Journal of Environmental Management 264 (2020) 110478

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Journal of Environmental Management

journal homepage: http://www.elsevier.com/locate/jenvman

Research article

Assessment of mining activity on arsenic contamination in surface water

and sediments in southwestern area of Santurba�n paramo, Colombia
David L. Alonso a, Rodrigo P�erez b, Coco K.Y.A. Okio b, Elianna Castillo b, *
a
Nuclear Affairs Division, Colombian Geological Survey, Carrera 50 N� 26-00, Bogot�a, Colombia
b
Laboratorio de Química Ambiental, Grupo de Estudios para la Remediaci�on y Mitigaci�
on de Impactos Negativos al Ambiente (GERMINA), Departamento de Química,
Facultad de Ciencias, Universidad Nacional de Colombia, Avenida Carrera 30 N� 45-03, Bogot� a, Colombia

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

Keywords: The current emphasis of developing countries on policies that favor the intensification of mining exploitation as
Arsenic the main source of incomes, has generated negative consequences for ecosystems and rural communities, mainly
Sediment pollution due to the release of highly toxic elements into the environment. This study was carried out to evaluate the effect
Enrichment factor
of the Vetas-California gold mining district on As distribution in stream sediments and surface water samples
Hierarchical cluster analysis
from Surat� a River, located in the southwestern area of Santurb� an paramo, Colombia. With this aim, samples
Surat�
a river
distributed along the high Surat� a River basin in areas near and far from mining areas were selected. Samples
were chemically characterized. The As mobility, enrichment and sources were evaluated using sequential and
single extractions, enrichment factor (EF), geoaccumulation index (Igeo), and hierarchical cluster analysis (HCA).
The results highlight high As content (reaching up to 484 mg/kg) in stream sediment sampled near the gold
mining district. For both sediment and water, the relative As content along the Surat� a River exceeded the
background content by 220 and 64.9 times, respectively. From the single-stage extractions performed, the
reducible fractions found in As(NaOH) and As(HCl) were higher in all cases, meaning a high level of mobility and
lixiviation of the As content in water samples by changes in pH and redox potentials. The correlations estimated
using Spearman coefficients show that most of the bioavailable fraction of As(Exch) is related to main sediment
constituents such as S, Fe2O3, SiO2, and Al2O3 and the relative As content. Calculation of the enrichment factor
(EF) confirms high enrichments around active sites of gold mining such as the municipalities of Vetas, California
and Matanza with EF values of 285, 204, and 133, respectively. In addition, the Igeo values suggest moderate to
strong As pollution due to the high Igeo found at the major mining effect points. The findings from this study are
valuable for providing effective management options for risk prevention and control of the persistent As accu­
mulation in Santurb� an paramo.

1. Introduction
Arsenic is considered by the World Health Organization as a highly
dangerous carcinogenic element for humans (Paula et al., 2012; Zhang
et al., 2019). One of the main sources of arsenic contamination is from
mining activities. However, its relationship with anthropic activities in
mining areas is often difficult to characterize since the high concentra­
tions found in environmental matrices may be a product of its natural
distribution. Besides, background concentrations for pollutants and
longterm monitoring data for many contaminated ecosystems are not
available (Alonso et al., 2014; Little et al., 2020). One way to approxi­
mate a differentiation between natural and anthropogenic sources of
arsenic enrichment is the use of environmental risk indexes (e.g., geo­
accumulation index, enrichment factor, and contamination factor)
(Gbolo and Lopez, 2015; Mondal et al., 2018; Pignotti et al., 2018). To
fully characterize the risk associated with arsenic-rich environments, the
interaction between arsenic and its matrix (sediment, soil, water) has to
be assessed. The nature of these interactions varies with the chemical
composition, pH, sorption, redox potential and, consequently, arsenic
speciation in the sediment. Sequential extraction and single-step
extraction are simple and straightforward methods to assess arsenic
chemical forms in the solid phase by selectively extracting arsenic bound
to a specific phase (Babar et al. 2013, Kim et al., 2014, Abad-Valle et al.,
2018). On the other hand, full understanding of arsenic interactions can

* Corresponding author.
E-mail address: ecastillo@unal.edu.co (E. Castillo).

https://doi.org/10.1016/j.jenvman.2020.110478
Received 6 December 2019; Received in revised form 24 February 2020; Accepted 22 March 2020
Available online 31 March 2020
0301-4797/© 2020 Elsevier Ltd. All rights reserved.
D.L. Alonso et al.
be simplified using statistical techniques that correlates the variation
and sort the variables phenomenologically allowing further association
(Rasool et al., 2016; Chen et al., 2016; Akopyan et al., 2018).
Colombia is a South American country with a thriving emerging
economy. The recent growth in international investment, especially in
mining activities, has made Colombia the second largest producer of
gold in Latin America (Arias et al., 2018; Parka et al., 2018). Unfortu­
nately, the largest mining areas are located in one of the world’s most
endangered ecosystems, the paramos. The paramos constitute the water
supply for 70% of the country (Abello, 2013). The seventh in size of this
water-rich protected area is the Santurba�n paramo, located between the
departments of Santander and Norte de Santander (Fig. 1). For hundreds
of years, artisanal and small-scale mining has been carried out in the
area formed by the municipalities of California and Vetas located
southwest of the paramo (Lo �pez and Díaz, 2009). More recently,
open-pit mining has been taken over by transnational companies (Rojas
and Cramer, 2013). The California-Vetas mining district (Fig. 2) is
located upstream of the Surata � River. 40 km southwest of the mining
district, is the Bosconia water treatment plant, one of the four water
treatment plants of Bucaramanga City (with more than 1,200,000 peo­
ple). Thus, public attention concerning potential contamination of this
water source has been increasing (Abello, 2013; Buitrago, 2014; Avel­
laneda et al., 2015). The main concern is related to waste management
Fig. 1. Santurb� an Paramo location. The region highlighted in green shows the extension of Santurb�
River basin. The yellow circle north of the Bucaramanga city indicates the location of Bosconia water treatment plant. (For interpretation of the references to colour
in this figure legend, the reader is referred to the Web version of this article.)
2
Journal of Environmental Management 264 (2020) 110478
of mine tailings, which causes the main source of environmental
pollution associated with this type of activity (Litter et al., 2020).
Exploratory research on the groundwater of Santander Massif, which
is the source of many important tributaries of the Surat� a River, showed
values of �1,0 μg As/L (9 boreholes at depths from 60 to 140 m)
(Greystar, 2009), suggesting that natural distribution in the aquifer is
not the source of arsenic contamination. However, to our knowledge,
there has been fewer studies reported on the potential enrichment of
arsenic and other heavy metals in areas close to the Vetas-California gold
mining district (Fig. 2), and arsenic toxicity data are severely insufficient
to accomplish the ecological risk assessment in the Santurba �n paramo
(Fig. 1). Therefore, the objective of this work was to investigate the ef­
fect of mining activity on the presence of As species in the stream sed­
iments and surface waters collected along the upper basin of the Surata �
River near the California-Vetas mining district by: i) performing physico
chemical characterizations of the samples ii) evaluating As distribution
mainly by sequential and single extractions. iii) Calculating the
enrichment factor (EF) and the geoaccumulation index (Igeo), and hier­
archical cluster analysis (HCA) to assess anthropogenic impact, and
identifying sources of As pollution.
an paramo. The blue box shows the area studied in the high Surat� a
D.L. Alonso et al.
Fig. 2. Localization of studied area (high Surat�
a River basin). The location of the mines in the California-Vetas Gold mining district is shown in the north-east area of
the map. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)
1.1. Study area
To study the environmental impact of California-Vetas gold mining
activities on the quality of surface waters in the top of the Surat� a sub­
basin, tributaries affected and unaffected by acid mine drainage (AMD)
were selected. The tributaries were chosen based on the results of
environmental monitoring of water and sediment carried out by the
regional environmental authority for the analysis of cyanide (CN ) and
mercury (Hg) (Wolff, 2001). The analysis showed the presence of direct
pollution caused by gold mining in the Vetas-California gold mining
district. Fig. 1 shows the location of the Santurb� an paramo. The
Vetas-California gold mining district is located in the NE of Bucar­
amanga, Colombia, in the center of Santander Massif within longitude
72� 520 10.1100 -72� 550 45.3800 W and latitude 7� 180 08.1000 -7� 230 48.5500 N
(Fig. 2).
The study area (hydrologically referred to as top of the Surata � River
subbasin, Santander, Colombia, Fig. 2) extends over 360 km2. The
Surata� River, as the main water source for the Surat� a subbasin, flows
from the Santurba �n paramo to the city of Bucaramanga. This river is fed
by tributaries such as Vetas and Charta Rivers, as well as streams such as
Pa�ez, La Baja and Mo �ngora Creeks. The water from the tributaries, Vetas
River and La Baja Creek is used for the California-Vetas gold mining
district (Fig. 1). However, water is also used for agronomic purposes. In
Surata� town, 20% of the lands are used to grow corn, tomatoes, beans
and onions, and the rest of the lands are dedicated to ranching. In rural
areas, water is brought to houses from tributaries by handcrafted pipes
3
Journal of Environmental Management 264 (2020) 110478
or directly from wells.
The mineral association found on site mainly consists of sulfur
minerals such as pyrite, rosickyite, arsenopyrite, erniggliite and sem­
seyite occurring in two ore deposit types: quartz veins and layered
skarnoids (Angel
� and Fierro, 2012; Ferna �ndez et al., 2016). The
California-Vetas mining district presents high- and low-sulfidation de­
posits associated with Miocene calc-alkaline volcanic rocks (Rojas and
Cramer, 2013). The weather in the Surat� a basin ranges from 0 to 35 � C
from the upper part of the paramo to the lower part of the Surat�a River
mouth in the Lebrija River. The annual precipitation pattern in the
Surat�a basin shows a distinct bimodal behavior: two rainy periods
(March to May and September to November) and two dry seasons
(December to February and June to August). The annual average pre­
cipitation can range from 60 to 2065 mm. From the monthly averages
reported from 2011 to 2015, the sampling month of this study, June
2014, is reported with 39.85 mm (CDMB, 2014).
2. Materials and methods
2.1. Sampling collection and analysis
In June 2014, exploratory sampling was performed. Samples
distributed along the high Surata
� River basin in areas affected and un­
affected by mining activities were collected. Access to the area was
granted by the Colombian Geological Survey. 11 point samples of river
water and 10 stream sediments were collected along the upper basin of
D.L. Alonso et al. Journal of Environmental Management 264 (2020) 110478

the Surata� River (Table 1). The exact location of gold mines and sam­
pling locations are shown in Fig. 2. Water collection was performed
during the dry season. For each sample, 1 L of water was collected in
polyethylene bottles, filtered (0.45 μm cellulose filter), acidified with
HNO3 2% v/v (pH < 2) and stored in a refrigerator (4 � C) until analyzed.
5 kg of sediment wet sample was collected with a plastic spatula to 10
cm and then stored in previously cleansed polyethylene bags. The
samples were dried at room temperature, ground in an agate mill, ho­
mogenized, sieved (0.149 mm mesh opening) and stored in plastic
bottles inside a glass desiccator as described by Litter et al. (2009).
2.2. Analytical methods
2.2.3. Arsenic quantification in single-stage extractions and sequential
procedures
For the analysis of As in aliquots of single-stage extractions,
sequential procedures and pseudo total content, (Asps) the volume of
each sample aliquot was treated 1 h before its analysis with 1 mL of KI
1% w/v to reduce all As present. Then, the total As was analyzed by
hydride generation atomic absorption spectroscopy (HG-AAS) using a
PerkinElmer AAnalyst 300 (Waltham, MA, USA) with deuterium lamp
background correction and equipped with a Perkins Elmer MHS-1515
hydride generator, a heated quartz cell with an air/acetylene flame
and a hollow cathode lamp as a radiation source.

2.2.1. Chemical characterization of sediments 2.3. Pollution indicators

Determination of the major elements was carried out on a PAN­
alytical AXIOS X-ray spectrometer (Almelo, Overijssel, Netherlands) 2.3.1. Enrichment factor (EF)
equipped with a rhodium tube at a maximum power of 4 kV. The sedi­ The enrichment factor represents the accumulation of a given
ment samples were homogenized and prepared in the form of molten element compared to a value of reference and relative to a conservative
beads (30 mm diameter) with a 1:10 sample:fusion flux ratio in an component of the soil in a given sample. It has been used to categorize
electric induction furnace (PANalytical Perl X3). A mixture of lithium the level of enrichment of multiple pollutants as anthropogenic (Abra­
tetraborate and lithium metaborate was used as the fusion flux; lithium him and Parker, 2008; Li et al., 2014).
iodide was added as a release agent. The samples were melted in an The EF can be described as follows:
inductive radiofrequency oven (1150–1310 � C). Finally, 37 mm diam­ � �
eter glass discs were obtained and subsequently analyzed by X-ray
YX
=

fluorescence. EF ¼ � �c (1)
The sediment samples were analyzed for As using instrumental
YX
=

neutron activation analysis (INAA), by which a small sample fraction,

b

together with appropriate standards (mass of 200 mg each), was
analyzed at the IAN-R1 Nuclear Reactor (Bogota �, Colombia) at a neutron
fluence rate of 2.5⋅1011 cm 2 s 1. Through INAA, it was possible to carry
out a multielement characterization of each sediment sample. For short-
term analysis (short-lived radionuclides), an irradiation time of 5 min,
decay times of 5 min and 3 h, and counting times of approximately 5 and
10 min, respectively, were used. For long-term analysis (long-lived ra­
dionuclides), an irradiation time of 4 h, decay times of 4–5 d and 21–25
d, and counting times of approximately 2.5 h and 4 h, respectively, were
used. As calibration standards, NIST-2704 (Buffalo River Sediment),
NIST-1646a (Estuarine Sediment), NIST-2709a (San Joaquin Soil) and
NIST-2710a (Montana I Soil) reference materials, as well as Al–Au
(metal foil), were considered. Gamma ray spectra were measured with a
spectrometric system based on an HPGe (Canberra GC-7020) detector of
70% relative efficiency and 2.0 keV resolution for 60Co. Gamma-ray
spectrum analysis was carried out using Canberra Genie 2000 soft­
ware (Meriden, CT, USA).
Where Y is the concentration of the element of interest, X is the con­
centration of the reference element, c is the concentration in the sam­
pling site, and b is the concentration in the background. For geochemical
normalization, aluminum was chosen as the reference element to iden­
tify possible enrichments. EF values less than 1 indicate no enrichment;
from 1 to 3, moderate enrichment; from 5 to 25, severe enrichment; from
25 to 50, very severe enrichment; and more than 50, extremely severe
enrichment (Li et al., 2014).
2.3.2. Geoaccumulation index (Igeo)
The geoaccumulation index (Igeo) is an indicator of enrichment, but
unlike the EF, it does not normalize using a conservative element.
Instead, this index compares the concentration of an element (X) directly
between the concentration in sample C and background B. The factor of
K ¼ 1.5 is used for possible variations in background values due to
lithological variability (Li et al., 2016). The Igeo was calculated as
follows:

2.2.2. Chemical characterization of water samples Igeo ¼ log2

Total As in waters was analyzed by the ICP-MS method using the
equipment Varian 820-MS (Palo Alto, CA, USA), and other elements in
addition to As were determined with the purpose of making a multi­
elemental characterization.
Xc
(2)
1:5XB
The definition of the background sample point was taken from a
sediment that shares the same geological unit as the sediment sampled
in the Surata
� River but without a direct entry point for the mining
leachates (point 11). Igeo values between 0 and 1 are considered class 1
or not contaminated; between 1 and 2, class 2 or moderately contami­
nated; between 2 and 3, class 3 or severely contaminated; between 3 and

Table 1
Description and coding of collected samples.
Pointa Sampling site Seb Wc Point Sampling site Se W

1 Agua Blanca Creek (Vetas) Se1 W1 7 Surat�

a River 1 (Surat�
a) Se7 W7
2 Vetas River 1 (Vetas) Se2 W2 8 Surat�
a River 2 (Matanza) Se8 W8
3 Vetas River 2 (California) Se3 W3 9 Surat�
a River 3 (Matanza) Se9 W9
4 La Baja Creek 1 (California) – W4 10 Surat�
a River 4 (Bucaramanga) Se10 W10
5 La Baja Creek 2 (California) Se5 – 11 Charta River (Charta) Se11 W11
6 La Baja Creek 3 (California) Se6 W6 12 Los Ranchos Creek (Vetas) – W12
a
Sampling point assigned in the map of Fig. 2.
b
Code given to stream sediment.
c
Code given to surface water.

4
D.L. Alonso et al. Journal of Environmental Management 264 (2020) 110478

4, class 4 or severely contaminated; and greater than 5, class 6 or filtered through a Whatman 40 filter paper and stored at 4 � C in a
extremely contaminated (Thuong et al., 2013). Class 6 reflects an polyethylene container until analyzed (modified procedure from the one
enrichment of at least 64 times the value of the basal concentration. by Alvarez et al. (2011)).
The three extracts are denoted as the exchangeable fraction As
(Exch), reducible fraction As(NaOH) and acid soluble fraction As(HCl),
2.4. Arsenic fractionation respectively. These extracts represent approximations to simulate
different stages of arsenic mobilization, allowing a preliminary rapid
Sequential extraction procedures: The fractionation of As was stud­ diagnosis about its possible release into the environment (Abollino et al.,
ied first, through Tessier sequential extraction procedures (Tessier et al., 2002; Van Herreweghe et al., 2003).
1979). 1.0 g of sample is weighed in a 50 mL Falcon tube. Then, step by
step, the corresponding reactants are added to extract each fraction. A
2.5. Statistical analysis
summary of extraction conditions and order used for sequential ex­
tractions are shown in Table 2. After each extraction step, the fraction is
The Shapiro-Wilk test and hierarchical cluster analysis (HCA) were
centrifuged for 15 min at 3300 rpm in order to get the supernatant for
performed using R (The R Foundation for Statistical Computing, version
analysis by HG-AAS (section 2.2.3). The precipitate from each step is
3.2.3) (Team, 2015). The Shapiro-Wilk test was performed to determine
washed with deionized water before going through the following
whether the variables followed a normal distribution. HCA was used for
extraction step. The recovery was evaluated by comparing the addition
the identification of contamination sources of As in water and sediments
of the five fractions versus a single step digestion by aqua regia (pseudo
samples (Rasool et al., 2016). HCA was performed using Euclidean
total extraction).
distances from the Spearman rank correlation matrix. The Spearman
Due to As anionic character (Carvalho et al., 2012), it is necessary to
correlation coefficients were calculated using scaled and centered data
develop specific procedures to achieve a correct evaluation of As
to avoid any possible bias.
bioavailability. Thus, three main single-step extractions to estimate the
more labile arsenic fractions in sediments were implemented:
3. Results and discussion
Deionized water extraction: the procedure described by Abollino et al.
(2002) was followed in order to calculate the soluble fraction. It consists
3.1. Total As distribution
in adding 6.0 mL of distilled and deionized ultrapure water to 1.0 g of
sample and fixing the pH at 5.0 � 0.2 by addition of HOAc 0.5 M. The
A summary of the physical and chemical characterizations of the
suspension is stirred with a circular stirrer (Glass Col 13,846) during 24
stream sediments (Se) and surface water (W) samples is shown in Table 3
h and monitoring the stability of the pH. After that, it was centrifuged
and Table 4, respectively. The structural analysis of sediments, mainly in
and the supernatant stored at 4 � C in a polyethylene container until its
their texture (sand, silt and clay factors, Table 3), reveals important
analysis.
differences in the distribution of particle sizes. The sediments farther
Sodium hydroxide extraction: To 1.0 g of sample were added 30 mL of
from the mining zone (Se7–Se11) showed remarkable similarity to each
NaOH 0.1 M. The obtained suspension is stirred for 17 h with a circular
other (sand: 96.2–96.6, silt: 1.2–1.4 and clay: 2.2–2.4%), while sedi­
stirrer (Glass Col 13,846) and filtered through Whatman 40 filter paper
ments close to the mine tailings (Se2–Se6) showed a more diverse dis­
and then stored at 4 � C in a polyethylene container until analyzed
tribution (sand: 75.3–89.7, silt: 8.4–17.1 and clay: 1.8–7.6%). This
(Manful, 1992).
finding suggests a direct relationship between small particle size sedi­
Hydrochloric acid extraction. To 2.0 g of sample in a test tube were
ments and mining activity. Taking into account that the geological de­
added 25 mL of HCl 1.0 M. The suspension is stirred with a circular
posits in the area are mainly from Miocene calc-alkaline volcanic rocks
stirrer (Glass Col 13,846) during 20 min at room temperature and then
with higher concentrations of SiO2 (69.66–74.12%) than AlO2
(10.32–16.62%) and iron (3.13–7.15%) (Rojas and Cramer, 2013), the
Table 2 sediment composition is mainly very stable silicates and aluminosili­
Operation conditions of sequential extraction scheme by Tessier et al. (1979).
cates. However, it is noteworthy that samples located close to the mining
Fraction Extraction Conditions Extractant Extractant district showed an increase in the percentages of Fe and S associated
time volume solution with the high content of sulfides, mainly pyrite (FeS2), tennantite
(mL)
(Cu12As4S13), sphalerite (ZnS), chalcopyrite (CuFeS2), and arsenopyrite
F1) 1h Continuous 8 MgCl2 1.0 M at (FeAsS) (Angel
� and Fierro, 2012; Rojas and Cramer, 2013), presumably
Exchangeable stirring pH 7.0
the sources of arsenic and other heavy elements found in the zone.
F2) Associated 5h Continuous 8 NaOAc 1 M at
to carbonates stirring at pH 5.0 The total As content and other trace elements found in the stream
room adjusted with sediments are listed in Table 3. The As background content in soil
temperature HOAc(con) typically ranges from 1 to 40 mg/kg, with an average of 5 mg/kg (Redon
F3) Associated 6h 96�3 � C 20 NH2OH.HCl et al., 2013; Sarkar and Paul, 2016). In this study, the sediment selected
to Mn and Fe Temporary 0.04 M in
oxides stirring HOAc 25% (v/
as background was collected in the municipality of Charta (Se11)
v) located outside the mining area (Fig. 2). The arsenic content found (2.1
F4) Associated 2h 85�2 � C 3 HNO3 0.02 M � 0.1 mg/kg, n ¼ 5, mean � SD) was associated with geochemical
to organic Temporary 5 H2O2 30% at natural distribution. Most of the studied stream sediments sampled near
matter and stirring pH 2.0 with
the mining district exceeded that value. Colombia does not have any
sulfide HNO3
3h 85�2 � C 3 H2O2 30% at regulations regarding the content of heavy metals in soils and sediments,
Temporary pH 2.0 with so the content of As(17 mg/kg) was evaluated according to the Canadian
stirring HNO3 guidelines (Canadian Council, 1999) and sediment quality guide
30 min Continuous 5 NH4OAc 3.2 M (Abrahim and Parker, 2008).
stirring at in HNO3 20%
room (v/v) - diluted
Higher concentrations of As were found in Vetas River 1 (Se2) and
temperature at 20 mL Vetas River 2 (Se3), 484 � 6 and 282 � 4 mg/kg (n ¼ 5, mean � SD)
F5) Residuala 56 min Ultrasonic- 9 HCl–HNO3 3:1 respectively, and downstream of the mining district in Surat� a River 2,
assisted (aqua regia) (Se8) 222 � 3 mg/kg (n ¼ 5, mean � SD) (Table 3). In other affected
digestion
zone like La Baja Creek, located close to only one gold extraction mining
a
Modification considering the optimal conditions set up in this work. project in the upper part of California district. (Se5–Se6), As content

5
D.L. Alonso et al. Journal of Environmental Management 264 (2020) 110478

Table 3
Physicochemical properties, major elements (oxides) and trace element contents in sediments of high Surat�
a River basin.
Factor Units Samples

Se1 Se2 Se3 Se5 Se6 Se7 Se8 Se9 Se10 Se11

Sand % 93.6 88.2 89.7 76.1 75.3 96.6 96.2 96.4 96.4 96.2
Silt % 4.3 10.0 8.4 16.4 17.1 1.2 1.4 1.4 1.4 1.4
Clay % 2.1 1.8 1.9 7.5 7.6 2.2 2.4 2.2 2.2 2.4
pH – 6.1 4.3 4.7 6.6 6.2 7.4 6.8 7.6 7.6 7.5
TBCa meq.kg 1 2.0 1.3 1.2 0.7 0.7 2.3 2.2 2.3 2.2 2.2
TOCb % 0.10 0.18 0.17 0.32 0.25 0.10 0.08 0.08 0.07 0.08
SiO2 % 69.7 � 2.1 72.1 � 2.2 71.4 � 2.2 71.5 � 2.2 74.1 � 2.3 71.3 � 2.2 73.6 � 2.3 72.4 � 2.2 71.7 � 2.2 71.6 � 2.2
Al2O3 % 16.6 � 0.5 13.6 � 0.4 10.3 � 0.3 10.60.3 10.8 � 0.3 14.3 � 0.4 13.3 � 0.4 13.9 � 0.4 14.6 � 0.4 14.7 � 0.4
Fe2O3 % 3.55 � 0.11 3.75 � 0.11 6.34 � 0.19 5.42 � 0.16 7.15 � 0.21 3.23 � 0.10 4.21 � 0.13 3.53 � 0.11 3.13 � 0.09 3.18 � 0.09
MnO % 0.09 � 0.00 0.13 � 0.01 0.16 � 0.02 0.16 � 0.02 0.18 � 0.02 0.08 � 0.00 0.09 � 0.00 0.08 � 0.00 0.08 � 0.00 0.08 � 0.00
S % 0.04 � 0.00 0.80 � 0.00 1.75 � 0.05 1.36 � 0.04 1.50 � 0.04 0.02 � 0.00 0.26 � 0.00 0.05 � 0.00 0.02 � 0.00 0.02 � 0.00
Sb mg.kg 1 1.4 � 0.1 31.1 � 1.1 28.2 � 1.1 6.1 � 0.3 6.8 � 0.3 0.9 � 0.1 19.1 � 0.7 9.2 � 0.4 0.5 � 0.1 0.3 � 0.0
As mg.kg 1 10.0 � 0.3 484 � 6 282 � 4 62.2 � 1.6 70.4 � 1.8 2.4 � 0.1 222 � 3 35.6 � 0.6 2.2 � 0.1 2.1 � 0.1
Aspsc mg.kg 1 9.1 � 0.2 419 � 6 227 � 3 52.6 � 1.6 60.4 � 2.3 1.8 � 0.1 187 � 3 29.7 � 1.0 1.7 � 0,1 1.6 � 0,1
Zn mg.kg 1 86.5 � 2.4 594 � 17 417 � 15 143 � 5 168 � 5 143 � 5 438 � 15 194 � 6 141 � 5 133 � 5
Zr mg.kg 1 140 � 4 211 � 5 197 � 5 458 � 7 473 � 7 115 � 3 182 � 4 142 � 3 111 � 3 113 � 3
Cu mg.kg 1 31.9 � 0.9 159 � 4 172 � 4 341 � 9 361 � 10 38.1 � 0.9 167 � 4 69.5 � 1.1 45.6 � 1.0 38.4 � 0.9
Au mg.kg 1 0.1 � 0.0 9.2 � 0.2 8.7 � 0.2 12.1 � 0.3 13.4 � 0.3 0.4 � 0.0 1.7 � 0.1 0.4 � 0.0 0.4 � 0.0 0.4 � 0.0
Ag mg.kg 1 2.4 � 0.1 38.7 � 1.3 31.6 � 1.2 32.3 � 1.2 33.4 � 1.3 0.02 � 0.00 17.4 � 0.7 3.11 � 0.2 0.02 � 0.00 0.02 � 0.00
W mg.kg 1 4.4 � 0.2 175 � 6 158 � 5 27.6 � 0.9 31.2 � 1.0 2.4 � 0.2 81.7 � 2.5 48.3 � 1.5 8.7 � 0.3 2.7 � 0.2
a
Total base cations.
b
Total organic carbon.
c
As pseudo total concentration. Results are expressed as: mean � SD (n ¼ 5).

Table 4
Physicochemical properties and trace element contents in surface waters (W) of High Surat�
a River basin.
Factor Units Samples

W1 W2 W3 W4 W6 W7 W8 W9 W10 W11 W12

pH – 7.40 7.13 7.09 7.59 6.38 7.62 7.52 7.64 7.84 7.85 7.32
Conductivity μS. 529.2 250.4 297.3 296.1 1575.2 163.4 201.1 160.8 152.6 140.9 34.8
1
cm
TDSa mg.L 1 371.2 155.1 169.2 214.3 1099.1 101.3 140 122.3 116.5 97 24.5
Salinity mg.L 1 261.3 184.7 199.2 194.4 782.1 59.6 99.9 82.4 78.3 71 17.4
Ehb mV 32 4 11 61 54 63 57 65 79 85 45
As μg.L 1 8.2 � 0.2 51.9 � 1.8 28.1 � 0.9 23.6 � 0.7 52.3 � 1.9 1.1 � 0.1 8.2 � 0.2 2.8 � 0.1 0.6 � 0.1 0.8 � 0.1 0.7 � 0.1
Ba μg.L 1 25.5 � 47.1 � 0.9 21.9 � 0.4 44.3 � 0.9 26.8 � 0.5 14.6 � 27.8 � 18.1 � 13.6 � 24.3 � 11.2 �
0.5 0.3 0.6 0.4 0.3 0.5 0.2
1
Zn μg.L 288 � 8 253 � 7 389 � 8 127 � 4 1980 � 35 19.2 � 91.1 � 45.4 � 21.2 � 24.1 � 18.1 �
0.4 1.8 0.9 0.4 0.4 0.4
1
Cu μg.L 59.8 � 35.3 � 0.8 47.1 � 1.0 589 � 14 7218 � 10.2 � 41.3 � 19.4 � 6.7 � 0.1 5.5 � 0.1 6.1 � 0.1
1.2 146 0.2 0.8 0.3
1
Fe μg.L 6720 � 12,760 � 11,820 � 11,240 � 14,250 � 780 � 16 9240 � 1740 � 410 � 11 380 � 10 490 � 12
42 72 68 62 91 54 21
1
Mn μg.L 3039 � 469 � 10 887 � 18 705 � 14 3987 � 82 65.1 � 226 � 5 82.8 � 27.3 � 23.9 � 78.6 �
64 1.3 1.7 0.5 0.5 1.6
1
Ag μg.L 1.3 � 0.1 0.2 � 0.1 0.1 � 0.0 0.7 � 0.1 0.2 � 0.0 0.2 � 0.0 0.1 � 0.0 0.1 � 0.0 0.1 � 0.0 0.3 � 0.0 0.2 � 0.0
a
Total dissolved solids.
b
Redox potential. Results are expressed as: mean � SD (n ¼ 5).

ranged from 62.2 to 70.4 mg/kg (n ¼ 5), respectively. The mining ac­
tivity is quite limited in this part and therefore As contents there are
lower than the values reported for Se2 and Se3 but were also above the
recommended limit for As. Downstream the Surata � River, there is a
decrease in As content from 35.6 mg/kg (n ¼ 5) in Surat� a River 3 (Se9)
to 2,2 mg/kg (n ¼ 5) in Surat�a River 4 (Se10, very close to Bucaramanga
City), where is located one of the water treatment plant.
The pH of the stream sediments ranges from 4.3 to 6.8 for those
directly exposed to mining activities (Se2–Se3, Se5–Se6 and Se8). Out of
the mining zone, the pH is higher and slightly alkaline (7.4–7.6)
(Table 3). The lower pH values in the sediments are a key point that
suggests gradual oxidation of sulfides present in the tails and mining
activity zones (Kreidie et al., 2011). In addition, the gold deposit of
Vetas, Santander, is an epithermal deposit of intermediate sulfuration
(Rojas and Cramer, 2013). Epithermal mine sites typically involve some
degree of acid rock drainage development, where acidification is driven
by abundant pyrite in the deposits themselves and in the widespread
alteration haloes surrounding the deposits (Bowell and Craw, 2014).
Table 4 shows the results of the multielemental analysis by ICP-MS
performed on all collected surface water samples. Four samples
located downstream of the gold mines in the California-Vetas mining
district (W2–W5) were identified with values of As ranging from 22.5 to
51.2 μg/L, which are higher than 10 μg/L, which is the allowed limit by
the legislation of Colombia (WHO, 2011). However, since the Vetas
River, located throughout the mining district, delivers its waters to the
Surat�a River, which descends in a north-south direction towards the city
of Bucaramanga, the arsenic concentration is significantly decreased to
8.4 μg/L in the municipality of Matanza and 0.6 μg/L north of Bucar­
amanga City. Although the arsenic content is below the legislation limit
for most water samples, and most areas have contents less than 10 μg/L,
The high arsenic level found in sediments (Table 3) exceeds the limit
value for the occurrence of probable effects established at 17 mg/kg by

6
D.L. Alonso et al.
the Canadian legislation (Canadian Council, 1999) for the same areas.
These results show that the stream sediments could be accumulating As
which can be leached into currents by physical and chemical changes
(Zhang et al., 2019).
The surface water samples from the downstream Vetas and California
districts (W1–W6) present pH values from 6.3 to 7.0, Eh of 4–54 mV,
conductivity of 250–1575 μS/cm, and total dissolved solids (TDS) from
155 to 1099 mg/L, while surface waters located in remote zone from
mining activity, (W10–W12), present pH values from 7.3 to 7.8, Eh of
45 to 85 mV, conductivity of 34.8–152.6 μS/cm, and total dissolved
solids (TDS) from 24.5 to 116 mg/L. These results suggest the presence
of a high amount of slightly acidic particulate material enriching the
natural composition of the stream sediments (Fig. 4). The above results
highlight that mining activity has altered the chemistry of many
chemical elements, including increasing arsenic concentrations in water
and stream sediments by several orders of magnitude above natural
levels.
3.2. Arsenic fractionation
To understand arsenic mobility and its interaction with sediments, a
sequential and a single-stage extraction procedures were carried out. For
this, the As pseudo total concentration (Asps) in the stream sediments
was determinated by a single step digestion with aqua regia, (section
2,4). The Asps content obtained was quite similar to the Arsenic total
concentration using neutron activation analysis INAA, (Table 3). The
recovery of As presented an average of 85%�% 4 in all samples with
concentration level in the affected zone Se2 and Se3 of 419 � 6 and 227
� 3 mg/kg (n ¼ 5, mean � SD) respectively. In other affected zone like
La Baja Creek, (Se5–Se6), As pseudo total content was 53 � 2 and 60 � 2
mg/kg (n ¼ 5), respectively; while in the sample of Surat�
a River 2 (Se 8),
located downstream of the mining district, 187 � 3 mg/kg (n ¼ 5, mean
� SD). The concentration of different As fractions are shown in Fig. 3
and Fig. 4 is about percentage of the As pseudo total content.
According to the results obtained from the sequential extraction
using Tessier procedure (Tessier et al., 1979) (Fig. 3), in the first two
fractions (F1, exchangeable and F2, associated with carbonates or easily
reducible fraction), the extraction percentages were extremely low, less
than 0.21% and 1.88% respectively in all samples, meaning there’s no
As bioavailable. In the fraction F3 (associated with Mn- and Fe-oxides)
Although, coprecipitation of As with Fe oxyhydroxides is known as the
major mechanism that strongly retains As in sediments (Wenzel et al.,
2001), and high percentages could be expected in this fraction, Arsenic
extracted in this fraction was surprisingly low, 4.9–12.9%. Value that is
not consistent with the high contents of Fe Oxydes (3,55–7,35%) found
in this study, (Table 3). In this fraction, we used NH2OH⋅HCl for the
Fig. 3. Arsenic fractionation trend from the Tessier sequential extraction
scheme expressed as a percentage of the As pseudo total concentration.
7
Journal of Environmental Management 264 (2020) 110478
Fig. 4. Arsenic extracted by single-stage procedures expressed as a percentage
of the As pseudo total concentration. The error bars show the maximum,
average and minimum values of each percentage (n ¼ 5).
extraction of (amorphous and crystalline) oxyhydroxides of Fe, Al and
Mn bound As, following a procedure suggested by Tessier. However, this
procedure was not effective, leading, in the last years several authors to
adjust it by using other reagents or by adding or reducing the number of
steps in order to improve the efficiency and selectivity of the protocol
(Babar et al., 2013).
F4 fraction, is mainly associated with oxidation of organic matter
and sulfides, and showed important results. As content in Vetas River 1
(Se2) and Vetas River 2 (Se 3), was 13.6–24.5% respectively, while in
the stream sediments located in the Baja Creek, which used to be a
mining zone, As content presented higher percentages in the sampling
points, Se5–Se6 (28.1–29.1%), and downstream of this zone in Surata �
River (Se8) a value of 11,8%. As content in this fraction should not be
attributed to organic matter because all stream sediments present a very
low level of TOC (Table 3). Moreover, we found a strong relationship
between S and As levels, the different stream sediments presented the
following S content: Se1 (0.04%), Se2–S3 (0.8–1.7%), Se5–Se6
(1,4–1,6%) and in the Se8 (0.3%), therefore we can affirm that As in this
fraction is due to the oxidation of sulfide minerals (Babar et al., 2013).
Moreover, As retained in these fractions (F3 and F4), is not readily the
more available or mobile, but it could be released if the sediments were
subjected to more reducing conditions.
As content found in the residual fraction F5 (defined by Tessier et al.
(1979) as primary and secondary minerals including silicates and
recalcitrant sulfides, which are therefore the most difficult to separate
from the sediments), was the highest among all the samples
(58.4–86.8%). This could be due to the major silicates concentration
found (69.7–74.1%, Table 3), the high sulfide minerals containing As in
the study area such as arsenopyrite and pyrite, (Rojas and Cramer, 2013;
Ferna �ndez et al., 2016), which suggests that this phase, though with a
higher As content than the other fractions, does not play a key role in the
mobilization/fixation of arsenic (Abad-Valle et al., 2018).
From the single-stage extractions (Fig. 4), the distribution and
lability of arsenic in each sediment was estimated (Zan et al., 2014). As
(Exch) was related to the concentration of labile arsenic associated with
arsenic adsorbed with electrostatic attraction forces, and in some mea­
sure, the solubility of arsenic associated with soluble inorganic salts. The
results indicate that the As leached under these conditions represents
less than 0.53% of the total content in the samples not affected by AMD.
In the samples directly affected (Se2–Se3, Se5–Se6), the exchangeable
As fraction ranged from 2.3 to 14.7 mg/kg and represented 3.5%–4.4%
of the pseudototal As, showing a substantial concentration of arsenic
mobile in the area near the mining district.
The acid soluble fraction As(HCl) has been linked with more intense
As interactions, such as carbonate-bound arsenate (Bolan et al., 2013).
This fraction was 4.2% and between 12.9% and 16.9% of the
D.L. Alonso et al. Journal of Environmental Management 264 (2020) 110478

pseudototal As content in unaffected and directly affected samples, Table 5

respectively. The resulting content in this fraction for the sediments Enrichment factor (EF) and geoaccumulation index (Igeo) of As in the sediments
directly affected by AMD, 36.4–54.2 mg/kg, greatly exceeded the limit of high Surat�
a River basin.
value for the occurrence of probable effects (17 mg/kg; Canadian Sample Sampling site EF Risk Igeo Pollution
Council, 1999). status
The reducible fraction, As(NaOH), was associated with arsenic Se1 Agua Blanca 5 Moderately 1.92 Moderately
bonding to amorphous Fe, Mn and Al oxides and oxy-hydroxides Creek, Vetas enrichment polluted
(Rieuwerts et al., 2014), which are sensitive to alkaline pH above 10. Se2 Vetas River 1, 285 Extremely high 7.46 Extremely
Vetas enrichment polluted
In this study, a strong positive correlation was found between the
Se3 Vetas River 2, 204 Extremely high 6.57 Extremely
leachable arsenic and NaOH (0.1 M) and the Al content because California enrichment polluted
single-step extraction is selective for As coordinated to amorphous Fe Se5 La Baja Creek 2, 46 Very high 4.46 Extremely
oxides but also releases arsenic associated with Al oxides. That leachable California enrichment polluted
fraction is one of the most important for this metalloid since it can reach Se6 La Baja Creek 3, 52 Very high 4.66 Extremely
California enrichment polluted
up to 50% of total arsenic. (Rieuwerts et al., 2014). High reducible As Se7 Surat�
a River 1, 1 Unenriched 0.39 Unpolluted
concentrations were found from sediments affected by AMD, 86.7 to Surat�
a
51.3 mg/kg, in Vetas and California sites (Se2–Se3), in La Baja Creek Se8 Surat�
a River 2, 131 Extremely high 6.29 Extremely
(Se5–Se6) from 13.2 to 14.1 mg/kg and in Surata � River 3 (Se8) 20.7 Matanza enrichment polluted
Se9 Surat�
a River 3, 20 Severe 3.64 Extremely
mg/kg (Fig. 4).
Matanza enrichment polluted
These results show that these extracted values can be attributed to Se10 Surat�
a River 4, 1 Unenriched 0.48 Unpolluted
the increase in iron in the affected samples due to the affinity of As for Bucaramanga
iron oxy-hydroxides (Table 1) (Wenzel et al., 2001), leading to the in­
crease in this metalloid in the reducible fraction. The Fe2O3 content in
unaffected and affected areas was 3.18% and from 6.34 to 7.15%, mg/kg) located in the municipality of Charta (Se11), indicating serious
respectively. Similarly, in all sediments near mining, the reducible influence of anthropogenic activities (Li et al., 2016).
fraction was much higher than the exchangeable and oxidizable fraction The Igeo indicates a similar tendency in the arsenic enrichment. In
(Fig. 4). The reducible As bound to iron oxy-hydroxides could not be this case, both EF and Igeo provided the same information. The sediments
released until the matrix is subjected to reducing conditions. A ratio were under moderate to strong pollution with As due to the high value of
between arsenic in the reducible phases of the sediment (attributed to Igeo found in the major mining effect points (Se1–Se3, Se5–Se6 and Se8).
the iron oxide and aluminum hydroxides) and the concentration of In summary, the Igeo values of the As in sediment decreased in the order
arsenic in the surface water samples was found by the cluster analysis. of Se2 >Se3 >Se8 >Se6 >Se5 >Se9 >Se7 >Se10. Therefore, we can
The As/Fe 0.001–0.005 ratios indicate that the adsorbed As (V) is not conclude that the EF and Igeo indicators showed similar trends.
significantly released from the mineral phase until 50% indicates that A comparison of the enrichment indexes for arsenic and other heavy
the oxyhydroxides have been reduced (Pedersen et al., 2006). In this elements (Ag, Au, Cu, Sb, Zn and Zr) shows that the effect of the mining
study, As/Fe ratios of 0.007 and 0.003 for stream sediments and surface site on the enrichment of gold ore-associated elements is evident, sug­
waters were found in the zone directly exposed to mining activities. This gesting the adverse impact of mining activity on stream sediments
result indicates that as it is adsorbed on the sediments it does not release quality from Surata River.
significantly from the sediments, it is likely that most of the amount of
As is in the residual phase. Apart from adsorption/desorption processes, 3.4. Hierarchical cluster analysis (HCA)
As mobility in soils is also importantly controlled by co-precipitation
with metal oxides. This agrees with the oxidation of arsenopyrite (pre­ The correlations estimated using spearman coefficients show the
sent in the zone near to mining district) into scorodite (FeAsO4⋅2H2O) linkages between the overall variability in the data when they are
and its further dissolution at pH � 3, like the pHs (4.3–4.7) exhibited by plotted in a cluster, the results of HCA helped in interpreting the data
the most contaminated stream sediments (Se2–Se3), in this study. and indicating patterns of similarities (Rasool et al., 2016). In this case,
(Abad-Valle et al., 2018). the cluster of analyzed factors for sediments and surface waters (Fig. 5)
showed 3 main arsenic species through the Surata � River system. Highly
3.3. Pollution indicators labile complexes such as As(Exch), adsorbed complexes such as As(HCl)
and As(NaOH) and stoichiometric or arsenious minerals such as As-Asps.
EFs were calculated to evaluate anthropogenic influences on As and Asps means pseudototal arsenic and represents the quantification using
other heavy metals found in sediments. The analyzed sediments showed the same quantification methodology as single-stage extraction for
enrichment using both the enrichment factor (EF) and the geo­ comparative purposes.
accumulation index (Igeo). A summary of arsenic EF and Igeo values is The first main cluster shows a strong relationship between the stoi­
provided in Table 5. chiometric arsenic minerals (As-Asps), Zn and W. This relationship
The EF indicates that arsenic enrichment at the site was due a process
foreign to the natural development of the Surata� River stream sediments.
EF values near the mining site were higher than 50, corresponding to
extremely severe enrichment of the sediments. A few kilometers farther
downstream in the Matanza (Se8), the enrichment continues. However,
following the Surata� River course towards Bucaramanga City, a decrease
in EF was observed. The values were 20 and 1 for sites 9 and 10,
respectively. Despite the decrease throughout the Surata � River system,
the obtained EF can still constitute a major problem, especially for the
rural population inhabiting the area (Mahecha et al., 2018). The rela­
tionship between arsenic content in both matrixes (sediments and sur­
face waters) suggests that the metalloid concentration has been
accumulating in the sediments where arsenic levels are 220 (sediments) Fig. 5. Dendrogram of the analyzed factors for sediments and surface waters,
and 65 (surface waters) times the arsenic background content (2.1 � 0.1 using Spearman correlations.

8
D.L. Alonso et al.
suggests an asymmetrical distribution of minerals associated with gold
and gold mining activities peaking at the Vetas-California mining dis­
trict. This distribution is related to the continual pouring of mine tailings
in the Surata � River stream system enriched with pyrites (FeS), iron ox­
ides (Fe2O3), arsenic-containing silica oxide (SiO2) and other major
components of pulverized ore after gold extraction (Sim and Altman,
2010; Bissig et al., 2014).
The second cluster showed that the arsenic in the reducible and acid
soluble fractions is closely related to its content in surface water sam­
ples. This finding indicates that the As concentration in surface water is
controlled to some measure by the reductive dissolution process of Fe
and Mn (hydro) oxides (Stüben et al., 2003; Henke, 2009). The reason
for this behavior has been linked to the overall variability in each
sampled point, (Tables 3 and 4). Near the mining site, the composition is
arsenic rich; however, iron sulfides are much more abundant, which
may mask the direct correlation between iron oxides and arsenic (Stüben
et al., 2003). This confirms once again that despite the fact that the As is
strongly retained in sediments, it can be mobilized from the sediments
under specific conditions, Litter et al, 2020.
In the third cluster, the main sediment constituents, such as S, Fe2O3,
SiO2, and Al2O3, are related to the most bioavailable fraction of As
(Exch). This finding highlights that the arsenic solubility in water de­
pends on the major characteristics attributed to the original physico­
chemical composition of the stream sediments studied. Therefore, the
use of this water from the Surat� a River for agronomic purposes, should
be considered unsafe.
4. Conclusions
The results from this study highlight current situation of arsenic
contamination in the Surat� a River and provide a new guideline for the
development of effective mechanisms for risk prevention and control of
arsenic water contamination in this zone. The main conclusions can be
summarized as follows:
The chemical characterization of stream sediments collected along
the upper basin of the Surata� River, indicated that the As concentrations
found in the study area near to mining zones (484 � 6 mg/kg in sedi­
ments and 51,9 � 6 μg/L in surface water) exceed the international
regulatory standards and the pollution is much more serious there than
in other zones far from the Vetas-California mining district, (2.1 � 0.1
mg/kg and 0.7 � 0.1 μg/L, respectively).
The results obtained for sequential and single-stage extractions
showed that although most As is immobilized, a considerable As con­
centration was found in, the reducible phase, mainly in affected zones by
mining activity; meaning an important risk of As transference towards
surface water of Surata � River.
The assessment of As pollution by EF suggested that the sampling
sites are seriously contaminated, the values of the EF for sediments may
indicate permanent pollution. Moreover, HCA showed through the first
main cluster that distribution of As total content is related to continuous
drainage of mine waste into the Surat� a River.
Despite the short number of samples in our study, the results high­
light the need of carrying out more exhaustive investigations in this zone
because of the weakness of environmental control and regulations
concerning mining activities in Colombia.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
CRediT authorship contribution statement
David L. Alonso: Methodology, Conceptualization. Rodrigo Pe �rez:
Formal analysis. Coco K.Y.A. Okio: Writing - review & editing. Elianna
9
Journal of Environmental Management 264 (2020) 110478
Castillo: Conceptualization, Writing - original draft, Supervision.
Acknowledgements
We are grateful to the Colombian Geological Survey, especially for
the support in carrying out the sampling and the geochemical charac­
terization of the samples, and to Universidad Nacional de Colombia,
where the main part of this research was performed through the project:
Determination of As traces in environmental matrix through nuclear and
spectroscopic analytical techniques.
References
Abad-Valle, P., Alvarez-Ayuso,
� E., Murciego, A., Mu~ noz-Centeno, L.M., Alonso-Rojo, P.,
et al., 2018. Arsenic distribution in a pasture area impacted by past mining activities.
Ecotoxicol. Environ. Saf. 147, 228–237. https://doi.org/10.1016/j.
ecoenv.2017.08.031.
Abello, R., 2013. Nueva cartografía de los p� aramos de Colombia: diversidad, territorio e
historia. Informe final. Instituto de Investigaci�on de Recursos Biol� ogicos Alexander.
Von Humboldt - Universidad Nacional de Colombia, Bogot� a (in Spanish).
Abollino, A., Aceto, M., Malandrino, M., Mentasti, E., Sarzanini, C., et al., 2002.
Distribution and mobility of metals in contaminated sites. Chemometric
investigation of pollutant profiles. Environ. Pollut. 119, 177–193.
Abrahim, G.M., Parker, R.J., 2008. Assessment of heavy metal enrichment factors and
the degree of contamination in marine sediments from Tamaki Estuary, Auckland,
New Zealand. Environ. Monit. Assess. 136, 227–238.
Akopyan, K., Petrosyan, V., Grigoryan, R., Melkom, D., 2018. Assessment of residential
soil contamination with arsenic and lead in mining and smelting towns of northern
Armenia. J. Geochem. Explor. 184, 97–109.
Alonso, D.L., Latorre, S., Castillo, E., Brandao, P., 2014. Environmental occurrence of
arsenic in Colombia: a review. Environ. Pollut. 186, 272–281. https://doi.org/
10.1016/j.envpol.2013.12.009.
Alvarez, M., Domini, C., Garrido, M., Lista, A., Fern� andez, B., 2011. Single-step chemical
extraction procedures and chemometrics for assessment of heavy metal behaviour in
sediment samples from the Bahía Blanca estuary, Argentina. J. Soils Sediments 11,
657–666.
Angel,
� A., Fierro, J., 2012. An�alisis y modelamiento del comportamiento de fluidos
líquidos de pilas de escombros en minería de oro. Tesis. Universidad Nacional de
Colombia, Bogot� a (in Spanish).
Arias, V.A., Rodríguez, A.R., Bardos, P., Naidu, R., 2018. Contaminated land in
Colombia: a critical review of current status and future approach for the
management of contaminated sites. Sci. Total Environ. 618, 199–209.
Avellaneda, L.M., Torres, E., Le� on, T., 2015. Alternatives to the conflict between
environmental authorities and communities of protected areas in Colombian
P�aramos. Mundo Agrar. 16 (31). ISSN 1515–5994.
Babar, M., Kachanoski, G., Siddique, T., 2013. A modified sequential extraction method
for arsenic fractionation in sediments. Anal. Chim. Acta 787, 102–110. https://doi.
org/10.1016/j.aca.2013.05.050.
Bissig, T., Mantilla, L.C., Hart, C.J., 2014. Petrochemistry of igneous rocks of the
California-Vetas mining district, Santander, Colombia: implications for northern
Andean tectonics and porphyry Cu (-Mo, Au) metallogeny. Lithos 200–201 (1),
355–367.
Bolan, N., Mahimairaja, S., Kunhikrishnan, A., Choppala, G., 2013. Phosphorus - arsenic
interactions in variable-charge soils in relation to arsenic mobility and
bioavailability. Sci. Total Environ. 464, 1154–1162.
Bowell, R., Craw, D., 2014. The characterization of arsenic in mine waste. Rev. Mineral.
Geochem. 79, 473–505.
Buitrago, E.A., 2014. Una historia y una vida alrededor del oro: territorialidad y minería
en el municipio de Vetas, Santander, Colombia. In: G€ obel, B., Ulloa, A. (Eds.),
Extractivismo minero en Colombia y Am�erica Latina. Universidad Nacional de
Colombia, Bogot� a (in Spanish). http://www.desigualdades.net/Resource
s/Publications/Extractivismo-minero-Goebel_Ulloa.pdf#page¼322 (accessed 20
February 2020).
Canadian Council of Ministers of the Environment, 1999. Canadian Sediment Quality
Guidelines for the Protection of Aquatic Life - Arsenic. Environment Canada
Guidelines and Standards Division (Winnipeg).
Carvalho, P., Neiva, A., Silva, M., 2012. Assessment to the potential mobility and toxicity
of metals and metalloids in soils contaminated by old Sb–Au and As–Au mines (NW
Portugal). Environ. Earth Sci. 65, 1215–1230.
CDMB, 2014. Plan de Ordenamiento y Manejo Ambiental – Subcuenca Río Surat� a.
Corporaci� on Aut� onoma Regional para la Defensa de la Meseta de Bucaramanga,
Bucarmanga (in Spanish). http://www.cdmb.gov.co/web/ciudadano/centro-de-de
scargas/1185-pomca-subcuenca-surata (accessed 20 February 2020).
Chen, H., Yanguo, T., Li, J., Wu, J., Wang, J., 2016. Source apportionment of trace metals
in river sediments: a comparison of three methods. Environ. Pollut. 211, 28–37.
Fern�andez, G., Ríos, C., Reyes, O., 2016. Auro-argentiferous mineralization hosted in a
hydrothermal gap in the vicinity of the La Baja mine, California-Vetas mining
district, Santander (Colombia). Bistua: Revista de la Facultad de Ciencias B� asicas 14,
58–92 (in Spanish).
Gbolo, P., Lopez, D., 2015. Analysis of trace elements pollution within streambed
sediments from the Shade River Watershed, southeastern Ohio. Environ. Earth Sci.
73, 7193–7204. https://doi.org/10.1007/s12665-014-3899-9.
D.L. Alonso et al.
Greystar, 2009. Estudio de Impacto Ambiental - Proyecto Angostura. Greystar Resources
Ltd., Bucaramanga (in Spanish).
Henke, K., 2009. Arsenic: Environmental Chemistry, Health Threats and Waste
Treatment. Wiley & Sons, ISBN 978-0-470-02758-5.
Kim, E.J., Yoo, J.C., Baek, K., 2014. Arsenic speciation and bioaccessibility in arsenic-
contaminated soils: sequential extraction and mineralogical investigation. Environ.
Pollut. 186, 29–35.
Kreidie, N., Armiento, G., Cibin, G., 2011. An integrated geochemical and mineralogical
approach for the evaluation of arsenic mobility in mining soils. J. Soils Sediments 11,
37–52. https://doi.org/10.1007/s11368-010-0274-7.
Li, P., Qian, H., Howard, K.W., Wu, J., Lyu, X., 2014. Anthropogenic pollution and
variability of manganese in alluvial sediments of the Yellow River, Ningxia,
northwest China. Environ. Monit. Assess. 186 (3), 1385–1398. https://doi.org/
10.1007/s10661-013-3461-3.
Li, P., Wu, J., Qian, H., Zhou, W., 2016. Distribution, enrichment and sources of trace
metals in the topsoil in the vicinity of a steel wire plant along the Silk Road economic
belt, northwest China. Environ. Earth Sci. 75 (909), 1–16. https://doi.org/10.1007/
s12665-016-5719-x.
Litter, M., Armienta, A., Farías, S., 2009. Metodologías analíticas para la determinaci� on y
especiaci�on de Ars�enico en aguas y suelos. IBEROARSEN, CYTED, Buenos Aires (in
Spanish).
Little, A.J, Sivarajah, B., Frendo, C., Sprague, D.D, Smol, J.P, Vermaire, J.C, 2020. The
impacts of century-old, arsenic-rich mine tailings on multi-trophic level biological
assemblages in lakes from Cobalt (Ontario, Canada). Sci. Total Environ 709, 1–14.
https://doi.org/10.1016/j.scitotenv.2019.136212, 136212.
L�
opez, I., Díaz, M., 2009. Gesti� on ambiental en el P� aramo de Santurb� an, Distrito Minero
California-Vetas. Monografía. Universidad Industrial de Santander, Bucaramanga (in
Spanish). http://noesis.uis.edu.co/bitstream/123456789/32995/1/131241.pdf
(accessed 20 February 2020).
Mahecha, Y.A., Púa, A.M., Ortiz, F.E., 2018. Minería, medio ambiente y desarrollo.
Efectos socio ambientales de la delimitaci� on del P�aramo de Santurb� an en los
Municipios de Vetas y California, durante el periodo de 2006-2016. Universidad de
la Salle, Monografia (in Spanish). http://repository.lasalle.edu.co/bitstream/hand
le/10185/28650/64131128_2018.pdf?sequence¼1&isAllowed¼y (accessed 20
February 2020).
Manful, G., 1992. Occurrence and Ecochemical behaviour of arsenic in a Goldsmelter
Impacted Area in Ghana. PhD dissertation. Centrum Voor Milieusaneringen de RUG.
Mondal, P., de Alc^ antara, R., Jonathanc, M.P., Jayanta, K., Kadarkarai, M., et al., 2018.
Seasonal assessment of trace element contamination in intertidal sediments of the
meso-macrotidal Hooghly (Ganges) River Estuary with a note on mercury speciation.
Mar. Pollut. Bull. 127, 117–130.
Parka, J., Díaz, N., Mejía, S., 2018. Challenges in implementing the extended producer
responsibility in an emerging economy: the end-of-life tire management in
Colombia. J. Clean. Prod. 189, 754–762.
Paula, J.F., Froes, R.E., Ciminelli, V.S., 2012. Arsenic determination in complex mining
residues by ICP OES after ultrasonic extraction. Microchem. J. 104, 12–16.
Pedersen, H.D., Postma, D., Jakobsen, R., 2006. Release of arsenic associated with the
reduction and transformation of iron oxides. Geochem. Cosmochim. Acta 70,
4116–4129. https://doi.org/10.1016/j.gca.2006.06.1370.
Pignotti, E., Guerra, R., Covelli, S., Fabbri, E., Dinelli, E., 2018. Sediment quality
assessment in a coastal lagoon (Ravenna, NE Italy) based on SEM-AVS and sequential
extraction procedure. Sci. Total Environ. 635, 216–227.
10
Journal of Environmental Management 264 (2020) 110478
Redon, P.O., Bur, T., Guiresse, M., Probst, J., Toiser, A., et al., 2013. Modelling trace
metal background to evaluate anthropogenic contamination in arable soils of south-
western France. Geoderma 206, 112–122. https://doi.org/10.1016/j.
geoderma.2013.04.023.
Rasool, A., Xiao, T., Farroqi, A., Shafeeque, M., Masood, S., et al., 2016. Arsenic and
heavy metal contaminations in the tube well water of Punjab, Pakistan and risk
assessment: a case study. Ecol. Eng. 95, 90–100. https://doi.org/10.1016/j.
ecoleng.2016.06.034.
Rieuwerts, J.S., Mighanetara, K., Braungardt, C.B., Rollinson, G.K., Oirrie, D., et al.,
2014. Geochemistry and mineralogy of arsenic in mine wastes and stream sediments
in a historic metal mining area in the UK. Sci. Total Environ. 472, 226–234. https://
doi.org/10.1016/j.scitotenv.2013.11.029.
Rojas, S., Cramer, T., 2013. Metalogenia de las mineralizaciones auríferas en la zona de
Vetas, Santander. Tesis. Universidad Nacional de Colombia, Bogot� a (in Spanish).
Sarkar, A., Paul, B., 2016. The global menace of arsenic and its conventional remediation
- a critical review. Chemosphere 158, 37–49. https://doi.org/10.1016/j.
chemosphere.2016.05.043.
Sim, R., Altman, K.A., 2010. Canadian national instrument 43-101, technical report for
La Bodega project California-Vetas district department of Santander. Colombia 2010,
1–105.
Stüben, D., Berner, Z., Chandrasekharam, D., Karmakar, J., 2003. Arsenic enrichment in
groundwater of West Bengal, India: geochemical evidence for mobilization of as
under reducing conditions. Appl. Geochem. 18, 1417–1434. https://doi.org/
10.1016/S0883-2927(03)00060-X.
Team, R.C., 2015. R: A Language and Environment for Statistical Computing. R
Foundation for Statistical Computing, Vienna.
Tessier, A., Campbell, P., Bisson, M., 1979. Sequential extraction procedure for the
speciation of particulate trace metals. Anal. Chem. 51, 844–851.
Thuong, N.T., Yoneda, M., Ikegami, M., Takakura, M., 2013. Source discrimination of
heavy metals in sediment and water of To Lich River in Hanoi City using multivariate
statistical approaches. Environ. Monit. Assess. 185 (10), 8065–8075. https://doi.
org/10.1007/s10661-013-3155-x.
Van Herreweghe, S., Swennen, R., Vandecasteele, C., Cappuyns, V., 2003. Solid phase
speciation of arsenic by sequential extraction in standard reference materials and
industrially contaminated soil samples. Environ. Pollut. 122, 323–342.
Wenzel, W., Kirchbaumer, N., Prohaska, T., Stingeder, G., Lombi, E., et al., 2001. Arsenic
fractionation in soils using an improved sequential extraction procedure. Anal.
Chim. Acta 436, 309–323.
Wolff, E., 2001. Proyecto Río Surat� a: líneas de acci� on para reducir contaminaci�on
proveniente de la peque~ na minería aurífera en Vetas y California (Departamento de
Santander, Colombia). Jornada Internacional sobre el Impacto Ambiental del
Mercurio utilizado por la minería aurífera artesanal en Iberoam�erica, Lima (in
Spanish).
WHO - World Health Organization, 2011. Arsenic in Drinking-Water. Background
Document for Development of WHO Guidelines for Drinking-Water Quality. WHO,
Geneva (WHO/SDE/WSH/03.04/75/Rev/1).
Zan, F., Huo, S., Zhang, J., Zhang, L., Xi, B., et al., 2014. Arsenic fractionation and
contamination assessment in sediments of thirteen lakes from the East Plain and
Yungui Plateau Ecoregions, China. J. Environ. Sci. 26, 1977–1984.
Zhang, Y., Xu, B., Guo, Z., Han, J., Li, H., et al., 2019. Human health risk assessment of
groundwater arsenic contamination in Jinghui irrigation district, China. J. Environ.
Manag. 237, 163–169. https://doi.org/10.1016/j.jenvman.2019.02.067.