Geothermics 72 (2018) 170–181

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Geothermics
journal homepage: www.elsevier.com/locate/geothermics

Heavy metal sources and anthropogenic enrichment in the environment T

around the Cerro Prieto Geothermal Field, Mexico
⁎
Z.I. González-Acevedoa, , M.A. García-Zarateb, E.A. Núñez-Zarcoc, B.I. Anda-Martínd
a
Centro de Investigación Científica y de Educación Superior de Ensenada, B. C. Geology Department, Carretera Ensenada-Tijuana 3918, Zona Playitas, C. P. 22860.
Ensenada, Baja California, México
b
Applied Physics Department, Carretera Ensenada-Tijuana 3918, Zona Playitas, C. P. 22860. Ensenada, Baja California, México
c
Earth Science Division/CeMIE-Geo, Carretera Ensenada-Tijuana 3918, Zona Playitas, C. P. 22860. Ensenada, Baja California, México
d
Posgraduate program on Environmental Geociences, Carretera Ensenada-Tijuana 3918, Zona Playitas, C. P. 22860. Ensenada, Baja California, México

A R T I C L E I N F O A B S T R A C T

Keywords: The Cerro Prieto Geothermal Field (CPGF) is the biggest in Mexico, fourth worldwide, and it started electricity
Anthropogenic generation in 1973. This work correlates heavy metals in environmental samples, tracing the geothermal energy
Sources fingerprint from water an air, into soil and plants around CPGF. By X-Ray Fluorescence, we identified heavy
Soil metals (Cr, Mn, Pb, Pd, Ru, V and Zn) from other different sources than the CPGF. Enrichment factors of soils
Plants
suggest that Sb, Cl and Na are naturally enriched in the zone, and S mainly from geothermal sources in air,
Air
Water
enriches leaves of Allenrolfea occidentalis.

1. Introduction environmentally attractive since they employ a renewable energy

The study of the distribution and accumulation of heavy metals is of
great interest because of negative consequences on human health and
on the environment (Järup, 2003) due to their potential bioaccumula-
tion in living organisms and their lack of biodegradation capacity
(Duruibe et al., 2007). To understand biogeochemical cycles of metals
in certain areas, studies of the environment should include chemical
elements from the hydrosphere, lithosphere, biosphere and atmosphere,
as well as anthroposphere to evaluate the human impact.
Whereas soil is the main source of biologically active elements
supporting plant and animal life, and can be a source of heavy metals,
depending on its geological nature, (Sharma and Aghrawal, 2005),
water serves as vehicle for the dissolution and transport of metals
(Schnoor, 1996). Meanwhile, the atmosphere also can transport heavy
metals as particulate matter, these can be deposited at great distances
from their initial source (Outridge et al., 2005; DeVries et al., 2013).
Plants have a natural capacity to selectively accumulate heavy metals
and nutrients derived from soil, water and air, and often are used as
Bio-indicator in pollution monitoring (Meers et al., 2008; Simon et al.,
2011).
Environmental pollution by heavy metals is due to several pro-
cesses, whether natural as weathering, or anthropogenic, related to
mining, metallurgy, agriculture, industrial activities, burning of fossil
fuels and vehicular emissions. Geothermal power plants are
source. Compared with other energy sources, such as natural gas or
fossil fuels, geothermal energy is considered one of the cleanest, even
though it releases large volumes of fluids (liquids and gases) from the
subsoil (Moore and Simmons, 2013). Geothermal activities can also
release heavy metals that can leach into groundwater (Kagel et al.,
2005), although dissolved chemicals in wastewater depend on the
geochemistry of the reservoir and operating conditions of each power
plant and can vary widely between geothermal fields (Hunt, 2012).
Geothermal gases are discharged to the atmosphere from different
punctual sources: silencers, cooling towers, pipe leaks, vent stack,
among others. Among these gases, hydrogen sulfide (H2S) is upmost
concern, since it could represent a health risk at relatively low con-
centrations. Once in the atmosphere, it changes to sulfur dioxide (SO2),
favoring the formation of small acid particles that can be absorbed by
the bloodstream and cause heart and lung diseases (NRC, 2010). For
H2S, the WHO recommends a maximum exposure of 150 μg m−3 in
24 h (WHO, 2000). In Iceland, where geothermal energy represents
29% of the electricity generation (Orkustofnun, 2014), the regulation
limit of H2S is 50 μg m−3 average in a 24 h floating period (Hansell and
Oppenheimer, 2004), and in Mexico, where geothermal energy re-
presents 5.52% of the electricity generation (SENER, 2016) the limit of
H2S is a remarkable 15000 μg m−3 in a shorter period of 8 h but the
regulation is only applicable to workers at the site (NOM-010-STPS-
1999).

⁎
Corresponding author.
E-mail address: zgonzale@cicese.mx (Z.I. González-Acevedo).

https://doi.org/10.1016/j.geothermics.2017.11.004
Received 24 May 2017; Received in revised form 2 November 2017; Accepted 6 November 2017
0375-6505/ © 2017 Elsevier Ltd. All rights reserved.
Z.I. González-Acevedo et al.
The Cerro Prieto region is located in the south of Mexicali Valley,
Baja California (BC), Mexico, inhabited by over one million people. In
this municipality, 211,000 ha are used as irrigated farmland, and some
industries are present mainly from the metallurgy sector. Located in
Cerro Prieto, is the biggest geothermal power plant of Mexico, named
Cerro Prieto Geothermal Field, which started operations in 1973, it
currently produces up to 4028.27 GWh (SENER, 2016). The water that
drains through this area flows from north to south with agricultural and
domestic wastewaters and variable amounts of unmanaged flows
(Cohen, 2002; Nelson et al., 2013).
Peralta et al. (2013), measured meteorological parameters and en-
vironmental concentrations of H2S, criteria pollutants and non-con-
densable gases from vent stacks at Cerro Prieto Geothermal Field
(CPGF). They found as a main conclusion that measured air pollutants
never exceeded local environmental standards (based on occupational
exposure). Measured gases linked to automotive exhaust emissions
were more significant than gases from CPGF. Environmental determi-
nations and dispersion modeling showed a radius of 5 km around CPGF
continuously covered by H2S.
Recent studies about groundwater quality in the agricultural area
adjacent to CPGF, evaluated the influence of the geothermal field in the
water chemistry. These studies found high Cl concentrations attributed
to chloride-enriched water from channels used for irrigation. Besides
As, Cd, Cr, Cu, Hg and Pb were found in concentrations within Mexican
irrigation water standards. No elements related with geothermal brines
and toxic metals and metalloids shown the influence of CPGF (Armienta
et al., 2014).
Previous studies have been focused on the presence and distribution
of heavy metals in the water or air, little attention has been put on soil
and plants (Mutia et al., 2016). In addition, it remains unclear how
those heavy metals are correlated and if they are from anthropogenic
sources. In this study we correlated heavy metal concentrations in en-
vironmental samples (soil, water, vegetation and air) around CPGF,
Mexico to identify possible sources and quantify anthropogenic en-
richment. These results will contribute to the understanding of bio-
geochemical cycles of heavy metals in the region of Cerro Prieto,
Mexicali, Mexico.
171
Geothermics 72 (2018) 170–181
2. Study area
This study was carried out in the vicinity of Cerro Prieto Geothermal
Field (CPGF) in Mexicali Valley, BC, Mexico (Fig. 1). The CPGF is lo-
cated in northern Mexico in an active rift basin developed into sands
and shales. The geothermal fluids at Cerro Prieto are contained in se-
dimentary rocks (Tertiary sandstones) whose original cement has been
replaced by hydrothermal minerals such as quartz, calcite, chlorite,
epidote, prehnite, etc. The heat source is a regional thermal anomaly
resulting from the thinning of the continental crust at the basin bottom
(Hiriart and Gutiérrez-Negrı́n, 2003). This geothermal field is located in
one main area of 74 km2 where there is an evaporation pool that oc-
cupies around 18 km2. This evaporation pool was originally built to
produce ammonia nitrogen in 1985, but it never worked out because of
high costs associated to this process. Then, CFE (Electricity Federal
Commission) used this facility as an evaporation pool, where geo-
thermal brines from cooling towers and residual fluids from geothermal
wells are disposed. These geothermal brines enter the pool at a tem-
perature between 50 and 30 °C. The pool has a maze arrangement, this
permits the geothermal brine to cool down in outside layers up to
ambient temperature (Miranda-Herrera, 2015).
The Irrigation District 014-Río Colorado intersects the agricultural
district of the Mexicali Valley, BC that is subdivided in 22 irrigation
modules and drains into the Gulf of California. The Reforma channel
and Morelos Dam receive 90% of the Colorado River flow and the water
is then distributed to the irrigation modules through a series of lined
and unlined channels (Carrillo-Guerrero et al., 2013).
It is reported that the water from the Colorado River reaches an
average concentration of 1000 mg L−1 of total dissolved solids, where
highly soluble salts are present. The Colorado River in its trajectory
(2300 km) transports an average water volume of 18,248 Mm3, car-
rying in solution around 9 Mt of salts. This represents for each m3 of
water that is applied to the soil during the irrigation process, that an
average of 1 kg of salt is incorporated to the soil. Eventually this salt has
to be removed from the soil profile; otherwise it will lead to a rapid soil
salinization and as consequence, will cause a progressive reduction in
their productive capacity (Glenn et al., 1998; SEDAGRO, 2009). In this
zone, the soil salinization is also attributed to a mineralization in the
aquifer detected with the increase of dissolved total solids in the well
Fig. 1. Map of the hydrology of the Mexicali Valley,
Baja California (BC), Mexico. Inset shows the loca-
tion of the study area within BC. CP- Sampling sites
in Cerro Prieto *[AGEB: Basic Geostatistical
Populated Area, it constitutes the fundamental unit
of the national geostatistical framework with a se-
lection of main concepts of the population census
(INEGI, 1992)].
Z.I. González-Acevedo et al.
extraction that normally is used for agricultural use (Giffard et al.,
2014). The soils of Mexicali Valley, BC are of recent alluvial origin and
formed by successive accumulations of suspended materials brought by
the Colorado River, where, the most frequent cations are Ca, K, Na and
Mg.
The main vegetation in the zone is dominated by species from sandy
lands. However, there are vast plant communities that contrast with the
surrounding desert vegetation, forming dense patches of donkey grass
(Allenrolfea occidentalis) and cattail (Thypa dominguensis) which are the
most common species. In addition, there are found reed (Phragmites
australis), salty grass (Distichlis spicata) and salty pine (Tamarix ramo-
sissima), and the latter is the only non-native species recorded in the site
(Felger, 1992; Ezcurra et al., 1988). The traditional uses of plants in BC
is little known. The knowledge of indigenous groups, through oral
traditions transmitted for generations has contributed to identify the
use of these plant species. Their uses are focused on the curative, nu-
tritional and textile properties of plants in the region, and are limited to
these groups (Ramírez-Hernández et al., 2013).
The Municipality of Mexicali, BC is immersed in the physiographic
province of the Sonora Desert, where the arid climate corresponds to a
desert (García, 1988), with winter rains, below 55 mm year−1, covering
the Mexicali Valley, Cerro Prieto and the Laguna Salada area. Infiltra-
tion rate ranges from 0 to 4.5 mm day−1 with an average of
1.687 mm day−1 (Bushira et al., 2017). This area has a very arid cli-
mate with extreme temperatures, in summer reaching up to 54 °C and
in winter descends to −7 °C. The average annual temperature is 22.5 °C
(García-Cueto et al., 2009). The wind throughout the year presents two
patterns. The first pattern matches to western winds with a frequency of
69% from the northwest, west and southwest directions, mainly in the
months of October to June. The second pattern agrees to easterly winds
with a frequency of 31% from the northeast, east and southeast direc-
tions, mainly in the months of July to September (Chow et al., 2000).
3. Materials and methods
The study consisted in one sampling campaign (May 2014) of water,
soil and plants to determine concentrations of heavy metals. A specific
and directed sampling was made, unique samples of water and soil were
taken for each site. The Reforma channel was considered as a reference
site. Heavy metal concentrations were statistically correlated to identify
their associations (source) in water, soil and plants. The anthropogenic
enrichment was quantified for soil samples and bioconcentration factor
for plants. For concentrations of heavy metals in air, the evaluation was
made with reported data.
3.1. Sample collection and analysis
3.1.1. Water
Fig. 2 shows water sampling sites, two in the Reforma channel and
three from the evaporation pool of CPGF. Water samples were taken,
filtered, acidified and preserved in the field according to the metho-
dology proposed by the U.S. Geological Survey (2006). Analyses of
water samples were done by inductively coupled plasma mass spec-
trometry (ICP-MS) in the Autonomous University of Baja California,
Ensenada, at the laboratory of the Oceanology Research Institute (IIO
for its name in Spanish). The samples were measured 10 times with
calibration curves of standards. All analyses presented errors less than
25%. The average temperature of the water from the Reforma channel
was 22 °C and from the evaporation pool of CPGF was 24 °C.
3.1.2. Soil
Eight sampling sites in the immediate vicinity around of the CPGF
were selected to take soil samples (Fig. 2). At each sampling site, soil
cores of 50 cm length and 5 cm diameter were taken, and sectioned at
the moment of sampling in five subsamples of 10 cm each. After sam-
pling, subsamples were placed in plastic bags at 4 °C awaiting analysis.
172
Geothermics 72 (2018) 170–181
The superficial fraction (sf) of the core corresponded to the subsample
of 0–10 cm depth. The basal fraction (bf) of the core was the subsample
from 30 to 40 cm depth.
For soil analysis, all samples were freeze dried during 72 h
(LABCONCO model 7751020), and milled to obtain particle diameters
less than 2 mm. Analysis of X-ray Fluorescence was carried out with 8 g
of sample, pressed at 10 t during 90 s to produce tablets of 4 cm dia-
meter and 8 mm of thickness. Prepared tablets of soil were analyzed
during 40 min with an equipment of X-ray Fluorescence S8 Tiger from
Bruker, of 3 MW and crystals of XS-5S, PET and LiF200. Analyses were
performed in the Faculty of Metallurgy at the Technological Institute of
Morelia, Mexico. A total of 78 elements can be detected (from Na to U)
in concentrations higher than 2 ppm in solid samples as powders.
To control accuracy, the sample analysis was performed together
with two reference materials of marine sediments (MESS-3 and PACS-
2), prepared and analyzed under same conditions as soil samples.
To analyze chemical results, and calculate enrichment factors, upper
crust concentrations were needed. These concentrations have been
computed worldwide from rock mapping, literature data, calculus of
granulite and mafic xenoliths terrains, etc. (Wedepohl, 1995). They are
a good reference of worldwide basal concentrations.
3.1.3. Plants
Plant samples were taken around CPGF next to the soil coring place,
the number of plant samples collected was according to their presence
in the site. Plants sampled were washed with 0.01 M HCl before freeze
drying. Every plant was cut and separated individually in two: one with
roots and the other with leaves plus stems (named leaves in the rest of
this manuscript). Tablets of plants (roots or leaves) were prepared for
chemical analysis as same as the soil procedure described above. In case
of few sample amounts, boric acid was used as neutral material to give
stability to the tablet and boric acid was measured as a blank in the
analysis. Plant tablets were analyzed during 15 min with the same
equipment as used for soils.
A total of 18 plants of 5 species were sampled. Allenrolfea occi-
dentalis (2 individuals per site), Thypa dominguensis, Phragmites australis,
Distichlis spicata and Tamarix ramosissima (1 individual per site).
To control accuracy, sample analysis was performed together with a
reference material of Tomato Leaves (SRM 1573a), prepared and ana-
lyzed under same conditions as plant samples.
3.1.4. Air
The information was taken from published reports of the General
Direction of Air Quality, Management and Record of Emissions and
Contaminant Transferences of Baja California (RETC for its name in
Spanish). This record is made from the reported air emissions by each
enterprise from Mexicali municipality, and their location can be seen in
Fig. 3 (INE-SEMARNAP R.E.T.C, 1997).
In this work the amount of inorganic compounds released to the
atmosphere by enterprises in Mexicali in 2013 was taken into account.
This year corresponds to a year before the water, soil and plant sam-
pling.
3.2. Data analysis
In water, 16 chemical elements were detected, in soil 25 and in
plants 23. In air, seven chemical elements were considered in this work.
Statistical tools according with the nature of data (normal, parametric)
were applied in order to find any correlation between these chemical
elements from each environmental matrix (water, soil, plant and air).
For elemental concentrations in soil samples, the Pearson's pro-
duct–moment correlation coefficient method was applied using Origin
Version 9.1., considering high correlations values from 0.7 to 1
(Rollingson, 2014). For elemental concentrations in plants and soils, the
statistical method of ANOVA (factorial) was applied to evaluate heavy
metal differences between sampling sites, and plant species among
Z.I. González-Acevedo et al. Geothermics 72 (2018) 170–181

Fig. 2. Location of water and soil sampling sites in

the immediate vicinity of the CPGF, Mexicali Valley,
BC, Mexico. CP- Cerro Prieto; RCh − Reforma
Chanel; EP − Evaporation pool.

sampling site, using Statistica Version 7.0. ANOVA (two ways) was (Cn ) surface ⎤
AF = ⎡
applied to evaluate heavy metal differences between sampling sites. ⎢
⎣ (Cn )basal ⎥ ⎦ (1)
The main criterion to identify the geothermal fingerprint was to
trace the measured elements from the evaporation pool of CPGF in each Where, AF is the anthropogenic factor, Cn is the concentration of the
environmental matrix. This criterion permitted to group chemical ele- chemical element. In our work, the surface sample, agrees to the frac-
ments according to their origin, i.e. geology, agriculture or industry, tion taken at 0–10 cm depth and the sample from the basal zone cor-
reducing the number of chemical elements for discussion. responds to the fraction taken at 30–40 cm depth.
The concentrations of traced chemical elements from geothermal
source were used to estimate four factors to calculate the anthropogenic (Cn/ Cl ) sample ⎤
EF = ⎡
impact. For soil concentrations: anthropogenic factor (AF) (Szefer et al., ⎢ (Cn/ Cl )upper crust ⎥
⎣ ⎦ (2)
1998), enrichment factor (EF) (Hernández et al., 2003), and geoaccu-
mulation index (Igeo) (Müller, 1979). For plant concentrations: bio- Where, EF is the enrichment factor, Cn is the concentration of the
concentration factor (BCF) (Krishnamurti and Naidu, 2003). All factors measured chemical element, and Cl is the concentration of the litho-
were calculated according to the following equations: genic element (Al). To evaluate the soil quality, the following scale was
considered: EF < 2 minimal enrichment, 2 < EF < 5 moderate

Fig. 3. Distance and direction between the industrial

sources indicated by black symbols, annual variation
in wind frequency rose and the CPGF.

173
Z.I. González-Acevedo et al. Geothermics 72 (2018) 170–181

enrichment, 5 < EF < 20 significant enrichment, 20 < EF < 40 very
high enrichment and EF > 40 extremely high enrichment (Barbieri,
2016).
Cn
Igeo = Log2 ⎡ ⎤ Certified materials recoveries were between 89.47–102.61% for major
⎢ (1.5*Cn upper crust) ⎦
⎥
⎣ (3)
Where Igeo is the geoaccumulation index and Cn is the concentration of the
chemical element. To evaluate the soil quality, the following scale was
considered: Igeo≤ 0 uncontaminated, 0 < Igeo < 1 uncontaminated to
moderately contaminated, 1 < Igeo < 2 moderately contaminated,
2 < Igeo < 3 moderately to heavily contaminated, 3 < Igeo < 4
heavily contaminated, 4 < Igeo < 5 heavily to extremely contaminated,
Igeo ≥ 5 extremely contaminated (Barbieri, 2016).
(Cn ) vegetation ⎤
BCF = ⎡
⎢
⎣ (Cn ) soil ⎥ ⎦ (4)
Where BCF is the bioconcentration factor and Cn is the concentration of
the chemical element. This factor was calculated for leaves and roots from
plants. The soil concentration corresponds to the site were the plant was
sampled.
4. Results
Heavy metal measured concentrations in water, soil and plants are
presented in order of abundance in the area of CPGF, while in air, are
shown reported chemicals released to the atmosphere.
4.1. Water
Table 1 shows concentrations of measured chemical elements in
water samples. In the evaporation pool of CPGF, measured elements in
order of major concentrations were: Na > K > Ca > Fe > As > Se >
Sb > Zn > Mo > Cd > Ti > Cu > Cr > V > Pb > Co. In the Reforma
channel, measured elements in order of major abundance were: Na >
Ca > Mg > K > Fe > Zn > Cd > Ti > Sb > Cu > Mo > As > Se >
Cr > V > Pb > Co.
Comparing our values with guidelines proposed by USEPA and the
Mexican guidelines, we observe that As is above those guidelines for
fresh and saltwater. In the case of Se, concentrations in the evaporation
pool of the CPGF exceeded recommended concentrations for
Freshwater.
Relating concentrations of Ti and Zn from the Reforma channel with
the evaporation pool of the CPGF resulted that higher concentrations
were found in the Reforma channel. This result demonstrates that Ti
and Zn are not from geothermal origin; their source can be either from
agricultural activities, natural geology or other industries. In contrast,
As, Ca, K, Mo, Na, Sb and Se are more concentrated in the evaporation
pool of the CPGF than in the Reforma channel; therefore, these ele-
ments indicate the geothermal fingerprint of the zone.
4.2. Soil
Detected elements in soil samples were 25 (Al, As, Ca, Cl, Co, Cr, Cu,
Fe, K, Mg, Mn, Mo, Na, Ni, P, Pb, S, Si, Sb, Sn, Sr, Ti, U, V and Zn).
elements and 83.33–109.09% for trace elements. After applying sta-
tistical analysis of Pearsońs correlation, elements that correlated posi-
tively (Table SM1) and negatively (Table SM2) in more than 0.7, were
considered to make a one-way analysis of variance to identify sig-
nificant differences between sampling sites. Chemical elements with
significant differences (P ≤ 0.05) were: As, Ca, Cl, Co, Cr, K, Mn, Mo,
Na, S, Sb, V and Zn. These elements were selected for discussion.
The concentration of major and trace chemical elements measured
in soil samples are presented in Table 2A and B respectively. To cal-
culate AF, EF and Igeo (equations 1- 3), in both tables are included
concentrations of surface and basal fractions (0–10 cm, 30–40 cm
depth), concentrations of Al (lithogenic element), and element con-
centrations in the upper crust reported by Wedepohl (1995).
Table 2A and B show that in the surface (0–10 cm), the average
abundance of major elements was: Al > Ca > K > Na > Cl > S
(6.79 > 5.22 > 2.14 > 1.49 > 0.90 > 0.39%w), while the
average abundance of trace elements was: Mn > Zn > V > Cr > Co >
Sb > As > Mo (587.13 > 99.13 > 84.50 > 63.75 > 14.88 >
8.63 > 8.38 > 2.50 ppm). These tables also show in the basal frac-
tion (−35 cm), that the average abundance of major elements was:
Al > Ca > K > Na > Cl > S (8.94 > 6.32 > 2.94 > 1.49 > 0.7 >
0.35%w), while the average abundance of trace elements was: Mn >
V > Zn > Cr > Sb > Co > As > Mo (627.25 > 106.00 > 103.25 >
75.13 > 34.13 > 20.63 > 8.88 > 6.13 ppm).
In general, concentrations of Mn, Zn and V were in the order of
thousands and hundreds mg kg−1; As, Co, Cr and Sb were in the order
of tenths mg kg−1, and Mo was found to be concentrated less than
10 ppm. In Table 2, are concentration levels regulated by the govern-
ment of Australia for soil with recreational purposes (NEPC, 2011),
Denmark as intervention value for soil remediation (MHSPE, 2000) and
UK for ecological investigation (DEC, 2010). Relating our values with
those guidelines, we observe: For ecological investigation Mn, S and V
exceed the recommended value by UK. For recreational purposes, none
element exceed the recommended value by Australia. For soil re-
mediation intervention, none element exceed the recommended value
by Denmark.
Concentrations of Na, Cl and Co; all three elements are more con-
centrated in sites CP5 and CP7. These sites are located in a superficial
hydrothermal activity associated with the Morelia fault (CP5) and in an
agricultural zone (CP7).
In case of Cl, it was less concentrated in CP1 and CP2 from the
Reforma channel, as well as in CP4 and CP6 from agricultural drains.
The distribution of Na and Co in the area is less concentrated in sites
CP6, CP4 and CP3 from agriculture activities.
Concentrations of Cr, V and Mn in the Reforma channel (CP1 and

Table 1
Concentrations of chemical major and trace elements dissolved in water samples around the CPGF. RCH: Reforma channel; EP: Evaporation pool of the CPGF. EPA Freshwater and
Saltwater are the guidelines provided by USEPA to preserve aquatic life (USEPA, 2017). NOM 001 is the Mexican regulation for water discharges in federal water bodies (NOM-001-ECOL-
1996). nd: not detected; nr: not reported.

Sampling Site Major Element (mg L−1) Trace Element (μg L−1)

Ca Fe K Mg Na As Cd Co Cr Cu Mo Pb Sb Se Ti V Zn

RCh 1 75 0.008 34.08 40 188 1.27 10 0.14 0.29 2.9 3.2 0.23 5.9 0.7 10 0.24 46.34
RCh 2 75 0.003 33.76 40 198 1.24 10 0.12 0.31 3.9 3.25 0.21 5.91 0.6 4.86 0.23 23.35
EP1 1350 0.069 2436 nd 13394 628 9.2 0.11 0.43 2.4 9.06 0.2 11.9 22.5 5.9 0.23 9.74
EP2 1025 0.058 2387 nd 14158 636 3.3 0.12 0.34 1.3 8.42 0.19 11.9 24.3 3.8 0.28 7.46
EP3 850 0.045 1694 nd 7641 656 10.8 0.11 0.33 5.9 8.57 0.2 12.2 23.9 4.0 0.25 14.22
NOM 001 nr nr nr nr nr 200 200 nr 1000 6000 nr 400 nr nr nr nr 20000
EPA Freshwater nr nr nr nr nr 360 3.7 nr 15 17 nr 65 nr 20 nr nr 110
EPA Saltwater nr nr nr nr nr 69 42 nr 1100 2.4 nr 210 nr 290 nr nr 90

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Z.I. González-Acevedo et al. Geothermics 72 (2018) 170–181

Table 2
Concentrations of major elements (A) in% by weight, and trace elements (B) in mg kg−1 in soil samples around the CPGF. Sf: surface fraction (0–10 cm depth); Bf: basal fraction
(30–40 cm depth). Sampling sites shown in Fig. 2; nd: not determined, SQI: Soil quality index, nr: not reported.

A)

Sampling site Major Element (%w)

Al Ca Cl K Na S

Sf Bf Sf Bf Sf Bf Sf Bf Sf Bf Sf Bf

CP1 10.57 11.3 8 6.78 0.2 0.4 3.05 3.26 0.9 1.03 0.44 0.54
CP2 9.93 6.23 6.54 3.48 0.1 0.1 2.87 2.49 0.69 0.85 0.28 0.1
CP3 11.54 11.82 6.42 6.39 0.4 0.6 3.19 3.16 0.76 0.89 0.57 0.65
CP4 nd 8.71 nd 4.73 nd 1.3 nd 3.45 nd 2.15 nd 0.32
CP5 6.65 6.9 5.54 5.28 1.1 1.1 2.36 2.36 1.92 1.95 0.35 0.37
CP6 nd 9.95 nd 6.23 nd 0.2 nd 3.08 nd 0.81 nd 0.41
CP7 6.19 6.72 8.63 9.23 0.6 0.8 2.43 2.52 1.31 1.93 1.16 0.28
CP8 9.46 9.88 6.63 8.45 4.8 1.7 3.18 3.2 6.31 2.3 0.33 0.15
Upper crust 7.744 2.645 0.064 2.865 2.567 0.0953
SQI-Australia nr nr nr nr nr nr
SQI-Denmark nr nr nr nr nr nr
SQI-UK nr nr nr nr nr 0.06

B)

Sampling site Trace element (mg kg−1)

As Co Cr Mn Mo Sb V Zn

Sf Bf Sf Bf Sf Bf Sf Bf Sf Bf Sf Bf Sf Bf Sf Bf

CP1 13 13 19 18 81 78 848 812 4 3 21 4 140 154 126 133

CP2 15 9 17 23 98 80 1328 289 3 6 0 35 131 57 247 55
CP3 16 14 15 15 85 80 1013 10- 3 7 7 38 161 163 189 188
44
CP4 nd 11 nd 22 nd 76 nd 488 nd 6 nd 28 nd 80 nd 80
CP5 6 4 24 23 83 70 397 400 4 7 4 41 57 59 52 55
CP6 nd 6 nd 21 nd 74 nd 592 nd 7 nd 46 nd 111 nd 95
CP7 8 5 24 24 86 63 522 617 3 7 16 46 68 84 81 99
CP8 9 9 20 19 77 80 589 776 3 6 21 35 119 140 98 121
Upper crust 2 11.6 35 527 1.4 0.31 53 52
SQI-Australia 300 300 240 9000 nr nr nr 30000
SQI-Denmark 55 240 380 nr 200 15 nr 720
SQI-UK 20 50 1(VI), 500 40 nr 50 200
400(III)

CP2) as well as CP3, show concentrations of 97.9, 161 and 1327 ppm,
respectively. In contrast, samples taken in CP4 and CP6 had lower
concentrations (Cr 40.1, V 47.5 and Mn 333.4 ppm). In CP5 where
geothermal activity is promoted by the Morelia fault, Cr was around
75 ppm. In CP4 and CP6, V and Mn presented similar concentrations.
For CP7 which belongs to agricultural fields, Cr is more concentrated
than V and Mn.
According to Barbieri (2016), EF > 40 shows an extremely high
enrichment, being the case of Sb and Cl, and 5 < EF < 20 shows a
significant enrichment, being the case of S. However, the AF in Table 3
shows an enrichment of Sb of 5.25 times, for Cl 2.82 and for S 4.14
times. For this factor, there are no classification of soil quality. But, the
fact to use the concentration of the same element in the same soil
profile from a deeper depth (considered as basal concentration), shows
that regionally, the enrichment is not equally high as EF calculations
indicate. When we look at the Igeo in Table 3, for the case of Sb and Cl,
resulted 5.49 and 5.64 times enriched respectively, and both agree to
extremely contaminated soil, while for S, Igeo is 3.01 which agrees to a
moderately contaminated soil.
4.3. Plants
Detected elements in leaves and roots of five species of plants
sampled around CPGF, were 23 (Al, Br, Ca, Cl, Cr, Cu, Fe, K, Mg, Mn,
Mo, Na, Ni, P, Pd, Rb, Ru, S, Si, Se, Sr, Ti, Zn) (Table 4A and B).
Reference material recoveries were between 63.42–200.02%, in con-
sequence, these results should be considered semi quantitative, showing
tendencies and not real concentrations. The blank (boric acid) pre-
sented traces of Cl, Cu, Fe, Na, Ni, Ru, S and Si, which were substracted
from the results of plant tablets made with boric acid. Statistical dif-
ferences between plant species (factorial ANOVA, P < 0.05) were
found in concentrations of Cl (ranging from 0.36 ppm of Thypa dom-
inguensis to 5.16 ppm in leaves of Allenrolfea occidentalis), Na (ranging
from 0.06 ppm in leaves of Praghmites australis to 8.81 ppm in leaves of
A. occidentalis) and Si (ranging from 0.04 ppm in leaves of A. occi-
dentalis to 3.42 ppm in roots of P. australis).
Two of trace elements found in plants were Pd and Ru. These two
elements belong to the platinum group and kept our attention, due to
their presence was not expected. Pd in leaves, was only found in A.
occidentalis sampled in CP4 (20 ppm) and CP8 (13 ppm) from agri-
cultural zones. In contrast, Pd in roots was found in all species of
sampled plants (Table 4B). Palladium concentrations were between
12–21 ppm in sampling sites CP1, CP3, CP5 and CP7. Concentrations of
Ru were found in leaves and roots from four species of sampled plants,
except for Ditschilis spicata which did not show Ru in its roots. This
element was distributed in the sampling area close to Reforma channel
(CP1, CP2 and CP3) with a concentration range of 10 ppm in roots of T.
dominguensis (CP1) to 19 ppm in roots of A. occidentalis and leaves of T.
ramosissima (Table 4B).
Differences in the number of replicates between sampled sites

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Z.I. González-Acevedo et al. Geothermics 72 (2018) 170–181

Table 3
Anthropogenic factor (AF), enrichment factor (EF), and geoaccumulation index (Igeo) of chemical elements from soil samples around the CPGF. The three top ranked maxima are
boldfaced.

Chemical Element Anthropogenic Factor Enrichment Factor Soil Quality Geoaccumulation Index Soil Quality

Max Min Median Max Min Median Max Min Median

As 1.67 1.00 1.32 5.85 3.49 4.88 ModE 2.41 1.00 1.85 ModC
Ca 1.88 0.78 0.73 4.08 1.63 2.14 ModE 1.12 0.48 0.73 ModC
Cl 2.82 0.86 0.50 61.4 1.22 7.96 SigE 5.64 0.06 2.35 HC
Co 1.06 0.74 1.02 2.59 0.87 1.31 MinE 0.12 −5.64 −2.64 UnC
Cr 1.37 0.96 1.13 3.07 1.63 1.99 MinE 0.90 0.55 0.68 ModC
K 1.15 0.94 1.00 1.06 0.75 0.85 MinE −0.43 −0.86 −0.53 UnC
Mn 4.6 0.76 0.98 1.97 0.88 1.21 MinE 0.75 −1.00 −0.16 UnC
Mo 1.33 0.43 0.50 3.33 1.44 1.92 MinE 0.93 0.52 0.52 ModC
Na 2.74 0.68 0.86 2.01 0.20 0.45 MinE 0.71 −2.47 −1.84 UnC
S 4.14 0.81 1.58 15.23 2.29 3.67 ModE 3.01 0.67 1.46 ModC
Sb 5.25 0.00 0.27 64.57 0.00 32.39 ExtHE 5.49 0.00 4.51 ExC
V 2.3 0.81 0.94 2.04 1.25 1.89 MinE 1.02 −0.47 0.65 ModC
Zn 4.49 0.81 0.95 3.70 1.16 1.87 MinE 1.66 −0.57 0.51 ModC

*MinE −minimal enrichment, ModE − moderate enrichment, SigE − significant enrichment, ExtHE −extremely high enrichment. UnC −uncontaminated, ModC −moderately con-
taminated, HC − heavily contaminated, ExC − extremely contaminated (Barbieri, 2016).

emphasized that A. occidentalis had the highest accessibility among
plant species. After statistical analyses (two way-ANOVA, P < 0.05) of
chemical elements in leaves and roots of A. occidentalis between sam-
pling sites, only Na and S presented significant differences (Table 5A
and B). The highest concentration of Na was found in leaves of plants
sampled at CP5 and CP4. These sampling sites are related to the in-
fluence of the Morelia fault. Other site with high Na concentration was
CP8 where agricultural activities are carried out. In contrast, the lowest
Na concentrations was presented in the Reforma channel (CP1)
(Table 5A).
According to results of concentrations, S in leaves and roots pre-
sented statistical differences between all sampling sites (Table 5A). In
the Morelia fault influenced area, the highest S concentrations in leaves
(CP4) and roots (CP5) were detected. Lowest concentrations of S were
found in leaves of sampled plants in site CP5 (0.16 ppm), and in roots
from CP8 (0.07 ppm).
Due to high concentrations of Ca, Cl, K, Mn, Mo and Zn in soil, these
elements were taken into account for plants, in order to relate them
with their biogeochemical role in the area and for discussion.
4.4. Air
According to the reports published by the RETC, Table 6 presents
the volume of inorganic compounds released to the atmosphere in
2013. This table, shows that the only source of H2S is the CPGF.
Sources classification depends on the process type. Emissions in-
ventory of 2013 reflects variability in the gas dispersion released to the
atmosphere. Most significant inorganic compounds in order of magni-
tude were CO2 ˃ H2S ˃ NO2. Emissions of CO2 represent the major
amount of gases released in the zone, the main source are thermic
centrals which produce electrical energy from fossil fuels. Other re-
leased emissions are distributed in different industries (Table 6) located
within Mexicali Valley (Fig. 3).
Associated to anthropogenic activities, NO2 is considered as quality
air indicator. This indicator is produced as consequence of electricity
production from fossil fuels.
5. Discussion
The aim of the study was to correlate heavy metal concentrations in
water, soil, plants and air to identify possible origin and quantify an-
thropogenic enrichment. The discussion is focused on the identification
of enriched metals in soils and plants from the geothermal fingerprint
presented in water and air. Subsequently, results made evident the
enrichment of metals from other natural and anthropogenic sources.
5.1. Elements of geothermal origin
Table 3 shows maximum, minimum and median values of AF, EF
and Igeo for each element in the soil samples. The maximum enrichment
in the zone was Sb with 64.57 times, followed by Cl (61.40) and S
(15.23). These three elements, according to water and soil analyses, are
from geothermal origin, and although the factors (EF and Igeo) show
high enrichment in soil samples, concentrations of Sb are in the order of
tenths μg L−1 in water and mg kg−1 in soil. This magnitude of con-
centration is very low compared with contaminated areas that normally
present hundreds or even thousands of ppm in water or soil (He, 2007).
Indeed, Sb is more concentrated in bottom layers than on the surface,
which makes it unavailable unless boring is made, decreasing its
availability. The presence of Sb in bottom layers might be an indicator
of older processes involving Sb enrichment in the zone, because the
average sedimentation rate has been reported as circa 1 cm year−1
(Lugo-Ibarra et al., 2011). Based on this rate, our basal fraction would
match years 1974–1984, corresponding to the beginning of CPGF
(1973). Therefore, this result questions if the zone was naturally en-
riched with Sb, before the geothermal power plant started producing
electricity?
The AF represents the magnitude of the anthropogenic element
input, comparing surface and bottom concentrations in the same sam-
pling site. Then, if we compare factor values for Cl from the EF (61.4)
and the AF (2.82), an important decrement is evident. This decrement
suggests that natural regional concentrations of Cl are higher than soil
concentrations in the world (upper crust average) (Wedepohl, 1995). In
the case of the Igeo for Cl was 5.64, this value is closer to the AF, in-
dicating moderately contamination of Cl in the zone, being evidence of
natural regional enrichment too. These results are not surprising, since
Truesdell et al. (1981) evaluated the origin of geothermal fluids in the
CPGF, finding that the fluids are a mixture of Colorado River water and
a saline brine of seawater. Besides, Armienta et al. (2014) mentioned
that groundwater quality was compromised by high Cl concentrations,
from Colorado River waters. These results make evident, the im-
portance to calculate soil enrichment on a regional base and not only on
a global base to determine if the soil is contaminated or not. As con-
sequence, Na is an element expected to be in the form of NaCl dissolved
in water. Observing in Table 6 the AF for Na (2.74), it is similar to the
AF for Cl (2.82), suggesting that both are together in soil samples.
According to the EF and Igeo, this relationship is not evident, because is
based on global average concentrations.
Lower enrichments were found for As, Ca, K, Mo and Se identified
from geothermal origin. In plants, As was below detection limit
(< 2 ppm). In soils, it was detected in a rate of 4–16 ppm. The

176
 Table 4
Concentrations of major elements in% of weight (A) and trace elements in mg kg−1 (B) in plants around CPGF. l: leaves and stems, r: roots, zero values mean the element was below detection limits (2 ppm). SD: standard deviation, (n = 2,
P ≤ 0.05).

A)

Plant Species Sampling site Major element (%w)

Z.I. González-Acevedo et al.

Al Ca Cl K Mg Na P S Si

l r l r l r l r l r l r l r l r l r

Allenrolfea CP1 0.03 0.04 0.81 0.18 2.73 2.91 1.25 0.98 0.33 0.2 3.25 2.68 0.06 0.05 0.41 0.09 0.1 0.16
occidentalis
SD ± 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
CP2 0.02 0.03 0.91 0.27 3.51 2.74 1.31 0.99 0.28 0.36 4.34 2.82 0.05 0.15 0.46 0.15 0.07 0.14
SD ± 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
CP3 0.25 0.17 2.06 0.78 4.35 0.83 1.27 0.65 1.43 0.27 3.95 0.91 0.38 0.07 0.38 0.25 0.72 0.39
SD ± 0.10 0.00 0.70 0.30 0.98 0.09 0.92 0.02 0.49 0.08 0.80 0.24 0.10 0.00 0.07 0.04 0.27 0.04
CP4 0.07 0.03 0.66 0.15 3.03 2.54 1.34 1.02 0.27 0.23 4.33 2.46 0.09 0.09 0.67 0.16 0.21 0.12
SD ± 0.02 0.00 0.20 0.08 0.48 0.57 0.07 0.17 0.01 0.07 0.04 0.84 0.00 0.02 0.11 0.04 0.03 0.04
CP5 0.01 0.02 0.22 0.12 2.62 0.97 0.77 0.62 0.34 0.23 8.61 3.74 0.09 0.08 0.16 0.45 0.04 0.07
SD ± 0.00 0.00 0.03 0.05 0.56 0.04 0.04 0.16 0.02 0.04 1.03 0.32 0.00 0.00 0.04 0.12 0.00 0.00
CP8 0.12 0.04 1.12 0.25 5.16 1.70 0.57 0.48 0.46 0.25 7.68 1.65 0.1 0.06 0.32 0.07 0.41 0.14
SD ± 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Thypa dominguensis CP1 0.02 0.05 0.13 0.17 0.36 1.93 0.77 1.09 0.06 0.14 1.08 1.05 0.08 0.2 0.12 0.07 0.05 0.12
CP6 0.03 0.41 0.32 0.84 1.37 7.25 1.01 0.83 0.17 0.57 2.13 7.25 0.07 0.16 0.17 0.33 0.08 1.6
Phragmites australis CP1 0.04 0.05 0.28 0.05 0.28 0.78 0.24 0.22 0.06 0.07 0.06 0.65 0.04 0.08 0.23 0.09 3.42 0.4
CP8 0.02 0.02 0.16 0.04 0.14 1.24 0.69 1.29 0.08 0.04 0.20 1.44 0.08 0.09 0.15 0.07 0.88 0.24
Distichlis spicata CP5 0.04 0.05 0.21 0.1 1.00 1.46 0.7 0.47 0.1 0.16 0.89 1.53 0.11 0.09 0.21 0.15 2.1 0.26

177
Tamarix ramosissima CP7 0.11 0.08 0.82 0.3 1.48 0.35 0.63 0.22 0.55 0.21 2.37 0.31 0.09 0.1 1.25 0.57 0.36 0.03

B)

Plant Species Sampling site Trace element (mg kg−1)

Br Cr Cu Fe Mn Mo Ni Pd Rb Ru Se Sr Ti Zn

l r l r l r l r l r l r l r l r l r l r l r l r l r l r

A. occidentalis CP1 92 62 0 0 9 9 97 79 13 8 11 15 0 0 0 0 11 18 11 18 0 0 24 10 14 11 6 8
SD ± 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
CP2 200 100 0 0 9 8 100 71 0 18 14 10 5 0 0 0 18 15 18 15 0 0 60 16 0 10 13 15
SD ± 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
CP3 200 18 0 0 17 11 80 50 64 37 0 11 6 4 0 0 0 0 11 19 0 0 100 47 91 44 53 38
SD ± 0.57 1.41 0.00 0.00 3.40 1.70 0.00 0.00 5.65 2.30 0.00 2.16 0.00 0.00 0.00 0.00 0.00 0.00 4.82 3.78 0.00 0.00 35.36 0.00 35.98 10.60 0.70 6.65
CP4 0 76 0 0 10 12 200 69 22 11 15 13 0 4 20 0 18 17 18 17 6 0 32 10 28 9 14 8
SD ± 0.00 22.6 0.00 0.00 2.12 3.53 0.00 0.04 1.41 1.41 2.82 2.82 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 9.89 0.00 4.94 0.00 0.00 1.41
CP5 100 20 0 0 10 9 55 57 0 0 15 10 0 0 0 0 0 0 16 0 0 0 10 5 0 0 22 11
SD ± 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.04 0.00 0.00 1.41 2.82 0.00 0.00 0.00 0.00 0.00 0.00 1.41 0.00 0.00 0.00 4.90 0.00 0.00 0.00 4.24 0.00
CP8 200 29 0 0 12 11 400 100 53 14 0 11 0 3 13 0 0 0 0 0 0 0 76 24 64 21 15 12
SD ± 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
T. dominguensis CP1 7 24 0 0 5 8 69 200 66 26 10 11 3 0 0 16 0 0 17 10 0 0 3 10 8 36 7 24
CP6 22 80 0 0 8 11 100 130 24 55 11 0 4 8 0 0 10 0 14 22 0 0 20 76 0 200 7 16
P. australis CP1 9 9 0 0 9 7 100 100 61 0 10 8 5 0 0 12 0 0 15 16 0 0 15 2 13 12 7 10
CP8 4 12 0 0 0 7 98 100 50 5 9 9 0 0 0 0 0 0 12 0 0 0 3 0 7 0 8 11
D. spicata CP5 28 24 0 0 7 8 100 100 16 4 12 10 0 3 0 21 0 0 17 0 0 0 7 3 15 17 13 13
T. ramosissima CP7 100 4 7 0 11 7 40 32 32 4 13 9 4 3 0 0 0 0 16 13 9 0 68 21 54 0 50 13
Geothermics 72 (2018) 170–181
 Z.I. González-Acevedo et al.

Table 5
Concentrations of major elements (A) in% by weight, and trace elements (B) in mg kg−1 in Allenrolfea occidentalis around the CPGF. Different letters indicate significant differences among sampling sites (Two way-ANOVA and Tukey a posteriori test,
n=2, P ≤ 0.05: a > b > c).

A)

Sampling site Major element (%w)

Ca Cl K Na S

leaves roots leaves roots leaves roots leaves roots leaves roots

abc abc ab
CP1 0.81 0.18 2.73 2.91 1.25 0.98 3.57 2.68 0.41 0.09b
CP2 0.91 0.27 3.51 2.74 1.31 0.99 4.34abc 2.82abc 0.46ab 0.15b
CP3 2.06 0.78 4.35 0.83 1.27 0.65 3.95abc 0.91c 0.38ab 0.25b
CP4 0.66 0.15 3.03 2.54 1.34 1.02 4.33ab 2.46bc 0.67a 0.16b
CP5 0.22 0.12 2.62 0.97 0.77 0.62 8.61a 3.74abc 0.16ab 0.45ab

178
CP8 1.12 0.25 5.16 1.70 0.57 0.48 7.68ab 1.65c 0.32ab 0.07b

B)

Sampling site Trace element (mg kg−1)

Mn Mo Zn

leaves roots leaves roots leaves roots

CP1 13 8 11 15 6 8
CP2 bdl 18 14 10 13 15
CP3 64 37 bdl 11 53 38
CP4 22 11 15 13 14 8
CP5 bdl bdl 15 10 22 11
CP8 53 14 0 11 15 12
Geothermics 72 (2018) 170–181
Z.I. González-Acevedo et al. Geothermics 72 (2018) 170–181

Table 6
Inorganic compounds released to the atmosphere in the region of the CPGF in 2013. n: number of industries; nr: not reported (INE-SEMARNAP R.E.T.C, 1997).

Industrial sector n Inorganic compounds in 2013 (ton year−1)

H2S CO2 NO2 As Cr Ni Pb

Geothermal Energy 1 7.13E + 03 2.66E + 05 nr nr nr nr nr

Generation of Electrical Energy 4 nr 3.66E + 06 2.79E + 02 2.82E-03 1.98E-02 2.96E-02 7.06E-03
Automotive 1 nr 3.01E + 03 13.80 1.90E-05 2.60E-05 4.70E-05 1.10E-05
Cellulose and paper 1 nr 6.94E + 04 nr nr 6.36E-04 2.08E-03 nr
Metallurgy, including steelworks 5 nr 2.73E + 04 nr 5.49E-07 4.00E-06 6.00E-06 3.00E-06
Oil and petrochemicals 1 nr 19.22 nr nr nr nr nr
Chemistry 3 nr 10.42 nr nr 5.30E-07 3.74E-06 nr
Glass 1 nr 2.86E + 04 nr nr nr nr nr

concentrations are low compared with other geothermal sites in Mexico 5-fold higher concentration in the former. This suggests that the source
as Los Humeros (162 ppm). This reported concentration of As is from of S is coming from air and stays in aerial parts of A. occidentalis. These
volcanic rocks of the geothermal reservoir from Los Humeros. In the results are in agreement with what Mutia et al. (2016) found in leaves
case of the CPGF which is hosted in sedimentary rocks, As concentra- of plants from the geothermal area of Olkaria in Kenya.
tions have been reported between 0.003–2 ppm (Bunschuh and Maity, Site CP 5 is affected by Morelia Fault showing surface hydrothermal
2015). The average AF was 1.32 times, establishing an enrichment in water. This could explain why in this site S is more concentrated in
the zone. Since this metalloid has been used as pesticide in agricultural roots. Here, the main origin of S would be the hydrothermal water and
activities of the area (Daesslé et al., 2009). Due to this facts, this en- not the air.
richment claims to be from geothermal and agricultural origin. Mexican regulation does not set limits for H2S emissions from a
Moreover, Se was not detected neither in plants nor in soil samples, fixed source and industries are not required to monitor nor report such
and this was unexpected since Se concentrations present in the emissions. Since the CPGF is the only industry that reports H2S emis-
Colorado River waters have been reported in previous studies sions in the area, the presence of this gas has historically been asso-
(Osmundson et al., 2000; Walters et al., 2015). This element has been ciated with geothermoelectric activity. However, H2S can be released
found in birds from Mexicali Valley (Mora and Anderson, 1995), in from other industries present in the area, including sewage water
breeding bird eggs from Colorado river Delta (García-Hernández et al., treatment, paper mills, production of S compounds and heavy water
2006), at levels that could cause slight reduction in avian reproductive (Quintero and Sweedler, 2005).
success, similar to the effects found at Salton Sea (García-Hernández No high enrichment of Mo was observed in soil samples; BCF values
et al., 2013). In addition, Desert Pupfish (Cyprinodon macularius) that were higher in leaves than in roots, suggesting that the source of Mo is
lives in the evaporation pool of CPGF, showed enrichment of Se 81 from air. In this area, there are no reported emissions of Mo to the
times above maximum allowable limits for consumption (Flores-Galván atmosphere. Besides geothermoelectric, the metal mechanic industry is
et al., 2017). This may indicate that Se is more mobile in its biogeo- a known source of Mo emissions (Davis, 2004). There are five such
chemical cycle since it has been detected as part of the food chain along companies within a 40 km radius from CPGF (Fig. 3) which could be
time. contributing to Mo presence in the area.
For Ca, K are considered as nutrients for plants; therefore, it is not
surprising finding these elements concentrated in leaves and roots. The
plant A. occidentalis around CPGF is a halophyte, characterized to resist 5.2. Elements of other natural and anthropogenic origin
great amounts of salts in soil and water (Flowers and Colmer, 2008). In
this study, A. occidentalis had Ca, Cl and Na more concentrated in According to AF, after Sb, Mn and Zn were the second and third
leaves, which was expected from its nature. It is important to mention elements more enriched around CPGF. Observing Table 2B, con-
that concentrations of Na and Cl were higher in plants (leaves or roots) centrations of Mn and Zn are similar in both fractions (surface and
than in the surface fraction of the soil, and this phenomenon was also basal), except for CP2 where the surface fraction was more con-
seen for S and Mo. centrated. Site CP2 belongs to Reforma channel, therefore, this result
Sulfur (S) is found naturally, where it is involved in enzymatic re- indicates another source than geothermal. Previous studies have re-
actions (Takahashi et al., 1997). Sulfur can form deposits on leaves as ported possible release of Mn and Zn in the zone, associated to agri-
part of the biogeochemical cycle. Our results show that in all but one cultural and industrial activities (Shumilin et al., 2002). The BCF
site (CP5), the BCF was higher in leaves than in roots (Table 7), with a (Table 7) showed low values for both chemical elements, while
Table 4B showed higher concentrations in leaves than roots in both
Table 7 cases. In plants from CP5, Mn was not detected, in soil (Table 2B) it was
Bioconcentration factor of chemical elements in Allenrolfea occidentalis around the CPGF. present in similar concentrations in both fractions (surface and basal).
Concentrations of Mn in soil samples were in the order of hundreds and
Element Bioconcentration Factor Bioconcentration Factor thousands ppm for all sites, with great differences in CP2.
Leaves Roots
Concentrations of V in soils are similar to Zn in magnitude and
concordance with superficial enrichment in CP2. Both chemical ele-
Max Min Median Max Min Median ments in soils were found in order of hundreds and the AF showed more
enrichment of Zn (4.49) than V (2.23). The BCF showed very low values
Ca 0.16 0.04 0.11 0.08 0.02 0.04
Cl 35.1 0.87 8.32 27.4 0.27 3.14
for Zn (0.05 in leaves and 0.06 in roots) with not significant differences
K 0.47 0.22 0.41 0.34 0.15 0.32 between them. Both Zn and V in plants have been associated with fossil
Mn bdl 0.05 0.02 0.03 0.01 0.01 fuels together with Pb (Morawska and Zhang, 2002). Positive statistical
Mo 4.67 1.33 2.78 3.67 3.00 3.34 correlation of 0.97 was determined for Pb and Zn (Table SM1), but not
Na 6.29 1.01 4.02 4.09 0.19 2.23
correlation higher than 0.7 was found for Pb and V. However, Pb pre-
S 1.64 0.02 0.06 0.06 0.01 0.01
Zn 0.05 0.37 0.13 0.06 0.21 0.09 sented high statistical correlations with Cu (0.94), P (0.81), Ni (0.79),
Fe (0.75) and Cr (0.74). These chemical elements have been reported to

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Z.I. González-Acevedo et al.
be from agricultural sources (Watson and Chow, 2001). Moreover, Pb is
released to the atmosphere from generation of electricity by fossil fuels,
automotive and metallurgy industrial sectors (Table 6). Therefore, Pb
can be from different sources in the zone. Another source of Pb that
cannot be overlooked is gasoline, knowing that Mexicali is one of the
most air polluted city in the world because of vehicular sources
(Quintero and Sweedler, 2005). It is documented that car catalyzers
emit traces of Pd and Ru (Djingova et al., 2003). In this work, Ru was
more concentrated in leaves and roots of the northwestern part of the
zone (CP1, CP2 and CP3), while Pd was more concentrated in leaves
from CP4 and CP7 and roots of CP3. These results show that even
though both elements (Ru, Pd) may come from the same source, its
distribution is different, perhaps associated to its natural characteristics
or the phase in which the element is transported.
In air, Cr and Ni are elements released to the atmosphere from the
same industrial sectors (Table 6). In plants, Cr was detected only in
leaves of T. ramosissima and Ni was detected at very low concentrations
(3–6 ppm) (Table 4B). In soils, Cr showed not significant differences
between superficial and basal fractions, suggesting that its enrichment
is natural in the zone, being minimal enriched compare to the upper
crust concentrations (EF) (Table 3). Finally, Co was negative correlated
with most of measured elements as shown in table SM2. This element is
particularly interesting to investigate in order to understand its bio-
geochemical cycle in the zone, because it seems to be opposite from the
other chemical elements around the CPGF.
The presence of NO2 in the atmosphere promotes the formation of
other pollutants as ozone, suspended particles, etc. (Moon, 2001) Ac-
cording to Table 6, NO2 in Mexicali is released mainly from the gen-
eration of electrical energy by fossil fuels, and the automotive sector.
These sources could be a precursor in the transport of pollutants as
suspended particles.
6. Conclusions and recommendations
This work, permitted the identification of elements in water and air
from geothermal origin. Those elements (As, Ca, K, Mo, Na, Sb and Se)
were considered as the fingerprint of geothermal power generation
activity in the CPGF. This fingerprint was statistical correlated in soil
and plant samples from the immediate vicinity of the CPGF.
According to EF, Igeo and AF, a natural regional enrichment of Cl, Na
and Sb was identified. For S concentrations, there was found a sig-
nificant enrichment in plants. Meanwhile, the soil was moderately
contaminated with S concentrations. The origin of S in the zone is
mainly from the CPGF air emissions as H2S, although, it is widely used
as fertilizer direct on the soil. Therefore soil AF of 4.14 times, was at-
tributed to agricultural and geothermal activities. The BCF of S in
Allenrolfea occidentalis was higher in leaves plus stems, than in roots,
showing that the origin of S in plants, comes mainly from the atmo-
sphere and not from the soil or water.
Soil from irrigation channels in the vicinity of the CPGF presented
AF of 4.5 times in average of Mn and Zn. Since those elements are not of
geothermal origin, their enrichment indicates other sources associated
to agricultural and/or industrial activities. Other elements enriched in
soil were V and Pb, elements that normally are associated with fossil
fuels sources.
Concentrations of Pd and Ru in leaves were higher than in roots,
attributed to vehicular sources from Mexicali city. The element negative
correlated with most of measured elements was Co, making it inter-
esting to investigate in future works.
Even though in this work only eight sampling sites were measured,
the results show strong evidence of anthropogenic impact from other
sources rather than the geothermal power plant of Cerro Prieto. These
findings motivate us to propose a broader sampling plan with a re-
ference site far enough from the influenced area. This study will allow
to determine spatial distributions of heavy metals around their poten-
tial sources.
180
Geothermics 72 (2018) 170–181
Acknowledgements
Authors like to thank the Fund [207032, years 2014–2018]
CONACYT-SENER-SUSTENTABILIDAD ENERGÉTICA to provide fi-
nancial support for P25 of CeMIE-Geo (Mexican Center of Innovation in
Geothermal Energy) to make chemical analyses. We acknowledge
support funding [internal project, years 2013–2015] from Earth
Sciences Division of CICESE to perform field work around Cerro Prieto
Geothermal Field, Oc. Gabriel Rendon and Disraely González A. for
their support.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.geothermics.2017.11.
004.
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