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Evaluation of ICP-OES Method for Heavy Metal and Metalloids Determination

in Sterile Dump Material

Article  in  Diffusion and Defect Data Pt.B: Solid State Phenomena · April 2018
DOI: 10.4028/www.scientific.net/SSP.273.159

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 Evaluation of ICP-OES method for heavy metal and metalloids determination in sterile
dump material

Darya Ilieva1,Andriana Surleva1, Manuela Murariu2, Gabi Drochioiu3, Mohd Mustafa Al

Bakhri Abdullah4
1
Analytical Chemistry department, University of Chemical Technology and Metallurgy, Sv. Kl. Ohridski 8blvd.,
1756 Sofia, Bulgaria
2
Petru Poni Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda 41A, 700487,Iasi, Romania
3
Faculty of Chemistry, “Alexandru Ioan Cuza” University of Iasi,Carol I 11blvd.,700506, Iasi, Romania
4
Center of Excellence Geopolymer & Green Technology, Universiti Malaysia Perlis, Perlis, Malaysia,
Corresponding author: e-mail: darjailieva@abv.bg, tel. +359888694674

Abstract
This study is aimed at development of an analytical method for the determination of heavy
metals and arsenicin waste material from barite recovery by dual view inductively coupled
plasma optical emission spectrometry (ICP-OES) after wet digestion. Aquaregia open
digestion method was used for sample preparation. A soil certified reference material was
used to study the efficiency of wet digestion procedure applied to sterile dump material. The
sensitivity, accuracy, and precision of the method were determined. The achieved detection
limits are: Arsenic(As) 0.80; Copper (Cu) 0.29; Lead (Pb) 0.29; Zink (Zn) 0.30;
Cadmium(Cd) 0.11; Chromium(Cr) 0.09; Nickel (Ni) 0.02, mg.kg-1.The developed method is
applied for the determination of hazardous metals and arsenic in sterile dump material from
closed barite mine in the region of Tarnita-Suceava, Romania.

keywords: ICP-OES, sterile dump material, method validation, multielement alanalysis

Introduction
In the recent decades EU has introduced a wide range of environmental legislations
within the 7th Environment Action Program 2020 aiming at reducing air, soil and water
pollution [1].The proposed plan, defining long-term objectives and provisions to protect the
environment and prevent potential direct and indirect impacts on human health and
biodiversities entered into force in January 2014. Management of current and historical waste
from mining industry aimed at preventing or reducing the adverse environmental impacts is
described in the Management of waste from extractive industries (2006/21/EC) [2] and the
Landfill directive (1999/31/EC) [3]. Each EU member country defines number of regulations
for assessing the environmental impact and recovery of contaminated areas at national level.
However, many challenges still remain. The migration of heavy metals, metalloids and other
harmful substances from waste deteriorates the quality of soil, surface and groundwater. It
affects biodiversity and human health directly and regular monitoring of the state of deposited

1
waste and surrounding environment is required. To support the implementation of the Water
Framework Directive (2000/60/ЕС) [4] and its additions 82/176/EEC; 83/513/EEC;
84/156/EEC; 84/491/EEC a number of requirements have been imposed to analytical methods
in order to ensure quality of chemical analysis and low limits of quantification of harmful and
hazardous substances (98/83/EC Annex III, points 2 and 3; 86/278/EEC, Annex II, point 3).
Although the published Opinion of the European Economic and Social Committee on
establishing a framework for the protection of soil (СОМ (2006) 232), a generally recognized
definition and values for soil quality still haven’t been proposed [5]. Quantity regulations of
heavy metals, metalloids and other pollutants in soil are proposed at national levels.The
regulator may include specific requirements to permitted values for certain parameters taking
into account the characteristics of the landfill, its surroundings, as well as the type of waste.
The provided risk assessment should demonstrate that the emissions (including leachate) from
the landfill will present no additional risk to environment (Landfill Directive 1999/31/ЕC) [3].
The main hazardous metals and their compounds that should be strictly monitored, are:
Arsenic (As), Lead (Pb), Cadmium (Cd), Chromium (Cr), Copper (Cu), Mercury (Hg), Nickel
(Ni), Zinc (Zn) [6; 7].
The region of Tarnita-Suceava, Romania is known as an intensive mining area. The
long-term activity of a barite mine in this region has resulted in an enormous amount of sterile
dump material, collected in several sterile dumps and tailing ponds. The deposited waste
exerts negative impact on the environment [6, 8] and its ecological fate should be regularly
monitored by determination of the chemical composition of sterile dump material and
surrounding soils. It imposes for a validated analytical method for determination of hazardous
metals. The total metal content of sterile dump material was determined in our previous work
[8] by sequential extraction with distillated water and Mg(NO3)2 and an acid digestion
procedures. The results have showed that the waste material samples contained elevated levels
of As, Cd, Cu, Pb and Zn.
ICP-OES determination is well known for the multicomponent determination of soil
components and some standard methods are described. An aquaregia wet digestion is the most
used digestion method for the base metal determination by ICP-OES multi-element analysis
of geological samples, soils and mine waste [9, 10, 11, 12, 13]. However, the appropriate
analytical procedure for sample preparation and ICP-OES measurements should be optimized
and validated in any laboratory.
The aim of this report is an estimation of analytical characteristics of ICP-OES
determination of heavy metals and metalloids in sterile dump material after wet sample
digestion. Efficiency of wet sample digestion with aqua regia was estimated. The extraction
effectiveness of metals of interest is verified byanalyzing certified reference soil material.
Limits of detection and quantification, sensitivity, accuracy, repeatability are estimated to
confirm the applicability of the optimized method for determination of target analytes in
sterile dump material. The method was applied for determination of heavy metals and
metalloids in waste sterile dump material and surrounding soils nearby closed barite mine in
Tarnita-Suceava area, Romania.

2
Experimental
Reagents and equipment.A multi element standard solution “Ultra scientific”
containing 24 elements in 5% HNO3 (Al, Bа, Bе, Bi, B, Cd, Ca, Cr, Co, Cu, Ga, Fe, Pb, Li,
Mg, Mn, Ni, K, Se, Na, Sr, Te, Tl, Zn) at concentration 100 ± 5 mg.L-1 of each element, and
arsenic standard solution (As in 5% HNO3) 1000 ± 3 mg.L-1 “VHG Labs” were used. HNO3
65% and HCl 37% from Thermo Fisher Scientific analytical grade were used for samples
digestion. A ERA Metals in soil certified reference material was used for the quality control
of metals determination. A Prodigy” high dispersion ICP-OES dual view spectrometer
Telledyne Leeman Labs USA, equipped with a dual view torch, cyclonic spray chamber, was
used for metal determination. The optical design of this spectrometer permitted high
dispersion and high spectral resolution.
Extraction procedure. Solid waste samples from sterile dump were dried at 110ºC for
2h and homogenized after cooling. Approximately 0.4g (± 0.0002 g) of sample were weighted
and transferred to digestion vessel. A 15 ml aquaregia was added. The beakers were covered
with watch glass and heated on a hot plate at 95ºC without boiling. The obtained solutions
were filtered, collected in 50 ml flasks and diluted with distillated water.
ICP-OES determination. Due to the nature of current sample matrices and digestion
procedure, the operating conditions of ICP-OES spectrometer recommend for metal in soils
determination were used. The chosen operating conditions were: coolant gas 18 L.min-1,
auxiliary gas 0.5 L.min-1, nebulizer gas 34 psi, RF power 1.2 kW, pump rate 1.2 mL.min-1,
sample uptake time 30 sec, integration time 30 sec axial view. Good reproducibility of 0.2%
RSD from three replicates for Cd, which concentrations in extracts are lower than 50 μg.L-1,
was achieved at chosen integration time. High purity Ar 99.999% supplied by SIAD BG was
used to sustain plasma and as a carrier gas. Two-point background correction and three
replicates were used to measure the analytical signal.
Samples: Three samples were analyzed in this study. Sample 2 was taken from one of
the sterile dumps in the region of Tarnita-Suceava area, Romania. Sample 1 and Sample 3
were collected at 30 m distance from the sterile dump and near the river in a close proximity
of the sterile dump from upper 30 cm soil.

Results and discussion

For evaluation of the analytical characteristics of the ICP-OES method for target
samples the following protocol was applied: (1) determination the linearity and sensitivity of
the ICP-OES measurement by multicomponent standards; (2) optimization of the wet
digestion extraction procedure by analyzing a certified soil CRM and sterile dump material;
(3) Study of the spectral interferences in soil matrix and choice of appropriate wavelength for
each analyte; (4) application of the method for analyzing real samples from Tarnita region and
estimation of method uncertainty in real samples.
Analytical characteristics of ICP-OES method were studied using external standard
method for calibration in the following concentration range: 10 - 100 μg.L-1 for Cd and 1-10
mg.L-1 for As, Cu, Pb, Zn, Cr, Ni. Each standard is analyzed in triplicate. The results

3
presented in Table 1 showed high sensibility and excellent linearity of the measurement in the
studied concentration interval.

Table 1.Calibrations characteristics of the ICP-OES method

(N=3 for Cd; N=5 As, Cu, Pb, Zn, Cr, Ni)
Correlation
Element Slope Intercept
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 0.9997
Nickel /Ni 3.59x10-7 -0.075 0.9998

An aquaregia open digestion extraction procedure was applied to the sterile dump material
sample to estimate the optimal extraction time. Approximately of 0.4 g in two baches were
extracted for 20, 40, 60 and 80 minutes. Blank sample wasalso prepare andtreated accoriding
to the described extraction procedure. The results presented on Fig. 1 showed that twenty
minutes extraction wasenough to fully extract hazardous metals and metalloids from sterile
dump material. Increasing the time of extraction didn’t affect the obtained total content of
metals. However, it should be noted that samples more then 0.4 g probably will require longer
digestion procedure.

Figure 1.Total metal content (mg.kg-1) as a function of extraction time.

4
The efficiency of the applied aquaregia open digestion method was verified by analyzing soil
reference material. After extraction and ICP-OES determination of the concentration the
results were compared with certified value and recovery is presented in Table 2. The obtained
recovery varied between 79.8% and 109.8% proving good accuracy of the extraction
procedure [14, 15, 16, 17]. The found concentrations fall in quality control acceptance limits,
given in the soil CRM certificate of analysis and their values do not exceed the certified
uncertainties intervals. The sterile dump material was assumed to be close in composition and
structure to the soil reference material. Based on the experimental results (Table 2), the
applicability of the used extraction procedure to sterile dump material was supposed.

Table 2. Comparison between certified and found value of soil CRM after aquaregia
extraction (N=3; P=95%)
Certified value Found value
Recovery,
Element Uncertainty, Uncertainty,
mg.kg-1 mg.kg-1 %
% %
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

The limits of detection (LOD) and qantification (LOQ) were evaluated by analyzing
blank solutions (N=5) and calculated accoriding the equations: LOD=xb+3xSb and
LOQ=3xLOD, where xb and Sb were intensity of signal and standard deviation [14, 18]. The
results are presented in Table 3.

Table 3. Estimated Limits of Detection and Limits of Quantification

LOD, LOQ,
Element RSD, %
mg.kg-1 mg.kg-1
Arsenic /As 0.80 2.40 14
Copper /Cu 0.29 0.87 1.6
Lead /Pb 0.29 0.87 1.8
Zinc /Zn 0.30 0.90 1.9
Cadmium /Cd 0.11 0.33 0.2

5
 Chromium /Cr 0.09 0.27 0.2
Nickel /Ni 0.0200 0.0600 0.3

In trace determination spectral interferences from the main components could be

expected. The study of the spectra of sterile dump material showed that thehigh
concentrations of potassium, sodium, calcium, magnesium and aluminum did not affect
determination of minor and trace metals. Twenty percents iron content increased background
at some of the sensitive emission lines of chromium and cadmium. Therefore two point
corrections at both sides of peaks was applied and free of interferences lines were chosen:
Chromium (Cr) 205.552 nm; Cadmium (Cd) 214.438 nm. Other elements are measured at:
Arsenic (As) 193.696 nm; Cobalt (Co) 228.616 nm; Cupper (Cu) 237.396, Lead (Pb) 220.353
nm, Nickel (Ni) 231.604 nm [19, 20].
The influence of matrix components was evaluated by determination of recovery after spike
of the dry sterile dump sample. The recovery was calculated by:

*100,
where Ca+spike is the analyte concentration after spiking, Ca - analyte concentration and Cspike–
concentration of analyte in spike. All concentrations were recalculated in mg.kg-1. The
recovery results are presented in Table 4. According to the literature [10, 13] when the spikes
were added at sample preparation stage, the recovery at the range 80 - 120% was acceptable
and did not require matrix corrections. This wide interval depended on the nature of the
samples, digestion procedure and concentration levels of the elements. Generally, small
deviation 90 – 100% was acceptable when the spikes were made at sample measurement stage
[18]. In the studied samples from sterile dump material and surrounding soil nomatrix
influence from metals at high concentrations was observed.

Table 4. Recovery of target metals estimated by spiking at sample preparation step

Recovery, %
Element sterile dump
soil sample 1 soil sample 2
material
Arsenic /As 99.70 99.78 100.0
Cupper /Cu 99.98 100.0 96.24
Lead/Pb 100.0 99.86 99.96
Zinc /Zn 100.0 99.97 100.0
Cadmium /Cd 99.77 100.1 100.0

6
 The proposed protocol was applied to the samples from Tarnita-Suceava region,
Romania. One sample from sterile dump material and 2 samples of surrounding soil were
analyzed. The measurement precision was estimated by ICP-OES measurement of an extract
in triplicate during 3 days. The full protocol precision was estimated by extraction of analytes
and ICP-OES measurement of samples in triplicate during 3 weeks. The extended uncertainty
was also calculated U = k.SD (к=2 at P= 95%) [21, 22]. The results are presented in Table 5.
Table 5. Results from analysis of real samples from
Tarnita region by the developed protocol
full
measurement protocol mean
U,
Element precision concentration,
precision mg.kg-1
RSD, % mg.kg-1
RSD, %
Sample 1 – soil, near to sterile dump
Arsenic /As 1.4 12 629 ±38
Coppe r /Cu 0.6 2 2631 ±100
Lead /Pb 1.2 2 2140 ±100
Zink /Zn 3.4 8 523 ±34
Cadmium /Cd 8.6 10 13.4 ±0.6
Sample 2 – sterile dump material
Arsenic /As 4.9 13 805 ±74
Copper /Cu 1.9 11 789 ±66
Lead /Pb 5.8 34 2218 ±69
Zink /Zn 0.9 1 341 ±41
Cadmium /Cd 0.5 16 13.3 ±1.6
Sample 3 – soil, near to sterile dump
Arsenic /As 1.7 5 323 ±13
Copper /Cu 0.9 6 1545 ±64
Lead /Pb 2.6 5 1282 ±66
Zink /Zn 2.1 14 93 ±4
Cadmium/Cd 0.3 15 6.9 ±0.5

Conclusions
The proposed analytical method was based on modified fast extraction method with aquaregia
and analysis of the obtained extracts by ICP-OES. The efficiency of the extraction procedure

7
and its compatibility with ICP-OES measurement was verified by analysis of certified
reference soil material. Obtained recoveries (89.8% - 109.8%) demonstrated high accuracy of
the developed protocol. The calculated extended uncertaintys howedt hat the method had
good precision. The limits of detection and quantification were determined. The used
approach in this evaluation protocol provides sufficient assessment of method applicability for
analyzing samples of waste material from barite mine.
Acknowledgements: The financial support of the Operational Programme "Science and
education for smart growth" 2014-2020 ofthe European Union cofounded bythe 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” is greatly acknowledged.

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