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Chromium, Cobalt and Nickel Contents in Urban Soils of Moa,
Northeastern Cuba
O. Dı
´
az Rizo
•
I. Coto Herna
´
ndez
•
J. O. Arado Lo
´
pez
•
O. Dı
´
az Arado
•
N. Lo
´
pez Pino
•
K. D
0
Alessandro Rodrı
´
guez
Received: 22 April 2010 / Accepted: 2 December 2010 / Published online: 15 December 2010
Ó Springer Science+Business Media, LLC 2010
Abstract Iron, chromium, cobalt and nickel concentra-
tion levels in urban soil samples collected from Moa city
(Holguı
´
n province), northeastern Cuba were determined.
Both chromium and nickel contents exceed the Dutch
Intervention Value soil quality standard in 2.8–5.4 and
1.3–3.3 times, respectively. Furthermore, cobalt content
exceeds the Target Value in 1.3–1.8 times. Metal-to-Iron
normalization predicts a natural origin for nickel and cobalt
(Enrichment Factor \1), and also a moderate chromium
enrichment (Enrichment Factor = 1.5–4.0) in all studied
stations. The application of the Urban Environment
Entropy Model show that residential area located near to
industrial area is slightly affected by industrial chromium
emissions and not affected by cobalt and nickel possible
emissions. A chromium speciation in soil samples is rec-
ommended in order to evaluate the real impact of the
current chromium content in Moa urban soils to local urban
and suburban agricultures.
Keywords Urban soils Heavy metals Pollution
Environmental entropy Cuba
In urban areas, soil environmental quality is closely related
to human health. Humans, and particularly small children,
are adversely affected by high concentrations of many heavy
metals. Due to their active digestive systems, children have
higher heavy metal absorption rates which, given the con-
nection between this system and the circulatory system, can
lead to imbalances in the blood composition. Heavy metals
that accumulate within our bodies can also affect the central
nervous system, cause poisoning, and act as co-factors of
many other illnesses (Goyer 1997; Finkelstein et al. 1998;
Brewster and Perazella 2004; Navas-Acien et al. 2007).
Furthermore, heavy metal contents in the urban soil tend to
increase with vehicular emissions (Surthland et al. 2000;
Mielke et al. 2010), industrial residues (Schumacher
et al.1997), the atmospheric deposition of dust and aerosols
(Simonson 1995), and other industrial sources such as
metallurgical industries and thermoelectric centers (Diaw-
ara et al. 2006; Biasioli et al. 2007).
The particular geological characteristics of the Moa
municipality (Holguı
´
n province, Northeast Cuba), charac-
terized by ultrabasic igneous rock (serpentine) abundance,
justify the location and exploitation of the biggest Ni mines
of the country. It is due to this that near Moa city [63 027
population, 23% – children (CNSO 2009)] are located
some Ni ? Co and Cr processing plants, which emissions
most likely might end up in the city, or at least up to a
certain percent. In that sense, the aim of this study is to
investigate the concentrations of iron (Fe), nickel (Ni),
cobalt (Co) and chromium (Cr) in the surface urban soils
throughout Moa city, and to evaluate the soil environment
quality in terms of metal contamination.
Materials and Methods
Surface soils (0–10 cm) were sampled at representative
sites from Moa city (Fig. 1) during the same journey.
Composite samples, consisting of four soil cores, were
collected at each site (approximately 1 9 1 m). This
O. Dı
´
az Rizo (&) I. Coto Herna
´
ndez
J. O. Arado Lo
´
pez O. Dı
´
az Arado N. Lo
´
pez Pino
K. D
0
Alessandro Rodrı
´
guez
Instituto Superior de Tecnologı
´
as y Ciencias Aplicadas,
Ave. Salvador Allende y Luaces, POB 6163,
10600 La Habana, Cuba
e-mail: odrizo@instec.cu
123
Bull Environ Contam Toxicol (2011) 86:189–193
DOI 10.1007/s00128-010-0173-z
sampling strategy was adopted in order to reduce the
possibility of random influences from urban wastes, and to
investigate trace metal concentrations in representative
soils: industrial (St. 1–4) and residential (St. 5–7). All
samples were collected with a spatula and kept in PVC
packages and dried at 50°C. Large rock and organic debris
were removed before sieving. The fraction smaller than
1 mm was ground to a fine powder (\125 lm) in an agate
mortar. The pulverized samples were newly dried at 60°C
until obtaining a constant weight.
The heavy metal concentrations were estimated by
X-Ray Fluorescence Analysis (XRF) using the Certified
Reference Materials (CRM) IAEA-SL-1 ‘‘Lake Sediment’’
(Dybczynski and Suschny 1974), IAEA-Soil-5 (Dybczyn-
ski et al. 2007), IAEA-356 ‘‘Polluted Marine Sediment’’
(IAEA 1994), BCR-2 ‘‘Basalt Columbia River’’ (Wilson
1997) and BCSS-1 ‘‘Marine sediment’’ from the Canadian
National Research Council as standards. All samples and
CRM were mixed with cellulose (analytical quality) in
proportion 4:1 and pressed at 15 tons into the pellets of
25 mm diameter and 4–5 mm height. Pellets were mea-
sured using a Canberra Si(Li) detector (150 eV energy
resolution at 5.9 keV, Be window thickness = 12.0 lm)
coupled to a MCA. A
238
Pu (1.1 GBq) excitation source
with ring geometry was used. All spectra were processed
with WinAxil code (Winaxil 2005). Detection Limits were
determined according to Padilla et al. (2007) (in concen-
tration units) as L
D
= 3r/mt, where m is the sensibility in
counts.seg
-1
per concentration unit, r is the standard
deviation of the area of the background windows (peak
window at 1.17 times the FWHM) and t is the measuring
time (6 h).
The accuracy was evaluated using the SR criterion,
proposed by McFarrell et al. (Quevauviller and Marrier
1995):
SR ¼
C
X
C
W
jj
þ 2r
C
W
100%
where C
X
– experimental value, C
W
– certified concentration
value and r is the standard deviation of C
X
. On the basis of
Fig. 1 Location of studied stations in Moa city
190 Bull Environ Contam Toxicol (2011) 86:189–193
123
this criterion the similarity between the certified value and
the analytical data obtained by proposed methods is divided
into three categories: SR B 25% = excellent; 25 \ SR B
50% = acceptable, SR [ 50% = unacceptable. The analysis
of five replica of the CRM IAEA Soil-7 (Pszonicki 1984)is
presented in Table 1. All heavy metals (Cr, Fe, Co and Ni)
determined by XRF are ‘‘excellent’’ (SR B 25%) and the
obtained results shows a very good correlation (R = 0.9999)
between certified and measured values.
The metal enrichment was assessed by normalizing the
results to a reference metal, using the Enrichment Factor
parameter (Schropp et al. 1990):
EF ¼ X
=
YðÞ
sample
.
X
=
YðÞ
background
where X is the concentration of potentially enriched metal
and Y is the concentration of the reference metal. If the EF
value of an element is close to unity, it means that its
observed concentration in samples can be considered as
crustal material. An enrichment value higher than unity
indicated non-crustal contribution on the corresponding
element concentration. Taking into account the geology of
the studied area, the (Turekian and Wedepohl 1961) results
for ultrabasic igneous rocks were used as background
values. In order to assess the possible anthropogenic
impact, the use of Fe to normalize the trace metal con-
taminants is recommended (Mucha et al. 2003). Iron is
abundant in the environment and is scarcely influenced by
anthropogenic inputs due to the natural high levels of this
element (Villares et al. 2003).
Additionally, the Urban Environment Entropy (UEE)
Model (Ouyang et al. 2008) was applied to assess the
impact induced by Cr, Ni and Co levels in residential soils
to the Moa city population. Knowing the concentration of a
potential pollutant and also its standard or background
concentration value, the UEE value for this pollutant can
be calculated as:
UEE
i
¼ ðÞ
DE
i
U
where, DE
i
stands for the percentage of the difference
between the measured value of the ith pollutant and its
standard or background value; U is the temporal urbani-
zation level of the sampling location. Here, the (Turekian
and Wedepohl 1961) results for ultrabasic igneous rocks
were also used as background values. The child percentage
in Moa population was used as urbanization level, being
them the most likely fraction of the population to be
affected by heavy metal pollution.
Results and Discussion
The average Cr, Fe, Co and Ni concentrations determined
by XRF in Moa city urban soils are shown in Table 2. The
highest chromium and nickel concentrations were recorded
in the nearest to the industrial area residential station 5,
while Co concentration is practically uniform through all
studied stations. It has been found before that Cr and Ni are
inherited from parent rocks. Particularly, soil on serpen-
tines contains high Cr and Ni concentrations (Kabata-
Pendias and Pendias 1992). Due to the lack of an official
Cuban guideline for proper concentrations of heavy metals
in soils, metal concentrations are compared with soil
quality standards which have been derived to assess soil
quality by the Dutch Authorities: Target Value (TV) and
Intervention Value (IV) (see Table 2) (Swartjes 1999).
These standards allow soil and groundwater to be classified
as clean, slightly contaminated or seriously contaminated.
The TV is based on potential risks to ecosystems, while the
IV is based on potential risks to humans and ecosystems.
According to Dutch classification, the Moa city urban soils
can be considered as ‘‘seriously contaminated’’ with Cr and
Ni and ‘‘slightly contaminated’’ with Co.
Table 1 XRF analysis of CRM Soil-7, SR values and detection limits
Metal Certified
value
Measured value* SR (%) L
D
(mg.kg
-1
)
Cr 60 59 ± 41022
Fe (%) 2.57 2.43 ± 0.19 22 9
Co 8.9 9.2 ± 0.8 20 6
Ni 26 25.6 ± 0.9 17 7
* Mean ± SD, n = 5, in mg kg
-1
, except Fe
Table 2 Average concentrations for heavy metals determined in Moa city urban soils
Metal Station 1 Station 2 Station 3 Station 4 Station 5 Station 6 Station 7 TV
a
IV
a
Cr 1823 ± 93 1737 ± 92 1366 ± 84 1056 ± 75 2052 ± 98 1804 ± 94 1582 ± 89 100 380
Fe (%) 3.5 ± 0.1 3.4 ± 0.1 4.8 ± 0.5 4.2 ± 0.1 3.0 ± 0.4 3.6 ± 0.2 4.5 ± 0.5 – –
Co 12 ± 112± 216± 214± 214± 114± 116± 2 9 240
Ni 419 ± 84 489 ± 65 272 ± 77 355 ± 42 701 ± 35 569 ± 45 311 ± 42 35 210
Mean ± SD, n = 4, mg kg
-1
, except Fe
a
Target Value (TV) and Intervention Value (IV)inmgkg
-1
(Swartjes 1999)
Bull Environ Contam Toxicol (2011) 86:189–193 191
123
On the other hand, calculating the Enrichment Factor
using Fe as reference metal for Cr, Co and Ni and (Ture-
kian and Wedepohl 1961) results for ultrabasic igneous
rocks as background (Table 3), a different result is
obtained. Here, according to Birch classification (Birch
2003), the natural Co and Ni origin is confirmed (EF \1),
meanwhile Cr origin is anthropogenic (EF [ 1). Thus, the
Moa city urban soils can be considered, according to this
criterion, as not contaminated with Co and Ni, indepen-
dently their relative high content values, and moderately
contaminated with Cr. The observed decrease of the Cr
enrichment in the residential area as the distance to the
industrial zone increases makes us believe that the Cr input
must be associated with atmospheric discharges from a Cr
processing plant.
The results of Urban Environment Entropy values for
Cr, Co and Ni contents in residential soils are listed in
Table 4. At sampling sites 5 and 6, only Cr UEE values
were positive. Moreover, their absolute values were rela-
tively low. On the other hand, Co and Ni UEE values in all
studied residential stations so as the Cr UEE value in the
station 7 (fairest from industrial area) were negative. Thus,
Moa residential soil quality is slightly affected by industrial
chromium emissions at these sites and not affected by the
possible Co and Ni emissions.
Urban agriculture in Cuba has rapidly become a sig-
nificant source of fresh food production for the urban and
suburban populations (Altieri et al. 1999). This system of
urban agriculture has been developed and managed along
agroecological principles, which eliminate the use of syn-
thetic chemical pesticides and fertilizers, emphasizing
diversification, recycling, and the optimal use of local soils.
As well known, soil Cr mobility to plants depends on its
oxidation state (from ?2to?6) (Kabata-Pendias and
Pendias 1992). Due to this fact, in order to evaluate the soil
Cr real impact to Moa urban agriculture, a soil Cr specia-
tion is recommended.
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