Journal Pre-proof

Arsenic contamination assessment in Brazil – Past, present and

future concerns: A historical and critical review

Mônica Cristina Teixeira, Alcylane Caldeira Santos, Carla Silva

Fernandes, Jack Chakmeng Ng

PII: S0048-9697(20)31730-7
DOI: https://doi.org/10.1016/j.scitotenv.2020.138217
Reference: STOTEN 138217

To appear in: Science of the Total Environment

Received date: 30 January 2019

Revised date: 12 March 2020
Accepted date: 24 March 2020

Please cite this article as: M.C. Teixeira, A.C. Santos, C.S. Fernandes, et al., Arsenic
contamination assessment in Brazil – Past, present and future concerns: A historical
and critical review, Science of the Total Environment (2018), https://doi.org/10.1016/
j.scitotenv.2020.138217

This is a PDF file of an article that has undergone enhancements after acceptance, such
as the addition of a cover page and metadata, and formatting for readability, but it is
not yet the definitive version of record. This version will undergo additional copyediting,
typesetting and review before it is published in its final form, but we are providing this
version to give early visibility of the article. Please note that, during the production
process, errors may be discovered which could affect the content, and all legal disclaimers
that apply to the journal pertain.

© 2018 Published by Elsevier.

 Journal Pre-proof

Arsenic contamination assessment in Brazil – Past, present and future concerns

A historical and critical review

a,
Mônica Cristina Teixeira *, Alcylane Caldeira Santos b, Carla Silva Fernandes b, Jack

Chakmeng Ng c

a
Pharmacy Department, Pharmacy School, Federal University of Ouro Preto, UFOP. Campus

Morro do Cruzeiro. Ouro Preto, MG, 35400-000, Brazil.

of
b

ro
Environmental Engineering Graduating Program – ProAmb, Federal University of Ouro

Preto, UFOP. Campus Morro do Cruzeiro. Ouro Preto, MG, 35400-000, Brazil.
-p
c
re
Queensland Alliance for Environmental Health Sciences (QAEHS), the University of

Queensland, 20 Cornwall Street, Woolloongabba, Brisbane, QLD 4102, Australia.

lP
na

Abstract
ur

This paper presents a summary of some relevant documents published during the last
Jo

decades regarding arsenic contamination in Brazil until December 2018, including scientific
papers, reports and regulatory documents. Natural and anthropogenic arsenic sources were
covered, excluding those related to agriculture. International “key” documents related to
arsenic contamination were used to support the discussion and comparative analysis. This
paper aims: (a) to summarize and discuss some available data (including Portuguese written
documents) concerning arsenic contamination in Brazil, mainly geographical, geological,
geochemical, environmental and health studies; (b) to critically review the published studies
comparing their main findings; (c) to describe and compare ancient and recent
contamination events; and (d) to highlight key knowledge gaps, and identify promising areas
for future researches.
 Journal Pre-proof

The arsenic contamination scenario in Brazil results not only from mining. Natural or
anthropogenic emissions caused by great magnitude phenomena as flooding, erosion,
landslide and, water scarcity equally impact arsenic mobilization/immobilization equilibria.

Our literature review demonstrates that arsenic contamination of soils, sediments and
water sources is observed at least at three of the five geographically defined Brazilian
regions (Northern, Southern and, Southeastern regions). Arsenic enriched soils, and waters
naturally occur all around the country and anthropogenic activities have been the main
contributory factor to the environmental contamination since the 18th Century. Geogenic
materials (topsoil and mining tailings), and water samples could contain extremely high

of
arsenic concentrations, i.e. 21,000 mg.kg-1 or 1,700,000 µg.L-1, respectively, have been
found mainly at the “Iron Quadrangle”. Moreover, if we consider both the Brazilian and

ro
international parameters, the health risks associated with the human exposition to arsenic
-p
are of significant concern.
re
For those reasons, constant monitoring of As contaminated areas in Brazil is mandatory.
Furthermore, it is necessary to learn from the mistakes made in the past in order to prevent
lP

or minimize future problems.

na

Keywords: Iron Quadrangle, mining wastes, potentially toxic elements -PTE, risk
ur

assessment, bibliometric analysis, Fundão Dam collapse.

Jo

1. Introduction

Arsenic toxicity to humans and other living organisms has long been recognized as a

significant health problem. The International Agency for Research on Cancer’s (IARC)

Working Groups in 1979, 1987, and 2002 has classified arsenic and its compounds as

carcinogens therefore, those compounds are included within Group 1. The three major

arsenic compounds groups, relevant from the biological and toxicological points of view are:
 Journal Pre-proof

(i) the inorganic arsenic compounds: arsenic trioxide, sodium arsenite, arsenic trichloride

(the most common AsIII compound), and arsenic pentoxide, arsenic acid and arsenates (lead

and calcium arsenates), the most common pentavalent compounds; (ii) the organic arsenic

compounds (arsanilic, methylarsonic, and dimethylarsinic or cacodylic acids), and finally (iii)

the gaseous arsenic (arsine) (IARC, 2012) whereas arsenobetaine is generally considered

non-toxic.

Arsenic is not an unusual element, according to the World Health Organization (WHO)

of
arsenic is the 20th most common element in the earth’s crust, and it is released to the

ro
environment as a result of natural (volcanic) or anthropogenic (industrial) activities (WHO,
-p
2001). Industrial activities as mining, metallurgical processes (smelting of non-ferrous
re
metals) and energy production (burning of fossil fuels) are the major anthropogenic sources

of arsenic contamination of air, water, and soil (primarily in the form of arsenic trioxide).
lP

Equally important is the historical use of arsenic-containing pesticides for agriculture (IARC,
na

2012), which has resulted in land and food contamination. The use of arsenic for preserving

timber is equally relevant from the environmental point of view. Additionally, arsenic is
ur

commonly employed during glass manufacturing and recently, arsenic trioxide has been
Jo

used for the treatment of acute promyelocytic leukemia. Because of its wide industrial

applications and it is ubiquitous in the environment, arsenic has led to the contamination of

all environmental compartments.

Arsenic sulfides, i.e. iron, manganese, silver, lead, copper, nickel, and antimony sulfides, are

the most typical arsenic inorganic compounds. Among them, arsenopyrite is the prevalent

arsenic bearing mineral. Arsenic occurrence in the earth’s crust is, on average, 5 mg kg- 1, or
 Journal Pre-proof

even higher in the case of sulfide deposits (IARC, 2012). Sedimentary iron and manganese

ores deposits may occasionally contain arsenic levels of up to 2900 mg kg-1 (IARC, 2012).

Arsenic levels in various environmental matrices have been widely reported. For examples, arsenic

levels in the air are typically averaged 0.2–1.5 ng m-3 for rural areas, 0.5–3 ng m-3 for urban areas and

< 50 ng m-3 for industrial sites (WHO, 2001), although >1,000 ng m-3 at industrial sites have been

reported (WHO, 2001, section 3.2). Arsenic level in the groundwater averaged about 1-2 µg L-1,

however, it can exceed 3 mg L-1 where the groundwater is impacted by volcanic rock or sulfide

of
minerals (these can be found in WHO, 2001 - section 1.4). Sediment arsenic levels range 5-3000 mg

kg-1 with the higher concentrations are found at contaminated sites (WHO, 2001 - section 1.4).

ro
Background arsenic in soil is within the range of 1-40 mg kg-1. Arsenic can be found in percent
-p
concentration in soil associated with sulfide minerals and anthropogenic waste materials (WHO,
re
2001).
lP

From this point forward, any mention to arsenic-contaminated samples or sites will follow

these benchmarks stated in the paragraph above.

na

Arsenic contamination in Latin America has been reported for more than one hundred
ur

years, seventy percent of the continent countries experience some arsenic contamination
Jo

issues. Taking the 10 μg L-1 limit for As in drinking water, the number of people whose

drinking water exceeding this limit is estimated to be about 14 million (Bundschuh et al.,

2012), including Brazilian citizens.

In this paper, we conducted a systemic and critical review of the existing database on

arsenic contamination in Brazil. The review focuses on English written scientific papers,

which would afford wider access to the general scientific community. Natural and

anthropogenic sources of arsenic contamination were considered, however those related to

 Journal Pre-proof

agricultural activities were excluded. Additionally, a significant number of documents

written and published in Portuguese that are not readily accessible to the majority of the

international scientific community, which including governmental and non-governmental

reports, Brazilian legislation standards and Brazilian demographic statistics data, were

included in this review, as a secondary bibliographic source.

It attempts to facilitate the access of the international scientific community to the existing

database on arsenic contamination in Brazil. It is worth to note that a comprehensive

of
assessment of the real context of the Brazilian contamination scenario is impaired by

ro
language limitations. In that way, international researches frequently cite the same scientific
-p
documents, repeatedly. Some of those papers aimed to present an understanding of the
re
arsenic contamination scenario in one specific Brazilian region. Those articles were

undoubtedly well written and unquestionably relevant and they are the most cited in the
lP

scientific literature. However, these widely cited studies (Bundschuh et al., 2012;
na

Matschullat et al., 2000) could lead to a false assumption by the readers that this is a recent

environmental problem restricted to a very small area.

ur

On the contrary, this paper argues that arsenic contamination in Brazil has been a long term
Jo

environmental and health problem that is widespread over an extended area covering a

major part of the country. Arsenic contamination in the Brazilian waters, sediments, and

soils is a natural phenomenon related to Brazilian soil composition, which is becoming an

environmental issue due to anthropogenic activities. The so-called Iron Quadrangle (IQ)

region will deserve special attention due to its historical and economical relevance but

discussions will also cover other Brazilian arsenic-contaminated regions.

 Journal Pre-proof

In order to prove this hypothesis a systematic and critical review focused not only on English

written scientific papers was conducted.

2. Methodological approach

A literature survey was conducted. Only English written peer-reviewed papers,

published between 1945 to 2018 and indexed on the electronic databases Web of

of
Science and Scopus, respectively, were considered for the primary database. All types of

ro
documents, including available conference abstracts, were included.
-p
Very general keywords were chosen for the first screening searches in any document
re
fields (title, abstract, topic, text). The chosen keywords (searching criteria) were:
lP

“arsenic”, “iron quadrangle”, “Brazil”, “contamination”, “mining”, “water”, “soil”,

“health”, “orpiment”, “realgar”, “quartz” and “sulfide”. In addition, also the Portuguese
na

written keywords “quadrilátero ferrífero” and “Brasil” were included. Combinations of

ur

keywords as pair or triplets were also searched.

Jo

Documents were retrieved after the combination of triplets of words: “arsenic/Iron

Quadrangle/Brazil”; “arsenic/Quadrilatero ferrifero/Brazil”; “arsenic/iron

Quadrangle/Brasil”, “arsenic/Quadrilatero ferrifero/Brasil”,

“arsenic/contamination/Brasil” and used for the construction of the reference database.

The retrieved documents were collected for analysis and discussion.

From each retrieved document the following information was recorded:

 Journal Pre-proof

(a) authors’ names; (b) year of publication; (c) bibliographic source (name and type); (d)

subject area; (e) country-county where the research was conducted, and/or country of

the corresponding author if the first information was not easily obtainable; (f) key words

defined by the authors and included in the papers; (g) times cited; (h) research aims; (i)

mining activity information (nature, number, metal or precious element processed, open

or underground, mineralogy, active or abandoned sites, tonnage, production); (j)

material studied (soil, surface- or ground-water, biological tissues, biological fluids); (k)

of
analytical methodology; and (l) main results (As content).

ro
The database was then quantitative and qualitatively analyzed and compared to other
-p
available scientific documents to correlate both the Brazilian and the international
re
scenario.
lP
na

3. Results and discussion

3.1 Arsenic contamination studies

ur
Jo

The total number of documents retrieved after each step of the bibliographic survey is

depicted in the Supplementary Material (Table 1). The amount of scientific papers published

by Brazilian researches is still incipient compared to the wider developed countries.

The most recurrent keywords are shown in the Supplementary material (Figure 1) -. The

recent predominance of some biological terms related to arsenic contamination, arsenic

toxicology mechanisms and risk assessment studies is a relatively new concern (Figure 1 -

Supplementary material).
 Journal Pre-proof

After analyzing several of the retrieved documents, some important parameters were

obtained and summarized in Tables 1 and 2 that depict the parameters of arsenic

contamination in different environmental compartments in Brazil (Table 1) and compare

those retrieved data with some World parameters. Arsenic contamination of Brazilian soil,

sediment and water is demonstrated and will be discussed in the following sections.

of
3.2. Arsenic contamination in Brazil – Natural and anthropogenic sources, historical and

recent contamination

ro
-p
Arsenic contamination can be due to both natural and anthropogenic sources. In Brazil,

natural contamination is exacerbated by anthropogenic activities of which many are related

re

to mining. Gold, precious stones, and other minerals mining were (and still are) a powerful
lP

driving force that has facilitated the development and urbanization of a very big portion of
na

the country even in very remote areas. In Brazil, one of the most important states of the

country in terms of the mining industry is named Minas Gerais, a Portuguese expression
ur

that means “General Mines”, in English. Brazilian streets, cities, and regions have been
Jo

named with words related to its mineral resources and richness. Words as Esmeralda,

Turmalina, Berilo, Diamante, Ametista, Quartzo, Topázio, Bauxita, Cassiterita, Manganês,

Ferro, Hematita, and Ouro which mean emerald, tourmaline, beryl, diamond, ametiste,

quartz, topaz, bauxite, cassiterite, manganese, iron, hematite, and gold, respectively, were

often used. Some native American language words, which define minerals or mining

activities, were employed, as well. Language expressions related to the words “stone, big,

small and brilliance” were used to describe some very important mining regions, in the past.

Nowadays, those expressions were incorporated into the Brazilian Portuguese and explain
 Journal Pre-proof

the origin of names given to the important mining cities such as Itabira and Itabirito, where

mining activities remain active, since the very early ancient times (16th Century). Mining

activity was, and still is, essential for the Brazilian economic development but environmental

impacts and sustainable development of this longstanding activity are equally important.

Mining activities in Brazil started with diamonds and gold artisanal mining. Millions of tons

of arsenic were released from those arsenic naturally bearing materials and translocated to

sediments, soils, and surficial and ground-water as a consequence of the mineral processing

of
and the mining wastes inappropriate disposal, over centuries of intensive mining activities.

ro
Arsenic contamination of the soil, sediment, and water in several Brazilian ancient mining
-p
regions has been reported by the Brazilian and the international scientific community
re
(Borba et al. 2000; Borba et al. 2003; Deschamps et al. 2002; Figueiredo et al. 2007;

Matschullat et al. 2000a; Bundschuh et al. 2012; Ono, Guilherme, Mendes, et al. 2012; Ono,
lP

Guilherme, Penido, et al. 2012).

na

During the last century, mechanized technologies have replaced artisanal mining. The
ur

extraction/mining of iron, manganese, zinc, bauxite, among others, has become equally or
Jo

even more popular enterprises than the gold mining industry. Iron mines in Brazil are open-

pit mines with tonnage and impacted areas usually bigger than those of gold mines since, in

Brazil, only a few gold mines are open-pit operations, and this is a particular feature,

important to highlight.

Over the years, environmental policies have been implemented and arsenic (and other

potentially hazardous elements) contamination is relatively well controlled as Brazilian laws

are becoming more stringent. Nonetheless, environmental contamination related to the

ancient mining waste material still deserves attention; this will be addressed later in the
 Journal Pre-proof

section “Arsenic contamination in the Iron Quadrangle - historical contamination”

(3.2.2.2.1).

To the best of our knowledge, the better well-documented Brazilian arsenic augmented

sites are found in three of the five Brazilian geographic regions, i.e. Northern, North-eastern

and Southern (Table 1, Figure 1 and Supplementary material, Figure 2). Arsenic

contamination in Brazil, regardless of the contamination source (natural or anthropogenic),

has been discussed during the last two decades and the most studied cases were those

of
which took place in Northern, Southeastern and at the very Eastern part of the Southern

ro
Region. Unfortunately, the scarcity of data related to the other areas is not an “arsenic
-p
safety guarantee certificate”, rather it emphasizes the need for paying attention to some
re
neglected sites involving long-term gold mining activities in the North-eastern and Central-

Western Region of the country and the coal processing activity at the Southern Region.
lP

Additionally, considering the mineralogy of the processed ores all around the country, some
na

arsenic contamination hot spots are likely to occur. Very few studies about arsenic

contamination in those areas had been reported as mentioned by Figueiredo in their

ur

Medical Geology studies (Figueiredo et al., 2010).

Jo

3.2.1. Arsenic contamination in the Northern region

 Journal Pre-proof

Santana municipality is one of the most frequently studied region in Northern Brazil

(Oliveira Santos et al., 2003). Santana is located in Amapá State (AP, Figure 1; Figure 2-

Supplementary Material) at the Amazon River delta (00°03' 30" S; 51°10'54" W).

The estimated current population is 119,610 inhabitants (101,262 inhabitants certified by

the 2010 national census). As expected for the Brazilian Northern Region municipalities, the

demographic density of Santana is low, with only 64.11 inhabitants per square kilometer

(Brasil, 2017). In the Serra do Navio deposits the manganese enrichment is related to

of
weathering and supergene alteration of manganese marbles and associated

ro
metasedimentary rocks of Vila Nova Group (Figure 1), which comprises a Paleoproterozoic
-p
metavolcanosedimentary sequence (Scarpelli & Horikava, 2017). In this region, the
re
conditions of extreme weathering of the Amazon rainforest allows the formation of large

blocks of massive manganese ores made essentially of oxides and hydroxides of manganese
lP

(Scarpelli & Horikava, 2017).

na

Arsenic contamination in Santana and other regions in Amapá State was a consequence of
ur

arsenopyrite-bearing wastes deposition, which started after 1949 (Brasil, 2017) when the

manganese mining operation started in Serra do Navio. This was the first Amazonian
Jo

commercial mining operation, conducted by the company Indústria e Comércio de Minérios

S.A. (ICOMI) and comprised 19 mines in the Serra do Navio region. A 193 km railway was

constructed to implement this commercial operation, thus allowing the ore to be

transported from the forest to the Amazon River delta, after crossing five rivers and

different biomes (Monteiro, 2003). The ICOMI operation lasted from 1957 to 1997. During

41 years of operation, more than 33 million tonnes of manganese oxide and 936 thousand

tonnes of manganese carbonate were produced. Approximately 123 million tonnes of

 Journal Pre-proof

minerals were excavated, 61 million tonnes of ores were processed and 28 million tonnes of

waste were produced (Monteiro, 2003). Some of the wastes were incorrectly disposed at

the mining vicinity as well as at the Santana port area during the ICOMI operations. High

iron, manganese, and arsenic levels were found in the waste materials. Averaged arsenic

content in the mining wastes and manganese ores was 1878 and 1497 mg kg-1, respectively.

These solid wastes, mainly fine particles produced during sintering, were collected around the

mining operation and mineral storage places, waste dumps, and ore processing sites

of
(Monteiro, 2003; Oliveira Santos et al., 2003). Waste containing arsenic produced during the

ro
manganese pelletizing process developed by ICOMI was discharged into an artificial lake
-p
during the period between 1973 and 1983. Eventually, arsenic and other potentially toxic

elements might have permeated into the aquifer, or could have leached out through the
re

cracks of dam walls, or during flood events, resulting in the contamination of soil and
lP

surficial and ground-water. Arsenic contents varied from 16 to 4054 mg L-1 and 7.9 to
na

1591 mg kg-1 in the water and sediment, with the mean values of 539 mg L-1 and 388 mg kg-1,

respectively (Monteiro, 2003). Considering the particulate material found in the river water,
ur

the As content was ranging from 30 to 695 mg kg-1 (Monteiro, 2003). This author observed
Jo

that the arsenic content diminishes as a function of distance from the mine facilities.

Another study reported arsenic contamination of waters of two Amazon River tributaries,

Elesbão 1 and Elesbão 2 (Lima et al., 2007). Those streams cross a 129-hectare region

inhabited by approximately 2600 people. During a time period from November (2003) to

March (2004), 52 drinking water samples were collected at Vila do Elesbão (ELB); Vila do

Matapi- Mirim (MAT); Rua Delta (DEL); Rua da Olaria (OLA); Bairro da Hospitalidade (HSP)

and analyzed to assess metal and metalloid contamination, and microbial quality (Lima et

al., 2007). Arsenic concentrations in the water were below the Brazilian legislation
 Journal Pre-proof

maximum limit (10 µg L-1) (CONAMA, 2005; CONAMA, 2011). These authors concluded: (i)

the high pluviosity observed during the rainy season in the forest zone could have positively

contributed to the arsenic and other contaminants dilution; (ii) regardless the water source,

bacterial quality of samples was in discordance to Brazilian drinking water standards (Brasil,

2011), clearly unveiling the sanitary problems which this population was exposed to; and (iii)

due to the high level of potentially toxic contaminants found in the wastes deposited

around their study site, a continuous monitoring of environmental quality and population

of
health was strongly recommended.

ro
Besides manganese, gold mining activities also contributed to arsenic contamination in
-p
Amapá State (Figure 1 and Figure 2-Supplementary Material). Contrary to the mining of
re
manganese, gold production was mainly conducted in artisanal mining operations named

“garimpos” (panning) which used mercury to concentrate gold and therefore, not only
lP

arsenic but also mercury was released to the environment (Oliveira Santos et al., 2003).
na

Arsenic contents in contaminated samples collected in that region were quite variable from

up to 1700 mg kg-1 in the solid mining wastes, and up to 2000 µg L-1 of arsenic in the highly
ur

contaminated waters (Figueiredo et al., 2010). However, some studies had reported As
Jo

levels found in the examined drinking water samples collected from the taps at this

municipality did not exceed 0.5 µg L-1, thus suggesting a low human exposure risk (Oliveira

Santos et al., 2003). Unfortunately, those documents have not mentioned only 6.3% of the

municipality area is urbanized and only 15.3% of the population has access to sanitized

sewage facilities. In such a scenario, free access to clean potable tap water by the whole

Santana’s population is not likely to occur. Despite these data, the sanitary conditions there

are not as bad as it could be found in some other Brazilian municipalities, considering
 Journal Pre-proof

general health indicators parameters. The average infant mortality rate in the city is 17.82

for 1,000 live births. The hospitalizations due to diarrhea are 0.5 for every 1,000 inhabitants.

Compared to all municipalities in the state, it ranked 9 of 16 and 5 of 16, respectively. When

compared to cities all around the country, they ranked 1418 and 3330 of 5570, respectively

(IBGE, 2019). The neonatal mortality rate (number of neonatal deaths per 1,000 live births)

observed at Santana was 13.08, in 2014 (Table 3) and unfortunately raised to 17.82 (IBGE,

2019), higher than the Brazilian national averaged rate which dropped from approximately

of
17, in 2010 (IBGE, 2010) to 14, in 2016 (Unicef, 2017). Demographical, health and

ro
environmental data of the arsenic affected Brazilian geographical regions is presented in

Table 3.
-p
re
Recently, high arsenic levels were also found in water, soils, sterile, wastes, and vegetables

collected close to an abandoned artisanal gold mine so-called Serra Pelada “garimpo”
lP

located at Pará State (de Souza et al, 2017). Arsenic concentrations found in those samples
na

are higher than the quality reference values and background concentrations of some

potentially toxic elements discussed and proposed by Fernandes et al in 2018, taking into
ur

consideration the particularities of the Pará State. Not only arsenic but also barium and
Jo

other potentially toxic elements concentrations in water samples exceeded the reference

values established by the World Health Organization for human consumption (de Souza et

al, 2017). The element with the highest concentrations in the sampled areas was Ba, with a

median value of 150 mg kg−1. This represents the prevention value established by the

Brazilian regulations (CETESB, 2014). The highest Ba concentration was 15,000 times higher

than the PV and 5000 times higher than the investigation value. For As, Co, Cu, Cr, Ni, Pb

and Zn, the 75th percentile of the concentrations were lower than the PV. As concentrations
 Journal Pre-proof

varied from 2 to 28 mg kg -1throughout the entire study area (de Souza et al, 2017). As was

found in two groundwater wells only, with a maximum concentration of 4.2 μg L−1, below

the prevention value (CETESB, 2014).

3.2.2. Arsenic contamination in the Southeastern and Southern regions

From the Brazilian Northern region to the Southeastern Region (Figure 1), the most studied

As contamination sites are those ascribed to the Ribeira Valley and Iron Quadrangle. While

of
Ribeira Valley extends from the South of São Paulo State-SP to the East of Paraná State-PR,

which actually is included in the Southern Region, the Iron Quadrangle area, is located

within Minas Gerais State-MG (Figure 1).

ro
-p
re
lP

3.2.2.1. Arsenic Contamination at Ribeira Valley

Ribeira Valley is located at Ribeira do Iguape River basin and covers an area of
na

approximately 22,000 Km2, with approximately 490,000 inhabitants distributed between 31

ur

municipalities (Table 3) from São Paulo to Paraná (24 and 7 municipalities, respectively).
Jo

Ribeira River extension is approximately 470 Km, 120 Km within Paraná State and 350 km

within São Paulo State.

The Ribeira Valley is well known for its polymetallic mineralizations of lead, zinc, silver, and

copper hosted chiefly in carbonate and calc-silicate metasedimentary rocks of the

Mesoproterozoic Lajeado Group (Figueiredo, 1992; Campanha et al., 2015; Lopes et al.,

2017). The main sulfide ores are made of galena (PbS), pyrite (FeS) and sphalerite (ZnS), with

subordinate pyrite group minerals such as chalcopyrite (CuFeS2) and arsenopyrite (FeAsS).

Its relative proportions vary for each specific deposit. Besides being located in the most
 Journal Pre-proof

developed Brazilian region, Ribeira Valley is historically renowned as one of the less

privileged areas in Brazil from both economic and social development points of view, as

could be noticed in Table 3. The economic and health indicators from Ribeira Valley could be

considered quite surprisingly albeit São Paulo and Paraná are included into the group of the

richest and most developed Brazilian states, four of the top ten Human Development Index

(HDI) Brazilian cities are located in Paraná and São Paulo States (IBGE, 2010). While for

several municipalities from both States the HDI data observed in 2010 were higher than 0.82

of
or 0.84, whereas the HDI varied between 0.64 and 0.75 in some municipalities from Ribeira

ro
Valley. In addition, very high infant mortality could be observed, some data are quite
-p
disconcerting. Despite the fact that nations all around the world are aiming to reduce

neonatal mortality to no more than 12 (deaths per 1,000 live births) (Unicef, 2017), at the
re

Ribeira Valley, infant mortalities rates of 32.26; 31.95; 46.51 and 63.83 were registered at
lP

Barra do Turvo, Iguape, Itaoca, and Ribeira cities, located in São Paulo State. In Paraná State,
na

the situation was not better. Adrianóplis and Cerro Azul registered infant mortalities of

43.48 and 53.72 (IBGE, 2019). The mean neonatal mortality rate, for the Ribeira Valley, is
ur

22.74. This value is not directly related only to arsenic contamination nonetheless, it
Jo

deserves attention as an indicator of the precariousness health of the entire population and

the young children, particularly. This is a sensitive issue since infants and children are the

most susceptible to the adverse effects of arsenic exposure (Ahamed et al., 2006). Elevated

levels of arsenic in food, water and dust are cause of concern because they are associated

with a number of adverse health outcomes, including cancer, vascular diseases,

dermatological problems, diabetes, respiratory diseases, cognitive impairments and, infant

mortality (Bundschuh et al., 2012; Litter et al., 2014). The more debilitated the human

being, the more vulnerable to the environmental hazards she/he is.

 Journal Pre-proof

Arsenic, lead, and other inorganic contaminants are found in soils, sediments and water

samples collected at Ribeira Valley as a consequence of mining activity (de Figueiredo et al.,

2007; Lopes Jr., 2016; Rezende et al., 2015; Sakuma et al., 2010) which started during the

first decades of the Brazilian colonial period, 16th Century. Municipalities such as Eldorado,

Sete Barras, Registro, and Apiaí were founded and developed during this so-called “The

Golden-Age” period.

Arsenic background levels of sediments in Ribeira Valley are in the range of 3-13.3 mg kg-1

of
(Lopes Jr., 2016) in almost the whole valley. Enriched and highly enriched regions with

ro
arsenic contents around 12-34 or higher than 34 mg kg-1, respectively, in sediment particles
-p
<180 µm, were found at the municipalities of Barra do Turvo, Iporanga, Cerro Azul and
re
Tunas do Paraná, located at the central part of the valley (Lopes Jr., 2016). Nonetheless, this

author recommended that testing of the finer particles (< 63 µm) in the municipalities of
lP

Eldorado Paulista (North) and Iguape (at the sea) should be included in the group of the
na

enriched and highly enriched regions.

ur

These areas coincided with the ancient gold (Piririca-São Pedro, Pedro Cubas River) and lead
Jo

(Rocha, Laranjal and Furnas mines) mining areas. Not only As, but high Pb, Zn, and Cu levels

were also found (Lopes Jr., 2016; Sakuma et al., 2010). Moraes et al. (2004) tracing the

sources of metal pollution with isotopic Pb, associates the elevated metal concentrations in

river sediments to vein-type ore deposits, hosted in the Lajeado Group metacarbonate

rocks. The São Paulo State Environmental Protection Agency, CETESB, also published some

environmental contamination reports and maps (CETESB, 2019).

 Journal Pre-proof

3.2.2.2. Arsenic contamination in the Iron Quadrangle region

Iron Quadrangle - geography

The economic development of the so-called Iron Quadrangle (IQ) region was similar to the

development of the Ribeira Valley. This name is a consequence of the geographical

limitation of this area which produces an imaginary quadrangle shaped map (Figure 1,

Figure 3 - Supplementary material) which extends through a 45000 km2 area

of
(19°30’S/21°00’S and 42°30°W/45°00°W) which is surrounded by several mountains,

namely, Curral (North), Moeda (West), Ouro Branco (South) and Caraça and Gandarela

ro
(East) (CPRM, 2014). IQ area comprises several municipalities: Bom Jesus do Amparo, São
-p
Gonçalo do Rio Abaixo, Barão de Cocais, Santa Bárbara, Catas Altas, Mariana, Ouro Preto,
re
Ouro Branco, Congonhas, Jeceaba, Belo Vale, Moeda, Itabirito, Rio Acima, Brumadinho,
lP

Mario Campos, Sarzedo, Ibirité, Nova Lima, Raposos, Sabará, Caeté, Santa Luzia and, Belo

Horizonte, the State Capital with a total population of 3,798,711 inhabitants as estimated in
na

2017 (Table 3).

ur

Not only the Iron Quadrangle but Minas Gerais (MG) is recognized as one of the largest
Jo

mineral provinces in the World. Metals (such as gold, iron, and manganese), minerals (e.g.

bauxite and calcite), ornamental rocks (e.g. serpentinite and quartzite), and precious stones

(e.g. diamonds, topazes, and emeralds) are found in the IQ (Roeser and Roeser, 2010;

Ruchkys and Machado, 2013). Iron-aluminum silicate minerals (SiO2 bearing -Al2O3 -Fe2O3-

H2O) are the main soil components while quartz, kaolinite, gibbsite, goethite, and hematite

are the most common minerals. IQ climate is predominantly sub-tropical and is affected by

the surrounding hills mainly at the central IQ region. The high hills are physical barriers that

influence the air movement thus creating different microclimatic environments in this
 Journal Pre-proof

region. Weather is tropical semi-humid with two well-defined seasons: the humid season

lasts from spring to summer and the dry season starts at the end of the autumn and usually

persists until the end of the winter. At the mesothermic humid to semi-humid region,

average temperatures are between 10 to 15o C and the dry season lasts from April to

September. At the higher temperature zones (mean temperatures between 15-18o C)

weather is humid or semi-arid and dry season may be longer, up to 6 months and finally, at

the hottest region (mean temperatures higher than 18o C), 4 or 5 months without rains are

of
expected (CPRM, 2014).

ro
From the hydrographical point of view, six river basins are completely or partially included in
-p
the IQ region: (i) Doce; (ii) Piracicaba; (iii) Velhas; (iv) Paraopeba; (v) Pará and, and (vi)
re
Paraná in Figure 4, Doce River and São Francisco River Basins are highlighted due to their

economic and environmental relevance. According to the last Brazilian demographic census,
lP

70% of the total IQ area is dedicated to agriculture, 6% is urbanized and only 3% is occupied
na

by the mining industry.

ur

Besides the geological features depicted in Figure 1, a very detailed geological description of
Jo

this region was provided by Lobato (Lobato et al., 2001) and an interactive map was

launched by the Brazilian Geological Service (CPRM, 2019). Additionally, a complete

geochemical mapping of the Iron Quadrangle region was published by the Brazilian Mining

and Energy Ministry (CPRM, 2014).

Iron Quadrangle Economy- Gold and Iron Mining

 Journal Pre-proof

Gold mining activity started from the early 18th century is still enduring and remains an

important component for the economy of the State and the country until the present days.

Materials of economic value, particularly gold and iron have been explored continuously for

more than 300 years in the IQ region (Costa et al., 2010; CPRM, 2014; Lobato et al., 2001;

Roeser and Roeser, 2010; Ruchkys and Machado, 2013). It has been estimated that more

than 1,000 tonnes of gold, almost 40% of the overall Brazilian gold production, came from

the IQ region during the last centuries. In Ouro Preto region, gold exploration started in

of
1698 when alluvial gold was artisanally mined. In 1817, the first Brazilian industrial gold

ro
extraction operation (20°23'36.704"S, 43°26'29.069"W ) started when the Mina da Passagem
-p
Company started. This facility produced 35 tonnes of gold during 284 years of continuous

operation (Costa et al., 2010). Another very productive underground mine named Morro
re

Velho is located at Nova Lima (19°58'55.2"S, 43°51'05.9"W), very close to the Minas Gerais
lP

State capital (Belo Horizonte - 19°48′57″S, 43°57′15″W), it has produced approximately

na

450 tonnes of gold over a period of 100 years. Gold was commercially explored at Morro

Velho Mine since 1834 (Lobato et al., 2001).

ur

An Au/As proportion in a range of 300 to 3000 has been reported considering the IQ gold-
Jo

bearing minerals composition since arsenic contents in primary gold ores, mainly

arsenopyrite and loellingite is remarkable, while gold content is quite discrete (Borba, 2002;

Borba et al., 2000). Therefore, considering the gold production, the estimated amount of As

released to the environment during the gold mining ages is around 390,000 tonnes or more

(Borba et al., 2003; de Figueiredo et al., 2007). The individual contributions of Passagem and

Morro Velho mines could be estimated as 10,500 and 135,000 tonnes of As being released

to the environment, respectively. Unfortunately, proper environmental management was

 Journal Pre-proof

not implemented at that time, almost all the produced arsenic wastes were spread through

different environmental compartments, mainly in the alluvial sediments. Carmo and

Gualaxo do Norte Rivers basins were particularly affected (Costa et al., 2010; Freitas et al.,

2016a; Palmieri, 2006; Rodrigues et al., 2013a; Santolin et al., 2015a; Segura et al., 2016).

The Gualaxo do Norte River basin geological aspects were very well described by Rodrigues

et al., (2013), prior to the recent event of a dam collapse that will be discussed with the next

sections. The effects of gold and iron mining activities were discussed. Those two

of
aforementioned rivers are tributaries to the Doce River basin.

ro
Nowadays, the most active and productive Iron Quadrangle gold complexes are located in
-p
the municipalities of Nova Lima, Santa Bárbara, and Sabará where Morro Velho, Cuiabá,
re
Lamego and Córrego do Sítio mines are active. These mines are controlled and explored by

AngloGoldAshanti-Brasil Company. The metallurgical complex located in Nova Lima

lP

processes gold minerals extracted from those other mines. Another gold extraction plant is
na

operated by the same company in the Central-West Brazilian region, at the municipality of

Crixás (Goiás State - 14°32'56"S, 49°58'09"W). The operation includes three underground
ur

and one open-pit gold mines (AngloGoldAshanti, 2018).

Jo

In the same IQ region, another mining complex is located in Caeté, including Pilar and Roça

Grande underground mines. They are 50 kilometers east of the State Capital, Belo Horizonte

(Jaguar Mining Inc., 2019).

The Iron quadrangle gold deposits contributed to more than 50% of the total Brazilian gold

production. An official gold production report was launched in 2016 stating that Minas

Gerais produced 31.97 tonnes of total production of 83.278 tonnes in Brazil. Furthermore, if

we consider the Au/As ratio of 300, approximately 10,000 tonnes of arsenic were released
 Journal Pre-proof

in Minas Gerais State alone in 2016. According to the Brazilian Mining and Energy Ministry

and also the Brazilian Geological Service Department, the Brazilian gold reserve is of around

2,300 tonnes (CPRM, 2018). Therefore, the total amount of arsenic that can be released via

gold mining could reach 350,000 tonnes, if we consider Minas Gerais production as being

50% of the total production in Brazil.

Gold is produced from numerous deposits, hosted primarily within Archean

metamorphosed volcano-sedimentary sequences of the Rio das Velhas and Pitangui

of
greenstone belts and in metasedimentary rocks, mostly Itabirites from the Cauê Fm., from

ro
the Paleoproterozoic Minas Supergroup (Lobato, et al., 2001; Lobato et al., 2007; Vial et al.,
-p
2007b). Gold mineralization in Turmalina, NW IQ, occurs in the fine sediment grains
re
associated with sulfides in sheared schists and banded iron formations (BIF) sequences of

the Pitangui greenstone belt (Tassinari et al., 2015). Gold particles are mostly associated
lP

with arsenopyrite, quartz, and micas (sericite and biotite) (Jaguar Mining Inc, 2019) thus
na

explaining the potential As release into the environment.

ur

As previously mentioned, gold production is not the only mining activity within the Iron
Jo

Quadrangle. Metals like iron, uranium, silver, manganese, barium as well as the non-metallic

elements like arsenic and sulfur and minerals as topaz, talc, kaolin, graphite, quartz,

dolomite, and clays were also mined at IQ. Of these, iron, gems (topaz) and manganese are

the most expressive (Lobato, 2018). The first two are enclosed in BIFs of the Cauê Fm.

(Renger et al., 1994; Rojas, 2008), while the last is hosted in metavolcanic and calc-silicate

rocks of the Barbacena greenstone belt (Pires, 1977). Besides gold mining, other mining

activities gained importance during the last century, particularly for iron mining from the

middle of the 20th Century. In 2015, more than 595.6 million tonnes of iron ores were
 Journal Pre-proof

processed with an averaged Fe content of 54.64% (DNPN, 2016). Other minerals including

Al, Cu, Sn, Mn, Nb, and Ni ores were also treated. Nonetheless, iron is the main product,

representing more than 50% of the exported ores (DNPN, 2016). According to the Brazilian

Department of Mining Production (DNPM), iron deposits in Brazil are estimated to be 58.3

billion tonnes and almost 68% of the mineral and related resources were located in Minas

Gerais (CPRM, 2014), within the IQ region (DNPN, 2016). These deposits had turned Brazil

into one of the major iron reservoirs in the World (DNPM, 2001).

of
ro
Arsenic contamination - a consequence of natural and anthropogenic aspects
-p
As a natural consequence of these intensive and long-term mining activities in the Minas
re

Gerais State, some environmental impacts have occurred and were widely reported. More
lP

specifically, environmental arsenic contamination in the IQ region is of concern for the

na

academics, governmental agencies and the wider communities. Arsenic contamination of

the sediments, soil, and water in IQ has been reported by several Brazilian research groups
ur

(Borba, 2002; Borba et al., 2004; Costa et al., 2010; Gonçalves, José Augusto Costa Pereira et
Jo

al., 2010; Gonçalves et al., 1999; Gonçalves and De Lena, 2013a; Gontijo and Bittencourt,

2005).

Unfortunately, most of the produced documents are written in Portuguese including

scientific papers, governmental reports, academic monographs, theses, and technical notes

(Borba, 2002; Borba et al., 2009, 2004; Costa et al., 2010; Figueiredo et al., 2002; Gonçalves

et al., 2007; Gonçalves and De Lena, 2013; Gontijo and Bittencourt, 2005; Palmieri, 2006).

Due to the language constraint, those documents are not readily accessible to the wider
 Journal Pre-proof

international scientific community. This literature often contains some very important

findings and insights. Fortunately, some studies were translated into English and published

in international journals, some of them in collaboration with overseas scientists (Borba et

al., 2000; Costa et al., 2015; De Andrade et al., 2012; de Figueiredo et al., 2007; Gonçalves et

al., 2007; Jörg Matschullat et al., 2000a; Matschullat and Deschamps, 2011; Menezes et al.,

2006; Ono et al., 2012b, 2012a, 2016; Pimentel, H.S. Lena and Nalini Jr., 2003). All studies

pointed to the same causal correlation: gold-bearing minerals are naturally contaminated

of
with arsenic. Mine waste and materials containing arsenic were discharged into the

ro
environment during gold processing. More than 390,000 tonnes of arsenic were released to
-p
the environment during three centuries of gold mining in the Iron Quadrangle mining

district alone (Borba et al., 2003; Garelick et al., 2008; Jörg Matschullat et al., 2000).
re

According to Borba (2002), arsenopyrite is naturally oxidized to scorodite (from non-

lP

carbonated minerals) or poorly crystallized Ca-Fe arsenates (from carbonated arsenopyrite

na

minerals deposits) and also, scorodite, kolfanite, yukonite, and pharmacosiderite, in a lesser

extension. Following the initial release, As is solubilized in the surficial and ground-water
ur

even though pH was neutralized by carbonates. Arsenic mobility and solubilization in the
Jo

surface- and ground-water are facilitated by weathering and oxidation processes as

discussed above (Ciminelli et al, 2012).

According to the Site Contamination Annual Inventory of the Minas Gerais State

Environmental Protection Agency (FEAM), soil contamination by metals and metalloids is

the second most prevalent (28%) amongst all chemical contaminants. Arsenic is the second

most important inorganic contaminant with 10% of the registered cases, surpassed only by

Pb (19%) (FEAM, 2018) (Figure 3).

 Journal Pre-proof

3.2.2.2.1. Arsenic contamination in the lron Quadrangle – historical contamination

Arsenic is a widely dispersed element in the Earth's crust and exists at an average

concentration of approximately 5 mg kg-1 (approximately 0.0001%) (Garelick et al., 2008;

Keim, 2011). In the case of the Iron Quadrangle, arsenic concentrations up to 4800 mg kg-1

were found in gold deposits and sediments. The highest arsenic concentrations were often

of
found in the water and sediments collected close to the mining areas (Garelick et al., 2008).

In the Carmo and Gualaxo do Norte Rivers, tributaries of the Rio Doce Basin, which were

ro
directly impacted by artisanal and industrial (Passagem Mine) gold mining for centuries,
-p
arsenic background values were established after analysis of several sediments and river
re
banks samples (Costa et al., 2010). Reference As values were established as 229-700 and
lP

10.21-241.0 mg As.kg-1 for the riverbanks and sediment samples, respectively. Sediments

collected at the flooding zone were more diluted, as expected (Costa et al., 2010). As we can
na

see, arsenic background in some IQ areas is quite high due to the anomalous arsenic
ur

content of IQ minerals. Reference values adopted for the IQ are fairly high if compared to
Jo

those established by the WHO in 2001, mentioned before, i.e. 1-40 mg kg-1 (WHO, 2001).

Likewise, the Technology and Environmental Sanitation Company (CETESB), an

environmental agency in the São Paulo State established, in 2014, some soil and water

quality guidelines that have been adopted by the other Brazilian States (CETESB, 2014)

(Table 2). This document recommends As contents in soils should be under 35, 55 or

150 mg kg-1 for agricultural, residential or industrial destination areas, respectively.

Moreover, according to the same regulations, values above those limits are indicative for

the need of some intervention. As we may notice, these values are lower than those found
 Journal Pre-proof

in Iron Quadrangle (Table 1). According to several authors (Table 1), arsenic content higher

than 100 mg kg-1 are often found in soil and sediment samples collected in the Iron

Quadrangle. Values are particularly high in the proximity of gold mining sites (Borba, 2002;

Borba et al., 2003; Costa et al., 2010; de Figueiredo et al., 2007; Guerra et al., 2017;

Matschullat et al., 2000; Matschullat et al., 2007; Matschullat e Deschamps, 2011; Menezes

et al., 2006; Rodrigues et al., 2013). For samples collected in Nova Lima, As content was 20

times higher than the local background (Matschullat and Deschamps, 2011). It is important

of
to reinforce the need for a continuous monitoring program in those areas. CETESB and WHO

ro
both recommend <10 µg L-1 of As in surficial and ground-water (CETESB, 2014).
-p
Arsenic contents in soils, sediments, water and other materials collected in IQ and other
re
Brazilian As contaminated sites are depicted in Table 1 (A, B and C) and should be compared

to those Brazilian legislation reference data compiled in (Table 2). Arsenic background
lP

values proposed by Costa and Nalini in 2010 are quite high, in comparison to international
na

parameters (Table 2) (Costa et al., 2010), and it is important to highlight.

ur

One can conclude that environmental samples with high levels of potentially toxic inorganic
Jo

contaminants, including elevated arsenic concentrations (higher than 100 mg.kg-1) are

commonly found in the IQ, around ancient gold mines and also in very densely populated

areas (Deschamps et al., 2002; Matschullat and Deschamps, 2011). Soil samples collected in

Nova Lima, Santa Bárbara and Mariana showed averaged As concentrations of 960, 100 and

53 mg.kg-1 respectively, while the estimated As average concentration in soils all around the

world is 5.0 mg.kg-1 (Deschamps et al., 2002) or in a range of 0.81-14.24 mg.kg-1 in São Paulo

State (Abreu et al., 2014). As previously mentioned, those arsenic anomalies are due to both

natural and anthropogenic factors. One of the main anthropogenic factors is the long-term
 Journal Pre-proof

mineral exploitation (Daus et al., 2005; Jörg Matschullat et al., 2000a; Matschullat et al.,

2007; Matschullat and Deschamps, 2011). Due to mineral composition and geologic aspects,

not only As but also other potentially toxic elements such as Cd, Pb, Mn, Cu, and Co are also

found in very high concentrations in the IQ soils, sediments and waters (Gonçalves et al.,

2010; Matschullat et al., 2000; Varejão et al., 2011). In 2011, Varejão et al determined the

total concentrations of some trace metals and arsenic in water and sediments collected at

IQ areas close to Mariana and Ouro Preto. Additionally, a four-step sequential extraction

of
procedure named BCR (European Bureau of Reference) was employed to assess the

ro
distribution of the identified elements within the different solid phases. Elements such as
-p
As, Cd, Zn, Co, Cr, Cu, Ni, and Pb were found and extracted from sediment samples. Less

than 1% of the total As was associated with the acid-soluble fraction, for all the studied
re

samples. Fortunately, the greatest portion of extracted As and trace metals were associated
lP

with the residual fraction (Varejão 2011; Silva et al, 2018) but, the potential risk of arsenic
na

re-mobilization should not be dismissed. Regarding the analyzed water samples, results

pointed out 100% of the samples presented As values higher than those established by the
ur

Brazilian regulations varying from 36.7 to 68.3 μg L−1. Not only arsenic but also other
Jo

potentially toxic elements, were found in soils, topsoil and sediments, all around the IQ,

easily. Ribeira Valley, Serra do Navio and other mining activity areas were impacted also

(Figures 1 and 3) (Borba et al., 2003; CPRM, 2014; Hatje et al., 2010; Lima et al., 2007;

Matschullat et al, 2003; Palmieri, 2006; Rezende et al., 2015; Sakuma et al., 2010; Silva et

al., 2018; Varejão et al., 2011).

Concerning surficial and groundwater samples collected within IQ, arsenic concentrations

cover a wide range from less than 10 µg L-1, the legislation requirements for drink water
 Journal Pre-proof

(Conama, 2005; CONAMA, 2011) to 1,700,000 µg L-1, within the Passagem Mine (Borba et

al., 2000). Those extremely high values were detected in some unfiltered water samples; in

that case, the total arsenic was measured. Assessed data were summarized in Table 1C.

According to Borba et al., 2000: “Potential risks of environmental accidents in the Iron

Quadrangle are related to As contaminated soils, which could be used for agriculture,

housing and leisure, and the As contaminated water for domestic consumption and

irrigation. It is necessary to carry out an inventory of the local sources of pollution, give

of
guidance to the local population as to the hazards of certain habits and implement low cost

ro
programs of environmental mitigation and countermeasures. Care must be taken in relation

to the consumption of underground water and of treated surface water, since the toxic
-p
effects of arsenic can take many years to become apparent and the conventional treatment
re
of water does not remove the dissolved arsenic.”
lP
na

3.2.2.2.2. Arsenic contamination in the lron Quadrangle – Recent contamination

ur

Brazilian historical mining waste materials had always been considered as a potential source

of environmental contaminants, particularly in the case of gold mines where waste

Jo

materials were expected to contain mercury, cadmium, manganese, lead, and arsenic thus

causing some concern. Arsenic mobility depends on the mineral composition, mineral

crystallinity and environmental conditions and is controlled by a sensitive precipitation-

dissolution and adsorption-desorption equilibrium during arsenopyrite weathering (Costa et

al., 2010; De Andrade et al., 2012; Deschamps et al., 2003; Ono et al., 2016; Rodrigues et al.,

2013a; Varejão et al., 2011). If kept under reducing (anoxic) environment, the stability of

arsenopyrite, scorodite and other Al, Fe and amorphous Fe arsenates, and Mn-
 Journal Pre-proof

oxyhydroxides is remarkable ensuring its safe storage over a long period time (Ciminelli et

al., 2012; Mello 2014). One alternative is keeping those materials water-saturated (Ono et

al., 2016), i.e. sediments in rivers beds, to prevent oxidation and minimize its

release/mobility and transfer into the other environmental compartments.

The reducing condition also favors arsenic precipitation as arsenic sulfides, a very stable

arsenic compound and its formation is usually microbiologically mediated (de Matos et al.,

2018; Le Pape et al., 2017; Lizama A et al., 2011). However, in some cases, organic material

of
discharged into the aquatic environment and its subsequent anaerobic biodegradation

ro
could lead to an acidic environment which may also cause As mobilization from goethite
-p
(Borba, 2002) or other As-bearing wastes. In some of their studies, Lopes (2014) observed
re
an As content in abandoned gold mines, located in Ouro Preto, i.e. Mina Velha, Chico Rei,

and Santa Rita, in the range of 465 mg kg-1 to 1,829 mg g-1. The leachability of soil samples
lP

was tested under low oxygen pressure conditions at the bench scale and the effect of
na

organic matter and anaerobic microbiota on As mobility was demonstrated. Arsenic

solubilization is a function of both, organic matter and microbial activity.

ur
Jo

Contrarily, under oxidizing conditions, arsenic ions could be solubilized as a consequence of

sulfide-minerals oxidation. After solubilization, oxidized As(V) species may adsorb onto iron

oxyhydroxides and clay minerals (Costa et al., 2010). The higher the crystallinity of the

material, the more effective the adsorption, resulting in the formation of some very stable

bidentate-binuclear adsorptive complexes (Ono et al., 2016). Unfortunately, gold mining

waste materials are often amorphous and highly soluble thus limiting arsenic stability in

such matrices (Arslan et al., 2016; Bowell et al., 2013; Bundschuh et al., 2012b; De Andrade

et al., 2012; de Mello et al., 2006; Ono et al., 2016).

 Journal Pre-proof

3.2.2.3 Some other Arsenic contaminated sites

Out of the iron quadrangle, two other regions in Minas Gerais should be mentioned: Riacho

dos Machados (North) and Paracatu (Northwest), both related to gold mining activities.

Great attention is dedicated to the second site, Paracatu, a 84,718 inhabitants city with an

HDI of 0.744 (IBGE, 2010) located at -46.8752 17° 13′ 21″ S and 46° 52′ 31″ W. Studies from all

of
over the country and abroad have been dedicating their attention to understanding the

arsenic contamination issues in Paracatu, which is located at another very important river

ro
basin, the São Francisco River Basin. In Paracatu, a very large gold deposit named Morro do
-p
Ouro (which means Gold Hills) has been exploited for decades. Gold mineralization in Morro
re
do Ouro deposit is hosted in carbonaceous phyllite with quartzite lenses of the
lP

Meso/Neoproterozoic Canastra Group (Figure 1) (Dardenne, 2000; Pimentel et al., 2011,

Costa, 2016). Thrust faults mark out the tectonic contact between this unit and the pelitic
na

and carbonate rocks comprised in the Vazante Group (Dardenne, 2000; Carvalho et al.,
ur

2016). The interface which links both units is also known for hosting major lead and zinc
Jo

deposits in the Paracatu-Vazante region (Carvalho et al. 2016, Monteiro et al., 2006).

Industrial gold mining activities began in 1976–77 and are estimated to continue until 2032

(Mertens et al., 2017). Up to 55 million tonnes of ore were expected to be processed

annually from 2014 to 2018. Gold ore deposits are low Au grade (0.4 to 0.6 g Au t-1) but very

rich in arsenic, more than 4000 mg kg-1 (Mertens et al., 2017). As a consequence of gold

mineral processing, As release to the environment is expected to occur.

 Journal Pre-proof

Average concentrations of total As in soils, sediments and mining tailings are relatively high,

Ono et al. (2009 and 2012) have reported up to 313 or 2,666 mg kg-1 of As in dust and pond

tailings from mine areas, respectively (Ono, 2009; Ono et al., 2012). Besides that, surface-

and ground-water As content are not high. Gasparon et al. (2012) reported As levels in

groundwater varying from 0.1 to 6.6 µg L-1 while Bidone et al. (2016) reported the arsenic

content in surface-water being in the range of <0.5 to 40 μgL−1 with 35% of the analyzed

water samples containing As content lower than 10 μg L−1 (the legal limit).

of
Furthermore, As bioavailability to humans from the soil collected at Paracatu assessed using

ro
the bioaccessibility method is very small (Ono et al, 2012 a and b). The low bioaccessibility
-p
(less than 4%) and bioavailability observed for the analyzed material were explained and
re
confirmed by some recent studies (Ciminelli et al., 2018; Ng et al., 2019). Those data are

following Paracatu’s minerals low solubility discussed by others (de Mello et al., 2006; de
lP

Andrade et al., 2012) and is attributed to the presence of gibbsite, high amounts of iron oxy-
na

hydroxides associated with a low carbon content (de Mello et al., 2006). It has also been

reported that arsenic in dust and soil has very low bioaccessibility due to its insoluble form
ur

as trapped in oriented aggregates of iron nanohydroxide particles (Freitas et al., 2015;

Jo

Ciminelli et al, 2018).

Despite those data, due to the long-term and high scale operation of Morro do Ouro mine,

the environmental risks and health threats to Paracatu citizens have been assessed to

quantify the potential health risk (Ciminelli et al., 2018; Mertens et al., 2017; Ono et al.,

2012b). A Recent study has shown that As exposure from the inhalation route is

insignificant, and incidental oral ingestion contributes a higher exposure of As from the
 Journal Pre-proof

geogenic sources, however, the dietary arsenic intake represents the major exposure

pathway in Paracatu (Ng et al., 2019).

3.3. As contamination in Brazil – Toxicology, Risk assessments, recommendations

Arsenic is a well-known human carcinogen (WHO, 2000; IARC, 2012). Some areas of Brazil,

Japan, Mexico, Thailand and Australia, as well as large areas of Bangladesh, China, West

of
Bengal (India), and smaller areas of Argentina, Australia, Chile, Mexico, Taiwan (China), the

ro
USA, and Vietnam are contaminated with arsenic (IARC, 2012). Anthropogenic activities
-p
have contributed to elevated concentrations of arsenic in local water sources and the fact

that water is the main vehicle for As in the environment is renowned.

re
lP

As reported by IARC (2012), and Tables 1 and 2 show arsenic levels may vary in affected

areas from quite normal to extremely high values. For instance, if we consider soil and
na

sediment samples, while for non-affected areas the background arsenic concentration in soil

is often around 5 mg kg-1 whereas in Brazil at the IQ region, the background is fairly high, in
ur

the range of 290 to 706.5 mg kg-1. Arsenic contents in solid samples collected in the whole
Jo

country by several authors (Table 1) have shown arsenic contents varying from less than 10

up to 21000 mg kg-1. The highest concentrations of As were very often found at IQ. All those

features have been addressed by the geological explanation discussed in previous sections.

The same features were observed for surface- and ground-waters (Table 1). The highest and

astonishing value (1,700,000 µg L-1) was observed in unfiltered water samples collected in

an abandoned gold mine 20 years ago (Borba et al, 2000). Total arsenic contents were two

to ten times higher than the dissolved As. Since then, to the best of our knowledge, no
 Journal Pre-proof

intervention or treatment has been carried out. This mine is nowadays used for touristic

activities, including cave diving. The potential risks to the visitors remain unclear.

The arsenic concentrations usually observed in different environmental samples in Brazil

and, mainly at the Iron Quadrangle are higher than the limits established by diverse

organizations worldwide (Table 2). According to Matschullat & Deschamps (2011), the

estimation of human risks based on the ingestion of food, mainly plants, is not an easy task.

It should be noted that the Joint FAO/WHO Expert Committee on Food Additives (JECFA) has

of
withdrawn its Provisional Tolerable Weekly Intake (PTWI) of 15 µg As kg-1 of body weight

ro
(b.w.) since 2011 (JECFA, 2011). In its place they have established a benchmark dose (lower
-p
confidence limit) i.e., BMDL0.5, of 3 µg As kg-1 b.w. per day.
re
Matschullat et al. (2007) reported arsenic concentrations in Brazilian urine might vary from
lP

15 to 40 µg L-1. Values below the minimum are considered normal, no toxicological effects

are expected. Arsenic contents within the range (15-40 µg L-1) deserve attention and
na

individuals should be monitored. Whereas As concentrations higher than 40 µg L-1 are

ur

indicative of elevated exposure and individuals should be submitted to toxicological

Jo

investigations. It should be noted that the background urinary arsenic levels may vary

among populations and that risk assessment based on urinary arsenic concentrations should

consider the speciation of inorganic arsenic and its methylated metabolites. Total arsenical

concentration could be misleading because it may contain arsenobetaine or other organic

species that are considered practically non-toxic (JECFA, 2011).

Considering atmospheric arsenic contamination, by assuming a linear dose-response

relationship, a safe level for inhalation exposure cannot be recommended (WHO, 2000). At

an air concentration of 1 µg m3, an estimate of lifetime risk is 1.5 × 10–3. This means that the
 Journal Pre-proof

excess lifetime risk level is 1:10,000, 1:100,000 or 1:1,000,000 at an air concentration of

about 66; 6.6 or 0.66 ng.m3, respectively (WHO, 2000). It is noted that the European Union

is advocating a target arsenic concentration of 6.0 ng m3 in the air (Anonymous, 2005).

Another important feature reinforced by WHO (WHO, 2001) is the influence of nutrition on

arsenic metabolism and arsenic-induced effects. Malnourishment, stress and other health

issues may influence arsenic effects on the affected population. Once more, social

development indexes HDI and neonatal mortality rate, as well as education and sanitary

of
data should be considered to better estimate the population risk. Unfortunately, the most

ro
vulnerable groups, from the social point of view, probably will be also, the most vulnerable
-p
from the toxicological point of view.
re
Risk assessment studies are relatively recent in Brazil starting from the 2000’s. To date,
lP

there are less than 30 scientific papers dedicated to arsenic monitoring and arsenic risk

assessment in Brazil could be retrieved from Web of Science website. Some of them, not
na

only the well-known ones (Matschullat et al., 2000b; Matschullat et al., 2007; Matschullat
ur

and Deschamps, 2011) are worthy to discuss and will be discussed from the oldest to the
Jo

newest.

As previously described, large amounts of arsenic-contaminated materials were abandoned

close to the urban area and caused contamination of drinking water sources thus increasing

the contamination risks for people. Similarly, the mining activity and mining wastes

associated risks were the driving force for some of the studies by Ono et al. (Ono, 2013,

2009b, Ono et al., 2016, 2012a, 2012b). Ono was one of the first to mention the importance

of the bioaccessibility tests as a tool for human health risk assessment and prediction in

Brazil. In their studies, the In Vitro Gastrointestinal (IVG) bioaccessibility protocol was
 Journal Pre-proof

adopted to evaluate the bioaccessibility of As in stratified samples (0-2 and 2-10 cm) from

Morro do Ouro, Paracatu, Minas Gerais (Ono, et al. 2012a). Similar experimental approaches

were equally used for determining the bioavailability of arsenic in air suspended particles

(Ono, 2013). The main results highlighted that arsenic, mainly AsV, bioaccessibility is low,

probably due to its chemical and mineralogical composition (Ono, 2013; Ciminelli et al.,

2018). The same authors reinforced the need of establishing reference values for trace

elements in suspended air particulates in Brazil, to enable the evaluation of air quality and

of
health impact, especially at sites close to mining/industrial areas. Human risk assessment of

ro
the population living in urban areas close to abandoned gold mines was the aim of the study
-p
by Gonçalves and Lena (2013). Theoretical As daily intake (from water, soil, and air) was

calculated based on the experimental results obtained using a conservative perspective i.e.,
re

100% As bioavailability was assumed. In that way, human risks for the exposed population
lP

were unacceptable. However, recent studies conducted in Paracatu (Ciminelli et al., 2017;
na

Ng et al., 2019) found that although the food was the most significant contributor to the

total daily intake, its associated risk is no higher than that associated with drinking water
ur

containing 10 µg L-1 (the limit in Brazil).

Jo

A group of 398 children, 7-14 y, living in four Ribeira Valley municipalities: Cerro Azul and

Adrianópolis in Paraná State; Ribeira and Iporanga in São Paulo State, was the study

population of Sakuma and colleagues (Sakuma et al., 2010). Urine samples (first void) were

collected from June 1999 to November 2001 for arsenic determination. Children living at

Iporanga (mining-impacted area with a high arsenopyrite occurrence) presented the highest

level of urinary arsenic 8.94 µg L-1 (mean value) while those living in other impacted areas

presented As urinary mean levels of 6.3 and 6.4 µg L-1. As level in the urine of children living
 Journal Pre-proof

in non-impacted areas was lower, 3.60 µg L-1. Therefore, it was suggested that the natural

presence of arsenic in Iporanga, allied to the anthropic contamination from mining activity

may have increased arsenic exposure and could explain elevated arsenic concentrations

detected in children living in Iporanga. Arsenic contribution from food ingestion was not

measured.

Concerning human contamination with arsenic through food, attention should be driven to

the unique study which dedicates to better understand the contribution of rice and beans

of
for the dietary As intake in Brazil assuming those grains are the main components of a

ro
typical Brazilian diet and both of them are cooked using contaminated or non-contaminated
-p
water (Ciminelli et al., 2017). Rice and beans ingestion contributed 67-90% of the total As
re
intake in Brazil. As in many country regions, beans are cropped at home, and this crop is

very important for the subsistence of many families, occasional As contamination due to
lP

beans consumption are likely to occur, mainly at the arsenopyrite rich regions. Not only
na

greens and vegetables but grains are important to be also assessed for dietary arsenic

intake.
ur
Jo

Recently, Azevedo et al. (2018) and de Souza et al. (2018) published some studies. The study

published by de Souza and colleagues is a mini-review focused on arsenic exposure and the

contaminations of food, as a consequence of the unrestricted use of arsenic in As-based

herbicides and wood preservatives. Geochemical and diffused sources of arsenic

contamination were discussed also. The hazards of contaminated meat and seafood

consumption were also pointed out. The risk of cancer associated with the intake of As by

ingesting beef, poultry, cattle liver, and chicken liver in a population living in a no-mining-

affected area was recently evaluated (Azevedo et al., 2018). The studied community is
 Journal Pre-proof

located in the North of Rio de Janeiro State, in the lower Paraíba do Sul River basin where

surface- and ground-water samples containing high As were found. The occurrence of

groundwater samples containing more than 50 μg L−1 of arsenic was described. Fortunately,

the obtained results indicated the risk of exposure to inorganic and total arsenic by

ingesting poultry is at a minimum level.

of
3.4. A very fragile equilibrium

ro
The hypothesis of the legacy of ancient and abandoned mines deposited over the years in
-p
the Iron Quadrangle region could produce a serious environmental impact of arsenic in the

areas was tested and confirmed recently. The As-adsorption desorption equilibrium proved
re

to be reversible when disturbed. In November 2015, a tailings dam named Fundão, located
lP

at Mariana, Minas Gerais State (20°12′23.4″S and 43°28′01.6″W) (Figure 4) collapsed and
na

spilled a massive amount of iron mine wastes into the Doce River basin. Approximately 50–

60 million m3 of mud were drained into the Doce River basin via its tributaries Gualaxo do
ur

Norte and Carmo Rivers (Carmo et al., 2017; Guerra et al., 2017a; Marta-Almeida et al.,
Jo

2016a; Menezes et al., 2006; Quadra et al., 2019; Segura et al., 2016). The Gualaxo do Norte

River was the first affected. Mud spilled without control, like a “Tsunami wave” (Guerra et

al., 2017) causing widespread contamination of approximately 60 km, destroying the

Gualaxo do Norte River riverbed and banks until it reaches the intersection with Carmo

River, close to Barra Longa (Figure 2). At this point, a surprising phenomenon took place.

Carmo River flow was reversed, for almost 8 km, due to the energy contained in the mud-

flood. After that mud, water, river sediments, and all sources of suspended materials were

drained into the riverbed and both rivers flowed together (named Carmo River from this
 Journal Pre-proof

point) until it reached the Piranga River and finally, the main basin river, the Doce River. On

November 22nd, mud plume carried by Doce River reached the Atlantic Ocean waters.

During this almost 600 km journey, countless amount of solid materials were drained into

the river plume. Materials were dispersed and solubilized in the mud and finally, discharged

into the ocean. Water quality parameters were completely disturbed. Water supply for

thousands of people was impaired for several days or months. Fauna and flora were, and

still are, affected. This was the worst environmental disaster in Brazil and one of the biggest

of
in the world. The long-term effects of this episode on the environment, the natural biota

ro
and the distressed population remain uncertain. Impacts on the ecosystem and human

population must be assessed.

-p
re
Mud wastes from iron mines are classified as “not hazardous” materials. Nevertheless,

chemical analyses of water, mud, soils, sediments, and dust collected at the affected area
lP

pointed to the presence of potentially hazardous metals and metalloids. Elements such as
na

Al, As, Mn, Ag, and Pb were detected at very high levels (Carmo et al., 2017; Guerra et al.,

2017; IBAMA, 2015; Segura et al., 2016). Apparently, the energy from the mud flooding was
ur

intense enough to cause the suspension, the re-suspension and re-solubilization of some
Jo

very old gold mining wastes and sediments historically deposited at the Gualaxo do Norte

and Carmo riverbeds and banks for the last centuries. This may explain elemental

contaminations in the environment resulting from the dam collapse. Those events are

graphically represented in Figure 5.

Water, mud and sediments samples collected hours (Quadra et al., 2019), days (Alves et al.,

2018; Guerra et al., 2017b; IBAMA, 2016) and months after this event presented

unexpected contents of several potentially hazardous elements, including arsenic. Water

 Journal Pre-proof

samples collected at Bento Rodrigues (Minas Gerais, Brazil), which was the first impacted

area, six days after the event presented high Ag, Fe and Mn contents (Segura et al., 2016).

Mud particle samples collected on the same day (mostly irregular particles with small

diameters varying from 1 to 200 μm) were contaminated with Ba, Pb, As, Sr, Fe, Mn and Al,

which could be solubilized in the water (Segura et al., 2016). Silva et al. (2018) observed

increased amounts of As (20%), Cd (13%), Co (5%), Cr (9%), Cu (11%), Ni (4%), Pb (7%) and

Zn (19%) in the easily remobilized fractions, after the Dam failure. It was achieved by

of
comparing the obtained results with those collected about six months before the accident.

ro
According to Quadra et al. (2019), Fe and Mn contents of water samples collected after the
-p
Fundão Dam collapse were 2 and 250 times higher when compared to the reference

samples, collected prior to the disaster. According to those authors, As, Cd and Pb contents
re

in water samples were below the limit of detection of the equipment they used, i.e. Atomic
lP

Absorption Spectroscopy (AAS) which is not the best detection methods for those
na

contaminants if we consider the legal limits: 0.01- 0.033; 0.001- 0.01 and 0.001-0.033 mg.L-1

for As, Cd and Pb, respectively (CONAMA, 2005) Therefore, the occurrence of As
ur

contamination in those samples is of concern. In a technical report, the Brazilian

Jo

Environmental Protection Agency (Instituto Brasileiro do Meio Ambiente e dos Recursos

Naturais Renováveis), therefore named IBAMA (IBAMA, 2016), objected to some of the

results presented by the reports produced by the Samarco company after the Dam rupture.

The disagreement was about the analytical approach adopted.

Guerra et al. (2017) found As and Mn levels of up to 164 or 2410 mg kg−1 respectively when

analyzing soil and mine waste samples collected in the affected area. The toxicity

characteristic leaching procedure (TCLP) of the material showed no evidence of hazards,

 Journal Pre-proof

regarding As (Guerra et al., 2017). These authors considered the As concentrations found

were within the range expected for the Iron Quadrangle mineral samples due to its naturally

high arsenic backgrounds but, at the same time, they also highlighted the importance to

study the longer term environmental effects of this mud-flooding event.

Before the Dam collapse, the most common inorganic contaminants found in the Doce River

basin were Cr, Cu, Hg, Pb, and Zn and 41 % of the sediment samples analyzed were above

the sediment quality guideline value, i.e. 37.3; 35.7; 0.17; 35.0 and 123.0 µg.g-1, respectively

of
(Santolin et al., 2015, CONAMA, 2012). During the first fortnight after the accident, almost

ro
all of the water quality parameters (CONAMA, 2005) were affected. Dissolved oxygen levels
-p
dropped, while turbidity and color raised abruptly. Organic (cyanide) and inorganic
re
contaminants (Al, Pb, Fe, Mn, P, Hg, and Zn) were detected at levels far higher than the

regulatory limits (IBAMA, 2016). With the dilution effect, some contaminants levels
lP

returned to the normal background levels. High manganese, arsenic and mainly iron levels
na

were still detectable, in some sampling points, for several months. Iron enrichment of

sediments found in Gualaxo do Norte and Doce River basins are not explained only by the IQ
ur

geology, rather iron enrichment is directly related to mining activities, which occur here for
Jo

centuries and this is important to realize (Rodrigues et al., 2013). Furthermore, it is

worthwhile to mention that iron-enriched materials like sediments could adsorb arsenic and

other potentially toxic elements thus contributing to its immobilization. On the other hand,

when those materials are exposed to new environmental conditions as a consequence of

the anthropogenic influence, these iron enriched materials could dissolve and some harmful

contaminants could be mobilized to the river waters (Rodrigues et al., 2013b; Santolin et al.,

2015). This feature is particularly relevant for fine particles, easily solubilized and dispersed
 Journal Pre-proof

to and from the river, mainly during flooding seasons, thus may increase inorganic

contaminants mobility and bioavailability (Segura et al, 2016 and Guerra et al, 2017). In that

way, the environmental impacts of the sedimentation of those iron-enriched fine particles

at the Rio Doce Basin is expected to be a long-lasting phenomenon.

Another unexpected consequence of the Fundão tailings dam collapse is the spreading of

mining contaminants, including arsenic, to the marine environment. It is a very new feature

for those interested in studying the environmental effects of the mining activities and

of
arsenic contamination in Brazil. Cagnin et al. (2017) discussed As contamination in the

ro
continental shelves and encourage the monitoring of the ore mine environmental impacts.
-p
In another study (Marta-Almeida et al., 2016) revealed mud contaminants could be
re
dispersed into the marine waters for hundreds of kilometers. Contamination may reach

regions as far as the shelf in front of the city of Rio de Janeiro (RJ) or Ilhéus (BA) since
lP

naturally, marine waters move to the South, or the North, depending on the wind directions
na

and force (Marta-Almeida et al., 2016). In that way, arsenic contamination, related to the

mining activity may affect other Brazilian regions, which never had been impacted by the
ur

gold or iron mining industry, historically.

Jo

4. Final remarks

This study presented and discussed more than one hundred documents covering more than

two decades of recent research on arsenic contamination in Brazil. As a result, it is possible

to affirm arsenic contamination issues should be addressed by a multidisciplinary approach

to better understand the arsenic-related effects on the different environmental

 Journal Pre-proof

compartments and living beings, including humans. Geological, geochemical, chemical,

biological, toxicological, as well as economic and social aspects should be considered during

risk assessment studies.

Although no acute or chronical arsenic poisoning related diseases were reported to date,

there is a consensus amongst the scientific and wider communities that arsenic hazards

from arsenic contamination of water, soil, dust, and food in those arsenic-contaminated

areas are likely to occur. The environmental compartments could be contaminated by dust

of
dispersion; dispersion of tailings and sediments due to flooding; construction of settlements

ro
on arsenic-contaminated soils; contaminated water ingestion; incidental soil or dust
-p
ingestion, and occasional consumption of contaminated food (including milk, meat, fish and
re
vegetables) and groundwater (Garelick et al., 2008) (Borba, 2002; de Figueiredo et al., 2007;

de Souza et al., 2107; de Souza et al., 2018; Lima et al., 2007; Matschullat et al., 2000a;
lP

Matschullat and Deschamps, 2011; Ono et al., 2016; Quadra et al., 2019b; Rodrigues et al.,
na

2013a; Sakuma et al., 2010). At Iron Quadrangle the monitoring need is even more relevant

after the Fundão Dam collapse (Guerra et al., 2017c; Quadra et al., 2019; Segura et al, 2016)
ur

to ensure environmental quality and human health.

Jo

Constant monitoring of arsenic natural or anthropogenic impacted areas was suggested by

the majority of the here mentioned authors. Some warnings are particularly worthy of

mention. After the Fundão accident, the contaminated plume dispersed to the sea following

a dispersion pattern. The inner shelf between the river mouth and the city of Vitória is the

region expected to be more often in contact with the riverine waters (Marta-Almeida et al.,

2016). Besides that, marine monitoring not only close to the Doce River mouth but through

the whole coastal region of the Espírito Santo State, from Bahia (at the North) to Rio de
 Journal Pre-proof

Janeiro (South) is extremely important since arsenic and other inorganic contaminants

effects on marine ecosystems are not completely predictable. Furthermore, strict protocols

for the prevention of contamination events like the mining tailings dam collapses (Guerra et

al., 2017) should be adopted.

Human impacts on nature as deforestation and soil erosion must also be constantly

monitored (Sakuma, 2010) since it can further increase arsenic mobilization. Moreover,

climate changes and fluctuations on rain distribution in Brazil, as observed in recent years,

of
could compel people to change from surficial to groundwater sources for supplying water

ro
for human and agricultural consumption but, regrettably, only a few scientific studies
-p
focused on arsenic contamination of groundwater have been carried out in Brazil (de Souza
re
et al, 2017 and de Souza et al, 2018). This is a really important consideration to keep in mind

since water is still considered the main vehicle for arsenic dispersion from the different
lP

environmental compartments to living beings.

na

By observing the recommendations for Arsenic focused future research made by WHO many
ur

years ago (WHO, 2001) some knowledge gaps (or opportunities) still persist and are possible
Jo

to identify in the Brazilian context.

Concerning human health, dose-response epidemiological studies are needed. The health

effects of arsenic at low levels of exposure should be conducted. The scarcity of longitudinal

studies on arsenic effects on cardiovascular morbidity, hypertension, and neurological

system justifies for further research. The influence of arsenic on diabetes prevalence and

the impact of nutrition on arsenic metabolism and arsenic-induced effects should be

addressed.
 Journal Pre-proof

Acknowledgments:

This work was supported by the Brazilian agencies CNPq, Capes and FAPEMIG. The support of the

Federal University of Ouro Preto is acknowledged. Queensland Alliance for Environmental

Health Sciences (QAEHS) is a partnership between the University of Queensland and

Queensland Health.

of
ro
References
-p
Abreu, C.A., Siva, R.O., Cantoni, M., Coelho, R.M., 2014. Natural contents of arsenic in soils of the
re
state of São Paulo, Brazil, in: Bundschuh, J., Bhattacharya, P. (Eds.), Arsenic in the Environment

- One Century of the Discovery of Arsenicosis in Latin America (1914-2014). Taylor & Francis,
lP

London, pp. 258–259.

na

Ahamed, S., Sengupta, M.K., Mukherjee, S.C., Pati, S., Mukherjeel, A., Rahman, M.M., Hossain, M.A.,

Das, B., Nayakl, B., Pal, A., Zafar, A., Kabir, S., Banu, S.A., Morshed, S., Islam, T., Rahman, M.M.,
ur

Quamruzzaman, Q., Chakraborti, D., 2006. An eight-year study report on arsenic contamination
Jo

in groundwater and health effects in Eruani village, Bangladesh and an approach for its

mitigation. J. Health. Popul. Nutr. 24, 129–41.

Alkmim, F.F., Teixeira, W. 2017. The Paleoproterozoic Mineiro Belt and the Quadrilátero Ferrífero.

In: Heilbron, M., Cordani, U.G., Alkmim F.F. (eds.), São Francisco Craton, Eastern Brazil –

geology of a miniature continent. Springer Switzerland, Cham, pp. 71-94

Alves, R.I.S., Machado, C.S., Beda, C.F., Fregonesi, B.M., Nadal, M., Sierra, J., Domingo, J.L., Segura-

muñoz, S.I., 2018. Water Quality Assessment of the Pardo River Basin , Brazil : A Multivariate

Approach Using Limnological Parameters , Metal Concentrations and Indicator Bacteria. Arch.
 Journal Pre-proof

Environ. Contam. Toxicol. 75, 199–212. https://doi.org/10.1007/s00244-017-0493-7

AngloGoldAshanti, 2018.

(http://www.anglogoldashanti.com.br/AreasNegocio/Paginas/MineracaoOuro.aspx).

(Accessed 15 December 2018)

Anonymous, 2005. Directive 2004/07/EC of the European Parliament and of the Council. Official

Journal of the European Union, L 23/3 of 26.1.2005.

Arslan, B., Djamgoz, M.B.A., Akün, E., 2016. ARSENIC: A Review on Exposure Pathways,

of
Accumulation, Mobility and Transmission into the Human Food Chain. Springer, Cham, pp. 27–

ro
51. https://doi.org/10.1007/398_2016_18 -p
Azevedo, L.S., Pestana, I.A., Meneguelli-Souza, A.C., Ramos, B., Pessanha, D.R., Caldas, D., Almeida,
re
M.G., de Souza, C.M.M., 2018. Risk of exposure to total and inorganic arsenic by meat intake
lP

among different age groups from Brazil: a probabilistic assessment. Environ. Sci. Pollut. Res. 25,

35471–35478. https://doi.org/10.1007/s11356-018-3512-y
na

Bidone, E., Castilhos, Z., Cesar, R., Santos, M.C., Sierpe, R., Ferreira, M., 2016. Hydrogeochemistry of
ur

arsenic pollution in watersheds influenced by gold mining activities in Paracatu (Minas Gerais

State, Brazil). Environ. Sci. Pollut. Res. 23, 8546–8555. https://doi.org/10.1007/s11356-016-

Jo

6089-3

Borba, R.P., 2002. Arsênio em ambiente superficial: processos geoquímicos naturais e

antropogênicos em uma área de mineração aurífera. Universidade Estadual de Campinas.

http://repositorio.unicamp.br/jspui/handle/REPOSIP/287173

Borba, R.P., Coscione, A.R., Figueiredo, B.R., Zambello, F., 2009. Estudo da especiação de arsênio

inorgânico e determinação de arsénio total no monitoramento ambiental da qualidade de

águas subterrâneas. Quim. Nova 32, 970–975. https://doi.org/10.1590/S0100-

 Journal Pre-proof

40422009000400027

Borba, R.P., Figueiredo, B.R., Cavalcanti, J.A., 2004. Arsênio na água subterrânea em Ouro Preto e

Mariana, Quadrilátero Ferrífero (MG). Rem Rev. Esc. Minas 57, 45–51.

https://doi.org/10.1590/S0370-44672004000100009

Borba, R.P., Figueiredo, B.R., Matschullat, J., 2003. Geochemical distribution of arsenic in waters,

sediments and weathered gold mineralized rocks from Iron Quadrangle, Brazil. Environ. Geol.

44, 39–52. https://doi.org/10.1007/s00254-003-0766-5

of
Borba, R.P., Figueiredo, B.R., Rawlins, B., Matschullat, J., 2000. Arsenic in Water and Sediment in the

ro
Iron Quadrangle , State of Minas Gerais , Brazil. Rev. Bras. Geociências 30, 558–561.
-p
http://dx.doi.org/10.21577/0100-4042.20170275
re
Bowell, R.J., Rees, S.B., Barnes, a, Prestia, a, Warrender, R., Dey, B.M., 2013. Geochemical
lP

assessment of arsenic toxicity in mine site along the proposed Mineral Tramway Project,

Camborne, Cornwall. Geochemistry - Explor. Environ. Anal. 13, 145–157.

na

https://doi.org/10.1144/geochem2012-137
ur

Brasil, 2017 - Instituto Brasileiro de Geografia e Estatística (IBGE), 2017. IBGE | Brasil em Síntese |

Amapá | Santana | História &amp; Fotos [WWW Document].

Jo

https://cidades.ibge.gov.br/brasil/ap/santana/historico.

Bundschuh, J., Litter, M.I., Parvez, F., Román-Ross, G., Nicolli, H.B., Jean, J.-S., Liu, C.-W., López, D.,

Armienta, M. a, Guilherme, L.R.G., Cuevas, A.G., Cornejo, L., Cumbal, L., Toujaguez, R., 2012.

One century of arsenic exposure in Latin America: a review of history and occurrence from 14

countries. Sci. Total Environ. 429, 2–35. https://doi.org/10.1016/j.scitotenv.2011.06.024

Cagnin, R.C., Quaresma, V.S., Chaillou, G., Franco, T., Bastos, A.C., 2017. Science of the Total

Environment Arsenic enrichment in sediment on the Eastern continental shelf of Brazil. Sci.
 Journal Pre-proof

Total Environ. 607–608, 304–316. https://doi.org/10.1016/j.scitotenv.2017.06.162

Campanha, G. A. C., Faleiros, F. M.; Basei, M. A.S.; Tassinari, C. C. G.; Nutman, A. P.; Vasconcelos, P.

M. 2015. Geochemistry and age of mafic rocks from the Votuverava Group, Southern Ribeira

Belt, Brazil: Evidence for 1490 Ma oceanic back-arc magmatism. Precambrian Research, 266,

530-55. https://doi.org/10.1016/j.precamres.2015.05.026

Carmo, F.F. do, Kamino, L.H.Y., Junior, R.T., Campos, I.C. de, Carmo, F.F. do, Silvino, G., Castro, K.J. da

S.X. de, Mauro, M.L., Rodrigues, N.U.A., Miranda, M.P. de S., Pinto, C.E.F., 2017. Fundão tailings

of
dam failures: the environment tragedy of the largest technological disaster of Brazilian mining

ro
in global context. Perspect. Ecol. Conserv. https://doi.org/10.1016/j.pecon.2017.06.002
-p
Carvalho, O.C., Valeriano, C.M., Gonzalez, P.A.A., Oliveira, G.D., Impiccini A., 2016. The thrust contact
re
between the Canastra and Vazante groups in the Southern Brasília Belt: structural evolution,

white mica crystallinity and implications for the Brasiliano orogeny. Braz. J. Geology. 46(4), 567-
lP

583. http://dx.doi.org/10.1590/2317-4889201620160052
na

CETESB, 2014. Diário Oficial Poder Executivo - Decisão de Diretoria 045/2014/E/C/I, de 20-02-2014 -

Dispõe sobre a aprovação dos Valores Orientadores para Solos e Águas Subterrâneas no Estado
ur

de São Paulo – 2014, em substituição aos Valores Orientadores de 2005 e dá outras

Jo

providências A. Companhia Ambiental do Estado de São Paulo, Brasil.

https://cetesb.sp.gov.br/aguas-subterraneas/valores-orientadores-para-solo-e-agua-

subterranea/ (accessed 14 January, 2019).

CETESB, 2017. Diário Oficial Poder Executivo -Decisão de Diretoria - Dispõe sobre a aprovação do

"Procedimento para a Proteção da Qualidade do Solo e das Águas Subterrâneas", da revisão do

"Procedimento para o Gerenciamento de Áreas Contaminadas" e estabelece "Diretrizes para

Gerenciamento de Áreas Contaminadas no Âmbito do Licenciamento Ambiental".

https://cetesb.sp.gov.br/areas-contaminadas/planilhas-para-avaliacao/ (accessed 28 January,

 Journal Pre-proof

2020).

Ciminelli, V.S.T., Antônio, D.C., Caldeira, C.L., Freitas, E.T.F., Delbem, I.D., Fernandes, M.M.,

Gasparon, M., Ng, J.C., 2018. Low arsenic bioaccessibility by fixation in nanostructured iron

(Hydr)oxides: Quantitative identification of As-bearing phases. J. Hazard. Mater. 353, 261–270.

https://doi.org/10.1016/j.jhazmat.2018.03.037

Ciminelli, V.S.T., Gasparon, M., Ng, J.C., Silva, G.C., Caldeira, C.L., 2017. Dietary arsenic exposure in

Brazil: The contribution of rice and beans. Chemosphere 168, 996–1003.

of
https://doi.org/10.1016/J.CHEMOSPHERE.2016.10.111

ro
CONAMA, 2005. Resolução n 357, 18 de
-p março de 2005. DOU 18/03/2005.

http://www2.mma.gov.br/port/conama/legiabre.cfm?codlegi=459 (accessed 14 January 2019)

re
CONAMA, 2011. Resolução CONAMA 430/2011. DOU 92 16/05/2011. https:
lP

http://www2.mma.gov.br/port/conama/legiabre.cfm?codlegi=646 (accessed 24 November

2019)
na

CONAMA, 2012. Resolução CONAMA 454/2012. DOU 08/11/2012, Seção 1, pág. 66.
ur

http://www2.mma.gov.br/port/conama/legiabre.cfm?codlegi=693. (accessed 29 June 2019)

Jo

Costa, A.T., Nalini Júnior, H.A., Castro, P. de T.A., Tatumi, S.H., 2010. Análise estratigráfica e

distribuição do arsênio em depósitos sedimentares quaternários da porção sudeste do

Quadrilátero Ferrífero, bacia do Ribeirão do Carmo, MG. Rev. Esc. Minas 63, 703–714.

https://doi.org/10.1590/S0370-44672010000400017

Costa, F.R., 2016. Caracterização tecnológica do minério de ouro da Mina Morro do Ouro –Paracatu,

MG. Dissertação Escola Politécnica da Universidade de São Paulo, São Paulo, 150p.

http://www.teses.usp.br/teses/disponiveis/3/3134/tde-22062016-144932/pt-br.php

Costa, R. de V.F. da, Leite, M.G.P., Mendonça, F.P.C., Nalini Jr., H.A., 2015. Geochemical mapping of
 Journal Pre-proof

arsenic in surface waters and stream sediments of the Quadrilátero Ferrífero, Brazil. Rem Rev.

Esc. Minas 68, 43–51. https://doi.org/10.1590/0370-44672015680077

CPRM, 2014. Serviço Geológico do Brasil. Mapeamento geoquímico do Quadrilátero Ferrífero e seu

entorno. João Henrique Larizzatti, Eduardo Duarte Marques, Francisco Valdir Silveira (Eds). –

Rio de Janeiro. 208 p. ISBN 978-85-7499-153-5 1.

http://rigeo.cprm.gov.br/jspui/handle/doc/14809. (Accessed 29 June 2019)

CPRM, 2018. Serviço Geológico do Brasil. http://www.cprm.gov.br/publique/Redes-

of
Institucionais/Rede-de-Bibliotecas---Rede-Ametista/Canal-Escola/Metais-Preciosos-1041.html

ro
(Accessed 29 June 2019).
-p
CPRM,2019. Serviço Geológico do Brasil. Excursão virtual pela Estrada Real no Quadrilátero Ferrífero.
re
https://www.cprm.gov.br/publique/media/gestao_territorial/geoparques/estrada_real/credito

s_institucionais.html. (Accessed, 30 January 2019)

lP

DNPM, 2001. Departamento Nacional de Produção Mineral.

na

(http://www.dnpm.gov.br/dnpm/paginas/balanco-mineral/arquivos/balanco-mineral-

brasileiro-2001-ferro). (accessed 29 June 2019).

ur

DNPN, 2016. Anuário Mineral Brasileiro. Departamento Nacional de Produção MIneral.

Jo

www.dnpm.gov.br/dnpm/publicacoes/serie-estatisticas-e-economia-mineral/anuario-

mineral/anuario-mineral-brasileiro/anuario-mineral-brasileiro-2016-metalicos. (Accessed 29

Jun 2019)

Dardenne, M.A., 2000. The Brasília fold belt. In: Cordani, U.G., Milani, E.J.,Thomaz Filho, A., Campos,

D.A. (Eds.), Tectonic Evolution of South America, Rio de Janeiro, Brazil, pp. 231–263.

Daus, B., Wennrich, R., Morgenstern, P., Weiß, H., Leonhardt Palmieri, H.E., Nalini, H.A., Leonel, L.V.,

Guedes Monteiro, R.P., Moreira, R.M., 2005. Arsenic speciation in plant samples from the iron
 Journal Pre-proof

Quadrangle, Minas Gerais, Brazil. Microchim. Acta 151, 175–180.

https://doi.org/10.1007/s00604-005-0397-5

de Andrade, R.P., De Mello, J.W.V., Windmöller, C.C., Da Silva, J.B.B., Figueiredo, B.R., 2012.

Evaluation of arsenic availability in sulfidic materials from gold mining areas in Brazil. Water.

Air. Soil Pollut. 223, 4679–4686. https://doi.org/10.1007/s11270-012-1224-3

de Figueiredo, B.R., Borba, R.P., Angélica, R.S., 2007. Arsenic occurrence in Brazil and human

exposure. Environ. Geochem. Health 29, 109–118. https://doi.org/10.1007/s10653-006-9074-9

of
de Matos, L.P., Costa, P.F., Moreira, M., Gomes, P.C.S., de Queiroz Silva, S., Gurgel, L.V.A., Teixeira,

ro
M.C., 2018. Simultaneous removal of sulfate and arsenic using immobilized non-traditional SRB
-p
mixed culture and alternative low-cost carbon sources. Chem. Eng. J. 334, 1630–1641.
re
https://doi.org/10.1016/j.cej.2017.11.035
lP

de Mello, J.W.V., Roy, W.R., Talbott, J.L., Stucki, J.W., 2006. Mineralogy and arsenic mobility in

arsenic-rich Brazilian soils and sediments. J. Soils Sediments 6, 9–19.

na

https://doi.org/10.1065/jss2005.09.144
ur

de Souza, E. S. T., da Costa, R. A., Costa, H.S.C., Oliveira, F.J., Melo, L. C.A., Faial, K.C.F., Fernandes,

A.R., 2017. Assessment of risk to human health from simultaneous exposure to multiple
Jo

contaminants in an artisanal gold mine in Serra Pelada, Pará, Brazil. Sci. Total Environ. 576,

683–695. https://doi.org/10.1016/j.scitotenv.2016.10.133

de Souza, A.C.M., de Almeida, M.G., Pestana, I.A., de Souza, C.M.M., 2018. Arsenic Exposure and

Effects in Humans: A Mini-Review in Brazil. Arch. Environ. Contam. Toxicol. 1–9.

https://doi.org/10.1007/s00244-018-00586-6

Deschamps, E., Ciminelli, V.S.T., Lange, F.T., Matschullat, J., Raue, B., Schmidt, H., 2002. Soil and

sediment geochemistry of the iron quadrangle, Brazil the case of arsenic. J. Soils Sediments 2,
 Journal Pre-proof

216–222. https://doi.org/10.1007/BF02991043

Deschamps, E., Ciminelli, V.S.T., Weidler, P.G., Ramos, A.Y., 2003. Arsenic sorption onto soils

enriched in Mn and Fe minerals. Clays Clay Miner. 51, 197–204.

https://doi.org/10.1346/CCMN.2003.0510210

FEAM, 2018. Inventário de áreas contaminadas estado de minas gerais: 2017. Belo Horizonte.

http://www.feam.br/images/stories/2018/AREAS_CONTAMINADAS/Inventario_%C3%81reas_

Contaminadas_2018.pdf (Accessed 29 Jun 2019)

of
Fernandes, A.R., Souza, E.S., Braz, A.M.S, Alleoni, L.R.F., 2018. Quality reference values and

ro
background concentrations of potentially toxic elements in soils from the Eastern Amazon,
-p
Brazil. J. Geochemical Exploration 190, 453-463. https://doi.org/10.1016/j.gexplo.2018.04.012
re
Figueiredo, B.R. 1992. Modelos de depósitos minerais. Boletim do Instituto de Geociências da
lP

Universidade de São Paulo, Série Científica, 23: 75-96. http://dx.doi.org/10.11606/ issn.2316-

8986.v23i0p75-95
na

Figueiredo, B.R., Litter, M.I., Silva, C.R., Mañay, N., Londono, S.C., Rojas, A.M., Garzón, C., Tosiani, T.,
ur

Di Giulio, G.M., De Capitani, E.M., Dos Anjos, J.Â.S.A., Angélica, R.S., Morita, M.C., Paoliello,

M.M.B., Cunha, F.G., Sakuma, A.M., Licht, O.A., 2010. Medical Geology Studies in South
Jo

America, in: Medical Geology. Springer Netherlands, Dordrecht, pp. 79–106.

https://doi.org/10.1007/978-90-481-3430-4_4

Freitas, C.M. de, Silva, M.A. da, Menezes, F.C. de, 2016. O desastre na barragem de mineração da

Samarco: fratura exposta dos limites do Brasil na redução de risco de desastres. Cienc. Cult. 68,

25–30. https://doi.org/10.21800/2317-66602016000300010

Freitas, E.T.F., Montoro, L.A., Gasparon, M., Ciminelli, V.S.T. 2015. Natural attenuation of arsenic in

the environment by immobilization in nanostructured hematite. Chemosphere 138, 340–347.

 Journal Pre-proof

https://doi.org/10.1016/j.chemosphere.2015.05.101

Garelick, H., Jones, H., Dybowska, A., Valsami-Jones, E., 2008. Arsenic Pollution Sources, Reviews of

environmental contamination and toxicology. Springer, New York, NY.

https://doi.org/10.1007/978-0-387-79284-2_2

Gonçalves, José Augusto Costa Pereira, J.C., Lena, J. de C., Nalini Jr, H.A., Paiva, J.F. de, 2010.

Hidrogeoquímica do Arsênio e de Outros Constituintes Inorgânicos Presentes nas Águas

Subterrâneas da Cidade de Ouro Preto-MG. Rev. Bras. Recur. Hídricos 15, 89–104. DOI:

of
10.21168/rbrh.v15n4.p89-104

ro
Gonçalves, J.A.C., De Lena, J.C., 2013. Avaliação de risco à saúde humana por contaminação natural
-p
de arsênio nas águas subterrâneas e nos solos da área urbana de Ouro Preto (MG). Geol. USP -
re
Ser. Cient. 13, 145–158. https://doi.org/10.5327/Z1519-874X2013000200008
lP

Gonçalves, J.A.C., De Lena, J.C., Paiva, J.F., Nalini, H.A., Pereira, J.C., 2007. Arsenic in the

groundwater of Ouro Preto (Brazil): its temporal behavior as influenced by the hydric regime
na

and hydrogeology. Environ. Geol. 53, 785–793. https://doi.org/10.1007/s00254-007-0691-0

ur

Gonçalves, J.A.C., Mpereira, M.A., Paiva, J.F. de, Lena, J.C. de, 1999. O Arsênio Nas Águas

Subterrâneas De Ouro Preto-MG. p. 155.

Jo

Gontijo, B., Bittencourt, F., 2005. Arsênio - Uma revisão histórica. An. Bras. Dermatol. 80, 91–95.

https://doi.org/10.1590/S0365-05962005000100014

Guerra, M.B.B., Teaney, B.T., Mount, B.J., Asunskis, D.J., Jordan, B.T., Barker, R.J., Santos, E.E.,

Schaefer, C.E.G.R., 2017a. Post-catastrophe Analysis of the Fundão Tailings Dam Failure in the

Doce River System, Southeast Brazil: Potentially Toxic Elements in Affected Soils. Water, Air,

Soil Pollut. 228, 252. https://doi.org/10.1007/s11270-017-3430-5

Hatje, V., Macedo, S.M., de Jesus, R.M., Cotrim, G., Garcia, K.S., de Queiroz, A.F., Ferreira, S.L.C.,
 Journal Pre-proof

2010. Inorganic As speciation and bioavailability in estuarine sediments of Todos os Santos Bay,

BA, Brazil. Mar. Pollut. Bull. 60, 2225–2232. https://doi.org/10.1016/j.marpolbul.2010.08.014

IARC, I.A. for R. on C., 2012. A review of human carcinogens. Part C: Arsenic, metals, fibres, and

dusts, 2012th ed. WHO Press, World Health Organization, Geneva.

IBAMA, 2016. Parecer Técnico Sobre os Resultados Obtidos nas Coletas De Amostras De Água E

Sedimento no Rio Doce e na Região da Foz, no Estado do Espirito Santo.

IBAMA, 2015. Laudo Técnico Preliminar - Impactos ambientais decorrentes do desastre envolvendo

of
o rompimento da barragem de Fundão, em Mariana, Minas Gerais.

ro
IBGE, 2010. Senso Demográfico 2010. https://censo2010.ibge.gov.br/
-p
IBGE, 2019. https://cidades.ibge.gov.br/. (accessed 14 January 2019).
re

Jaguar Mining Incorporation., 2019. https://www.jaguarmining.com/en/operations/caete-complex/.

lP

(Accessed 29 June 2019.

na

JECFA, 2011. Evaluation of Certain Contaminants in Food. The seventy-second report of Joint
FAO/WHO Expert Committee on Food Additives. WHO, 1-115.
ur

Keim, C.N., 2011. Arsenic in biogenic iron minerals from a contaminated environment. Geomicrobiol.
Jo

J. 28, 242–251. https://doi.org/10.1080/01490451.2010.493571

Le Pape, P., Battaglia-Brunet, F., Parmentier, M., Joulian, C., Gassaud, C., Fernandez-Rojo, L.,

Guigner, J.-M., Ikogou, M., Stetten, L., Olivi, L., Casiot, C., Morin, G., 2017. Complete removal of

arsenic and zinc from a heavily contaminated acid mine drainage via an indigenous SRB

consortium. J. Hazard. Mater. 321, 764–772. https://doi.org/10.1016/J.JHAZMAT.2016.09.060

Lima, M. de O., Faial, K.R.F., Brabo, E. da S., Santos, E.C. de O., Angélica, R.S., Mendes, R. de A.,

Carneiro, B.S., Sá, L.L.C. de, Vale, E.R., Jesus, I.M. de, 2007. Avaliação de Arsênio Total, de

elementos traços e bacteriológica em águas de consumo na comunidade do Elesbao, Município

 Journal Pre-proof

de Santana, Estado do Amapá, Brasil. Cadernos Saúde Coletiva (Rio Janeiro) 15, 467–482.

http://bases.bireme.br/cgi-

bin/wxislind.exe/iah/online/?IsisScript=iah/iah.xis&src=google&base=LILACS&lang=p&nextActi

on=lnk&exprSearch=527825&indexSearch=ID

Litter, M.I., Nicolli, H.B., Meichtry, M., Quici, N., Bundschuh, J., Bhattacharya, P., Naidu, R., 2014. One

Century of the Discovery of Arsenicosis in Latin America (1914–2014) As 2014, 2014–Arse ed,

One Century of the Discovery of Arsenicosis in Latin America. CRC Press/Balkema, Buenos

of
Aires. https://doi.org/10.1201/b16767

ro
Lizama A, K., Fletcher, T.D., Sun, G., 2011. Removal processes for arsenic in constructed wetlands.

Chemosphere 84, 1032–43. https://doi.org/10.1016/j.chemosphere.2011.04.022

-p
re
Lobato, L.M., Ribeiro-Rodrigues, L.C., Vieira, F.W.R., 2001. Brazil’s premier gold province. Part II:

Geology and genesis of gold deposits in the Archean rio das velhas greenstone belt,
lP

Quadrilátero ferrifero. Miner. Depos. 36, 249–277. https://doi.org/10.1007/s001260100180

na

Lobato, L.M., Santos, J.O.S., McNaughton, N., Fletcher, I.R., Noce, C.M. 2007. U-Pb SHRIMP monazite

ages of the giant Morro Velho and Cuiabá gold deposits, Rio das Velhas greenstone belt,
ur

Quadrilátero Ferrífero, Minas Gerais, Brazil. Ore Geology Reviews, 32(3-4):674-680. doi:
Jo

10.1016/j.oregeorev.2006.11.007

Lopes, A.P., Ribeiro, L.M.A.L., Salvador, E.D., Pavan, M., Silva, A.D.R. 2017. Áreas de elevante

interesse mineral – Vale do Ribeira: Mineralizações polimetálicas (Pb, Ag, Zn, Cu e Au – “tipo

Panelas”) em zonas de cisalhamento rúptil, Cinturão Ribeira meridional, SP-PR. Brasil, Serviço

geológico do Brasil (CPRM), 120 p.

Lopes Jr., I., 2016. Atlas geoquímico do Vale do Ribeira: geoquímica dos sedimentos ativos de

corrente. http://rigeo.cprm.gov.br/jspui/handle/doc/17642 (Accessed 19 June 2019)

 Journal Pre-proof

Lopes, L.R., 2014. Influência de Fatores Biológicos na Mobilidade de Arsênio Presente em Solos da

Cidade de Ouro Preto – Estudos “ in vitro .” Thesis. UFOP.

https://www.repositorio.ufop.br/handle/123456789/3693

Marta-Almeida, M., Mendes, R., Amorim, F.N., Cirano, M., Dias, J.M., 2016. Fundão Dam collapse:

Oceanic dispersion of River Doce after the greatest Brazilian environmental accident. Mar.

Pollut. Bull. 112, 359–364. https://doi.org/10.1016/j.marpolbul.2016.07.039

Matschullat, J., Birmann, K., Borba, R.P., Ciminelli, V., Deschamps, E.M., Figueiredo, B.R., Gabrio, T.,

of
Habler, S., Hilcher, A., Junghänel, I., de Oliveira, N., Rabbach, K., Schmidt, H., Schwenk, M., de

ro
Oliveira Vilhena, M.J., Weidner, U., Hasler, 2007. Long-term environmental impact of arsenic-

dispersion in Minas Gerais, Brazil. Arsen. Soil Groundw. Environ. - Biogeochem. Interact. Heal.
-p
Eff. Remediat. 9, 365–382. https://doi.org/10.1016/S1875-1121(06)09014-6
re

Matschullat, J., Deschamps, E., 2011. Arsenic : natural and anthropogenic. CRC Press. Leiden
lP

Matschullat, J., Perobelli Borba, R., Deschamps, E., Figueiredo, B.R., Gabrio, T., Schwenk, M., 2000.
na

Human and environmental contamination in the Iron Quadrangle, Brazil. Appl. Geochemistry

15, 181–190. https://doi.org/10.1016/S0883-2927(99)00039-6

ur

Menezes, M.A.B.C., Palmieri, H.E.L., Leonel, L. V., Nalini Jr, H.A., Jaćimović, R., 2006. Iron Quadrangle,
Jo

Brazil: Elemental concentration determined by k0-instrumental neutron activation analysis Part

I: Soil samples. J. Radioanal. Nucl. Chem. 270, 111–116. https://doi.org/10.1007/s10967-006-

0316-1

Mertens, F., Távora, R., Nakano, E.Y., Castilhos, Z.C., 2017. Information sources, awareness and

preventive health behaviors in a population at risk of Arsenic exposure: The role of gender and

social networks. PLoS One 12. https://doi.org/10.1371/journal.pone.0186130

Monteiro, M.A., 2003. A ICOMI no Amapá: meio século de exploração mineral. Novos Cad. NAEA 6,
 Journal Pre-proof

113–168.

Monteiro, L.V.S., Bettencourt, J.S., Juliani, C., Oliveira, T.F., 2006. Nonsulfide and sulfide-rich zinc

mineralizations in the Vazante, Ambrósia and Fagundes deposits, Minas Gerais, Brazil: mass

balance and stable isotope characteristics of the hydrothermal alterations. Gondwana

Research. 11(3),362-381. [doi: 10.1016/j.gr.2006.04.017].

Moraes, R.P., Figueiredo, B.R., Lafon, J.M. 2004. Pb-isotopic tracing of metal pollution sources in the

Ribeira Valley, Southeastern Brazil. Terrae, 1 (1), p. 26-33

of
Ng, J.C., Ciminelli, V., Gasparon, M., Caldeira, C., 2019. Health risk apportionment of arsenic from

ro
multiple exposure pathways in Paracatu, a gold mining town in Brazil. Sci. Total Environ. 673,
-p
36-43. https://doi.org/10.1016/j.scitotenv.2019.04.048
re
Nogueira, T.A.R., Abreu-Junior, C.H., Alleoni, L.R.F., He, Z., Soares, M.R. Vieira, C.S., Lessa, L.G.F.,
lP

Capra, G.F. 2018. Background concentrations and quality reference values for some potentially

toxic elements in soils of São Paulo State, Brazil. J. Environ. Manage. 221, 10-19.
na

https://doi.org/10.1016/j.jenvman.2018.05.048
ur

Oliveira Santos, E.C. de, Maura de Jesus, I., Carrera Sá Filho, G., de Oliveira Lima, M., Marcos

Miranda, A.M., Mascarenhas, A.S., Canto de Sá, L.L., Pessoa da Silva, A., 2003. Exposição ao
Jo

mercúrio e ao arsênio em Estados da Amazônia: síntese dos estudos do Instituto Evandro

Chagas/FUNASA. Rev. Bras. Epidemiol 6 (2), 171-185. http://dx.doi.org/10.1590/S1415-

790X2003000200010.

Ono, F.B., 2009. Bioacessibilidade de arsênio em área de mineração de ouro, paracatu (MG). Thesis.

Universidade Federal de Lavras.

http://repositorio.ufla.br/bitstream/1/2410/1/DISSERTA%C3%87%C3%83O_Bioacessibilidade%

20de%20ars%C3%AAnio%20em%20%C3%A1rea%20de%20minera%C3%A7%C3%A3o%20de%2

0ouro%2C%20Paracatu%20%28MG%29.pdf
 Journal Pre-proof

Ono, F.B., 2013. Bioacessibilidade de Cd e Pb em áreas de beneficiamento de metais e especiaçao de

As por XANES em áreas de mineração. Universidade Federal de Lavras. Thesis

http://repositorio.ufla.br/jspui/handle/1/1210

Ono, F.B., Guilherme, L.R.G., Mendes, L.A., Carvalho, G.S., 2012a. Replication of an ivg protocol to

estimate bioaccessible arsenic in materials from a gold mining area in Brazil. Rev. Bras. Ciência

do Solo 36, 1355–1360. https://doi.org/10.1590/S0100-06832012000400029

Ono, F.B., Guilherme, L.R.G., Penido, E.S., Carvalho, G.S., Hale, B., Toujaguez, R., Bundschuh, J.,

of
2012b. Arsenic bioaccessibility in a gold mining area: a health risk assessment for children.

ro
Environ. Geochem. Health 34, 457–65. https://doi.org/10.1007/s10653-011-9444-9
-p
Ono, F.B., Tappero, R., Sparks, D., Guilherme, L.R.G., 2016. Investigation of arsenic species in tailings
re
and windblown dust from a gold mining area. Environ. Sci. Pollut. Res. 23, 638–647.

https://doi.org/10.1007/s11356-015-5304-y
lP

Palmieri, H.E.L., 2006. Distribuição, especiação e transferência de HG e As para a biota em áreas do

na

sudeste do quadrilátero ferrífero, MG. Thesis.

http://www.repositorio.cdtn.br:8080/jspui/handle/123456789/911
ur

Pimentel, M.M., Rodrigues, J.B., Dellagiustina, M.E.S, Junges, S., Matteini, M., Armstrong, R., 2011.
Jo

The tectonic evolution of the Neoproterozoic Brasília Belt, central Brazil, based on SHRIMP and

LA-ICPMS U–Pb sedimentary provenance data: a review. Journal of South American Earth

Sciences. 31(4), 345-357. [doi:10.1016/j.jsames.2011.02.011]

Pimentel, H.S. Lena, J.C. de, Nalini Jr., H.A., 2003. Studies of water quality in the Ouro Preto region ,

Minas Gerais , Brazil : the release of arsenic to the hydrological system. Environ. Geol. 1999,

725–730. https://doi.org/10.1007/s00254-002-0671-3

Pires, F.R.M. 1977. Geologia do Distrito Manganesífero de Conselheiro Lafaiete. Tese de Mestrado,
 Journal Pre-proof

Instituto de Geociências, Universidade Federal do Rio de Janeiro, 344 p

Quadra, G.R., Roland, F., Barros, N., Malm, O., Lino, A.S., Azevedo, G.M., Thomaz, J.R., Andrade-

Vieira, L.F., Praça-Fontes, M.M., Almeida, R.M., Mendonça, R.F., Cardoso, S.J., Guida, Y.S.,

Campos, J.M.S., 2019. Far-reaching cytogenotoxic effects of mine waste from the Fundão dam

disaster in Brazil. Chemosphere 215, 753–757.

https://doi.org/10.1016/j.chemosphere.2018.10.104

Renger, F.E., Noce C.M., Romano A.W., Machado N. 1994. Evolução sedimentar do Supergrupo

of
Minas: 500 Ma de registro geológico no Quadrilátero Ferrífero, Minas Gerais, Brasil.

ro
Geonomos, 2(1):1-11. doi: 10.18285/geonomos.v2i1.227
-p
Rezende, P.S., Costa, L.M., Windmöller, C.C., 2015. Arsenic Mobility in Sediments from Paracatu
re
River Basin, MG, Brazil. Arch. Environ. Contam. Toxicol. 68, 588–602.

https://doi.org/10.1007/s00244-015-0134-y
lP

Rodrigues, A.S. de L., Malafaia, G., Costa, A.T., Nalini, H.A., 2013. Evaluation of the mineral
na

exploration influence on sediment composition in the Gualaxo do Norte River Basin (MG-Brazil)

based on geochemical and stratigraphic data. Environ. Earth Sci. 68, 965–972.
ur

https://doi.org/10.1007/s12665-012-1799-4
Jo

Rojas, A.J. 2008. Estudos químico-mineralógicos e microtermométricos do topázio imperial da região

de Antônio Pereira, Ouro Preto, Minas Gerais. 2008. Dissertação de mestrado, Universidade

Federal de Ouro Preto, Ouro Preto, 111 p

Roeser, H.M.P., Roeser, P.A., 2010. O Quadrilátero Ferrífero -Mg, Brasil: Aspectos Sobre Sua História,

Seus Recursos Minerais E Problemas Ambientais Relacionados. Geonomos 18, 33–37.

https://www.repositorio.ufop.br/handle/123456789/8341

Ruchkys, Ú.A., Machado, M.M.M., 2013. Geological and mining heritage of iron quadrangle, Minas
 Journal Pre-proof

Gerais - Characterization and strategies for education and geotourism [Patrimônio geológico e

mineiro do Quadrilátero Ferrífero, Minas Gerais - Caracterização e iniciativas de uso para

educação e geoturismo. Bol. Parana. Geosci. 120–136.

https://www.researchgate.net/publication/282559616_Geological_and_mining_heritage_of_ir

on_quadrangle_Minas_Gerais_-

_Characterization_and_strategies_for_education_and_geotourism. (accessed 29 June 2019)

Sakuma, A.M., Capitani, E.M. De, Maio, F.D. De, Gonçalves, F., Duran, M.C., 2010. Arsenic exposure

of
assessment of children living in a lead mining area in Southeastern Brazil Avaliação da

ro
exposição de crianças ao arsênio em área de mineração de chumbo na Região Sudeste do Brasil

Cad. Saúde Pública 26 (2), 391-398. http://dx.doi.org/10.1590/S0102-311X201000020001

-p
Santolin, C.V.A., Ciminelli, V.S.T., Nascentes, C.C., Windmöller, C.C., 2015. Distribution and
re

environmental impact evaluation of metals in sediments from the Doce River Basin, Brazil.
lP

Environ. Earth Sci. 74, 1235–1248. https://doi.org/10.1007/s12665-015-4115-2

na

Scarpelli, W., Horikava, E.H., 2017. Gold, iron and manganese in central Amapá, Brazil. Brazilian

Journal of Geology. 47(4), 703-721. https: //doi: 10.1590/2317-4889201720170114

ur

Segura, F.R., Nunes, E.A., Paniz, F.P., Paulelli, A.C.C., Rodrigues, G.B., Braga, G.Ú.L., dos Reis Pedreira
Jo

Filho, W., Barbosa, F., Cerchiaro, G., Silva, F.F., Batista, B.L., 2016a. Potential risks of the residue

from Samarco’s mine dam burst (Bento Rodrigues, Brazil). Environ. Pollut. 218, 813–825.

https://doi.org/https://doi.org/10.1016/j.envpol.2016.08.005

Silva, D. de C., Bellato, C.R., Marques Neto, J. de O., Fontes, M.P.F., 2018a. Trace elements in river

waters and sediments before and after a mining dam breach (Bento Rodrigues, Brazil). Quim.

Nova 41, 857–866. https://doi.org/10.21577/0100-4042.20170252

Tassinari, C.C.G., Mateus, A.M., Velásquez, M.E., Munhá, J.M.U., Lobato, L.M., Bello, R.M., Chiquini,
 Journal Pre-proof

A.P., Campos, W.F. 2015. Geochronology and thermochronology of gold mineralization in the

Turmalina deposit, NE of the Quadrilátero Ferrífero Region, Brazil. Ore Geology Reviews,

67:368-381. https://doi: 10.1016/j.oregeorev.2014.12.013

Unicef, 2017. Levels and Trends in Child Mortality Child Mortality Report 2017.

https://www.unicef.org/publications/index_101071.html. (Accessed 29 June 2019).

USEPA, 1989. Risk Assessment Guidance for Superfund – Volume I – Human Health Evaluation

Manual (Part A). https://www.epa.gov/sites/production/files/2015-09/documents/rags_a.pdf.

of
(accessed 28 January 2020).

ro
Varejão, E.V.V. V., Bellato, C.R., Fontes, M.P.F.F., Mello, J.W.V. V., 2011. Arsenic and trace metals in
-p
river water and sediments from the Southeast portion of the Iron Quadrangle, Brazil. Environ.
re
Monit. Assess. 172, 631–642. https://doi.org/10.1007/s10661-010-1361-3
lP

Vial, D.S., Groves, D.I., Cook, N.J., Lobato, L.M. (eds.). 2007b. Preface – Special issue on gold deposits

of Quadrilátero Ferrífero, Minas Gerais, Brazil. Ore Geology Reviews, 32(3-4):469-470.

na

https://doi: 10.1016/j.oregeorev.2006.11.006
ur

WHO, 2001. Environmental Health Criteria 224 Arsenic and arsenic compounds. United Nations

Environ. Program. 70. https://doi.org/NLM Classification: QV 294

Jo

WHO, 2000. Air quality guidelines for Europe. Environ. Sci. Pollut. Res. 3, 23–23.

https://doi.org/10.1007/BF02986808
 Journal Pre-proof

Conflict of interest

All authors mutually agree for submitting their manuscript to this journal

• There are no conflicts of interest in this study.

• The study was financially supported by the Federal University of Ouro Preto (UFOP), and also by
the Brazilian Agencies FAPEMIG, CAPES and CNPq.

Figure 1. Location of the most relevant sites of Arsenic contamination in Brazil and their respective
geologic maps. A) Serra do Navio deposit with location of manganese ore bodies (adapted from
Scarpelli &amp; Horikava, 2017); B) Geological map of the region of Paracatu and location of the
Morro do Ouro and Morro Agudo deposits (adapted from Monteiro et al., 2006); C) Simplified
Geologic map of Iron Quadrangle with main gold and iron mines (extracted from Alkmim &amp;
Teixeira, 2017); D) Simplified Geologic map of Ribeira Valley with location of Pb-Zn-Ag mines

of
(adapted from Lopes et al., 2017)

ro
-p
re
lP
na
ur
Jo
 Journal Pre-proof

Figure 2. Iron Quadrangle - Doce and Sao Francisco rivers basins limits within Iron Quadrangle.

of
ro
-p
re
lP
na
ur
Jo
 Journal Pre-proof

Figure 3. Iron Quadrangle (IQ) contaminated sites in Minas Gerais State (MG). Influence of mining
and metallurgical activities.

of
ro
-p
re
lP
na
ur
Jo
 Journal Pre-proof

Figure 4. Satellite images from Samarco Company tailing dams complex. Fundão collapse
affected and destroyed a smaller dam named Santarem (S). Images collected before
(11/12/2015, left) and, after Fundão Dam burst (12/11/2015, right). Modified from
https://earthobservatory.nasa.gov/images/86990/flooding-in-brazil-after-dam-breach

of
ro
-p
re
lP
na
ur
Jo
 Journal Pre-proof

Figure 5. Arsenic contamination in Iron Quadrangle - Timeline

of
ro
-p
re
lP
na
ur
Jo
 Journal Pre-proof

Table 1A – Arsenic occurrence in Brazilian soils

As content State/ Additional

Material Sample Period Sampling site Reference
Min. Max. Region Information
Soil Carmo River
(topsoil, (Mariana and
tailings) Monsenhor
and Horta) and Minas Gerais
B. Daus et
waste 6 900 6 2003 Agua Suja Southeastern
al (2005)
mg kg-1 Stream Region
(Antonio
Pereira
district)

of
Tailings
Nova Lima Minas Gerais from Nova
1998 - Matschullat

ro
6 21,000 117 and Santa Southeastern Lima 300 -
2003 et al., 2007
Barbara Region 21000
mg kg-1
-p
Honório
Bicalho (Nova
re
Dry Lima),
Minas Gerais
and Ecological Menezes et
0.25 809 5 Southeastern
wet Park of Tripuí al., 2006
lP

Region
season (Ouro Preto),
Barreiro (Belo
Horizonte)
na

Overbank:
São Paulo
<0,250mm
and Paraná
(60#)
Southeastern
ur

Lopes Jr, As
<2.5 >38 25 N/A Ribeira Valley and
2016 background
Southern
( 2.5 – 24.6
Regions
Jo

mg kg-1)

topsoil
<63 µm
Nova Lima, Deschamps,
Minas Gerais As
Santa 2002
13 13,400 38 N/A Southeastern anomalies,
Barbara, Matschulat
Region mean As
Mariana et al, 2011
content
≥100 mgKg-1
Mine
Minas Gerais tailings.
Ono et al,
37 2,666 5 N/A Paracatu Southeastern AV is the
2012
Region main arsenic
species
May, Minas Gerais Windblown
Ono et al,
38 313 8 June Paracatu Southeastern dust
2012
and Region samples
 Journal Pre-proof

August (particles
2011 <10 μm)
collected
around
mining
areas.

Minas Gerais
Santos et
283.2 1,694 2 2016 Ouro Preto Southeastern
al, 2018
Region
Minas Gerais
1,340 3,035 5 2014 Ouro Preto Southeastern Lopes, 2014
Region
São Paulo
São Paulo Nogueira et
0.2 8.8 30 N/A Southeastern

of
State al., 2018
Region
Pará
Pará, Eastern Fernandes

ro
0.06 7.75 132 N/A Northern
Amazon et al., 2018
Region
-p
re
lP
na
ur
Jo
 Journal Pre-proof

Table 1B – Arsenic occurrence in Brazilian sediments.

As content State/
Sample Period Sampling site Reference Additional Info
Min. Max. Region
Minas Gerais
Costa et al,
0.63 1,691 512 N/A Iron Quadrangle, all around Southeastern Sampling every
2015
Region
Rio Grande do Estuarine sed
Mirlean et al.,
0.6 62.5 41 1999 - 2002 Patos Lagoon Sul suspended
2003
Southern Region matter
Minas Gerais
Matschullat
15 3,300 39 1998 - 2003 Nova Lima and Santa Barbara Southeastern
et al., 2007
Region

of
BCR sequenti
Minas Gerais
Tripui Creek and Carmo River - Varejão et al., method: value
188.7 521.3 4 2006 Southeastern

ro
Minas Gerais 2011 first step, i.e.
Region
and acid-solub
Sedimentologic
-p
analysis was
Minas Gerais using 16
Rodrigues et
re
203 528 111 N/A Gualaxo do Norte River Basin Southeastern sections (cut
al., 2013
Region alluvial terrace
detected at ar
lP

sites. Recent ac
Minas Gerais and
São Paulo
Iron Quadrangle,
na

(Southeastern
Ribeira Valley and Santana Figueiredo et
<LOD 4,000 N/A 1998-2003 Region) and
(area in the Amazon deltaic region al, 2007
Amapá
of northern Brazil)
ur

(Northern
region)
Minas Gerais
Matschullat Particle size
Jo

47 140 39 1998-2003 Nova Lima and Santa Bárbara Southeastern

et al, 2007 Median values
Region
Das Velhas Riv
and Eh=115-2
April 1997, contents in un
June 1997, Minas Gerais Borba, 2000 samples were
<20 >4,000 N/A April 1998, Das Velhas and Do Carmo rivers Southeastern Borba et al, times higher
July 1999 Region 2003 content meas
filtered sample
Carmo River:
Eh=170-240 m
São Paulo and
Paraná
Lopes Jr,
<2.3 >30 187 N/A Ribeira Valley Southeastern Sediments: <0,
2016
and Southern
Regions
20 50 101 2003 and Todos os Santos Bay (BTS) Bahia Hatje, et al Marine Sedime
 Journal Pre-proof

2007 Northeastern 2010 Sampling poin

Region 12°500S-38°38
Sample sieved
As (III) reached
the total As con
Sediments we
classified acco
sizes: 2–0.063
October, 0.063 mm.
Minas Gerais
2010 and Rezende et al, Arsenic conten
738 2,750 5 Corrego Rico creek Southeastern
November, 2015 times greater
Region
2011 limits.
Positive and
correlation am
and Mn concen

of
232.32
Doce
November Abrolhos Continental Shelf and Eastern Cagnin et al.,
N/A 6

ro
River
2013 Doce River Continental Shelf continental shelf 2017
17.14
Abrolhos -p The maximum
Minas Gerais and shown is from
April 2015 Espírito Santo was collected
re
Tripuí Creek and the entire length of Silva et al.,
28.6 301.9 13 and June States Fundão dam
the Carmo River 2018
2016 Southeastern concentration
lP

Region higher even

rupture.
Rio Acima, Nova
Lima, Raposos
na

Silva et al.,
30.80 206.7 4 July 2016 Velhas River Basin and Sabará
2018
Southeastern
Region
ur
Jo
 Journal Pre-proof

Table 1C – Arsenic occurrence in Brazilian waters

As content Sampling State/ Additional

Material Sample Period Reference
Min. Max. site Region Information
Surface Iron Minas Gerais
Costa et al,
Water 57.7 414 512 N/A Quadrangle, Southeastern
2015
µg L-1 all around Region
Samples of
water,
Passagem Minas Gerais yellowish
1,320 2,030 14 2007 Mine - Southeastern Keim, 2011 flocculent
Mariana Region material and
biofilm were

of
collected
Local

ro
waterways are
utilized as
Tripui Creek Minas Gerais
Varejão et water sources
36.7 68.3 4 2006
-p
and Carmo Southeastern
al., 2011 for both
River Region
human and
re
agricultural
supply
Nova Lima Minas Gerais
lP

1998 - Matschullat
0.4 3,300 69 and Santa Southeastern
2003 et al., 2007
Barbara Region
N/A Main Gallery
na

and lateral
April 1997, Passagem Mine adit:
Minas Gerais
June 1997, de Mariana Borba, Eh=250 mV,
740,000** 1,700,000** Southeastern
ur

April gold mine 2000 pH values of

Region
1998 7.8-8.3 and
4.8-7.7,
Jo

respectively
October,
Minas Gerais As content is
2010 and Córrego Rezende et
0.55 110 5 Southeastern up to 11 times
November, Rico creek al, 2015
Region the legal limits
2011
September
2010 - Pardo River Alves et al.,
<LOD* 7.38 12 Southeast
September Basin 2018
2012
Belo SW-
Oriente, Minas Gerais supplementary
Governador and Espírito water supply
1.2 (SW) 1.3 (SW) Carvalho et
48 July 2016 Valadares, Santo States RW – River
0.1 (RW) 3.0 (RW) al. 2018
Colatina Southeastern (natural) water
Region Water for
public supply.
10.4 50.4 13 June 2016 Tripuí Creek Minas Gerais Silva et al.,
 Journal Pre-proof

and the and Espírito 2018

entire Santo States
length of Southeastern
the Carmo Region
River
Rio Acima,
Nova Lima,
Velhas River Raposos and Silva et al.,
78.1 85.3 4 July 2016
Basin Sabará 2018
Southeastern
Region
Pará
De Souza et Serra Pelada
0 4.2 23 N/A Curionópolis Northern
al, 2017 “garimpo”
region
Belo Minas Gerais
WW- water

of
Groundwater Oriente, and Espírito
Carvalho et well
µg L-1 1.1 10 July 2016 Governador Santo States
al. 2018 water for

ro
Valadares Southeastern
public supply.
and Colatina Region
Minas
-p Gerais Gonçalves Only AsV was
9 224 17 2004 Ouro Preto
Southeastern et al (2007) found.
Region
re
October,
Minas Gerais
<LOD 2010 and Corrego Rezende et
15 12 Southeastern
lP

* November, Rico creek al, 2015

Region
2011
Gasparon
0.1 6.6 9 2001 Paracatu
et al, 2012
na

Elesbão This study is

Amazonas
near to Santos et dedicated to
0.5 1,970 33 N/A Northern
Serra do al., 2003 assess Hg
ur

Region
Navio contamination
Water (Fish Pernambuco
Santos Dry season;
Jo

and Shrimp Itapessoca North-

0.12 1.51 35 days Pontes, pH = 6.6-7.1;
farms) River Easthern
2014 BOD ≤ 2.0
µg L-1 Region
* LOD – limit of detection; ** Total arsenic, unfiltered water samples.
 Journal Pre-proof

Table 1D – Arsenic occurrence in Brazilian biological matrices (human fluids, animal tissues) and air.

As content State/ Additional

Material Sample Period Sampling site Reference
Min. Max. Region Information
Plant, Carmo River * 6 sampling
vegetable (Mariana and points
(terrestrial Monsenhor Pteris vittata,
and aquatic) Horta) and Pityrogramma
Minas Gerais
µg kg-1 Agua Suja Daus et al calomelanos,
0.00075 2.55 * 2003 Southeastern
Stream (2005) Baccharis
Region
(Antonio trimera
Pereira AsIII as the
district, predominant

of
Mariana) arsenic species
Nova Lima Minas Gerais
1998 - Matschullat

ro
0.003 6 171 and Santa Southeastern Aquatic plants
2003 et al., 2007
Barbara Region
Edible plants
-p
Vegetable
samples,
re
purchased from
small farmers (n
= 17) or markets
lP

(n = 10): lettuce
(n = 7), endive (n
= 3), spring
na

onion (n = 2),
86 October, kale (n = 9),
Minas Gerais
(parsley) 2010 and Rezende et mustard (n = 1),
<LOD variable Paracatu Southeastern
ur

100 November, al, 2015 and parsley (n =

Region
(endive) 2011 5).
Samples were
Jo

stored in sealed
plastic bags,
frozen for
transportation,
triturated and
lyophilized prior
to digestion and
chemical
analysis
Edible plants.
2001, Backyard
2002, 2004 Vasconcelos cultivated.
Minas Gerais
100 10,900 and 2005 Nova Lima et al, in Cabbage,
N/A Southeastern
(lettuce) (lettuce) (dry and Santa Bárbara Matschullat lettuce, taro
Region
wet et al, 2011 root, squash,
seasons) mustard,
parsley, mint,
 Journal Pre-proof

fennel, spinach,
tomato, carrot,
beetroot,
collard-green,
sugarcane and
sweet potato.

Blood This study is

Elesbão near Amazonas
µg L-1 Santos et dedicated to
70 19,310 1927 N/A to Serra do Northern
al., 2003 assess Hg
Navio Region
contamination
Hair This study is
Elesbão near Amazonas
µg kg-1 Santos et dedicated to
60 5,850 1927 N/A to Serra do Northern
al., 2003 assess Hg
Navio Region
contamination

of
Urine Santa Bárbara
µg L-1 (Brumal),

ro
Nova Lima
Minas Gerais
1998 - (Mingú and Matschullat Children (8–14
0.6 59 982 Southeastern
2003 Galo), and et al., 2007 years)
-p
Ouro-Preto –
Region
Mariana
(Mariana)
re
Cerro Azul
(Paraná
lP

State),
Southeastern
Adrianópolis
1999 - and Sakuma et Children (7 - 14
1 60 398 (Paraná),
2001 Southern al., 2010 years)
Ribeira (São
na

Regions
Paulo) and
Iporanga (São
Paulo)
ur

Matschullat
June, 1997 Minas Gerais Children- (7-14
Nova Lima et al, 1998,
2.2 106 126 and April, Southeastern years
Jo

Santa Bárbara Matschullat

1998 Region (mean=9.8±1.12)
et al, 2000
Chapter 14. 30%
of the total As
species found
are inorganic;
Couto et al As(III)
Minas Gerais
Nova Lima in to As(V) ratio of
9.01 106 1,600 1998-2005 Southeastern
Santa Bárbara Matschullat 0.85–2.93 (mean
Region
et al, 2011 1.72)
Results refer to
μg As g−1
creatinine

Air Nova Lima Minas Epilithic lichens

1998 - Matschullat
(atmosphere) 0.5 23 26 and Santa Gerais (Xantho-
2003 et al., 2007
mg kg-1 Barbara Southeastern parmelia
 Journal Pre-proof

Region farinose and

Parmotrema
grayanum) were
used like bio-
monitor
Fish This study is
Elesbão, near Amazonas
mg kg-1 Santos et dedicated to
20 180 262 N/A Serra do Northern
al., 2003 assess Hg
Navio Region
contamination
The fish species
(corvina, catfish
and shorthead
Rio de
drum) were
Janeiro Gao et al.,
8.9 42.5 7 2013 Port Açu caught in 2013
Southeastern 2018
by local

of
Region
fisherman in the
Açu Port area,

ro
Rio de Janeiro
Cananéia- In general,
Iguape- higher loads
-pPeruíbe São Paulo Gusso- were found at
0.0004 1.145 18 N/A Environmental Southeastern Choueri et the sampling
re
Protected Region al., 2018 sites closer to
Area (APA- the Cananéia
CIP). city
lP

Fish collected
from tilapia
Southern Steckert et farms. High
27.5 49.2 240 2015 Santa Catarina
na

Brazil al., 2018 arsenic contents

sediments (5.9
mg kg-1).
ur
Jo
 Journal Pre-proof

Table 2 – Arsenic concentrations in different environmental compartments (air, water,

minerals, biota) – reference values, regulatory parameters, national and international data.

As content

Compartment/matrix (range or Comments

maximum
limit)

Iron Quadrangle Sediment Lower than the natural reference value

of
-1
2.31-51
(mg kg ) Very low environmental risk

ro
Costa and Nalini, 2010
≤ the natural reference value
51.01-229.30
Very low environmental risk
-p
229.31-350.0 Indicative of natural or anthropogenic sources
re
350.01-706.50 Indicative of natural or anthropogenic sources

As anomalies.
lP

706.01-
Anthropogenic influence (direct or indirect)
1098.50
High environmental risk
na

Iron Quadrangle ≤ natural reference value

0.73 – 10.21
Flooded plains Very low environmental risk
ur

-1
(mg kg )
≤ natural reference value
Costa and Nalini, 2010 10.22-88.70
Jo

Very low environmental risk

88.71-180.0 Indicative of natural or anthropogenic sources

180.01-241.40 Indicative of natural or anthropogenic sources

As anomalies.
241.41-
Anthropogenic influence (direct or indirect)
1027.67
High environmental risk

Soil 3.5 Reference quality

-1
(mg kg )
15 Caution
CETESB, 2014; Conama,
2009 35
Interventive actions are required
(agricultural
 Journal Pre-proof

use)

55
(residential Interventive actions are required
use)

150
Interventional actions are required
(industrial use)

Soil 32
(mg kg-1) (residential)
Defra and Environmental
43
Agency, 2004
(allotment)

of
640

ro
(commercial)

Soil
-p
(mg kg-1)
Regardless the use: agricultural, residential/
re
12
Canadian Council of parkland commercial, Industrial
Ministers of the
Environment, 2001
lP

Soil 5-40
(mg kg-1) (rural soils)
na

APVMA, 2003
3-31 Background arsenic levels in urban and rural soils
(new suburb) (Queensland-Australia)
ur

3-27
Jo

(old suburb)

Sediment
(mg kg-1) 1-4,000 The higher values are indicative of contamination
WHO, 2001

Soil
Background 1 -40
-1
(mg kg ) (mean value =
WHO, 2001 5)

Drinking water 10
 Journal Pre-proof

(µg L-1)
WHO, 2001 and Brasil,
2011

Natural Freshwater
(µg L-1) 5 Toxicity to algae
WHO, 2001

Seawater
arsenic concentrations increased with increasing
(µg L-1) 1-2
salinity
WHO, 2001

Groundwater 1-2

of
(µg L-1) Sulfide minerals deposits
up to 3,400

ro
WHO, 2001 Geothermic or volcanic areas

Groundwater
-p
(µg L-1) 10 Values above that should be investigated
re
Conama, 2009

Air 0.02-4
lP

(ng m3) (Background, Rural or remote areas

0.2-1.5)
WHO, 2001
na

3 to 200
(Background, Urban or industrial areas
0.5-3)
ur

Living organism - terrestrial

Jo

(mg kg-1, fresh weight) <1

WHO, 2001

Living organism -Marine Predominantly organic arsenic species

-1
(mg kg , fresh weight) < 100 arsenosugars (macroalgae) and arsenobetaine
WHO, 2001 (invertebrates and fish).

Plants - Freshwater
mg kg-1, dry weight) < 10 uncontaminated environments
WHO, 2001

Plants - terrestrial 0.02-5 No arsenic-containing pesticides

(mg kg-1, dry weight)
350 to 2040 arsenic-contaminated soils (or wastes)
WHO, 2001
 Journal Pre-proof

Human hair <1 Non exposed

-1
(mg kg )
Couto et al in Matschullat 0.04–32.5 Exposed population
et al, 2011

Human Blood
(µg L-1)
0.5–32
Couto et al in Matschullatet
al, 2011

Refers to the sum total of the common inorganic As

Human Urine species. As concentrations in urine consist to 10–
below 10 30% of inorganic As species, 10–20% of
(µg L-1)

of
monomethylarsonic acid (MMA), and 60–80% of
Couto et al in Matschullatet dimethylarsinic acid

ro
al, 2011
5.8–170 Exposed population

Human daily intake

-p
μg person day−1
63
re
Matschullat in Matschullat
et al, 2011
lP
na
ur
Jo
 Journal Pre-proof

Table 3 – Arsenic affected municipalities within the Northern, Southeastern and Southern
Brazilian regions. Demographic, health and environmental data. Data source: general
national demographic census, 2010 (Population estimation, 2017), official report, Brazilian
Institute of Geograpghy and Statistics - IBGE. https//cidades.ibge.gov.br

Demography Health Environment Economy

Infant

of
Municipality mortality
Sanitary
Population Density Urbanization
Area (km²) (deaths Sewage HDI

ro
(2017) (inhab/km²) (%)
per 1,000) access (%)
-p live births

Northern Region – Amapá (AP)

re
Santana 1,541.224 101,262 64.21 13.08 15.30 6.3 0.692

Total 1 * 1,541.224 101,262 64.21 13.08 15.30 6.3 0.692

lP

South-eastern Region – São Paulo State (SP)

Ribeira Valley
na

Apiaí 974.322 25,191 25.85 5.18 54.40 32 0.710

ur

Barra do
405.681 5,244 12.93 28.57 25.40 49.3 0.660
Chapéu
Jo

Barra do Turvo 107.670 7,729 7.67 32.26 44.90 36.4 0.641

Cajati 454.436 28,870 62.43 13.86 69.10 25.7 0.694

Cananeia 1,237.357 12,226 9.86 16.39 76.00 4.9 0.720

Eldorado 1,654.256 14,621 8.85 23.70 61.40 59.2 0.691

Iguape 1,978.795 30,644 14.58 31.95 76.20 24.4 0.726

Ilha Comprida 196.567 10,656 47.01 14.81 94.40 3.5 0.725

Iporanga 1,152.059 4,299 3.73 13.70 69.60 16 0.703

Itaoca 183.015 3,341 17.64 46.51 35.10 17.5 0.680

Itapirapuã
406.478 4,186 9.55 - 51.60 2.7 0.661
Paulista
 Journal Pre-proof

Itariri 273.667 17,062 56.53 20.13 56.00 9.8 0.677

Jacupiranga 704.189 17,900 24.44 11.72 80.40 30.6 0.717

Juquiá 812.799 19,192 23.68 - 62.45 11.8 0.700

Juquitiba 522.169 31,027 55.03 22.22 46.80 31.1 0.709

Miracatu 1,001.484 20,288 20.56 9.55 58.90 12.7 0.697

Pariquera-Açu 359.414 19,537 51.34 34.38 72.70 10.1 0.736

Pedro de
670.440 11,136 15.22 25.00 81.10 0 0.696
Toledo

Registro 722.201 56,430 75.11 16.90 87.20 33.5 0.754

of
Ribeira 335.748 3,390 10.00 63.83 34.90 30.6 0.698

ro
São Lourenço
186.456 15,465 74.99 13.95 75.70 41 0.728
da Serra -p
Sete Barras 1,062.699 13,053 12.24 5.21 75.50 13 0.673

Tapiraí 755.100 7,973 10.61 - 75.30 10.5 0.681

re
Total 2 * 16,157.002 379,460 28.25 22.97 0.699
lP

Southern Region -Paraná State (PR) - Ribeira Valley

na

Adrianópolis 1,349.335 6,254 4.73 43.48 36.30 36.1 0.667

Bocaiúva do
826.344 12,477 13.30 10.64 58.90 10.4 0.640
ur

Sul

Cerro Azul 1,341.190 17,885 12.63 53.72 49.70 19.9 0.573

Jo

Doutor Ulysses 781.450 5,781 7.33 15.38 56.80 2.2 0.546

Itaperuçu 320.578 27,500 75.96 11.19 18.90 13 0.637

Rio Branco do
812.288 32,504 37.73 11.44 54.00 20.6 0.679
Sul

Tunas do
668.478 7,971 9.36 13.33 4.60 8.4 0.611
Paraná

Total 3 * 6,099.663 110,372 23.01 22.74 0.622

South-eastern Region - Minas Gerais State (MG) - Iron Qadrangle –IQ

Alvinópolis 599.443 15,599 25.46 13.79 74.40 30.5 0.676

Belo Horizonte 331.401 2,523,794 7,167.00 9.99 96.20 44.2 0.810

 Journal Pre-proof

Caeté 542.531 44 75.11 5.77 83.30 16.3 0.728

Congonhas 304.067 53,843 159.57 12.20 78.50 43.9 0.753

Igarapé 110.942 41,127 316.07 8.52 64.80 5.9 0.698

Itabira 1,253.704 119,285 87.57 12.25 92.00 62.4 0.756

Itabirito 542.609 50,816 83.76 10.61 87.30 39.5 0.730

Itatiaiuçu 295.145 10,979 33.64 13.25 74.70 4 0.677

Itaúna 495.769 92,696 172.38 8.12 96.20 40.3 0.758

Jeceaba 236.250 5,209 22.84 - 47.70 36.1 0.661

of
João
99.158 79,590 742.35 16.86 92.80 52.9 0.758
Monlevade

ro
Mariana 1,194.208 59,857 45.40 12.67 78.00 34.5 0.742

Mateus Leme 301.383 30,678 92.02 16.81 60.90 7.9 0.704

-p
Moeda 155.112 4,957 30.23 - 32.50 48 0.638
re
Nova Lima 429.004 92,178 188.73 6.49 94.00 46.8 0.813
lP

Ouro Preto 1,245.865 74,659 56.41 9.54 75.60 30.6 0.741

Raposos 72.228 16,390 212.88 8.81 85.60 59 0.730

na

Rio Acima 229.812 10,123 69.55 15.50 83.60 25.6 0.673

Rio Manso 231.540 5,276 22.79 23.26 3.20 2.7 0.648

ur

Rio Piracicaba 373.037 11,149 37.93 - 73.70 47.8 0.685

Sabará 302.419 135,968 417.84 10.25 88.20 21.3 0.731

Jo

Santa Luzia 235.076 218,897 862.38 11.15 84.00 22.2 0.715

São Gonçalo
363.828 9,777 26.87 14.39 67.20 45.2 0.667
do Rio Abaixo

São Joaquim
71.758 25,537 356.88 16.87 69.40 6.5 0.662
de Bicas

São João del

1,452.002 84,469 57.68 17.88 85.80 20.8 0.758
Rei

Sarzedo 62.134 25,814 415.46 4.05 85.50 18.2 0.734

Total 4 * 11,530.425 3,798,711 453.03 12.13 0.717

South-eastern Region - Minas Gerais State (MG) - Other impacted areas

 Journal Pre-proof

Paracatu 8,229.595 84,718 10.29 9.77 79.30 28.3 0.744

Barra Longa 383.628 6,143 16.01 - 60.90 43.8 0.624

Total 5 9,613.223 90,861

TOTAL* 77,941.537 4,480,666

* Total: area and population = sum; other data=average.

of
ro
-p
re
lP
na
ur
Jo
 Journal Pre-proof

of
ro
-p
re
lP
na

Graphical abstract
ur
Jo
 Journal Pre-proof

Arsenic contamination assessment in Brazil – Past, present and future concerns – A

historical and critical review

a,
Mônica Cristina Teixeira *, Alcylane Caldeira Santosb, Carla Silva Fernandesb, Jack
Chakmeng Ngc

a
Pharmacy Department, Pharmacy School, Federal University of Ouro Preto, UFOP. Campus
Morro do Cruzeiro. Ouro Preto, MG, 35400-000, Brazil.

of
b
Environmental Engineering Graduating Program-ProAmb. Federal University of Ouro Preto,

ro
UFOP. Campus Morro do Cruzeiro. Ouro Preto, MG, 35400-000, Brazil.
-p
c Queensland Alliance for Environmental Health Sciences (QAEHS), the University of
Queensland. 20 Cornwall Street, Woolloongabba, Brisbane, QLD 4102, Australia.
re
lP

Highlights
na

• A scenario of arsenic contamination in Brazil was depicted

• Arsenic contamination from mining activities in Brazil is an ongoing concern
ur

• Collapse of Fundão Dam led to extensive As contamination in the Rio Doce

Jo

Basin
• Mobility of As in and out of different environmental compartments is
complex
• Arsenic equilibrium is influenced by anthropogenic factors