Microchemical Journal 103 (2012) 158164

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Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Assessing urban soil pollution in the cities of Zacatecas and Guadalupe, Mexico by
instrumental neutron activation analysis
F. Mireles a,, J.I. Davila a, J.L. Pinedo a, E. Reyes a, R.J. Speakman b, M.D. Glascock c
a
b
c

Unidad Acadmica de Estudios Nucleares, Universidad Autnoma de Zacatecas, Ciprs 10, Frac. La Peuela, Zacatecas, Zac., C.P. 98068, Mexico
Center for Applied Isotope Studies, University of Georgia, Athens, GA, 30602, USA
Research Reactor Center, University of Missouri, Columbia, MO, 65211, USA

a r t i c l e

i n f o

Article history:
Received 8 February 2012
Received in revised form 14 February 2012
Accepted 14 February 2012
Available online 18 February 2012
Keywords:
Urban pollution
Heavy metals
Urban soils
Mine tailings
Enrichment factor
INAA

a b s t r a c t
The cities of Zacatecas and Guadalupe in the state of Zacatecas, Mxico, have strong mining traditions since
they were founded in 1546 by Spanish conquers, and the rapid growth of vehicle trafc in the last 30 years
has had the side effect of introducing toxic metals into the urban soils. For this study, urban soil samples
were collected from eight locations around the cities of Zacatecas and Guadalupe; and mine tailing samples
were collected from two nearby tailing dams named Barones and Pedernalillo. The ten samples were analyzed by instrumental neutron activation analysis for 33 major, trace, and rare earth elements to estimate
the health risk to the public by urban soil contamination with heavy metals. The results of the contamination
levels for elements such as As, Ba, Cr, Fe, Mn, Ni, Ta, V, and Zn were compared to the Mexican regulations and
the guidelines of United States Environmental Protection Agency. Enrichment factors for quantied elements
identied high Cs, Zn, As, and Sb contents using Al as a crustal reference.
2012 Elsevier B.V. All rights reserved.

1. Introduction
The cities of Zacatecas and Guadalupe in the state of Zacatecas,
Mxico, have a strong mining tradition since they were founded in
1546 by Spanish conquers, and the rapid growth of vehicle trafc in
the last 30 years has had the side effect of introducing toxic metals
into the urban soils. The location of these cities in mining areas places
the population at higher risk of exposure to various heavy metals
[13]. The general public has great concerns about the environmental
quality of the regions in which they are living and want to maintain a
healthy life style. The quality of the urban environment is of vital importance for the population because human health depends heavily
on the status of the soil [4,5].
The main anthropogenic sources of pollution in urban soil of Zacatecas and Guadalupe include mine tailings, vehicular trafc, and air
pollution [4,68]. The most hazardous wastes include the mine tailings that can represent a risk to health, by their content of heavy
metals such as Pb, Cd, As, Cu, Zn, Se, and Ni, among others. These elements tend to accumulate in the topsoils most accessible to the population [2,3,9]. Measuring the concentrations of elements in
environmental samples (soil, water, sediment, airborne, etc.) is one
of the most important steps in the process of diagnosis and resolution
of pollution [5,10].

Corresponding author. Tel./fax: + 52 492 922 7043.

E-mail address: fmireles@uaz.edu.mx (F. Mireles).
0026-265X/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.microc.2012.02.009

Individual countries have issued regulations stating the limits of

concentrations of heavy metals or other pollutants that can be considered acceptable or dangerous. In Mxico, these limits have been
established by the Minister of the Environmental Protection and published in the Mexican Ofcial Norm NOM-147-SEMARNAT/SSA12004. The expressed limits refer to soils and sediments used for agricultural, residential, commercial and industrial purposes [5,11]. They
include both soils and sediments; but between these categories there
are no differences. In this way, to be considered as a pollutant, any potentially harmful compound must satisfy simultaneously two criteria:
(1) be present at increased concentrations near the urban soil surface
and (2) exceed the legal limits. In the present work, the results are
compared to the limits of concentrations established by the Mexican
Ofcial Norm; and as well as to the concentration guidelines of the
United States Environmental Protection Agency (US EPA) [12].
The high-precision, nuclear quantitative analytical technique of
instrumental neutron activation analysis (INAA) was used in this investigation of urban soils due to its very high sensitivity [13,14]. In
the present work, this analytical technique was used to determine
the concentrations of major, trace, and rare-earth elements (REEs)
in eight urban soil samples collected from locations around urban
areas of Zacatecas and Guadalupe and two samples collected from
nearby tailing dams at Barones and Pedernalillo [1518]. This study
was aimed at applying INAA for the analysis of eight urban soils and
two mine tailing samples to uncover evidence of possible pollution
in urban areas of the two cities for the elements in question. Using
Al as a crustal reference, the enrichment factors (EF) values were

F. Mireles et al. / Microchemical Journal 103 (2012) 158164

159

Fig. 1. Geographic location of the cities of Zacatecas and Guadalupe. Major roads are shown.

Fig. 2. Site locations of urban soil and mine tailing samples.

calculated by comparing the means of element concentrations found

in the eight urban soil samples with the continental crust average to
conrm the existence of pollution in urban soils [1921].
2. Experimental
2.1. Description of eld area
The cities of Zacatecas and Guadalupe are located in the mountains
of the state of Zacatecas, Mexico. The climate is dry and temperate,
with average annual rainfalls of 469 and 428 mm, temperatures of
15.6 and 15.6 C, and altitudes of 2420 and 2280 masl, respectively.

The extreme geographic coordinates of Zacatecas and Guadalupe are

22 51 N and 22 37 S of North latitude, 102 32 E and 102 51 W of
West longitude; and 23 00 N and 22 32 S of North latitude; 102
11 E and 102 39 W of West longitude, respectively [22]. Guadalupe
is located about 6 km east of the city of Zacatecas. Fig. 1 shows the geographic location of the state of Zacatecas on a map of Mxico, as well as
the locations of the cities of Zacatecas and Guadalupe [23].
2.2. Sampling and sample preparation
Soil samples were collected at eight sites, where ve cores of soil
were taken over an area of ~ 1000 m 2 during the autumn season of

Table 1
Irradiation and counting conditions.
Elements and half-life

Sample weight mg

Irradiation ux (n cm 2 s 1)

Irradiation time

Decay time

Counting time

Short-lived elements:
Al, Ba, Ca, Dy, K, Mn, Na, Ti, V
Medium-lived elements:
As, La, Lu, Nd, Sm, U, Yb
Long-lived elements:
Ce, Co, Cr, Cs, Eu, Fe, Hf, Ni, Rb, Sb, Sc, Sr, Ta, Tb, Th, Zn, Zr

150

8 1013

5s

25 min

12 min

200

5 1013

24 h

7 days

2000 s

200

5 1013

24 h

28 days

3h

160

F. Mireles et al. / Microchemical Journal 103 (2012) 158164

Table 2
Estimated detection limits for INAA using decay gamma rays. Assuming irradiation in a
reactor thermal neutron ux of 1 1013 n cm 2 s 1.
Sensitivity (picograms)

Elements

1
110
10100
1001E3

Dy, Eu
In, Lu, Mn
Au, Ho, Ir, Re, Sm, W
Ag, Ar, As, Br, Cl, Co, Cs, Cu, Er, Ga, Hf, I,
La, Sb, Sc, Se, Ta, Tb, Th, Tm, U, V, Yb
Al, Ba, Cd, Ce, Cr, Hg, Kr, Gd, Ge, Mo, Na,
Nd, Ni, Os, Pd, Rb, Rh, Ru, Sr, Te, Zn, Zr
Bi, Ca, K, Mg, P, Pt, Si, Sn, Ti, Tl, Xe, Y
F, Fe, Nb, Ne
Pb, S

1E31E4
1E41E5
1E51E6
1E7

2000. In the same way, two mine tailing samples were collected from
Barones and Pedernalillo. Each core was taken to a depth of 5 cm at a
randomly chosen point within the site area. The only constraint was
that no core should be taken near a eld boundary, tree, building, or
other physical obstruction. In order to obtain a representative sample,
the soil cores collected at each site were thoroughly mixed together,
sieved to remove stones and pebbles, and crushed to pass through a
2-mm mesh sieve. After homogenization, a sample of 3 L was airdried for several days to remove water content [5,24]. Sampling was
performed in such a way as to obtain, as far as possible, a uniform
and representative distribution of the sampling sites for soil collection throughout the urban regions of interest and from the mine tailing dams at Barones and Pedernalillo. These tailing dams are close to
urban areas. The region was divided into NE, NW, SE, and SW areas,
and two samples were collected from each. Fig. 2 shows the ten sampling sites [5,24].

2.3. Instrumental neutron activation analysis

Upon arrival at University of Missouri Research Reactor (MURR) of
the University of MissouriColumbia, USA, the sample powders were
transferred to glass vials and dried for 24 h at 100 C. For INAA, two
aliquots of powdered soil and mine tailing samples weighing
150 mg and 200 mg each were placed in separate clean highdensity polyethylene vials and high-purity quartz vials used for
short and long irradiations, respectively. The irradiation and counting
parameters utilized for the element analyses are reported in Table 1.

The short-irradiation samples in polyvials were sequentially irradiated in a thermal neutron ux of 8.0 10 13 n cm 2 s 1 for 5 s,
allowed to decay for 25 min so that radioactivity from short-lived radioisotope 28Al (half-life of 2.24 min) could decrease to a level comparable to the remaining radioisotopes. The samples were counted
for 12 min each on a high-purity intrinsic germanium (HP Ge) detector with 25% relative efciency and FWHM resolution of 1.85 keV for
the 1332 keV gamma ray of 60Co [5,14]. Elements measured from the
short-irradiation samples were the following: Al, Ba, Ca, Dy, K, Mn,
Na, Ti, and V (Table 2).
The long-irradiation samples in quartz vials were irradiated as a
single bundle using a thermal neutron ux of 5.0 10 13 n cm 2 s 1
for a period of 24 h. Two counts were made on the samples after
the long irradiation also using a HP Ge detector. The rst count for
2000 s per sample was made after the samples decayed for 7 days
to permit the activity for 24Na (half-life of 15 h) to decay to a safe
handling level. This count enabled successful measurement of the following medium-lived elements: As, La, Lu, Nd, Sm, U, and Yb. A second count for 3 h per sample was made after the samples decayed
for an additional 21 days and enabled measurement of the following
long-lived elements: Ce, Co, Cr, Cs, Eu, Fe, Hf, Ni, Rb, Sb, Sc, Sr, Ta,
Tb, Th, Zn, and Zr. Concentrations in the unknown samples were determined relative to the National Institute of Standards and Technology (NIST) certied standards SRM-1633a Coal Fly Ash and SRM-688
Basalt Rock which were prepared and irradiated under identical conditions along with the urban soil and mine tailing samples. Measurement uncertainties for almost all of the elements are under 5% [5,14].

3. Results and discussion

The results for 33 elements from the eight soil and two mine tailing samples are presented in Tables 3, 4, and 5 according to their respective half-life: short, medium and long. The mean concentrations
of the major elements such as Al, Ca, Fe, K, Na, and Ti were 6.78%,
1.15%, 4.61%, 2.05%, 0.658% and 0.364%, respectively. Mean concentrations for the hazardous elements such as As, Ba, Cr, Mn, Sb, V and Zn
were 109 ppm, 487 ppm, 135 ppm, 878 ppm, 13.1 ppm, 144 ppm,
and 766 ppm, respectively. The relative errors (%) of most of the determined elements were within 5%.
INAA is also favorable for the determination of several rare earth
elements (REE), such as, Ce, Eu, La, Lu, Nd, Sm, and Yb. Table 6

Table 3
Concentrations of major and trace elements in eight urban soils and two mine tailing samples for short-lived elements (in mg kg 1).
Element

ZG-1

ZG-2

ZG-3

ZG-4

ZG-5

ZG-6

ZG-7

ZG-8

JBA1

JPE1

Al (%)
Ba
Ca (%)
Dy
K (%)
Mn
Na (%)
Ti (%)
V

7.030
233.6
3.366
3.289
1.354
815.8
0.6172
0.3259
188.9

6.432
305
1.304
3.937
1.682
1631
0.4683
0.4019
156.1

7.660
664.8
0.812
3.311
3.101
1417
0.5034
0.4550
195.7

7.858
382.3
0.514
3.391
1.748
996.9
0.4592
0.4632
198.6

6.419
968.4
0.788
7.564
2.793
348.2
0.4685
0.1900
51.76

5.602
577.5
0.486
3.424
2.451
445.7
0.6045
0.2404
87.5

8.092
408.3
1.435
3.932
1.878
909.7
1.598
0.5138
202.4

5.162
355.9
0.511
3.562
1.373
463.3
0.5431
0.3205
73.36

3.981
173
3.305
2.099
1.388
4378
0.4080
0.1690
132.8

6.173
572.7
2.093
3.695
1.965
1264
0.8688
0.3731
184.5

Table 4
Concentrations of major and trace elements in eight urban soils and two mine tailing samples for medium-lived elements (in mg kg 1).
Element

ZG-1

ZG-2

ZG-3

ZG-4

ZG-5

ZG-6

ZG-7

ZG-8

JBA1

JPE1

As
La
Lu
Nd
Sm
U
Yb

44.42
12.86
0.2773
15.34
3.271
1.267
2.128

340.2
15.93
0.3117
13.14
3.770
1.887
2.525

196.6
10.14
0.3347
11.96
3.176
0.7555
2.478

98.55
13.92
0.3517
14.79
3.666
1.377
2.540

57.45
34.15
0.4270
31.41
6.901
3.066
3.490

38.35
17.70
0.2922
16.27
3.300
2.550
2.109

56.58
12.83
0.3118
13.56
3.606
1.202
2.383

40.27
17.15
0.3122
16.30
3.600
2.287
2.380

511.5
3.923
0.1604
5.908
1.424
0.0
1.047

150.6
14.18
0.3121
14.52
3.741
1.183
2.254

F. Mireles et al. / Microchemical Journal 103 (2012) 158164

161

Table 5
Concentrations of major and trace elements in eight urban soils and two mine tailing samples for large-lived elements (in mg kg 1).
Element

ZG-1

ZG-2

ZG-3

ZG-4

ZG-5

ZG-6

ZG-7

ZG-8

JBA1

JPE1

Ce
Co
Cr
Cs
Eu
Fe (%)
Hf
Ni
Rb
Sb
Sc
Sr
Ta
Tb
Th
Zn
Zr

26.64
20.45
203.6
29.48
0.7734
4.781
4.521
46.63
100.5
8.302
19.86
52.60
0.5943
0.5
3.52
346
167.3

32.00
15.09
125.3
12.43
0.9242
6.077
4.928
36.95
120.0
19.82
14.51
0.0
0.7695
0.62
4.13
3951
139

22.45
21.28
130.8
31.86
0.8973
6.422
3.954
41.16
235.7
28.62
25.05
0.0
0.5854
0.5
2.7
1016
87.6

29.48
24.50
233.3
13.25
0.8916
6.378
4.265
68.05
130.2
6.912
23.33
103.0
0.6911
0.58
3.91
373.6
103.3

69.55
5.679
44.29
28.88
0.7124
1.937
6.501
0.0
203.1
17.90
7.848
69.80
1.256
1.02
11.54
143.6
174.1

57.77
13.74
59.89
12.22
0.5773
2.479
4.538
0.0
115.9
9.437
7.087
61.04
0.7979
0.51
5.66
85.2
127.9

34.51
24.60
183.3
16.84
0.9676
5.325
3.751
0.0
183.1
9.206
21.50
76.21
0.5673
0.58
3.6
101.5
132

40.24
7.678
99.13
7.349
0.6683
3.469
8.786
28.35
89.69
4.517
7.863
52.18
1.005
0.54
6.3
112
224

7.686
19.35
148.3
10.53
0.9151
7.527
0.8986
0.0
70.38
50.75
16.28
0.0
0.0
0.3
0.41
4345
0

30.40
20.71
164.9
16.12
0.9273
5.091
3.562
51.31
98.47
47.57
20.33
.00
0.6092
0.6
3.61
2608
118.5

Table 6
Concentrations of rare-earth elements in eight urban soils and two mine tailing samples (in mg kg 1).
Element

ZG-1

ZG-2

ZG-3

ZG-4

ZG-5

ZG-6

ZG-7

ZG-8

JBA1

JPE1

Ce
Eu
La
Lu
Nd
Sm
Yb

26.64
0.7734
12.86
0.2773
15.34
3.271
2.128

32.00
0.9242
15.93
0.3117
13.14
3.770
2.525

22.45
0.8973
10.14
0.3347
11.96
3.176
2.478

29.48
0.8916
13.92
0.3517
14.79
3.666
2.540

69.55
0.7124
34.15
0.4270
31.41
6.901
3.490

57.77
0.5773
17.70
0.2922
16.27
3.300
2.109

34.51
0.9676
12.83
0.3118
13.56
3.606
2.383

40.24
0.6683
17.15
0.3122
16.30
3.600
2.380

7.686
0.9151
3.923
0.1604
5.908
1.424
1.047

30.40
0.9273
14.18
0.3121
14.52
3.741
2.254

shows the mean concentration of the REEs in the eight urban soil
samples in ppm.
For an assessment of the contamination level of the urban soils of
the cities of Zacatecas and Guadalupe, the elemental concentrations
for As, Ba, Cr, Fe, Mn, and Zn were compared with the guidelines of
the US EPA [12] which are presented in Table 7. By this comparison,
it can be concluded that As and Ba in ten samples, Cr and Fe in eight
samples, Mn in seven samples, and Zn in six samples were highly polluted in some of the sampling locations for urban soils and mine tailings in the cities of Zacatecas and Guadalupe. According to the
Preliminary Remediation Goals (PRGs) from USEPA, As levels of
4.5 ppm increase the risk of cancer to one per million through dermal
absorption [25]. Elements generally known to be associated with air
pollution, such as As, showed heavily polluted levels [10,15,26]. On
the other hand, for the assessment of the contamination levels in
urban soils of Zacatecas and Guadalupe, the elemental concentrations
for As, Ba, Cr, Ni, Ta, and V were compared with the guidelines of
Mxico, NOM-147-SEMARNAT/SSA1-2004 which are presented in
Table 8. By this comparison, it can be concluded that concentration
values of Ba, Cr Ni and Ta are below guidelines of Mxico. However,

As
Ba
Cr
Fe
Mn
Zn

EFX X=Alurbansoilorminetailing =X=AlContinentalCrust

where EFX stands for the enrichment factor of element X in urban soil
or mine tailing samples, after having its concentration (X) in urban
soil or mine tailing samples is normalized to (Al) concentrations in
urban soil and mine tailing samples or crust. A value of EF > 1 greater
than one for a particular element indicates the enrichment of that element in urban soil and mine tailing samples [20,27,28]. The data
used to calculate enrichment factors of various elements in urban
soil and mine tailing samples, and the enrichment are shown in
Table 9 and in Figs. 3 and 4, respectively. It is clear from these gures
Table 8
Comparison of elemental contents with NOM-147-SEMARNAT/SSA1-2004 guidelines
of Mxico (mg kg 1).
Element

Table 7
Comparison of elemental contents with USEPA guidelines (mg kg 1) [12].
Element

As in ten samples and V in eight samples are above guidelines of Mexico, by a factors of 5 and 2, respectively.
By comparing the elemental concentrations in urban soils and
mine tailing samples with continental crust values, enrichment factors (EF) have been calculated using following expression:

USEPA guidelines for classication of

great lakes harbor sediments

Present work

Not
polluted

Moderately
polluted

Heavily
polluted

In urban soils
Range

Mean

b3
b20
b25
b17,000
b300
b90

38
2060
2575
17,00025,000
300500
90200

>8
>60
>75
>25,000
>500
>200

38.35340.2
233.6968.4
44.29233.3
19,37264,217
348.21631.3
85.233951.4

109
487
134.9
46,084
878.5
766.1

As
Ba
Cra
Ni
Ta
V
a

NOM-147-SEMARNAT/SSA12004 guidelines of Mxico

Present work

Commercial,
agricultural,
and
residential
use

Industrial
use

In urban soils
Range

Mean

22
5400
280
1600
5.2
78

260
67,000
510
20,000
67
1000

38.35340.2
233.6968.4
44.29233.3
0.068.5
0.56731.256
51.76202.43

109
487
134.9
27.64
0.7833
144.3

Hexavalent chromium

162

F. Mireles et al. / Microchemical Journal 103 (2012) 158164

Table 9
Enrichment factors of elements in urban soils, mine tailings of Barones and Pedernalillo relative to continental crust, taking Al as a crustal reference.
Element

This work
Urban soils
Mean
(mg kg 1)

This work
Mine tailing
Barones
(mg kg 1)

This work
Mine tailing
Pedernalillo
(mg kg 1)

Continental crust averagea

(mg kg 1)

Urban soils
EF

Mine tailing
Barones
EF

Mine tailing
Pedernalillo
EF

Al
As
Ba
Ca
Ce
Co
Cr
Cs
Dy
Eu
Fe
Hf
K
La
Lu
Mn
Na
Nd
Ni
Rb
Sb
Sc
Sm
Sr
Ta
Tb
Th
Ti
U
V
Yb
Zn
Zr

67,817
109.0
487
11,522
39.08
16.63
134.9
19.04
4.051
0.8015
46,084
5.156
20,474
16.83
0.3273
878.5
6578
16.60
27.64
147.3
13.09
15.88
3.912
51.85
0.7833
0.6114
5.172
3638
1.799
144.3
2.504
766.1
144.4

39810.00
511.50
173.00
33047.00
7.69
19.35
148.30
10.53
2.10
0.92
75274.00
0.90
13878.00
3.92
0.16
4378.00
4080.00
5.90
0.00
70.38
50.75
16.28
1.42
0.00
0.00
0.31
0.41
1690.00
0.00
132.80
1.05
4345.00
0.00

61731.00
150.60
572.70
20926.00
30.40
20.71
164.90
16.12
3.70
0.94
50915.00
3.56
19649.00
14.18
0.31
1264.00
8688.00
14.52
51.31
98.47
47.57
20.33
3.74
0.00
0.61
0.60
3.61
3731.00
1.18
184.50
2.25
2608.00
118.50

82,300
1.80
425
41,500
60
25
100
3
3
1.2
56,300
3
20,900
30
0.5
950
23,600
28
75
90
0.2
22
6
375
2
0.9
9.6
5700
2.7
135
3
70
165

1.0
73.5
1.4
0.3
0.8
0.8
1.6
7.7
1.6
0.8
1.0
2.1
1.2
0.7
0.8
1.1
0.3
0.7
0.4
2.0
79.4
0.9
0.8
0.2
0.5
0.8
0.7
0.8
0.8
1.3
1.0
13.3
1.1

1.0
587.5
0.8
1.6
0.3
1.6
3.1
7.3
1.4
1.6
2.8
0.6
1.4
0.3
0.7
9.5
0.4
0.4
0.0
1.6
524.6
1.5
0.5
0.0
0.0
0.7
0.1
0.6
0.0
2.0
0.7
128.3
0.0

1.0
111.5
1.8
0.7
0.7
1.1
2.2
7.2
1.6
1.0
1.2
1.6
1.3
0.6
0.8
1.8
0.5
0.7
0.9
1.5
317.1
1.2
0.8
0.0
0.4
0.9
0.5
0.9
0.6
1.8
1.0
49.7
1.0

Taylor, S.R. 1964 [20].

1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0

Urban Soils

Mine Tailing of Barones

The result, when EF 1 indicates that the element of study is not

enriched by additional sources and its origin it is purely natural. If
the EF > 1, the contribution of the element is probably of two kinds
both natural and anthropogenic. If the EF > 10, the element is considered to be highly enriched, and conrms that an anthropogenic
source has contributed to the metal concentration; see Table 10 [28].
For a better overview of the data, the metal concentration variations in the urban soils were plotted. See Fig. 5. The As and Cr concentrations were multiplied by 10, and the Sb concentration was
multiplied by 100 to improve the visualization of the data. For a better
overview of the data, the rare-earth element concentration variations
in the urban soils were also plotted. See Fig. 6. The Eu and Lu concentrations were multiplied by 10, to improve the visualization of the
data [4,6].

Mine Tailing of Pedernalillo

Urban Soils

Mine tailing of Barones

Mine tailing of Pedernalillo

14.0

Enrichment Factor

Enrichment Factor

that the concentrations of several elements are slightly higher in the

urban soil samples compared to the background continental crust.
This indicates that there is some contamination and accumulation of
these elements in the urban soils. While EF 1 are usually regarded
as nondescript for the elements, in increasing order Sr, Ca, Na, Ni,
Ta, Th, La, Nd, Ti, Ce, Sm, Lu, Co, U, Eu, Tb, Sc, Fe, Al, and Yb. Elements
with EF values that are considerably higher than 1, EF > 1, can be considered not originated from the local soil background and may be attributed to anthropogenic sources such as trafc vehicles, mine
tailings and air pollutants [2628]. Those elements in increasing
order are Zr, Mn, K, V, Ba, Cr, Dy, Rb, Hf, Cs, Zn, As, and Sb in urban
soil samples. However, the elements Cs, Zn, As, and Sb showed highest enrichment factors. The widely accepted threshold for substantial
enrichment over the natural continental crustal background is EF 10
[5,21,27].

Sr Ca Na Ni Ta Th La Nd Ti Ce Sm Lu Co U Eu Tb Sc

Elements
Fig. 3. Enrichment factors (EF) for major, minor, and trace elements in urban soils with
EF b 1 and mine tailings.

12.0
10.0
8.0
6.0
4.0
2.0
0.0
Fe

Al

Yb

Zr Mn

Ba

Cr

Dy

Rb

Hf

Cs Zn/10 As/100 Sb/100

Elements
Fig. 4. Enrichment factors (EF) for major, minor, and trace elements in urban soils with
EF 1 and mine tailings.

F. Mireles et al. / Microchemical Journal 103 (2012) 158164

Table 10
Enrichment factor and element origin for urban soils.
EF

Elements

Element origin

Sr, Ca, Na, Ni, Ta, Th, La, Nd, Ti, Ce, Sm,
Lu, Co, U, Eu, Tb, Sc, Fe, Al, Yb
Zr, Mn, K, V, Ba, Cr, Dy, Rb, Hf, Cs

Natural origin

>1

> 10 Zn, As, Sb

Natural origin with slight

anthropogenic enrichment.
Element highly enriched by some
anthropogenic sources.

Concentration, mg / kg

80.0

163
ZG03

ZG05

ZG08

ZG09

ZG13

ZG15

ZG17

ZG19

JBA1

JPE1

Lu x10

Nd

70.0
60.0
50.0
40.0
30.0
20.0
10.0

Finally, the elements may be divided into the following three

groups according to their median values [5,29]:
(1) Major elements (110%): Al, Ca, Fe, K.
(2) Minor elements (10 ppmb1%): As, Ba, Ce, Co, Cr, Cs, La, Mn,
Na, Nd, Ni, Rb, Sb, Sc, Sr, Ti, V, Zn, Zr.
(3) Trace elements (b10 ppm): Dy, Eu, Hf, Lu, Sm, Ta, Tb, Th, U, Yb.

4. Conclusions
In this study, eight urban soil samples from the cities of Zacatecas
and Guadalupe and two mine tailing samples from tailing dams of
Barones and Pedernalillo were analyzed by INAA and 33 elements
were determined, using short- and long-irradiation samples. When
the elemental contents for As, Ba, Cr, Fe, Mn, and Zn were compared
with the guidelines of the US EPA, the urban soils turned out to be
heavily polluted.
The differences in the elemental concentrations between guidelines of US EPA and guidelines of Mxico are large. The results of
this study indicated that urban soils from the cities of Zacatecas and
Guadalupe present concentration levels of As, Ba, Cr, Fe, Mn, and Zn
higher than the heavily polluted US EPA guidelines values. Concentration levels for Ba, Cr, Ni, and Ta, are lower than residential Mxico
Guideline values, but As and V are higher than residential Mxico
Guideline values.
The results of the elemental concentrations of urban soils show
that Al, Dy, Eu, Fe, Hf, La, Lu, Na, Nd, Sm, Ta, Tb, Th, Ti, U, Yb and Zn
have a more or less uniform distribution, otherwise As, Ba, Ca, Ce,
Co, Cr, Cs, K, Mn, Ni, Rb, Sb, Sc, Sr, V, and Zr have a greater variation
between samples. Comparing elemental concentrations of the urban
soil to mine tailing samples, we nd that the urban soil samples
have a largest concentration of some elements, such as Al, Ce, Cs,
Dy, Hf, K, La, Lu, Nd, Rb, Sm, Sr, Ta, Tb, Th, U, B, and Zr. Also, the average elemental concentrations in urban soil samples have more similar
to the elemental concentrations of the mine tailings from
Pedernalillo.

0.0
Ce

Eu x10

La

Sm

Yb

Fig. 6. Concentrations of rare-earth elements in urban soils of the City of Zacatecas and
Guadalupe, and mine tailings of Barones and Pedernalillo.

The main lessons learned from the present study can be expressed
as follows: (1) urban soils in the cities of Zacatecas and Guadalupe are
polluted with As, Ba, Cr, Fe, Mn, and Zn in all the eight urban soil samples. The contamination is probably derived from air pollutants, vehicle trafc and mine tailing pollution. (2) In all cases, the urban soil
concentrations for As, Ba, Cr, Fe, Mn, and Zn exceed the heavily polluted by factors of 14, 8, 2, 2, 2, and 4 according to US EPA legislation, respectively. (3) In eight cases for As and in six cases for V in urban soil,
the concentrations exceed the minimum threshold of safety according to Mexican legislation, by a factors of 5 and 2, respectively. The
enrichment factors found through this study show that urban soils
are efcient accumulators of elements from the environment. The
Calculated EF for quantied elements identied Cs, Zn, As, and Sb as
elements with very high EF values of 7.7, 13.3, 73.5, 79.4, respectively,
suggest that these elements may be derived from vehicle trafc (Zn
and Sb), from mine tailing (As, Zn, and Sb), from air pollutants (As)
that are anthropogenic sources.
Disclaimer
Any opinions, ndings, and conclusions or recommendations
expressed in this material are those of the author(s) and do not necessarily reect the views of the Department of Energy.
Acknowledgments
The authors are grateful to Dr William H. Miller and operators of
the University of Missouri Research Reactor for their valuable assistance in the INAA. This work was supported in part by the US Department of Energy grant DE-FG07-02ID14380.
References

ZG03
ZG15

6000

ZG05
ZG17

ZG08
ZG19

ZG09
JBA1

ZG13
JPE1

Concentration, mg / kg

5000
4000
3000
2000
1000
0
As x10

Ba

Cr x10

Sb x100

Zn

Fig. 5. Concentrations of metal elements in urban soils of the City of Zacatecas and Guadalupe, and mine tailings of Barones and Pedernalillo.

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