1. 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, ,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" of the European Union cofounded by the European Social Fund through the project BG05M2ОP “Support for the development of capacity of doctoral students and young researchers in the field of engineering, natural and mathematical sciences”

2. 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.

3. 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

4. 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

5. 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

6. 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
0.006
0.0002 Cd
0.0004 Cd
0.067
0.0009 Cr
0.150
0.0012 Cr
0.079
0.0011 Cr
0.286
0.0007 Cr
0.057
0.0001 Ni
0.018
0.0005 Ni
0.022
0.0006 Ni
0.845
0.0016
Emission
line
LOQ
mg.kg-1
LOQ by Q conception Cd
0.02
0.6 Cd
0.04 Cd
0.09
1.8 Cr
0.12
21.3 Cr
0.11
21.6 Cr
0.07
47.4 Cr
0.01 Ni
0.05
2.4 Ni
0.06
1.5 Ni
0.16
56.4 6

7. 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 nm line wings and Al, Ca, Mg, Mn, Ti, V causes high background at Cr nm.
Superposition with Fe nm and influence of Ca, Cr, Cu, Ni at Cd nm;
A partial spectral overlap of zinc and low background from Al, Ca, Mn, Ti, V occurs at Cr nm.
Nickel sensitive lines are ; ; nm.
Free from spectral interferences are booth and nm.
The background at depends only from Fe ; ,
nm and Fe nm. 7

8. 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
% when spikes are added at sample extraction stage.
90 – 100% when spikes are added at sample measurement stage. 8

9. 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

10. 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, SGEM2016 Conference Proceedings, ISBN / ISSN , June 28 - July 6, 2016, Book3 Vol. 2, ppDOI: /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, pp; DOI: /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 , 2018
Acknowledgment:
„The research networkhas been financially supported by the Operational Programme "Science and education for smart growth" of the European Union cofounded by the European Social Fund through the project BG05M2ОP “Support for the development of capacity of doctoral students and young researchers in the field of engineering, natural and mathematical sciences” 10

11. 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" of the European Union cofounded by the European Social Fund through the project BG05M2ОP “Support for the development of capacity of doctoral students and young researchers in the field of engineering, natural and mathematical sciences”