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Arch Environ Contam Toxicol

DOI 10.1007/s00244-015-0134-y

Arsenic Mobility in Sediments from Paracatu River Basin, MG,

Patrcia Sueli Rezende Letcia Malta Costa
Claudia Carvalhinho Windmoller

Received: 18 September 2014 / Accepted: 27 January 2015

Springer Science+Business Media New York 2015

Abstract Paracatu River Basin, Minas Gerais, Brazil,

houses long areas of irrigated agriculture and gold-, lead-,
and zinc-mining activities. This region has a prevalence of
sulfide minerals and a natural occurrence of high levels of
arsenopyrite. In this work, surface water, groundwater,
sediments and local vegetable samples were collected in
October 2010 and November 2011 and were analyzed to
evaluate arsenic (As) distribution, mobility, and transport
in these environmental compartments. All sediment samples (7382,750 mg kg-1) and 37 % of the water samples
[less than the limit of detection (LOD) to 110 lg L-1]
from the rivers and streams of Paracatu had As concentrations greater than the quality standards established by
national and international environmental organizations
(5.9 mg kg-1 for sediments and 10 lg L-1 for water).
Most vegetable samples had As concentrations within the
normal range for plants (lower than the LOD to
120 mg kg-1). A correlation among As concentrations in
water, sediment, and vegetable samples was verified.
Electronic supplementary material The online version of this
article (doi:10.1007/s00244-015-0134-y) contains supplementary
material, which is available to authorized users.
P. S. Rezende (&)  L. M. Costa  C. C. Windmoller
Departamento de Qumica, ICEx, UFMG - Universidade Federal
de Minas Gerais, Belo Horizonte, MG, Brazil
e-mail: patriciarezende@des.cefetmg.br
L. M. Costa
e-mail: leticia@qui.ufmg.br
C. C. Windmoller
e-mail: claudiaufmg@hotmail.com
P. S. Rezende
Departamento de Qumica, CEFET-MG - Centro Federal de
Educacao Tecnologica de Minas Gerais, Belo Horizonte, MG,

The Agency for Toxic Substances and Disease Registry

(ATSDR) from the Department of Health of the United
States biannually classifies the most dangerous substances
to human health. Since 1997, As is at the top of the list
(Assis 2010; ATSDR 2011; World Heath Organization
(WHO) 2010). As can be found in the environment in organic and inorganic forms (Maity et al. 2004; Assis 2006;
Baig et al. 2009; Tuzen et al. 2010). It is distributed in
several chemical forms and may transform itself through
the action of microorganisms, through changes in geochemical conditions, or through involvement in other
equilibriums that are affected by the presence of other ions
or compounds in the environment (such as Fe3?, S2-, and
iron [Fe] oxi-hydroxides) (Assis 2006). The inorganic
forms are more toxic than organic As species because
arsenite (AsO33-) is approximately 100 times more toxic
than arsenate (AsO43-) (Tuzen et al. 2010).
Approximately 99 % of As in the environment is associated with rocks and minerals. It is present in [200 minerals with approximately 60 % as arsenate; 20 % as
arsenosulfides associated with Fe, lead, copper, silver (Ag),
and thallium; and the remainder as arsenites, arsenides,
oxide, and elementary As (Mandal and Suzuki 2002; Assis
2006). As has a high affinity with sulfur, which results in a
low mobility to other environmental compartments as a
constituent of sulfide minerals (Mandal and Suzuki 2002;
Figueiredo 2010). Its most common mineral is arsenopyrite,
which is usually associated with gold (Au) and Ag mineralizations (Mandal and Suzuki 2002; Andrade 2007). As is
liberated from mineralized rocks when arsenopyrite is oxidized by oxygen (O2) through biotic or abiotic processes
(Rodrigues 2008). Mining activities are the main anthropogenic sources of As release to the environment (Assis
2006). The exposition of the source material favors the
weathering process, thus leading to sulfide oxidation, which


Arch Environ Contam Toxicol

may generate sulfuric acid (mine acid draining) by way of a

series of reactions (Figueiredo 2010; Andrade et al. 2012).
Some factors, such as grain size distribution, low pH values,
heat, and exposure to water and oxygen, may favor mineral
oxidation (Andrade et al. 2008) with the consequent release
of As to the soil solution and watercourse.
Arsenopyrite oxidation creates As oxyanions, which are
found in the form of arsenious acid (H3AsO3), As
(H3AsO4), and their deprotonated speciesH2AsO4-,
HAsO42-, AsO43- (arsenate ion), H2AsO3-, HAsO32-,
and AsO33- (arsenite ion)in solutions. The prevalent
forms vary according to the pH and redox potential of the
environment (Rodrigues 2008). As release into surface
water and groundwater occurs in steps and may suffer
various influences of the medium conditions and presence
of other ions and compounds. Thus, it has been verified that
As transportation among different environmental compartments and its assimilation with other living organisms
depend on its oxidation state, environmental redox conditions, and biological activities (Mandal and Suzuki 2002;
Welch et al. 2000).
As concentrations in air are usually low, although there
is an increase in more populated and industrialized areas.
Beavington et al. (2004) showed metal concentrations in air
particulate from Port Kembla, Australia, from 1978 to
2002. As varied in the range of 13.529.0 ng kg-1 of
particulate matter. Benin et al. (1999) determined As and
other elements in dust from different Mexican cities, and
median As values were 32, 42, and 113 ng kg-1 in Chihuahua, Monterrey, and Torreon, respectively. The investigators observed that dust As levels decreased with
distance from the industrial sites. As usually enters the
atmosphere through erosion caused by winds, volcanic
emissions, volatilization from soils, ocean aerosols, and
pollution. It is predominantly found in its inorganic form
and is adsorbed on particulate matter usually at \2.5 lm.
Dust is the main transport means of As emissions to the
atmosphere. These particles are spread by the wind and
return to the soil and watercourses because of wet and dry
deposition (Mandal and Suzuki 2002; Carabantes and de
Fernicola 2003; Palmieri 2006; Csavina et al. 2012).
When assimilated by living organisms, As is biotransformed (Goering et al. 1999; Vahter 2002; Carabantes and
de Fernicola 2003; Assis 2006; Palmieri 2006; Deschamps
and Matschullat 2007; Lomax et al. 2012; Cullen 2014;
Hunt et al. 2014). First, it suffers reduction reactions that
later lead to methylation and make it less toxic as well as
glutathione conjugation in the liver to form more polar
metabolites for excretion (detoxification process) (Goering
et al. 1999; Vahter 2002; Lomax et al. 2012; Cullen 2014;
Hunt et al. 2014). At the cellular basis, it may interfere in
methyltransferase activity and oxidative phosphorylation
and compete with phosphorus in metabolic reactions


(Goering et al. 1999; Vahter 2002; Lomax et al. 2012). It is

a toxic bioaccumulative element to mammals (Goering
et al. 1999; Vahter 2002; Carabantes and de Fernicola
2003; Assis 2006; Palmieri 2006; Deschamps and
Matschullat 2007; Lomax et al. 2012; Cullen 2014; Hunt
et al. 2014). Historically, the methylation of inorganic As
was believed to detoxify the metalloid because methylated
metabolites, such as monomethylarsinous acid (MMAsIII)
and dimethylarsinous acid (DMAsIII), were found in the
urine of exposed animals (Cullen 2014; Hunt et al. 2014).
For the past decade, however, studies have shown that
methylated arsenites, including MMAsIII and DMAsIII,
are more toxic than As (Hunt et al. 2014).
Several studies have shown that As exposure by way of
drinking water is the main form of human exposure
(Mandal and Suzuki 2002; Carabantes and de Fernicola
2003; WHO 2010; Bundschuh et al. 2012). Cases of
chronic exposition to high levels of As in water have been
reported from many countries. Contaminations that occurred in Bangladesh (Nickson et al. 1998, 2000; Anawar
et al. 2011), India (Nickson et al. 2000; Chakraborty and
Saha 1987), Taiwan (Tseng et al. 1968; Chen et al. 1994;
Liao et al. 2011), Vietnam (Nguyen and Itoi 2009; Nguyen
et al. 2009; Phuong et al. 2012), Mexico (Cebrian et al.
1983), Chile (Carabantes and de Fernicola 2003; Bundschuh et al. 2012) and Argentina (Smith et al. 1992;
Hopenhayn-Rich et al. 1996, 1998; Faras et al. 2003;
Bundschuh et al. 2012) are among the most serious cases.
In Brazil, one of the most problematic areas is the Iron
Quadrangle in the state of Minas Gerais (MG; Matschullat
et al. 2000; Deschamps et al. 2002; Borba et al. 2003, 2004;
Mello et al. 2006, 2007; Deschamps and Matschullat 2007;
Bundschuh et al. 2012) where the increase of As concentrations in water and sediments is related to the element
released by mining activities. In addition to this region,
other areassuch as the Ribeira Valley (Parana and Sao
Paulo) (Companhia de Pesquisa de Recursos Minerais
[CPRM] 2003; Figueiredo et al. 2007; Rodrigues 2008),
Santana (Amapa) (CPRM 2003) and Paracatu (MG)
(CPRM 2003; Mello et al. 2006; Figueiredo et al. 2007;
Mello et al. 2007; Andrade 2007; Andrade et al. 2008,
2012; Rezende 2009)have shown high As concentrations
in water and/or sediments,
Paracatu River Basin is located predominantly in the
northwest of MG [19 cities (92 %)] including also three
cities in the state of Goias and a small area of the Federal
District. It amounts to approximately 10 % of the total area
of the Sao Francisco River Basin and is responsible for
draining a basin of about 45,000 km2 accounting nearly
24 % of the total flow of the Sao Francisco River (Instituto
guas 2010) The Paracatu River
Mineiro de Gestao das A
Basin was first occupied by bandeirantes (scouts) and adventurers during the colonial period after the discovery of

Arch Environ Contam Toxicol

Au in the region in the eighteenth century, which accelerated the settlement of this region. This area is known as
Morro do Ouro (Gold Mountain) and is located in Paracatu.
After the decrease of Au production, the population began
to dedicate themselves to farming activities. Although the
exploration of Au in Paracatu began in the eighteenth
century, in the mid 1980s there was a boom of mining
activities with an indiscriminate use of mercury and consequential degradation of the area. (Tannus et al. 2001;
Gurgel 2007; Almeida 2009; Mulholland 2009) The most
important points of mining exploration were located along
Corrego Rico (Santos 2012). Au extraction still exists in
this region and is executed by a mining company, but
prospectors are prohibited (Santos 2012). It is also relevant
to note that there is a natural occurrence of arsenopyrite in
this region (Mello et al. 2006; Monteiro et al. 2006; Andrade et al. 2008).
Considering the naturally increased levels of As and the
history of Au mining in the region, it is important to assess
the availability of As in the environment. The goal of this
work was to evaluate the As distribution, mobility and
transport in Paracatu, MG, Brazil.

Table 1 Geographical coordinates of the sampling points

Sampling point code


Asub 01

S 17o140 16000

Asub 02


S 17 13 062


S 17 120 0800

Asub 04

S 17o120 41000

Asub 06

W 46o530 30600
W 46o510 5500

Asub 03
Asub 05

W 46o520 54800

W 46o540 02900


W 46o520 54800


W 46o530 30600

S 17 14 160
S 17 13 062

W 46o510 5500


Asub 07

S 17 12 08

Asub 08

S 17 120 41000

W 46o540 02900

Abica 01

S 17o110 50300

W 46o550 35500


W 46o550 35500

Asup 01/Sed 01
Asup 02/Sed 02


S 17 12 698
S 17o140 41300

W 46o530 46200
W 46o510 69700

Asup 03/Sed 03

S 17o130 86800

W 46o520 47100

Abica 02

S 17 11 503

Asup 04/Sed 04

S 17 130 05700

W 46o530 42700

Asup 05/Sed 05

S 17o120 08100

W 46o510 55100

Asup 06/Sed 06
Asup 07/Sed 07


W 46o490 44300


W 46o570 66200


W 46o520 50000

S 17 08 856
S 17 15 360

Asup 08/Sed 08

S 17 12 249

Asup 09/Sed 09

S 178180 1500

W 468460 1500

Materials and Methods

Water and Sediments
Two samplings (October 2010 and November 2011) were
performed in Paracatu, MG, Brazil. The most important
points of Au-mining exploitation were located in Corrego
Rico (Santos 2012), which has its source close to the area
of mining in the Morro do Ouro. After draining the city, the
stream travels a distance of approximately 60 km and flows
into the left bank of the Rio Paracatu (Tannus et al. 2001;
Gurgel 2007). Five sampling points of surface water and
sediment were chosen in the Corrego Rico to take account
of samples near the mining area, in the urban area, and
after draining the city (downstream). One point in a
tributary of the Corrego Rico and three points in streams
outside of the mining influence, with one of them being in
the source area that supplies the city, were also chosen. The
groundwater samples were also collected to cover areas
near the mining activity, the central urban area and rural
areas. Table 1 lists the geographical coordinates of the
collection points. Figure 1shows a map of the area.
In each sampling, the surface water and margin sediments samples were collected at nine points in different
rivers and streams. At every point, surface water and
sediment samples were collected next to the margin and in
the superficial layer (30-cm deep) using a bucket and

plastic shovel, respectively. Surface water samples were

collected before sediment samples.
Surface water (Asup) and sediment (Sed) samples were
collected and preserved according to United States Environmental Protection Agency (USEPA) recommendations
(USEPA 2001, 2007a). Immediately after sampling, all
water samples were filtered through a 0.45-lm nitrocellulose membrane and were divided in two subsamples: one
was reserved for the speciation analysis (nothing was added
to this subsample), and the other one was acidified with
concentrated HNO3. They were stored in high-density
polyethylene bottles and maintained frozen until analysis.
The sediment samples were stored in plastic flasks and
were refrigerated until further use. In the laboratory, these
samples were dried at room temperature, manually disaggregated in a morta, and sifted in two fractions (20.063
and \0.063 mm). The finest fraction was used in the analysis because is the most important fraction to show the
processes occurring in this matrix.
Twelve groundwater samples (Asub) were collected
(five in the first collection and seven in the second collection) in both urban and rural areas of Paracatu, which
totaled ten different points. We were unable to collect at
exactly the same place at all points during the first and
second collection. Sometimes we collected samples near
points as can be seen on the map shown (Fig. 1). Preservation recommendations were performed according to
USEPA guidelines (USEPA 2007b).


Arch Environ Contam Toxicol

Fig. 1 Paracatu city map. a Location of Paracatu. b Paracatu sampling points of surface water and sediments. c Paracatu sampling points of

Vegetable samples were directly purchased from small
farmers (n = 17) or markets (n = 10): lettuce (n = 7),
endive (n = 3), spring onion (n = 2), kale (n = 9), mustard (n = 1), and parsley (n = 5). Then, they were stored
in sealed plastic bags, frozen during transportation, and
triturated and lyophilized in the laboratory.
Standard Solutions and Reagents
All chemicals were of analytical grade. All solutions and
dilutions were prepared using deionized water from a MilliQ system (18.2 MX cm-1; Millipore Direct-Q 3, Molsheim, France). Stock solutions (100 mg L-1) of As(III) and
As(V) were prepared from As2O3 (Merck, Darmstadt, Germany) and Na2HAsO4.7H2O (Quimibras, Rio de Janeiro,
Brazil), respectively. A mass of 0.1321 g of As2O3 (Merck,
Darmstadt, Germany) was accurately weighted, dissolved in
40.0 mL of a NaOH (Vetec, Rio de Janeiro, Brazil) 20 %
(w/v) solution, neutralized with 80.0 mL of a 10 % (v/v)


HCl (Merck) solution, and diluted to 1,000 mL. To prepare

the As(V) solution, 0.2082 g of Na2HAsO47H2O was dissolved in 500 mL of deionized water. For total As, a certified standard solution (1,000 mg L-1) was obtained from
Merck (Darmstadt, Germany). Working solutions were daily
prepared by dilution of the stock solutions.
In the sediment sample digestion, HCl, HNO3, HF, H2O2,
and H3BO3 (Merck, Darmstadt, Germany) were employed.
In the hydride-generation process, NaBH4 (Isofar, Duque de
Caxias, Brazil), NaOH (Vetec, Rio de Janeiro, Brazil), and
thiourea (Merck, Rio de Janeiro, Brazil) were also used.
As determination in water and vegetables was performed
using a Perkin-Elmer AAnalyst FIAS 100 hydride generator system coupled to a Perkin-Elmer AAnalyst 200
flame atomic absorption spectrometer (FAAS) (PerkinElmer, Shelton, USA). An MHS-20 mantle heating system
was used to heat the quartz cell, and a deuterium lamp was
used as the background corrector. An electrodeless

Arch Environ Contam Toxicol

discharge lamp of As that operated at 400 mA was used as

the energy source, and the As signal was detected at
193.7 nm. The instrumental conditions were optimized as
in previous work (Rezende et al. 2013) to perform total As
and trivalent As determination in water.
Total As determination in sediment samples was performed using the previously described FAAS, the same
lamp, and air-acetylene flame (99.5 %, White Martins,
Brazil) 10:3.3. The software WinLab 32 was used to obtain
and process data.
A digital pH meter (Marte MB-10, Sao Paulo, Brazil), a
Perkin-Elmer PE 2400 Series II CHNS/O Elemental Analyzer
(Perkin-Elmer, Shelton, USA), a Hanna Instruments HI 9146
portable dissolved oxygen (DO) meter (Hanna Instruments,
Sao Paulo, Brazil), and a Hanna Instruments HI 8424 N
portable pH, redox potential, and temperature meter (Hanna
Instruments, Sao Paulo, Brazil) were used for the physicochemical characterization. An analytical balance (AX200;
Shimadzu, Sao Paulo, Brazil), a Fanen Excelsa II 206 BL
centrifuge (Sao Paulo, Brazil), a TECNAL TE 394/1 oven for
drying with renewal and air circulation (Sao Paulo, Brazil), a
Milestone Ethos 1 microwave oven for closed-vessel acid
digestion (Milestone, Sorisole, Italy), a Thermo Scientific
Modulyod-230 freeze dryer, two sievers Bertel (Thermo
Scientific, Caieiras, Brazil), and a Bronzinox sieve (Bronzinox, Santo Amaro, Brazil) were also used.
Analytical Procedure
Physicochemical Characterization of the Samples
The redox potential, pH, temperature, and DO were determined using portable devices to characterize the physicochemical properties of the water samples in the field. For
the physicochemical characterization of the sediment
samples, the procedures included a grain size analysis and
pH determination according to Soil Survey Laboratory
Staff (1992) cited by EMBRAPA guidelines (1997). Cationic exchange capacity (CEC) estimates were calculated
according to the proposed method of Keng and Uehara
(1974). Organic matter content was estimated from a CHN
elemental analysis, which was executed in duplicate according to Machado et al. (2003) and Segnini et al. (2008).
Sediment-Sample Digestion
Sediment samples were digested using a cavity-microwave
oven and acid attack as described in Vieira et al. (2005).
Approximately 200 mg of the sample (\0.063 mm) was
directly weighted in the perfluoroalkoxy (PFA) vessels, to
which 6.00 mL of aqua regia and 2.00 mL of concentrated
HF were added. This mixture was left for approximately
30 min; then, 2.00 mL of hydrogen peroxide was added to

each vessel. The vessels were closed and submitted to the

digestion program for 38 min. After the digestion program
finished, the vessels were cooled to room temperature; then
they were opened, and the mixture was transferred to
polyethylene flasks that had been previously decontaminated. In each flask, 1.0 g of boric acid was added, and
the volume was adjusted to 30.0 mL. The procedure was
executed in triplicate for all samples. To evaluate the accuracy of the digestion procedure, the certified materials
NIST 2711 Montana Soil and GBW 8301 River Sediment
were digested under the same conditions. All flasks and
glassware were maintained in an acid bath (10 % v/v
HNO3) for at least 24 h and subsequently washed three
times with deionized water before their use.
Vegetable-Sample Digestion
The vegetables samples were also digested with acid attack
using a cavity-microwave oven. Approximately 250 mg of
a triturated and lyophilized sample was directly weighted
in the PFA vessels, to which 3.00 mL of deionized water
and 3.00 mL of concentrated HNO3 were added. This
mixture was left for approximately 30 min, and 2 mL of
H2O2 30 % m/m was later added to each vessel. The vessels were closed and submitted to the digestion program for
20 min. After the digestion program completed, the bottles
were cooled to room temperature; then they were opened;
the solution was transferred to polyethylene flasks that had
been previously decontaminated; and their volumes were
adjusted to 25.0 mL. The procedure was executed in triplicate for all samples. To evaluate the accuracy of the digestion procedure, the certified materials GBW 10016 Tea
Leaves and NIST 1515 Apple were used.
Determination of As in Water Samples
For total As determination, a prereduction step using
thiourea was employed to determine As(V) as As(III). An
aliquot of thiourea prepared in 0.01 mol L-1 HCl was added
to the samples at a final concentration of 0.10 % w/v. This
solution was kept in contact at least for 1 h before the analysis. The following instrumental conditions were applied:
0.2/0.05 % w/v NaBH4/NaOH (46 mL min-1) as the reducing agent, 10 % v/v HCl (812 mL min-1) as the carrier
acid, and argon (50 mL min-1) as the carrier gas.
Based on the kinetic mechanisms of formation of arsine
from As(III) and As(V) ions, the measurements of the
As(III) concentration in water samples were performed by
selective hydride generation. The As(III) species was determined without prereduction step. All samples were diluted by adding citrate buffer (pH 5) to a final dilution of
50 % v/v. The operational conditions were as follows: reducing agent 0.2/0.05 % w/v NaBH4/NaOH w/vw/v


Arch Environ Contam Toxicol

(46 mL min-1), carrier acid 0.1 mol L-1 C6H8O7 (citric

acid) (812 mL min-1), and carrier gas Ar (50 mL min-1).
The samples were divided into two parts: one part was
diluted with citrate buffer (pH 5.0) for the determination of
trivalent species; and to the another part, a thiourea solution was added for the determination of total As determination. The As(V) concentration was estimated as the
difference between total inorganic As and As(III).
Statistical Analysis
Statistical analysis of the data was performed using Microsoft Excel 2007 for Windows and Statistica 8.0.

Results and Discussion

Average concentrations of total As in surface water,
groundwater, and sediment from Paracatu, MG, Brazil, are
listed in Tables 2 and 3, respectively. To better characterize the environmental conditions that may influence As
release and transport among these compartments, other
physical and chemical parameters were also determined
and are listed in the same tables.
According to the Director Plan for Water Resources
from the Paracatu River Basin (CBHParacatu 2005) and
the Brazilian legislation (CONAMA Resolution 357/2005),
the rivers and streams studied in this work are classified as
watercourse class 2, which indicates that these waters can
be used for human supply (after conventional treatment),
primary-contact recreation, protection of aquatic communities, irrigation, aquaculture, and fishing activities.
Surface-water samples had an average temperature of
26 C, pH levels close to neutrality, low values of redox
potential, and DO \6.5 mg L-1. Four samples from the
first collection had DO values \5 mg L-1, which is the
quality level for this watercourse class. Furthermore, this
parameter concentration increased in the second collection
in all sampling points.
Six surface-water samples (Asup 01, Asup 02, Asup 03,
Asup 06, Asup 08, and Asup 09) exceeded the tolerable
limits of As established to watercourse classes 1 and 2
(10 lg L-1). It is important to mention that the international limit of As in drinking water is 10 lg L-1 according
to WHO (2010). In the first collection (October 2010), the
samples had 1849 % of the total As in arsenite form. In
the second collection (November 2011), the trivalent species increased in percentage at most sampling points with a
variation of 773 % of the total As concentration in water.
Four surface-water samples (Asup 02, Asup 03, Asup
07, and Asup 08) had Al concentrations greater than the
limit for watercourse class 2 (100 lg L-1). Surface-water
samples Asup 01 and Asup 08 had manganese (Mn)


concentration levels greater then the limits established for

class 2 (100 lg L-1). The Fe concentration in most surface-water samples also exceeded the limit value
(300 lg L-1) established for class 2.
Groundwater samples generally had a lower pH, redox
potential, temperature, and DO than the surface-water
samples. Sample Asub 03 exceeded the limits of Fe for
human consumption and recreation (300 lg L-1) and was
only appropriate for irrigation (500 lg L-1), according to
CONAMA Resolution 396/2008. Sample Asub 02 exceeded the tolerable limits of As (10 lg L-1), aluminum
(Al; 100 lg L-1), Mn (100 lg L-1), and Fe for human
consumption, according to CONAMA Resolution 396/
2008. Both As and Al levels satisfied the limits for animal
watering. Al also approached the limit for irrigation, and
As levels were appropriate for recreation according to the
values established by the legislation. Manganese levels
exceeded the limits for all uses. Therefore, the water is
unsuitable for human consumption, animal watering, irrigation, and recreation.
In general, the surface water samples from the second
collection presented greater concentrations of Fe and Mn
and lower concentrations of As than those from the first
collection. Total As ranged from 0.55 to 110 lg L-1 in the
first sampling and from 0.50 to 31.4 mg lg L-1 in the
second one. In the time between the two collections, there
was a revitalization of the Corrego Rico removing waste
from the banks and building retaining walls to decrease
erosion and recovery in margins. Moreover, the results
showed an increase of DO in the second collection, which
favored a decrease of total As concentration because the
oxidant medium favors the presence of the As(V), which is
less mobile and coprecipitates with Fe oxides in pH near
The sediment samples were characterized by greater
percentages of the sandy fraction and lower percentages of
organic matter (\5.5 %). Their pH values in water were
close to neutral, and they were slightly alkaline with a few
exceptions. They had low DpH values, although most
samples had increased this parameter in the module in the
second collection. Considerable pH variations were not
detected in either sampling. In general, the samples had
greater DpH values and greater organic matter content in
the second collection, whereas the fine sieve fraction percentage (\0.063 mm) was greater in the first one.
All of the analyzed sediment samples presented As
concentrations greater than the threshold effect level
(TEL), probable effect level (PEL), and severe effect level
(SEL) limits of the Canadian Council of Minister of the
Environment (Canadian Council of Ministers of the Environment [CCME] 1999: They were, respectively, 5.9, 17,
and 33 mg kg-1. As previously mentioned, this region
presents naturally high levels of arsenopyrite (Mello et al.































































Data from Rezende et al. (2013)











































CRM 1643e

















potential (mV)


700 100
1000 100
2000 100
1900 100
700 100
2200 100
400 100


96.2 2.1

98.1 1.4


141.8 8.6

105 17


57 7

406 13

1090 36

100 7

53 7

386 13

230 13

306 13

353 13





93 7

808 36

204 13


590 30

3700 100





Fe (lg L-1)


139.7 29.3

96 13

912 92

187 8

54 1

32 1

43 5

109 2

107 1

48 2

49 1

80 2

43 2

380 30

128 9


















Al (lg L-1)


















(mg L-1)

36.84 5.89

38.97 0.45

19 1

300 25

22.9 0.6

9.0 0.1

14.5 0.1

47 1

78 3

90 4

115 1

2.2 0.1

9.0 0.2

4.4 0.2

1648 72

68 3




19 33

41 33

22 33

19 33

20 33

10 33

31 33

65 33




38 33

43 33

134 33

12 33


Mn (lg L-1)

63.80 3.70

60.45 0.72

73.7 3.2

110.0 0.3

0.55 0.01

28.6 0.9

9.21 0.13

3.19 0.03

40.0 0.1

54.8 0.2

18.7 0.5

0.27 0.03

1.11 0.04

1.62 0.03

15.7 1.2

0.38 0.02



6.4 0.2

31.4 0.2

0.50 0.02

26.9 0.1

15.2 0.4

6.3 0.1

19.9 0.3

28.0 0.2

8.8 0.2

3.6 0.5

1.4 0.2

3.3 0.4

2.1 0.3

0.35 0.03

10.0 0.3

1.9 0.1


Total As (lg L-1)

Table 2 Physicochemical parameters of water samples from Paracatu, MG, Brazil, and certified reference material NIST 1643e trace elements in water

13.6 0.5

0.47 0.02

4.3 0.7


53.7 2.2

13.7 0.4

7.4 0.1

3.6 0.1

14.5 0.5

17.1 0.5

5.0 0.1






13.5 0.6

3.8 1.1


13.4 0.7

21.8 1.0

8.5 0.4





9.9 0.5




Arsenite (lg L-1)a

Arch Environ Contam Toxicol


1283 39
680 24
620 4
1364 83
1062 53
1734 12
444 12
1056 72
62 3
671 28
1934 96
215 9
310 12
895 31
1084 33
361 31
232 20
354 27
638 28
648 23
975 34
918 38

7.1 0.2 9.1

6.1 0.2 9.1
6.0 0.1 7.3
3.1 0.1 9.4
4.1 0.1 3.7
4.4 0.2 3.4
3.7 0.1 4.0
7.8 0.1 5.8
4.7 0.3 4.8
2.89 0.06
2.85 0.06
3.94 0.13
3.71 0.01
2750 160
1410 73
1350 120
952 130
818 38
1030 65
738 15
946 80
789 75
2480 120
2090 250
1870 110
1670 190
1530 180
1940 130
941 110
1930 110
1430 110
105 8
101 3
56 10
54 3

4.7 0.2
5.6 0.2
6.5 0.1
5.4 0.3
5.6 0.7
3.9 0.3
5.1 0.1
4.2 0.1
5.63 0.02
6.53 0.09
5.61 0.33

2.87 0.3
1.8 0.1
4.4 0.1
4.4 0.3
6.3 0.1
1.86 0.05
2.4 0.2
3.5 0.8
5.0 0.1
2.0 0.2

GBW 8301

1.0 0.1
5.1 1.2
3.4 0.1
1.2 0.2
2.8 0.1
2.3 0.1
5.44 0.01
2.8 0.1
3.4 0.1
NIST 2711















Mn (mg kg-1)
Fe (%)
As (mg kg-1)
Al (%)
OM (%)
fraction (%)
\0.063 mm

Table 3 Physicochemical parameters of sediment samples from Paracatu, MG, Brazil, and certified reference materials NIST 2711 Montana Soil and GBW 8301 River Sediment

Arch Environ Contam Toxicol

2006; Monteiro et al. 2006; Andrade et al. 2008, 2012;

Costa Jr 1997). As concentrations in the samples varied
from 125 to 466 times the TEL limit.
Because the sediments are formed with different mineralogical substrates and organic matter deposition at the
bottom of watercourses, the As content in this compartment
was expected to be greater than in other areas because
arsenopyrite is a common mineral in this region. Consequently, the most important issue is the risk of As release to
the watercourse, which depends on several previously
mentioned factors such as pH, redox potential, substrate
grain size, type of clay mineral, and physical parameters of
the hydrous bodies including water flow and temperature.
In a previous study (Rezende et al. 2013), a method to
quantify arsenite in water was developed and applied to
some samples from Paracatu. The information related to
As speciation is important because of the difference in the
toxicity and in the mobility variation in the environment.
The total As and arsenite in water and total As in the
sediment data were compared, and Fig. 2 shows that there
is a relation between the As concentration in the sediment
and that in the surface water, i.e., the As concentration in
water was greater at the points with greater As levels in the
sediment. It is worth emphasizing that the total As concentration in water ranged from 0.35 to 110 lg L-1, i.e., up
to 11 times the legal limits, whereas in the sediments the
total As concentration varied from 738 to 2750 mg kg-1,
i.e., 125466 times greater then the legal limits. It is important to note that the As concentration at point Asup 07,
which corresponds to the water body from which the water
for public supply of Paracatu is obtained, is considerably
low, which satisfies the legislation requirements regarding
water for human consumption. Looking at Figs. 1 and 2
together, it is possible note that the As concentration of the
sediment decreases with increasing distance from the
mining area. Sampling points P1 and P8 are located close
to the mine. Point P7 is located approximately 20 km away
from the urban area of the city (source used for the water
catchment for public supply of the Paracatu). Point P9 is
located on the Corrego Rico outside of town. A significant
positive correlation between As in surface water and in
sediment was verified. As in water can be provenient by
particulate matter that was deposited in the sediment or if
the sediment releases the As into the water column. In
addition, it is possible there is atmospheric deposition of
dust, but this matrix was not analyzed. Furthermore, to
verify As transport among environmental compartments in
the studied area, the total As level in the vegetables sold in
town was measured. The results are listed in Table 4.
As concentrations in the analyzed vegetables are lower
then the critical range of values according to KabataPendias and Pendias (1992) cited by Palmieri (2006),
above which the toxicity effects are likely, and to McNihol

Arch Environ Contam Toxicol

Fig. 2 Correlation among total
and trivalent As in water and
total As in sediment

and Beckett (1985) cited by Palmieri (2006), above which

As may cause at least a 10 % weakening of the plant vitality (Table 4).
The obtained As concentrations in this work were also
lower than the rates found in other studies. Anawar et al.
(2012) determined As and Pb in various vegetables sold in
supermarkets in Spain and Bangladesh. The samples from
Bangladesh had high concentrations of AS B423 lg kg-1
because of the As contamination problems in the area.
Some vegetables from Bangladesh had B3 times greater
concentrations than the samples from Spain. Baig and Kazi
(2012) determined As in various vegetables grown in
contaminated areas in Pakistan and found amounts
B1,700 lg kg-1. As absorption from contaminated soils
was identified in both studies. Monitoring in food produced
in this regions is important because of the risks of attaining
the maximum tolerable amount of ingestion, particularly in
As absorption by land plants from soil is usually low.
One of the proposed mechanisms is that arsenate may be
absorbed by the plant against the phosphate anion because
of their ion size. Other factors, such as irrigation and atmospheric deposition, may contribute to increase absorption. Although the concentrations are low, we can observe
the relation among total As concentrations in water, sediment, and vegetable samples (Fig. 3). To better determine
this correlation, only vegetables with known place of cultivation were used (n = 17) (see Table 4 and Supplementary Information Table S1).
Figure 3 shows that the second sampling had lower total
As concentrations in water, sediment, and vegetable samples than the first sampling. The results show a relation
between As amounts in the different environmental compartments studied, which suggests that As was transported
among them. However, mobility may be low if the As
amounts in the vegetables are considered normal.

To understand the factors that contribute to As transport

and speciation, the obtained data for the total As and
As(III) in water, total As in the sediment, and other determined physicochemical parameters were submitted to
statistical treatment to search for the correlations. Pearson
correlation (P \ 0.05) was used, and several significant
correlations were identified (Tables S1 and S2). A high
correlation (?0.89 and ?0.77, respectively, for the first and
second collections) was observed between total As in
sediments and that in water.
In the second collection, the Al content and fine-particle
percentage in the sediment had a significant and positive
correlation (?0.57). Al silicates are frequently the main
constituents in clay minerals. Other works (Costa Jr 1997;
Mello et al. 2006; Andrade et al. 2008; Rezende 2009) that
involved soil or sediment samples from this region identified kaolinite, gibbsite, and muscovite as some of the
main minerals in the samples. A negative correlation between the As concentrations in the waterboth total and
trivalentand sediment and in the \0.063-mm particle
percentage was observed.
The pH values in water correlate positively with total As
(?0.79) and As(III) (?0.64) in water and negatively with Al
(-0.49), Fe (-0.89), and Mn (-0.58) concentrations in water. Fe and Mn amounts in sediment also correlate positively
with the total As concentration in water (w/Fe ?0.71; w/Mn
?0.74), As(III) in water (w/Fe ?0.88; w/Mn ?0.65), and total
As in sediment (w/Fe ?0.88; w/Mn ?0.62). It was also observed that trivalent As positively correlated with Mn in water
(?0.49), which suggests that As dissolution may be associated with Mn oxide dissolution. The increase in pH values
may favor the dissolution of As bound in the sediment
through an electrostatic interaction (Welch et al. 2000;
Mandal and Suzuki 2002; Rodrigues 2008; Figueiredo 2010).
Total and trivalent As concentrations in water in the first
collection negatively correlated with the pH in sediment


Arch Environ Contam Toxicol

Table 4 Total As concentration
in vegetables from Paracatu and
critical values in plants

Place of cultivation

Endive 01a

Next to Asub 01, P3

100 5

Endive 02



Endive 03a

Next to P6

59 1

Kale 01a

Next to Asub 07, P5


Kale 02


81 1

Kale 03


125 15

Kale 04


12.0 0.5

Kale 05a

Next to P6

8.0 0.2

Kale 06



Kale 07



Kale 08
Kale 09a

Next to P3
Next to P3


Lettuce 01a

Next to Asub 08, P5


Lettuce 02a

Next to Asub01, P3

28 2

Lettuce 03a

Next to P7


10 1

Vegetables with a known

place of cultivation







Lettuce 04

Next to P6

60 1

Lettuce 06a

Next to ASub 04

22 1

Lettuce 07


44 1

Mustard 01a

Next to ASub 04

73 6



Parsley 01

Next to P2

120 4



Parsley 02


86 4

Parsley 03a

Next to P3

80 10

Parsley 04a

Next to P1

18 4

Parsley 05a

Next to P1

18 3

Spring onion 01





Next to P1

26 2
90 10

Spring onion 02
GBW 10016 Certified

88 7

CRM 1515 Certified

38 7


36 7

(w/total As -0.72; w/As(III) -0.38) and DpH (w/total As

-0.54; w/As(III) -0.56), whereas with As in the sediment,
these correlations were positive. The second collection has
lower total and trivalent As concentration in water than the
first collection and positively correlated with pH values in
the sediment (w/total As ?0.66; w/As(III) ?0.57) and DpH
(w/total As ?0.67; w/As(III) ?0.60). In the second collection, DO increased in water at all points; the sediments
had greater pH values; the Fe and Mn contents in the
sediment increased at most points; and the percentage of
\0.063-mm particles was decreased. During total or partial
dissolution of As secondary minerals, part of the soluble As
adsorbed by Al, Fe, and Mn oxides in the soil or sediment
may be retained. Because of the increase of Fe and Mn in
the sediment, more As may be retained in the solid phase,
which contributes to its reduction in water. Anawar et al.


Critical concentration (lg kg-1)

Lettuce 05

A the level with probable toxic

effects (Kabata-Pendias and
Pendias 1984 cited by Palmieri
2006); B probable values that
weaken plant vitality by 10 %
(McNihol and Beckett; 1985
cited by Palmieri 2006)

As (lg kg-1)

Vegetables samples
(wet mass)

(2011) also found a positive and significant correlation

among As, Fe, and Mn concentrations in sediments. The
investigators suggested that the decrease of As in sediments might occur because of the coprecipitation with Fe
and Mn ions, which may occlude the As in the oxide, or
because of specific adsorption, which proves their strong
interaction and contributes to the As low mobility from the
sediment. According to Nriagu (1994), arsenate is predominant in alkaline and oxygenated media. In addition,
this species has lower mobility and greater affinity with Fe
and Mn oxides, which may justify the decreased As concentration in water in the second sampling. The total As
concentration in water and, consequently, As(III) concentration were also lower in the second collection; however,
the trivalent species presented greater percentages in this
collection in relation to the total concentration possibly

Arch Environ Contam Toxicol

Fig. 4 a Correlation between total As in water and redox potential

(Eh). b Correlation between Arsenite in water and redox potential (Eh)

Fig. 3 Box-plot graphics. a Total As in water samples. b Total As in

sediment samples. c Total As in vegetable samples

because the trivalent species had greater mobility and more

weakly interacted with the solid particles.
A correlation between the arsenite concentration in
water and DO and the Fe concentration in sediments and
redox potential was also observed, which shows that these
parameters are important to As speciation in the aquatic
environment. Because As is found in an anionic form, its
behavior is opposite to that of other trace elements; thus, its
mobility increases when pH increases as well as in reducing conditions (Assis 2010). Some sampling points had
negative redox potential values, which indicate reducing
conditions and alkaline pH, favoring its mobility. Figure 4 shows that the sampling points with low redox

potentials also had high total As concentrations in water.

The correlation with Fe suggests that the arsenite concentration in water may be associated with this species dissolution coprecipitated with Fe oxides or superficially
adsorbed through electrostatic interaction because there is
also a significant and positive correlation with DpH. In
addition, a more oxidant medium corresponds to a lower
total As concentration in water.
Some investigators have showed that in addition to the
pH conditions, organic matter contents, and Al, Fe, and Mn
oxi-hydroxides, microorganisms also play an important
role in the As-dissolving process and As transport from
sediments to surface water and groundwater. Anawar et al.
(2011) studied groundwater contamination in Bangladesh.
The investigators determined that the As concentration in
surface water, groundwater, and sediments was 0.45.0,
47.5216.8, and 0.2713.26 mg kg-1, respectively. Low
redox potential and DO values, virtually neutral pH, and
high Al, Fe, and Mn oxide amounts were also observed.
The investigators suggested that As mobilization in the
studied area is correlated with reducing conditions. Liao
et al. (2011) studied As mobility in aquifers in Taiwan. The
investigators found an As concentration of B562.7 lg L-1
in water, approximately 7 mg kg-1 in sediments, low organic matter content, and high Fe oxide amounts. Phuong
et al. (2012) evaluated the factors and sources of groundwater contamination in Vietnam and found As concentration B703 lg L-1 in water and 7.3725.1 mg kg-1 in


Arch Environ Contam Toxicol

sediments, which were characterized by high Fe and Mn

amounts in sediments, low redox potential and DO values,
and virtually neutral pH.
In these three works, notably similar physicochemical
conditions were observed, and the investigators concluded
that the high As mobility, which contaminated the hydric
resources, occurred because microorganisms participated
in the process of reductive dissolution of Fe oxides and
organic matter decomposition, which are two important
means of fixation of As in sediments. These works only
differ from the present study in Paracatu regarding the As
concentration in water and sediment. In Paracatu, the As
concentration is high in sediment and low in water compared with the values in these works. Despite the high
concentration of As in sediment at these points, the presence of Fe oxi-hydroxides and aluminosilicates may explain its retention in the sediments. The same behavior was
observed in other areas in Brazil such as Nova Lima and
Santa Barbara (Deschamps and Matschullat 2007; Mello
et al. 2006, 2007). Studies performed (Pereira et al. 2007;
Andrade et al. 2008; Rezende 2009) with sediment samples
from Brazilian areas with high As, Fe, and Mn concentrations, which were submitted to sequential extraction
procedures, show that even at high concentrations As remains virtually immobile.
When high Fe oxi-hydroxide amounts are available,
even in oxic surfaces of water or soil, the diluted As concentration is low, and they are also low when Fe sulfides
exist. (Figueiredo 2010; Sun et al. 2012) In both oxidation
states, arsenite and arsenate may be adsorbed by Al, Fe,
and Mn oxi-hydroxides, which illustrates the important role
of these elements in As mobility control (Deschamps and
Matschullat 2007; Mello et al. 2006, 2007; Silva et al.
2010, 2012). However, As(III) is more mobile, toxic and
soluble than As(V). The greater mobility of As(III) may be
explained by the nature of the interaction of this species
with the solid surface in the soil, which makes superficial
complexation, whereas As(V) produces ligand exchange
(Rodrigues 2008; Ladeira and Ciminelli 2000, 2004). At
pH [ 5 and in environments that are rich in particles
containing Fe, As remains virtually still (Rodrigues 2008;
Nriagu 1994).
Mello et al. (2006) studied the As mobility in soils and
sediments in contaminated areas in MG, Brazil. The investigators verified that As mobility does not depend on the
total As concentration, but it is correlated with the Fe and
Mn oxi-hydroxide, gibbsite amounts, and organic matter
content. Even in the presence of microorganisms and under
reducing conditions, As has low mobility because there is
continuous solubilization and precipitation processes even
if in low proportions.
Our study is consistent with other works in the literature suggesting that As in water is mostly solubilized


because of reducing conditions with low oxygenation and

alkaline pH. Nevertheless, the nature of the interaction of
Fe and Mn oxides with a high As concentration in the
sediment is sufficiently strong to retain most parts of As in
the solid phase, which considerably decreases its solubility and the surface water and groundwater contamination
in Paracatu.
In addition, it is emphasized that although the As concentration in water is greater than the legal limit at some
points, it does not follow the same proportions of violation
of established limits to sediments. The presence of high Al,
Fe, and Mn concentrations in the sediment, the slightly
basic pH, and the low redox potential retain most of the As
in the sediment. In the second collection, the increased DO
concentration was important to the decrease of As concentration in the water. Preservation and maintenance of
riverbanks, revegetation, and sewage treatment before its
discharge in rivers, which are some alternatives that may
favor a DO concentration [ 5 mg L-1, decreases the total
As concentration in water and favors oxidation in the
arsenate form.

All of the analyzed sediment samples and 37 % of the
water samples from the rivers and streams of Paracatu
presented As concentrations greater than the quality standards established by CCME and USEPA. The vegetable
samples presented low As concentrations. Although the As
concentration in vegetables is normal, we observed a relation with As concentrations in water and in sediment
from nearby areas, which indicates that these plants absorbed As. Systematic studies, including a greater number
of vegetable samples and variables, are necessary to better
elucidate the transport of the metalloid to this matrix.
Despite the high amounts of As in sediments (125466
times greater than the TEL standard), the results show low
disponibility to the watercourse and even to plants, mainly
because Fe and Mn oxyhydroxides and Al minerals are
present, which significantly immobilizes As in the solid
phase. However, it is advisable to frequently monitor the
concentration of these elements in the water and sediments
of the region, as well as the pH, the redox potential, and the
DO determination, so that if there is any variation in the
environment conditions, corrective actions may be
executed to stop or minimize the contamination caused by
the solubilization of the elements in the sediments.
Acknowledgments The authors thank the Coordenacao de Aperfeicoamento de Pessoal de Nvel Superior, Conselho Nacional de
Desenvolvimento Cientfico e Tecnologico, Fundacao de Amparo a`
Pesquisa do Estado de Minas Gerais, and Centro Federal de Educacao
Tecnologica de Minas Gerais for their financial support. They are also

Arch Environ Contam Toxicol

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