, Se, Cu and Zn using the DGT devices;
  • Optimization report on the working conditions for SSETV as device for direct liquid microsampling after DGT preconcentration;
  • Software to control the thermal program of the Rh filament;
  • Optimization report on the working conditions for plasma microtorch interfaced with a low resolution microspectrometer for simultaneous multielemental determination by DGT-SSETV-μCCP-OES;
  • Report on improved analytical performance (limit of detection, quantification, and compensation of non-spectral effects) for DGT-SSETV-μCCP-OES methods in low power plasma microtorch after DGT analytes preconcentration/separation compared to direct liquid microsampling without DGT;
  • Comparative study of analytical performance of DGT-SSETV-μCCP-OES with traditional methods, GFAAS, TDAAS, ICP-OES and European Legislations demands for official laboratory control;
  • Validation report for microanalytical methods based on DGT-SSETV-μCCP-OES for simultaneous multielemental determination in environmental samples;
  • Validation report for microanalytical methods based on DGT-SSETV-μCCP-OES for simultaneous multielemental determination in food samples;
  • Microanalytical methods for environmental samples using DGT preconcentration and multielemental determination by implementation of DGT-SSETV-μCCP-OES as TRL4 on real samples;
  • Microanalytical methods for food samples using DGT preconcentration and multielemental determination by implementation of DGT-SSETV-μCCP-OES as TRL4 on real samples;
  • Demonstration of the utility and capability report for the new DGT-SSETV-μCCP-OES microanalytical methods for environment and food control quality;
  • 2 Internal Operating Procedures based on DGT-SSETV-μCCP-OES;
  • National patent application;
  • Dissemination of results through participation in scientific national and international events;
  • Dissemination of results through papers in WoS indexed journals.

Project start: 27/06/2022
Project end: 26/06/2024
Project duration: 24 months

Partners:

  • P1 – BABES BOLYAI UNIVERSITY Cluj-Napoca
    Project responsible: Prof. Dr. Tiberiu Frențiu
  • P2 – TECHNICAL UNIVERSITY OF CLUJ – NAPOCA
    Project responsible: Prof. Dr. Dorin Petreuș

Budget:

Project budget 598.795,00 RON
Co-financing: 0,00 RON

Contact

Project coordinator
Senior Researcher I Dr. Marin Senila
Str. Donath nr. 67, Cluj-Napoca, Romania
E-mail: marin.senila@icia.ro; icia@icia.ro
Tel/Fax: +40 264 420590 / +40 264 667

Obtained results – Stage 1

  1. Testing and optimization of the working conditions for in-situ and ex-situ preconcentration of Hg, Pb, Cd, As, Sb, Se, Cu and Zn using the DGT devices
  2. Optimization report of the working conditions for DGT-SSETV-µCCP-OES equipment for Zn, Cd, Cu, Hg and Pb determination
  3. Development of specialized software to control the thermal program of the Rh filament (electrothermal evaporation of Zn, Cd, Cu, Hg and Pb)
  4. DGT-SSETV-μCCP-OES experimental model developed at TRL4
  5. Participatio at national scientific events

Eniko Covaci, Zsofia Sandor, Bogdan Simion Angyus, Marin Senila, Tiberiu Frentiu. Optical emission spectrometry by electrothermal vaporization in a capacitively coupled plasma microtorch as a specific detector in simultaneous multielemental passive sampling by diffusive  gradients in thin films (DGT-SSETV-μCCP-OES): Preliminary studies on the optimization of working parameters. Conferința Națională de Chimie, ediția XXXVI, secțiunea Chimie anorganică, chimie-fizică și analitică, Călimănești-Căciulata, 04–07 octombrie 2022 – Oral communication

Zsofia Sandor, Eniko Covaci, Bogdan Simion Angyus, Marin Senila, Tiberiu Frentiu. Microanalytical method for monitoring of toxic elements in surface waters using passive sampling in diffusive gradients in thin films and detection by capacitively coupled plasma microtorch optical emission spectrometry with electrothermal vaporization  (DGT-SSETV-μCCP-OES). Conferința Națională de Chimie, ediția XXXVI, secțiunea Chimie anorganică, chimie-fizică și analitică, Călimănești-Căciulata, 04–07 octombrie 2022 – Poster

Stage 1 report (PDF)

Obtained results – Stage 2

  • Optimization report of the working conditions for DGT-SSETV-µCCP-OES equipment for As, Sb and Se determination
  • Experimental report on the improvement of analytical performance for DGT-SSETV-μCCP-OES methods with and without DGT sampling
  • Comparative study of analytical performance of DGT-SSETV-μCCP-OES with traditional methods, GFAAS, TDAAS, ICP-OES and European Legislations
  • Validation report of microanalytical methods based on DGT-SSETV-µCCP-OES for simultaneous multielemental determination in environmental samples
  • Validation report of microanalytical methods based on DGT-SSETV-µCCP-OES for simultaneous multielemental determination in food samples
  • specialized software to control the thermal program of the Rh filament (electrothermal evaporation of As, Sb and Se)
  • Participation at scientific events – 8 participations at national si international condeference: 6 poster presentations and 2 oral presentation
  • 8. 3 papes published / submitted at WoS indexed journals

Participation at scientific events

3 presentations at 49th International Conference of Slovak Society of Chemical Engineering (SSCHE), Tatranske Matliare, Slovacia, 15–18 May 2023

1. Eniko Covaci, Simion Bogdan Angyus, Marin Senila, Maria Frentiu, Tiberiu Frentiu. Elimination of spectral interference between Cd and As in their monitoring in water by using in-situ diffusive gradients in thin film passive sampling and detection by ex-situ microplasma optical emission spectrometry set-up equiped with a low-resolution microspectrometer. (Poster)

2. Eniko Covaci, Simion Bogdan Angyus, Marin Senila, Maria Frentiu, Tiberiu Frentiu. Evaluation of green and white degree of a method based on in-situ diffusive gradients in thin film passive sampling coupled with ex-situ microplasma optical emission spectrometry set-up for determination of toxic elements in river water. (Poster)

3. Simion Bogdan Angyus, Marin Senila, Eniko Covaci, Tiberiu Frentiu, Maria Frentiu. Monitoring of toxic trace metals in river water using in-situ diffusive gradients in thin film passive sampling and small-sized electrothermal vaporization capacitively coupled plasma microtorch optical emission spectrometry. (Poster)

2 presentations at 4th Young Researchers’ International Conference on Chemistry and Chemical Engineering (YRICCCE IV), Debrecen, Ungaria, 1–3 June 2023

4. Simion Bogdan Angyus, Marin Senila, Eniko Covaci, Tiberiu Frentiu. Diffusive gradients in thin film and electrothermal vaporization capacitively coupled plasma optical emission spectroscopy method for the evaluation of bioavailable Cu, Zn, Cd and Pb fraction in agricultural soils (Oral presentation)

5. Eniko Covaci, Simion Bogdan Angyus, Marin Senila, Maria Frentiu, Tiberiu Frentiu. Greenness and whiteness of small-sized electrothermal vaporization capacitively coupled plasma optical emission spectrometry with in-situ diffusive gradients in thin films passive sampling (DGT-SSETV-μCCP-OES) (Oral presentation)

One presentation at 14th International Conference Processes in Isotopes and Molecules, Cluj-Napoca, Romania, 19-22 September 2023

6. Sergiu Cadar, Dorin Petreus, Toma Patarau, Eniko Szilagyi, Bogdan Angyus, Frentiu Tiberiu, Optimization of the electrothermal evaporation process based on intelligent control of the power source. (Poster)

One presentation at IEEE 29th International Symposium for Design and Technology in Electronic Packaging (SIITME), Craiova, Romania. 17-21 October 2023

7. Sergiu Cadar, Dorin Petreus, Toma Patarau, Eniko Szilagyi. Comparative analysis of two types of filaments with COMSOL for electrothermal process. (Poster)

One presentation at the Conference Agriculture and Food – current and future challenges, AGRIFA, Cluj-Napoca, Romania. 20 October 2023

8. Marin Senila, Marius Roman, Bogdan Angyus. Mercury fractionation in soil using Diffusive Gradients in Thin-films coupled with thermal decomposition – atomic absorption spectrometry. (Poster)

Papers published / submitted for publication at WoS indexed journals

  1. Simion Bogdan Angyus, Marin Senila, Tiberiu Frentiu, Michaela Ponta, Maria Frentiu, Eniko Covaci. In-situ Diffusive Gradients in thin-films passive sampling coupled with ex-situ small-sized electrothermal vaporization capacitively coupled plasma microtorch optical emission spectrometry as green and white method for the simultaneous determination of labile species of toxic elements in surface water. Talanta, 2023, 259, numar articol 124551, DOI: 10.1016/j.talanta.2023.124551 (IF 6.1)
  2. Simion Bogdan Angyus, Marin Senila, Eniko Covaci, Michaela Ponta, Maria Frentiu, Tiberiu Frentiu. Simultaneous determination of Cd, Pb, Cu and Zn as total and labile fraction in soil using small-sized electrothermal vaporization capacitively coupled plasma microtorch optical emission spectrometry after diffusive gradients in thin-films passive accumulation. Journal of Analytical Atomic Spectrometry, accepted 2023, DOI: 10.1039/D3JA00258F (IF 3.4)
  3. Marin Senila, Metals and metalloids monitoring in water by passive sampling: A review, Reviews in Analytical Chemistry, accepted 2023, DOI: 10.1515/revac-2023-0065, (IF 4.3)

Stage 2 report (PDF)

Obtained results – Stage 3

  1. Microanalytical methods developed for environmental samples (DGT-SSETV-μCCP-OES) TRL4
  2. Microanalytical methods developed for food samples (DGT-SSETV-μCCP-OES) TRL4
  3. Developed analytical methods based on DGT and classical methods for comparison with (DGT-SSETV-μCCP-OES)
  4. Report on the demonstration of the usefulness and functionality of the new microanalytical methods DGT-SSETV-μCCP-OES
  5. 2 Standard operating procedures based on DGT-SSETV-μCCP-OES
  6. VP on intellectual property rights for industrial research
  7. National patent application
  8. 3 Participation at scientific events – international conferences
  9. 5 papers published at WoS indexed journals with IF>3

Conference participations
• 2 Participations at the 50th International Conference of Slovak Society of Chemical Engineering (SSCHE), Tatranske Matliare, Slovakia, 20–24 May 2024
1. S. Angyus, T. Frentiu, M. Frentiu, E. Covaci, M. Senila Evaluation of mercury concentration and mobility in soils around a former chlor-alkali plant using diffusive gradients in thin films (DGT) technique (Poster)
2. E. Covaci, S. Angyus, M. Senila, M. Frentiu, T. Frentiu Speciation of toxic metals in soil as total and labile fraction using diffusive gradients in thin films (DGT) passive sampling and determination by capacitively coupled plasma optical emission spectrometry (Poster)
• 1 Participation at the International Spring Seminar on Electronics Technology, 15-19 May 2024, Prague, Czech Republic
1. S. Cadar, D. Petreus, T. Patarau, E. Szilagyi Design of a flat coil electrothermal vaporization device for inductively coupled plasma optical emission spectrometry (Poster).

Published scientific articles
1. M. Senila, M.A. Resz, L. Senila, I. Torok, Application of Diffusive Gradients in Thin-films (DGT) for assessing the heavy metals mobility in soil and prediction of their transfer to Russula virescens, Science of The Total Environment, 2024, 909, 168591 (FI = 9.8)
2. M. Senila, E. Kovacs, Use of diffusive gradients in thin-film technique to predict the mobility and transfer of nutrients and toxic elements from agricultural soil to crops—an overview of recent studies, Environmental Science and Pollution Research, 2024 (FI = 5.8).
3. M. Senila, E.A. Levei, T. Frentiu, C. Mihali, S.B. Angyus, Assessment of mercury bioavailability in garden soils around a former nonferrous metal mining area using DGT, accumulation in vegetables, and implications for health risk. Environmental Monitoring and Assessment, 2023, 195, 1554 (FI = 3.0)
4. M. Senila, M.A. Resz, I. Torok, L. Senila, Nutritional composition and health risk of toxic metals of some edible wild mushrooms growing in a mining area of Apuseni Mountains, Western Carpathians, Journal of Food Composition and Analysis, 2024, 128, 106061 (FI = 4.3)
5. M. Senila, O. Cadar, T. Frentiu, L. Senila, S.B. Angyus, Diffusive Gradients in Thin-films as passive sampling tool for the measurement of labile species in fractionation analysis of metals (Fe, Mn, Cu, Zn and Pb) in beer, Microchemical Journal, 2024, 198, 2024, 110195 (IF = 4.8)

Stage 3 report (PDF)

Final report (PDF)