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 NIM B
Beam Interactions
with Materials & Atoms
Nuclear Instruments and Methods in Physics Research B 262 (2007) 81–86
www.elsevier.com/locate/nimb

Elemental analysis of mining wastes by energy dispersive

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X-ray fluorescence (EDXRF)
a,*
O. Gonzalez-Fernandez , I. Queralt a, M.L. Carvalho b, G. Garcia c

co
a
Laboratory of X-ray Analytical Applications, Institute of Earth Sciences ‘‘Jaume Almera’’, CSIC, Sole Sabaris s/n, 08028 Barcelona, Spain
b
Centro de Fı́sica Atómica, Universidade de Lisboa, Av. Prof. Gama Pinto, 21649-003 Lisboa, Portugal
c
Área Edafologı́a y Quı́mica Agrı́cola, Departmento de Ciencia y Tecnologı́a Agraria, Universidad Politécnica de Cartagena,
Paseo Alfonso XIII 48, 30203 Cartagena, Spain

Received 9 March 2007; received in revised form 7 May 2007

Available online 16 May 2007

Abstract
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An energy dispersive X-ray fluorescence (EDXRF) tri-axial geometry experimental spectrometer has been employed to determine the
concentrations of 13 different elements (K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr and Pb) in mine wastes from different depths of
two mine tailings from the Cartagena-La Union (Spain) mining district. The elements were determined and quantified using the funda-
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mental parameters method. The concentrations of Cr, Ni, Cu, Zn and Pb were compared to the values from the European and Spanish
legislation to evaluate the environmental risk and to classify the wastes as inert wastes or as wastes that have to be control land-filled. The
results obtained demonstrate that these wastes can be considered as inert for the considered elements, apart from the concentration levels
of Zn and Pb. Whilst Zn slightly overpasses the regulatory levels, Pb mean value exceeds three to six times the value to be considered as
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Class I potential land-filling material.

Ó 2007 Elsevier B.V. All rights reserved.

PACS: 07.85. m; 32.30.Rj; 32.50.+d; 91.67. y

Keywords: Cartagena; EDXRF; Tri-axial geometry; Metals; Mine tailings; Trace elements
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1. Introduction 1840 and 1930 the mining at Cartagena-La Union reaches

its maximum exploitation levels. Finally, there was an
o

The Cartagena-La Union mining district is one of the important new exploitation period between 1953 and
more ancient Spanish mining regions. This region is situ- 1991 due to the improvement of the hydrometallurgical
th

ated at the south-eastern part of Spain, and contains one techniques, with the development of the flotation extrac-
of the largest lead and zinc ore deposits in South Europe, tive processes. These techniques allowed to have a bigger
which was exploited since the Phoenician and Carthaginian recovering percentage and to maintain the mean pro-
Au

times. However, this activity was only important during ductions of Pb and Zn during the 19th and 20th centuries
some determined historical periods. At the age of the [3].
Roman Empire, Pb production peaked to 45 000 tons per Mining activities also have an important environmental
year during the II and I century BC [1,2]. Later, between impact because the interaction of metals with the different
compartments of the environment constitutes a serious
potential hazard [4–8]. There are many studies evaluating
the problems connected to metal content in superficial soils
*
Corresponding author. Tel.: +34 934095410; fax: +34 934110012. in mining and smelting zones [9–11], but the elemental
E-mail address: [email protected] (O. Gonzalez-Fernandez). chemistry in these works is mainly determined by atomic

0168-583X/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.nimb.2007.05.006
82 O. Gonzalez-Fernandez et al. / Nucl. Instr. and Meth. in Phys. Res. B 262 (2007) 81–86

absorption spectroscopy. Also there are some studies on ques de Pejar tailing, is near the La Union village. The sam-
the determination of the elemental content of vegetal ples were extracted using an Eijkelkamp hand auger. The
samples and organic materials with EDXRF [12,13], but use of this kind of sampler allows us to make a depth lay-
there are not many studies on mining wastes and the sur- ered sampling, to lately undertake detailed studies at each
rounding soils. depth level. From the Portman dumping site, seven samples
One of the more important effects of the mining activi- from the first 45 cm of top of the mine tailing were
ties is the production of large quantities of wastes in extracted. At the Marques de Pejar tailing, we extracted
the process of separation of the benefiting minerals from 10 samples from the first 50 cm of the surface mining

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the whole ore mass. This has led to the creation of mine residues.
tailings that are big structures for the deposition of
wastes. The quantities of metals in these areas could be 2.2. Sample preparation
an important environmental hazard. Therefore, it is extre-

co
mely important to have analytical methodologies that Samples were air-dried, and after desiccation in a 105 °C
allow us to quickly quantify the metal content of the min- oven, they were sifted through a 63 lm sieve, due to the
eral wastes. grain-size dependency of the metal content, and following
In the present work, the elemental contents of the upper the common procedures in soil metal content studies [14].
50 cm of two mine tailings were evaluated by an energy dis- The samples were prepared for analysis by taking 5 g of
persive X-ray fluorescence spectrometer. each sample mixed with 0.4 g of Elvacite (methyl-methac-
rylate) used as a binding agent and then homogenised in

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2. Experimental details an agate mortar. This mixture was pressed (20 tons) to
obtain a homogeneous pressed powder pellet of 4 cm in
2.1. Sample collection diameter. These pellets were analysed using an energy dis-
on
persive X-ray spectrometer.
The samples were collected at two mine tailings at
the mining region of Cartagena-La Union (Murcia prov- 2.3. Experimental
ince, SE Spain). The sample locations are shown in
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Fig. 1. The first sampling site called Portman tailing is near The spectrometer used in the present work is an experi-
the Portman village and the second one, the so called Mar- mentally designed spectrometer that consists of an X-ray
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Fig. 1. Location of the two mine tailings studied at the Cartagena-La Union mining district.
 O. Gonzalez-Fernandez et al. / Nucl. Instr. and Meth. in Phys. Res. B 262 (2007) 81–86 83

179.7 ± 2.1
714 ± 28
750 ± 80

404 ± 60
435 ± 55
(mg kg 1)

220 ± 5
Pb
(mg kg 1)

277 ± 50
320 ± 50
Sr

–
–
–
–
(mg kg 1)
66 ± 10
55 ± 10

824 ± 70 211 ± 15
870 ± 70 175 ± 55
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As

130.6 ± 1.4 1055 ± 14 –

145 ± 30 1150 ± 50 –
1720 ± 70
1730 ± 50
)
1

co (mg
Zn

109 ± 19

452 ± 40
495 ± 35
(mg kg 1)

112 ± 5
Cu
(mg kg 1)

298 ± 20
44 ± 10
35 ± 10
46 ± 3
40 ± 5
299 ± 5
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Ni

2.96 ± 0.03 0.10 ± 0.01 11.30 ± 0.12

4.00 ± 0.50 0.09 ± 0.01 12.00 ± 0.10

0.06 ± 0.01 3.80 ± 0.05

Fig. 2. Experimental EDXRF set-up (tri-axial geometry): (1) X-ray tube,
(2) silver absorber, (3) molybdenum secondary target, (4) beam collima-
on
tors, (5) sample, (6) Si(Li) detector.

(%)
Fe

–
–
0.06 ± 0.01 –
904a ± 13a
950a ± 50a
tube with W as primary excitation target and addition-
rs
MnO
ally equipped with a secondary target of molybdenum. (%)
The X-ray tube, the secondary target and the sample are
Determined and certified values of Certified Reference Materials (NBS 1645, BCR143R and PACS-1)

positioned in a tri-axial geometry (Fig. 2). This allows a

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decrease in the background, using the advantages of the

(%)

effect of polarization of the incident X-ray beam from

Cr

–
0.97 ± 0.04 0.47 ± 0.025 –
2.92 ± 0.12 0.7 ± 0.045 –
2.80 ± 0.10 0.65 ± 0.075 –
the tube. The spectrometer is a self-constructed system,
using a Philips X-ray generator (PW 1140/00/60 3 kV). To
reduce the background signal and improve the detection
TiO2
(%)

limits, some special details are of importance. An absorber

–
–
–

in silver was placed between the primary X-ray beam

The standard deviation was calculated from three different measurements.
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and the secondary target to absorb the low energy part of

CaO

the spectrum’s Bremsstrahlung. The other important

(%)
Certified 1.52 ± 0.01 –
EDXRF 1.49 ± 0.02 –
–

feature of the system is the presence of two pairs of collima-

tors in silver, to precisely define the directions of the
o

secondary beam impinging on the sample, and the direction

K2O
(%)

of the beam penetrating into the detector. The diameters

IRMM Certified –
EDXRF –
Certified –
EDXRF –
th

were adjusted to ensure that only the active area of the

detector is used. Incomplete charge of the radiation does
not enter in the detector, avoiding a degradation of the
Source
Au

background.
USGS
NIST

The characteristic radiation emitted by the elements

present in the sample was detected by a Nitrogen-cooled
PACS-1

Si(Li) detector with an effective energy resolution of

CRM

143R
Sewage sludge amended BCR
NBS
1645
code

130 eV at 5.9 keV. Quantitative calculations were made

Values are in mg kg 1.

using the fundamental parameters method described by

Rindby [14]. The experimental parameters were obtained
Marine Sediment

by calibration of the whole system by means of three Cer-

River sediment

tified Reference Materials (CRMs) of soils and sediments

(NBS-1645 from the National Institute of Standards and
Table 1

soil

Technology, USA; BCR-143R from the European Institute

Type

for Reference Materials and Measurements, and PACS-1

84 O. Gonzalez-Fernandez et al. / Nucl. Instr. and Meth. in Phys. Res. B 262 (2007) 81–86

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Fig. 3. Spectrum plot of a sample from the Portman mine tailing. Only the evaluated elements are labelled.

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from the United States Geological Survey). The X-ray of Pb we have very elevated values ranging from 5500
generator was operated at 50 kV and 20 mA and a typical to 15 000 mg kg 1, and should be clearly considered as
acquisition time of 1000 s was used. Each sample was mea- class II. Although these wastes can be included in
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sured three times and the mean value was calculated. A class II and deposited in controlled landfills, further
comparison made of certified and experimental results for research needs to be carried out to analyse the Pb leaching
CRMs is reported in Table 1 for the different elements con- potential from these tailings and to determine its true
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sidered. The reported data results have a good accuracy, hazard.

enabling the system to adequately analyse such kind of Regarding the variation in-depth of the elemental con-
samples. tent, we can observe a marked homogeneity in-depth layers
from the same tailing, seeming not be specially affected by
3. Results and discussion weathering processes after deposition. However, the metal
content from one tailing to another can be markedly differ-
An example of the spectrum obtained by the EDXRF ent. We could see that Marques de Pejar mine tailing is
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spectrometer can be seen in Fig. 3. In the spectrum only more enriched in Pb than Portman mine tailing. This could
the peaks of the determined elements are marked. The be explained from differences in the extraction methodol-
results are summarized in Table 2. In this table we also ogy processes in each site or by the dumping of Pb-bearing
include the values of the current legislation [15,16] metal wastes, caused by a less efficient recovery of lead in the fac-
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guidelines for land-filling residues. The class I values are tory near Marques de Pejar tailing.
the values that must not be exceeded to consider waste as
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one inert residue. If we pass the class I level value, the 4. Conclusions
wastes have to be deposited on a special landfill. Also in
Table 2 we insert the class II values that are the levels clas- From the presented results we can conclude that
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sifying the wastes as hazardous wastes. The nowadays EDXRF is a valid and fast analytical tool for elemental
landfill legislation affecting inorganic by-products basically analysis of mine tailings wastes. The EDXRF results can
classifies the wastes according to the metals level. The con- also be used as a classifying methodology to determine
tent of metals such as Cr, Ni, Cu, Zn and Pb is one of the the land-filling disposal of mining wastes and the
criteria to qualify the wastes as belonging to one of the dif- requirement for a more in-depth study of these residues.
ferent classes. The mine tailings existing at the Cartagena-La Union min-
If we observe the results we could observe that for ing district could be hazardous because of the level of Pb.
the case of Cr, Ni and Cu the levels are below class II Also Zn sometimes overpasses the regulatory level to con-
and we can consider these wastes as inert material of sider them inert wastes. EDXRF analysis allows us to
class I. For Zn we have a different situation because quickly observe differences between different tailings and
mean values slightly overpass the class I level, making it the effectiveness of metal extraction of the hydrometallurgi-
suspicious to be of environmental concern. For the case cal processes.
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Table 2
Elemental concentrations of the two mine tailings, the variation on depth of these samples and their comparison with landfill legislation

O. Gonzalez-Fernandez et al. / Nucl. Instr. and Meth. in Phys. Res. B 262 (2007) 81–86
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Location Depth K (%) Ca (%) Ti (%) Cr Mn (%) Fe (%) Co Ni Cu Zn Rb Sr Pb
(cm) (mg kg 1) (mg kg 1) (mg kg 1) (mg kg 1) (mg kg 1) (mg kg 1) (mg kg 1) (mg kg 1)
Portman 0–10 1.1 ± 0.2 6.82 ± 0.2 0.75 ± 0.03 455 ± 130 1.0 ± 0.1 26.2 ± 0.3 1900 ± 145 23 ± 1 90 ± 11 7600 ± 100 43 ± 1 170 ± 2 5600 ± 40
mine 10–15 0.77 ± 0.07 5.34 ± 0.07 0.75 ± 0.04 865 ± 100 0.99 ± 0.09 32.4 ± 0.4 2200 ± 30 32 ± 5 83 ± 9 10 700 ± 135 27 ± 5 110 ± 2 6400 ± 145
tailing 15–20 1.0 ± 0.2 9.87 ± 0.08 0.78 ± 0.01 520 ± 230 1.0 ± 0.1
on
25.4 ± 0.4 1800 ± 45 30 ± 2 93 ± 6 7900 ± 90 37 ± 1 255 ± 4 5900 ± 60
20–25 1.0 ± 0.2 10.3 ± 0.1 0.80 ± 0.08 375 ± 40 1.2 ± 0.2 30.30 ± 0.09 2200 ± 60 41 ± 6 94 ± 9 9000 ± 10 41 ± 3 270 ± 1 6300 ± 30
25–33 1.0 ± 0.2 9.8 ± 0.1 0.73 ± 0.08 435 ± 165 1.36 ± 0.03 27.2 ± 0.1 1900 ± 30 24 ± 1 92 ± 7 7400 ± 35 33 ± 2 244 ± 5 5200 ± 50
33–40 1.3 ± 0.2 10.9 ± 0.2 0.75 ± 0.02 320 ± 50 1.40 ± 0.03 25.6 ± 0.2 1800 ± 40 35 ± 12 118 ± 5 7800 ± 54 44 ± 2 232 ± 4 5500 ± 50
40–45 1.45 ± 0.07 11.26 ± 0.04 0.81 ± 0.04 250 ± 30 1.67 ± 0.01 27.6 ± 0.2 1900 ± 30 31 ± 8 122 ± 1 8400 ± 60 47 ± 3 260 ± 6 5800 ± 50
Mean 1.1 ± 0.1 9.2 ± 0.1 0.77 ± 0.04 460 ± 106 1.25 ± 0.08 27.8 ± 0.2 1957 ± 54 31 ± 5 99 ± 7 8400 ± 70 39 ± 2 220 ± 3 5814 ± 61
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value

Marques de 0–4 2.07 ± 0.05 5.24 ± 0.04 0.41 ± 0.17 360 ± 80 0.69 ± 0.05 23.6 ± 0.2 1700 ± 74 27 ± 8 134 ± 3 7800 ± 50 92 ± 3 200 ± 7 8200 ± 160
Pejar 4–10 1.91 ± 0.04 4.48 ± 0.07 0.39 ± 0.17 370 ± 45 0.83 ± 0.04 23.0 ± 0.2 1600 ± 55 25 ± 2 138 ± 5 7800 ± 60 85 ± 2 193 ± 4 7500 ± 45
mine 10–15 2.96 ± 0.07 4.2 ± 0.1 0.24 ± 0.08 400 ± 75 0.41 ± 0.05 20.8 ± 0.1 1500 ± 20 25 ± 3 245 ± 14 8300 ± 62 161 ± 1 305 ± 3 12 600 ± 95
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tailing 15–20 2.32 ± 0.02 5.7 ± 0.1 0.31 ± 0.11 535 ± 220 0.41 ± 0.01 21.8 ± 0.1 1600 ± 77 30 ± 6 205 ± 9 9000 ± 40 130 ± 3 274 ± 4 14 800 ± 140
20–25 2.8 ± 0.1 3.17 ± 0.03 0.29 ± 0.09 535 ± 170 0.22 ± 0.03 17.2 ± 0.2 1200 ± 34 21 ± 2 240 ± 5 6000 ± 45 153 ± 5 318 ± 3 16 200 ± 95
25–30 1.95 ± 0.01 6.27 ± 0.03 0.25 ± 0.02 600 ± 190 0.52 ± 0.08 23.9 ± 0.2 1600 ± 67 35 ± 4 221 ± 8 7800 ± 25 101 ± 2 257 ± 3 14 700 ± 45
30–35 1.62 ± 0.04 5.74 ± 0.03 0.13 ± 0.04 550 ± 200 0.68 ± 0.01 24.1 ± 0.2 1700 ± 40 30 ± 3 174 ± 6 6000 ± 20 76 ± 1 220 ± 3 9400 ± 70
35–40 2.5 ± 0.2 4.01 ± 0.06 0.23 ± 0.02 560 ± 170 0.37 ± 0.03 24.0 ± 0.2 1700 ± 95 28 ± 5 285 ± 6 8500 ± 53 135 ± 4 270 ± 3 13 100 ± 65
40–45 2.68 ± 0.08 4.8 ± 0.1 0.24 ± 0.05 330 ± 50 0.36 ± 0.03 18.4 ± 0.2 1300 ± 30 24 ± 2 247 ± 6 8500 ± 115 149 ± 2 250 ± 6 14 000 ± 120
45–50 2.41 ± 0.06 7.60 ± 0.06 0.28 ± 0.04 430 ± 130 0.57 ± 0.05 21.1 ± 0.1 1500 ± 80 20 ± 2 219 ± 3 8400 ± 70 124 ± 7 354 ± 1 13 100 ± 95
Mean 2.32 ± 0.07 5.13 ± 0.07 0.25 ± 0.05 467 ± 133 0.51 ± 0.04 21.8 ± 0.2 1540 ± 57 27 ± 4 211 ± 7 7810 ± 54 121 ± 3 264 ± 4 12 360 ± 95
value

Landfill Class – – 0–3000 – – – 0–2000 0–6000 0–8000 – – 0–2000

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legislation I
Class – – 3000– – – – 2000– 6000– 8000–75 000 – – 2000–50 000
II 50 000 50 000 60 000
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86 O. Gonzalez-Fernandez et al. / Nucl. Instr. and Meth. in Phys. Res. B 262 (2007) 81–86

Acknowledgments [6] R. Clemente, A. Escolar, M. Pilar Bernal, Bioresour. Technol. 97 (15)

(2005) 1894.
[7] E. Marguı́, V. Salvadó, I. Queralt, M. Hidalgo, Anal. Chim. Acta 524
This research was made on the framework of the project (2004) 151.
CGL2004-05963-C04 of the Spanish National Research [8] A.F. Marques, I. Queralt, M.L. Carvalho, M. Bordalo, Spectrochim.
Programme. Also Oscar Gonzalez Fernandez acknow- Acta Part B 58 (12) (2003) 2191.
ledges a grant from the Spanish Government (BES-2005- [9] X. Bi, X. Feng, Y. Yang, Q. Guangle, G. Li, F. Li, T. Liu, Z. Fu, Z.
6810). Jin, Environ. Int. 32 (7) (2006) 883.
[10] Q. Yang, W. Shu, J. Qiu, H. Wang, C. Lan, Environ. Int. 30 (2004)
883.

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