ICP-OES ANALYSIS METHOD DEVELOPMENT FOR MINE WASTES EUROPEAN UNION EUROPEAN SOCIAL FUND OPERATIONAL PROGRAMME SCIENCE AND EDUCATION FOR SMART GROW Green Technologies Innovative Materials Research network GreTInMat Four-day working meeting Starosel, Bulgaria, June 18 – 21, 2018 ICP-OES ANALYSIS METHOD DEVELOPMENT FOR MINE WASTES AND ENVIRONMENTAL SAMPLES RESEARCH GROUP: Darya Ilieva and Andriana Surleva, Analytical Chemistry department, University of Chemical Technology and Metallurgy, Sv. Kl. Ohridski 8blvd., 1756 Sofia, Bulgaria Manuela Murariu, Petru Poni Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda 41A, 700487,Iasi, Romania Gabi Drochioiu and Marius Zaharia, Faculty of Chemistry, “Alexandru Ioan Cuza” University of Iasi, Carol I 11blvd.,700506, Iasi, Romania „The research networkhas been financially supported by the Operational Programme "Science and education for smart growth" 2014-2020 of the European Union cofounded by the European Social Fund through the project BG05M2ОP001-2.009-0015 “Support for the development of capacity of doctoral students and young researchers in the field of engineering, natural and mathematical sciences”

EUROPEAN UNION EUROPEAN SOCIAL FUND OPERATIONAL PROGRAMME SCIENCE AND EDUCATION FOR SMART GROW Purposes - Development of an analytical methods for determination of heavy metals and arsenic in waste material, soils and plants from barite mine by inductively coupled plasma optical emission spectrometry (ICP-OES) after aside extraction. - Evaluate the parameters of the analytical method - detection limits, limits of quantification, sensitivity, accuracy, repeatability, reproductibility.

Method development Sampling Sample preparation EUROPEAN UNION EUROPEAN SOCIAL FUND OPERATIONAL PROGRAMME SCIENCE AND EDUCATION FOR SMART GROW Method development Sampling Sample preparation aqua regia open extraction procedure 3

Correlation coefficient EUROPEAN UNION EUROPEAN SOCIAL FUND OPERATIONAL PROGRAMME SCIENCE AND EDUCATION FOR SMART GROW Spectrometer conditions of measurements Analytical characteristics of ICP-OES measurements - sensitivity Element Slope Intercept Correlation coefficient Arsenic /As 7.10x10-5 0.035 0.9999 Copper /Cu 5.39x10-7 -0.062 0.9992 Lead /Pb 4.83x10-6 -0.043 0.9994 Zinc /Zn 4.98x10-7 -0.110 0.9997 Cadmium /Cd 2.89x10-7 -0.028 0.9998 Chromium /Cr 1.18x10-6 -0.033 Nickel /Ni 3.59x10-7 -0.075 4

checking the extraction procedure by CRM EUROPEAN UNION EUROPEAN SOCIAL FUND OPERATIONAL PROGRAMME SCIENCE AND EDUCATION FOR SMART GROW checking the extraction procedure by CRM Table. Comparison between certified and found value of soil CRM after aquaregia extraction (N=3; P=95%) Element Certified value Found value Recovery, % mg.kg-1 Uncertainty, Arsenic /As 99.6 11.0 91.9 10.8 92.2 Copper /Cu 102 9.10 112 10.2 109.8 Lead /Pb 115 20.9 91.8 5.1 79.8 Zink /Zn 161 17.9 158 19.5 98.1 Cadmium /Cd 182 13.3 172 15.0 94.5 % Recovery = Cfound / Ccertified *100 5

LOD=xb+3xSb and LOQ=3xLOD EUROPEAN UNION EUROPEAN SOCIAL FUND OPERATIONAL PROGRAMME SCIENCE AND EDUCATION FOR SMART GROW Limits of Detection; Limits of Quantification LOD=xb+3xSb and LOQ=3xLOD CLconv=2√2 x 0.01 x RSDBLxI x [BEC+QI(λa) x CI+Qw(Δλa) x CI] CL true=2/5 QI(λa) x CI + CL conv Emission line CL true mg.L-1 LOD Cd 214.441 0.006 0.0002 Cd 226.502 0.0004 Cd 228.802 0.067 0.0009 Cr 206.149 0.150 0.0012 Cr 267.716 0.079 0.0011 Cr 283.563 0.286 0.0007 Cr 205.552 0.057 0.0001 Ni 231.604 0.018 0.0005 Ni 221.648 0.022 0.0006 Ni 232.003 0.845 0.0016 Emission line LOQ mg.kg-1 LOQ by Q conception Cd 214.441 0.02 0.6 Cd 226.502 0.04 Cd 228.802 0.09 1.8 Cr 206.149 0.12 21.3 Cr 267.716 0.11 21.6 Cr 283.563 0.07 47.4 Cr 205.552 0.01 Ni 231.604 0.05 2.4 Ni 221.648 0.06 1.5 Ni 232.003 0.16 56.4 6

Nickel sensitive lines are 231.604; 232.003; 221.648 nm. EUROPEAN UNION EUROPEAN SOCIAL FUND OPERATIONAL PROGRAMME SCIENCE AND EDUCATION FOR SMART GROW Iron 205.299 nm line wings and Al, Ca, Mg, Mn, Ti, V causes high background at Cr 205.552 nm. Superposition with Fe 214.445 nm and influence of Ca, Cr, Cu, Ni at Cd 214.441 nm; A partial spectral overlap of zinc 206.200 and low background from Al, Ca, Mn, Ti, V occurs at Cr 206.149 nm. Nickel sensitive lines are 231.604; 232.003; 221.648 nm. Free from spectral interferences are booth 231.604 and 221.648 nm. The background at 232.003 depends only from Fe 221.706; 221.600, 231.485 nm and Fe 231.738 nm. 7

80 - 120% when spikes are added at sample extraction stage. EUROPEAN UNION EUROPEAN SOCIAL FUND OPERATIONAL PROGRAMME SCIENCE AND EDUCATION FOR SMART GROW Evaluation of spectral interferences by recovery *100 Element Recovery, % soil sample 1 sterile dump material soil sample 2 Arsenic /As 99.70 99.78 100.0 Cupper /Cu 99.98 96.24 Lead/Pb 99.86 99.96 Zinc /Zn 99.97 Cadmium /Cd 99.77 100.1 Acseptance criteria 80 - 120% when spikes are added at sample extraction stage. 90 – 100% when spikes are added at sample measurement stage. 8

repeatability reproducibility EUROPEAN UNION EUROPEAN SOCIAL FUND OPERATIONAL PROGRAMME SCIENCE AND EDUCATION FOR SMART GROW Precision repeatability reproducibility Expanded uncertainty U = k.SD (к=2 at P= 95%) 9

EUROPEAN UNION EUROPEAN SOCIAL FUND OPERATIONAL PROGRAMME SCIENCE AND EDUCATION FOR SMART GROW G. Drochioiu, A. Surleva, D. Ilieva, L. Tudorachi, R. Necula, Heavy metal toxicity around a closed barite mine in Tarnita-Romania, 16th International Multidisciplinary Scientific GeoConference SGEM 2016, www.sgem.org, SGEM2016 Conference Proceedings, ISBN 978-619-7105-62-9 / ISSN 1314-2704, June 28 - July 6, 2016, Book3 Vol. 2, 525-532 ppDOI: 10.5593/SGEM2016/B32/S14.06 D.M. Ilieva , A.R. Surleva , М. Murariu, G. Drochioiu, Evaluation of icp-oes method for arsenic determination in sterile dump material, Bulletin of M. Kozybaev State University, series 2,  2 (2017) 3. M. Zaharia, G. Drochioiu, D. Ilieva, A. E. Butnariu, A. Surleva, Heavy metal toxicity and decontamination: tarnita closed mine pollution case, SGEM2017 Vienna GREEN Conference Proceedings, Vol. 17, Issue 43, 397-404 pp; DOI: 10.5593/sgem2017H/43/S19.050 D. Ilieva, A. Surleva, G Drochioiu, М. Murariu, "Evaluation of ICP-OES Method for Heavy Metal and Metalloids Determination in Sterile Dump Material", Solid State Phenomena, Vol. 273, pp. 159-166, 2018 Acknowledgment: „The research networkhas been financially supported by the Operational Programme "Science and education for smart growth" 2014-2020 of the European Union cofounded by the European Social Fund through the project BG05M2ОP001-2.009-0015 “Support for the development of capacity of doctoral students and young researchers in the field of engineering, natural and mathematical sciences” 10

Research network GreTInMat Starosel, Bulgaria, June 18 – 21, 2018 EUROPEAN UNION EUROPEAN SOCIAL FUND OPERATIONAL PROGRAMME SCIENCE AND EDUCATION FOR SMART GROW Green Technologies Innovative Materials Research network GreTInMat IInd working meeting Starosel, Bulgaria, June 18 – 21, 2018 Research network GreTInMAT Green Technologies & Innovative Materials Coordinated by the University of Chemical Technology and Metallurgy, Bulgaria Darya Ilieva, Analytical Chemistry department, University of Chemical Technology and Metallurgy, Sv. Kl. Ohridski 8blvd., 1756 Sofia, Bulgaria Acknowledgment: „The research network establishment and development is financially supported by the Operational Programme "Science and education for smart growth" 2014-2020 of the European Union cofounded by the European Social Fund through the project BG05M2ОP001-2.009-0015 “Support for the development of capacity of doctoral students and young researchers in the field of engineering, natural and mathematical sciences”