Water 14 03057 v3

water
Review
Environmental Impact Assessment of Mine Tailings Spill
Considering Metallurgical Processes of Gold and Copper
Mining: Case Studies in the Andean Countries of Chile
and Peru
Carlos Cacciuttolo 1, * and Deyvis Cano 2
1 Civil Works and Geology Department, Catholic University of Temuco, Temuco 4780000, Chile
2 Programa Académico de Ingeniería Ambiental, Universidad de Huánuco, Huánuco 10001, Peru
* Correspondence: ccacciuttolo@uct.cl or carlos.cacciuttolo@gmail.com
Abstract: The generation of tailings in the world today is immense, since only ounces or pounds of
metals are extracted for each ton of ore processed. In 2022, it was estimated that more than 14 billion
metric tons of mining tailings were produced per year in the world. Currently, many environmental
problems associated with tailings management in both Chile and Peru are related to the potential
contamination of soil, water, and air. In this article, the environmental impacts caused by tailings
storage facility accidents where spills have occurred are analyzed, describing and characterizing:
(i) the magnitude of the impacted area, (ii) identification of the sources, i.e., exposure routes, receptors,
and (iii) an interpretive analysis of the physicochemical quality of the spilled material, the soil, the
water, and the air with respect to local and international regulations. The case studies analyzed in
this article correspond to tailings spills derived from the extraction of precious metals (Au, Ag) and
heavy metals (Cu, Pb, and Zn) present in the minerals that dominate Chilean and Peruvian mining.
Citation: Cacciuttolo, C.; Cano, D. Finally, environmental management measures are proposed aimed at mitigating the environmental
Environmental Impact Assessment of impacts caused by the spill and remediation alternatives for the sites impacted.
Mine Tailings Spill Considering
Metallurgical Processes of Gold and Keywords: copper mine tailings; gold mine tailings; tailings storage facility; spillage; heavy metals;
Copper Mining: Case Studies in the flotation reagents; environmental impacts
Andean Countries of Chile and Peru.
Water 2022, 14, 3057. https://
doi.org/10.3390/w14193057
Academic Editors: Margarida 1. Introduction

Antunes and Alicja Kicińska The main technology to obtain concentrates of valuable metals such as copper and
Received: 18 August 2022
thus generate mining tailings (residues) from the processing of sulphide minerals on an
Accepted: 22 September 2022
industrial scale (more than 100,000 metric tons per day) is froth flotation. Tailings are a
Published: 28 September 2022
residue of the froth flotation mining–metallurgical process, usually a very fine mud or
powder, left over after the ore is processed and the valuable minerals are extracted. There
Publisher’s Note: MDPI stays neutral
are different and varied processes for the extraction of minerals used in the current mining
with regard to jurisdictional claims in
industry, where physical and chemical processes for mineral benefit are usually the most
published maps and institutional affil-
used, mainly because they are cheaper to operate [1].
iations.
On the other hand, for gold and silver-rich sulfide ores, the commonly used benefit
process has some differences. The crushing and grinding stages are carried out in a similar
way, except the conventional gold concentration process is carried out by cyanidation
Copyright: © 2022 by the authors.
leaching in tanks, where the cyanide solution that contains the dissolved metals is separated
Licensee MDPI, Basel, Switzerland. from the tailings through thickeners by means of counter-current decantation (CCD).
This article is an open access article Similar processes are carbon-in-pulp (CIP) and carbon-in-leach (CIL), which add carbon to
distributed under the terms and milled ore to recover gold and silver from the cyanide solution. The CIP and CIL tailings
conditions of the Creative Commons are the same, but the cyanide concentrations in the effluent that accompanies these tailings
Attribution (CC BY) license (https:// are higher than the tailings obtained with CCD [2].
creativecommons.org/licenses/by/ The generation of tailings in the world today is immense, since only ounces or pounds
4.0/). of metals are extracted for each ton of ore processed. In 2022, it was estimated that more
Water 2022, 14, 3057. https://doi.org/10.3390/w14193057 https://www.mdpi.com/journal/water

Water 2022, 14, 3057 2 of 30
than 14 billion metric tons of mining tailings were produced per year in the world from
the extraction of metals and minerals [3]. The foamy flotation for the benefit of copper and
gold minerals uses various chemical reagents, e.g., sodium ethyl xanthate, sodium cyanide,
copper sulfate, pine oil tar, fatty acid soaps, dithiophosphates, collectors, foaming agents,
and lime, among others [4], which are classified from an aqueous suspension with the help
of aeration and controlled mixing. In froth flotation, the use of reagents that can act at the
solid/liquid and liquid/gas interface is essential to successfully separate the mineralogical
species of interest from the pulp [5].
However, the collector and foaming reagents currently used in mining processes have
different characteristics of toxicity and persistence. For example, sodium ethyl xanthate
presents a high level of danger in humans and a medium level of toxicity for other living
beings [6]. Other reagents, such as dithiophosphate-1404, methylisobutylcarbinol (MIBC)
and Dawfroth 250 (foaming agent), are considered toxic chemicals, showing various po-
tential risks to human health and the environment [7]. Therefore, tailings may contain
anthropogenic chemicals used in the metallurgical process (Xanthates, organic compounds,
corrosive chemical reagents, etc.) as well as the presence of high concentrations of naturally
occurring heavy metals (Cd, Cr, Mn, As, Pb, Zn, Mo, among others), which must be taken
into account to carry out safe tailings management. Therefore, from a geochemical and
toxicological point of view, most tailings cannot be classified as inert or harmless materials,
respectively, and must be disposed of with due care in the environment [8–11].
Currently, many environmental problems associated with tailings management in both
Chile and Peru are related to the potential contamination of soil, water (surface/underground
water), and air. In recent years, there have been significant advances in tailings dewatering
technologies [12–14], infiltration control from tailings storage facilities, and operational
management of mine tailings. However, tailings spill accidents still occur in the world, e.g.,
Mount Polley case in Canada (2014), Fundao Samarco case in Brazil (2015), Corrego do
Feijao Brumadinho case in Brazil (2019) and Jagersfontain case in South Africa (2022) [15,16].
Failures of tailings occur mainly due to: (i) causes of human origin (e.g.: failure of dams, in-
adequate management of tailings/water, etc.) [17], and (ii) natural causes (e.g., floods, earth-
quakes, alluviums, etc.) [18], which indicates that for these hazardous wastes there is still no
degree of safety that allows to provide confidence to vulnerable communities and ecosys-
tems. This has meant that tailings transport and storage activities today represent a matter
that requires adequate environmental management and responsible management [19,20].
In this article, the environmental impacts caused by tailings storage facility accidents
where spills have occurred are analyzed, describing and characterizing: (i) the magnitude
of the impacted area, (ii) identification of the sources, i.e., exposure routes, receptors,
and (iii) a simplified interpretive analysis of the physicochemical quality of the spilled
material, the soil, the water, and the air with respect to local and international regulations.
The case studies analyzed in this article correspond to tailings spills derived from the
extraction of precious metals (Au, Ag) and heavy metals (Cu, Pb, and Zn) present in the
minerals that dominate Chilean and Peruvian mining. Finally, environmental management
measures are proposed aimed at mitigating the environmental impacts caused by the spill
and remediation alternatives for the sites impacted by this type of event.
The methods used to store tailings have developed due to environmental pressures,
changing grinding–flotation practices, and the realization of cost-effective applications.
The first methods included: (i) discharge of tailings into rivers, streams, and the sea, as
in the case of Bahía de Chañaral in Chile [21] and Bahía de Ite in Peru [22], and (ii) the
construction of dams with cycloned tailings sand in an upstream direction. Due to the
damage caused by such methods and the much finer grinding required in most modern
ores, other techniques have been developed. These new techniques consider the best
available technologies (BATs), e.g., (i) conventional tailings, (ii) thickened tailings, (iii) paste
tailings, and (iv) filtered tailings [12–14].
It is economically advantageous to locate the tailings storage facility close to the mine,
but this imposes limits on site selection. The type of tailings storage facility is generally
Water 2022, 14, 3057 3 of 30
determined by local seismic activity, process water clarification requirements, tailings

properties and physical/geochemical stability; tailings size distribution, topographic and
foundation aspects of the dam, hydrological conditions, and environmental factors [23].
Tailings storage increases production costs, so it is essential that disposal be as eco-
nomical as possible. This requirement initially led to the development of the upstream
construction method of tailings dams once commonly used, but some accidents at Bara-
hona tailings dam in Rancagua Chile (1928), the El Cobre tailings dam in Nogales Chile
(1965), and the Amatista tailings dam in Nazca Peru (1996) [15,18] resulted in a ban on
upstream dam construction technique in both countries. Actually, considering conventional
tailings technology, the most popular methods applied in copper tailings storage facility
are downstream and centerline dam construction methods [24].
2. Metallurgical Processes Generating Tailings from Gold and Copper Sulfide Ores
2.1. Process of Extracting Gold from Sulphide Minerals and Generation of Mining Tailings
Conventional cyanide tank leaching methods are used on gold ores with adequate
grade (gold content per ton) and tonnage (amount of ore available for leaching) to justify
design complexity and higher capital cost. This compared to cyanide heap leach methods.
A sulfide ore gold mining project can be divided into four main areas: ore extraction and
size reduction, tank leaching, gold recovery, and tailings disposal. Once the ore is extracted
from the ground, it is crushed in 1–3 stages of crushing to prepare the ore for grinding.
Milling is usually performed wet using recycled water from the tailings storage facility,
and additional cyanide is usually added to the milling process water to start leaching as
soon as possible [25].
The ore and the grinding process water generate the pulp, which is processed through
a flotation process in a series of cells. During the first stage of flotation (rougher), cyanide-
free tailings are generated and deposited in a rougher flotation tailings storage facility
(Figure 1), while the concentrates are taken to a second stage of flotation (cleaner).
Water 2022, 14, x FOR PEER REVIEW 4 of 32 In
cleaner flotation cells, sodium cyanide is usually added along with air and/or oxygen,
which are necessary catalysts for the dissolution of gold and silver [26].
Figure 1. Typical
Figure Gold
1. Typical GoldOre
OreSulphide Process.
Sulphide Process.
Dissolved
The design gold
andcan be recovered
operation fromstorage
of the tailings the gold-containing
facility are very cyanide
important, solution (loaded
since they
solution),
serve twoeither by adsorption
purposes: on activatedtank
(i) as a sedimentation carbon or process
for the by precipitation
water thatwith zinc
is then dust. When
recycled
to the grinding
activated carbon and leaching
is used, circuits;
it can and (ii)
be added as theleaching
during final tailings impoundment
(carbon in leach) for cyanide
or after leaching
leach and flotation tailings. The size of the tailings storage facility is based
(carbon in pulp). These techniques, commonly known as tank or vat methods, are generally on the expected
total
used tovolume
benefitofores
tailings produced
containing over than
more the life of the
0.04 mine,[27].
oz/ton the settling
Once thetimedissolved
required togold is
separate the water from the tailings, proper management of mill process water (contact
water) that will remain available, and the possible volume of storm water (non-contact
water).
Tailings generated from gold cyanide milling operations contain small amounts of
used cyanide solution; residual cyanide; and solubilized metal-cyanide complexes, which
Water 2022, 14, 3057 4 of 30
removed from solution, the tailings and the resulting “sterile solution” are pumped into
the cyanide leach tailings storage facility (Figure 1). Then, at the gold recovery processing
plant, the gold is chemically extracted from the carbon, electrowinning from solution, and
smelted into impure bars called doré [25,28].
The design and operation of the tailings storage facility are very important, since
they serve two purposes: (i) as a sedimentation tank for the process water that is then
recycled to the grinding and leaching circuits; and (ii) as the final tailings impoundment
for cyanide leach and flotation tailings. The size of the tailings storage facility is based
on the expected total volume of tailings produced over the life of the mine, the settling
time required to separate the water from the tailings, proper management of mill process
water (contact water) that will remain available, and the possible volume of storm water
(non-contact water).
Tailings generated from gold cyanide milling operations contain small amounts of
used cyanide solution; residual cyanide; and solubilized metal-cyanide complexes, which
could be toxic to humans, flora, and wildlife [29]. For this reason, the detoxification of
cyanide-containing tailings is incorporated into the process in some projects, prior to the
deposition of tailings in the tailings storage facility. In addition, cyanide leach tailings
storage facilities are typically lined, where a geotextile geomembrane liner is placed on
the upstream face of the dam and the contour of the reservoir base to prevent subsurface
seepage through the reservoir [26]. Another alternative to the detoxification process is to
apply the filtered tailings technology in some mining projects in Chile and Peru [12].
2.2. Process of Extracting Copper from Sulphide Minerals and Generation of Mining Tailings
Currently, copper sulfide minerals are being exploited both in Chile and Peru, since
sulfide minerals predominate over oxides minerals. Chalcopyrite (CuFeS2 ) is the main
sulfide ore of copper, also containing variable amounts of unwanted and invaluable pyrite
(FeS2 ). On an industrial scale, copper sulfide minerals are concentrated using froth flotation
processes (Figure 2) [30]. Froth flotation uses chemical reagents (collectors, foamers,
Water 2022, 14, x FOR PEER REVIEW 5 of 32
and
modifiers) to control the wettability of solid surfaces, solution electrochemistry, solid
particle dispersion and aggregation, and foam generation [4]. In this way, it is possible to
recover mineral species of interest and avoid the flotation of unwanted gangue minerals [30].
Figure 2. Typical
Figure Copper
2. Typical Ore
Copper OreSulphide
Sulphide Process.
Process.
Because thethe
Because average
averagegrades
grades of
of copper sulphideminerals
copper sulphide minerals in both
in both Chile
Chile and Peru
and Peru have have
decreased from
decreased from1.25%
1.25%toto0.90%
0.90% during thelast
during the lastdecade,
decade, a higher
a higher consumption
consumption of water,
of water,
energy, andand
energy, chemical reagents
chemical is required
reagents toto
is required efficiently
efficientlyprocess
processlow-grade
low-grade copper sulphide
copper sul-
phide minerals
minerals [18]. In [18]. In particular,
particular, the consumption
the consumption of of collectors, frothers,
collectors, frothers, and
andmodifiers
modifiers in
in froth flotation is increasing as larger amounts of low-grade copper ore are processed.
For example, the average concentration of collectors and frothers used in 2012 in both
Chile and Peru was 50 g/ton of ore and 30 g/ton of ore, respectively. These concentrations
correspond to 26,243 tons of collectors and 15,745 tons of foaming agents per year [30].
Conventional flotation cells consist of a tank with an agitator designed to disperse air into
Water 2022, 14, 3057 5 of 30
froth flotation is increasing as larger amounts of low-grade copper ore are processed. For
example, the average concentration of collectors and frothers used in 2012 in both Chile and
Peru was 50 g/ton of ore and 30 g/ton of ore, respectively. These concentrations correspond
to 26,243 tons of collectors and 15,745 tons of foaming agents per year [30]. Conventional
flotation cells consist of a tank with an agitator designed to disperse air into the suspension,
as shown schematically in Figure 2, typically assembled in a multi-stage circuit with cells:
“rougher”, “cleaner” and “scavenger”. Finally, the copper concentrate obtained is taken to
a recovery plant, and the tailings obtained are normally dewatered using thickeners and
stored in the tailings storage facility.
Copper tailings storage facilities are generally partially lined [25]. To prevent seepage
through the foundation and core of the dam, the following are installed: (i) a stop-leak
trench and a grout curtain control system along the foot upstream of the dam (ii) and a
HDPE geomembrane with geotextile. The liner is placed on the upstream face of the dam.
This means that the dam has a continuous impermeable barrier that runs the length and
width of its upstream face, which waterproofs this part of the reservoir [18].
3. Socio-Environmental Context of Mining Tailings

One of the most complex socio-environmental problems facing Chile and Peru today is
the sustainable management of mining tailings, since these represent a high risk of physical
and geochemical instability in the long term [11]. The challenge focuses on the proper
management of mining tailings, both active (currently in operation) and passive (mining
environmental liabilities), an issue that has not been addressed through a vision under a
socio-environmental concept [31], producing a significant exposure of the urban and rural
population to a situation of vulnerability, both for their safety and physical health [32].
Currently, in both Chile and Peru, there are no regulations that regulate the spillage
of tailings and remediate contamination in the area of influence and receiving bodies,
considering: (i) soils, (ii) liquid waste discharged to ground water or surfaces receiving
bodies, (iii) air quality (PM2.5 emission), and (iv) that explicitly establishes that mining
tailings must be managed from their generation as a hazardous waste.
There is a regulatory framework for Environmental Impact Studies (EIA) that focuses
on any mining waste deposited in a natural environment, where impacts are evaluated
and there are management and monitoring plans. These plans are considered to assess
the influence or possible negative impact on watercourses, air, and soil, assuming the
physical and geochemical stability of the mining tailings storage facility. A spill is a special
case that is considered in contingency plans and the measures after a spill are not well
outlined. In Chile, tailings are not considered as hazardous waste, while in Peru this is
not explicitly stated not. In this context, today, there is no practice under a rationality
of precautionary/preventive principle by the industry or government, thus making it
necessary to wait until there is environmental damage (spill or collapse of tailings storage
facility) in order to make decisions with a socio-environmental approach and carry out
specific remediation actions.
Considering these antecedents, it is key to analyze the management of mining tailings
from a comprehensive perspective with a scientific basis (holistic approach), which thus
allows the implementation of policies, programs, and environmental management plans
for mining tailings, promoting eco-systemic research on the phenomenon of contamination
and its effects. In this way, it will be possible to avoid violating the right to live in a clean
and pollution-free environment of millions of people and ecosystems (flora, fauna, soil,
water and air), who live in basins of the territory together with billions of tons of mine
tailings. Along with this, it is necessary to educate the population about the environmental
risks that living in areas surrounding tailings storage facilities present, preventing people
from being in permanent contact with them [33,34].
Water 2022, 14, 3057 6 of 30
4. Conceptual Model for Sites Contaminated by Mining Tailings Spills

To analyze the phenomenon of environmental contamination due to a tailings spill
event, it is necessary to define an adequate conceptual model of the contaminated site and
its surroundings. In this model, the situation must be outlined in terms of the factors that
affect the chain of environmental risks: (i) source of contamination, (ii) identification of con-
taminants of interest, their spatial-temporal distribution in the environmental components
(air, soil and water) and chemical properties (speciation), (iii) mobilization mechanisms,
(iv) exposure pathways, and (v) existing potential receptors [35]. Based on all the data
collected on the site, the contaminants that have a greater probability of being present in
the potentially contaminated environmental components must be evaluated, selecting for
analysis those that pose greater risks to the health of the population and/or the ecosystem.
Figure 3 presents a conceptual site model for the case of a mining tailings spill.
Figure 3. Conceptual Model ofModel

Figure 3. Conceptual Contamination from
of Contamination Mining
from MiningTailings Spill
Tailings Spill (Modified
(Modified from [36]).
from [36]).
Water 2022, 14, 3057 7 of 30
From a conceptual model perspective, the catastrophic erosion or collapse of a tailings

storage facility built in a watershed result in a rapid and violent movement of a mass of
mine tailings (slurry), flowing in a downstream direction to through riverbeds, increasing
its affected area, the spatial and temporal distribution of contamination. Some factors of
interest to consider are: slope of the land, flow of rivers, climate, types of pollutants and
their physical-chemical characteristics, edaphological characteristics of the soil, and the
presence of underground water, among others. A tailings spill produces effects in the space
(physical environment of soil, water and air), both immediate and in the long term (time),
for flora, fauna, and the neighboring human population.
Considering the conceptual model described and the tailings spill cases that will be
presented, it is necessary to define some hypotheses and limitations. A mine tailings spill
in a river implies the contamination of an aquatic system, which requires: (i) a sediment
analysis and (ii) water quality analysis to study the dissolved and suspended contami-
nants in the watercourses, in order to have indicators of environmental impact. This is
due to the fact that the sediments (tailings) continuously interact with the liquid phase
(sediment–water column interaction). Sediments act as carriers and possible sources of con-
tamination, behaving as a reservoir of contaminants. Under certain physical and chemical
conditions, these can have adverse effects on the biota, transferring toxic compounds to the
food chain by bioaccumulation, such as heavy metals [37].
Based on experience, the source of contamination, which in this case is tailings, is
considered to contain high concentrations of heavy metals, which have components of
natural origin (earth’s crust), as well as an anthropogenic component, since tailings are
residues generated from an industrial process, where metallurgical reagents are added,
which correspond to concentrations of artificial organic chemical compounds (Xanthates,
alcohols, cyanide, among others.) [9].
When there is a tailings spill in the environment, there is a risk of generating contami-
nation, mainly due to the high concentration of heavy metals and chemical reagents that
mine tailings have. From the chemical point of view, we can identify five categories: (i)
cations and metal cations, (ii) anions, (iii) amphoteric species, (iv) cyanide complexes, and
(v) flotation chemical reagents. Table 1 shows the potentially mobile chemical species in
mine tailings slurries that may be present in a spill situation:
Table 1. Potentially Mobile Chemical Species in Tailings Slurries [21].
Mine Tailings
Chemical Groups
Flotation Concentrate Undifferentiated
Calcium, ammonia, transition
Calcium, transition metals, Calcium, transition metals,
Cations and Metal Cations metals (1), lead, mercury, and
lead, mercury and barium lead, mercury, and barium
barium
Anions Nitrate, sulfate Nitrate, chloride, sulfate Nitrate, chloride, sulfate
Arsenic, antimony, chromium, Arsenic, antimony, chromium, Arsenic, antimony, chromium,
Amphoteric species cadmium, molybdenum, cadmium, molybdenum, cadmium, molybdenum,
selenium selenium selenium
Cyanide Complexes (Where Free cyanide (CN and HCN)
cyanide is used as a process (2) Weak metal cyanide complexes (e.g. zinc, copper, nickel,
reagent) cyanides)
Sodium ethyl xanthate,
sodium cyanide, copper Pine oil tar, fatty acid soaps, dithiophosphates, collectors,
Flotation Chemical Reagents
sulfate, flocculants, among foaming agents, lime, flocculants, among others
others
Note(s): (1) Transition metals include Chromium, cobalt, copper, nickel, zinc, iron, manganese. (2) Trace amounts
of cyanide may be present for a short period of time if sodium cyanide is used as a modifier on the flotation circuit.
Water 2022, 14, 3057 8 of 30
According to the table above, it is possible to find heavy metals in a tailings spill, such
as: (i) Arsenic, (ii) Chromium, (iii) Molybdenum, (iv) Mercury, (v) Copper, (vi) Cobalt, (vii)
Cadmium, (viii) Selenium, (ix) Iron, and (x) Manganese, among others. In addition, it is
possible to find cyanide complexes, where cyanide is mainly used in the flotation stage as a
chemical reagent, being able to find free cyanide (CN and HCN) and cyanide complexes
due to zinc, copper, and nickel.
5. Mine Tailings Spill Case Studies

5.1. Polymetallic Tailings in the Escalera River, Huancavelica Department–Peru
5.1.1. Description of the Characteristics of the Site and Its Physical Environment
The region or department of Huancavelica is located in the mountains of Peru, a high
Andean area with altitudes around 4000–5000 m above sea level, characterized by abrupt
topography and steep slopes. The climate is characterized by being cold and presenting a
dry season (without rain) between the months of May and October, and a wet season (with
rain) between the months of November and April. The region is characterized by livestock
grazing, where the cows are found in lowlands and inter-Andean valleys, where alfalfa is
used in addition to natural grass. These pastures feed alpacas, sheep, and goats, generating
grazing activity [38].
Another relevant activity in the region is mining, which is characterized by being poly-
metallic, producing mainly Cu, Zn, and Pb, through flotation processes and the generation
of sulphide tailings. Huancavelica currently has more than 1,000,000 (Ha) of land under
mining concession, which represents 52% of the regional territory. Due to the increase in
mining production, mining tailings are an environmental problem throughout the geo-
graphical area, which puts agricultural–livestock activities and the lives of residents at risk.
Minera Caudalosa S.A. (MCSA) is a medium-sized mining company that has been
active in Huancavelica for more than 50 years. Established in 1942, its main exploitation
unit is Huachocolpa Uno, located at 4550 m above sea level, in the province and region
of Huancavelica. MCSA is controlled by LP Holding, the parent company of the Raffo
Group. This mining unit has three tailings disposal sites, tailings dams A–C, respectively.
Currently, the mining unit has experienced high growth in its production, which is why
stored tailings have increased [39].
The Caudalosa mine is located at the head of the basin of the Escalera, Huachocolpa,
Lircay, and Opamayo rivers, in Huancavelica. The flow of these rivers varies between
0.9–3.0 (m3 /s) in the dry and wet seasons, respectively. The average width of the riverbed
is equivalent to 20 m and its slopes are in the range of 0.2–5.0% [40]. Despite agriculture,
livestock, and mining, the factors of: (i) abrupt geography, (ii) transportation difficulties,
and (iii) precariousness of towns next to tailings deposits, have generated poverty in the
region, hindering development and well-being of people [39].
5.1.2. Causes of the Tailings Spill Event

On Friday, 25 June 2010, the tailings storage facility A dam failed and broke (Figure 4).
This event happened at 8 p.m, and generated a tailings spill composed of Pb, Zn, Cu, and
As metals, among others, along with chemical reagents used in the process (Xanthates and
organic compounds) (Figure 4). Once the spill from the tailings storage facility A dam
became uncontrollable and poured into the tailings storage facility C dam that stored acid
mine water, the tailings together with the acid mine water flowed out uncontrollably to the
Escalera River [41–43].
Water 2022,
Water 14, 14,
2022, 3057x FOR PEER REVIEW 10 of 932of 30
Figure 4. Breaking of the Tailings Dam A—Caudalosa Mine [42,43].

5.1.3. Identification
Finally, of the
the expert Area ofcarried
opinion Influence outbyonPollution
the dam of tailings storage facility A by
The tailings
specialists from thespill generated an environmental
Environmental Assessment and impact on the waters
Enforcement Agency of the Escalera
(OEFA) of the
River, a of
Ministry tributary of the Huachocolpa
the Environment concluded River, toThe
that: (i) continue
dam waslaterbuilt
towards
with the plain
coarse of theand
tailings
Huachocolpa
was peasant
not reinforced. (ii)community,
The dam did advancing
not haveuncontrollably along thewastewater.
a system to evacuate riverbed, leaving
(iii) The
a layer ofthat
overload sediment
the damdownstream
had was due for to
theexcess
Lircaywater
and Opamayo
that was rivers,
stored finally reaching
there, and the
(iv) MCSA
Mantaro
did river after 120 km (Figure 5) [42–44]. Sampling in the spill area
not have an environmental management plan for tailings, lacking a contingency plan was carried out 5
days after the event.
for tailings spills [41–43].It must be considered in the case of Peru that the environmental au-
thorities are located in the city of Lima and reaching mining sites in regions takes a long
5.1.3. Identification of the Area of Influence by Pollution
time Identification
5.1.3. due to the complexof thetopography of the country
Area of Influence and long distances to travel by car on
by Pollution
The tailings spill generated an environmental impact on the waters of the Escalera
highways.
Thea tailings
River, tributaryspill
of thegenerated
Huachocolpaan environmental impact
River, to continue ontowards
later the waters the of the of
plain Escalera
the
River, a tributary of the Huachocolpa River, to continue later
Huachocolpa peasant community, advancing uncontrollably along the riverbed, leavingtowards the plain of the
Huachocolpa peasant community, advancing uncontrollably along
a layer of sediment downstream for the Lircay and Opamayo rivers, finally reaching the the riverbed, leaving
aMantaro
layer of river
sediment downstream
after 120 km (Figurefor 5) the Lircay
[42–44]. and Opamayo
Sampling rivers,
in the spill area finally reaching
was carried out 5 the
Mantaro
days after the event. It must be considered in the case of Peru that the environmental au-out
river after 120 km (Figure 5) [42–44]. Sampling in the spill area was carried
5thorities
days afterarethe event.
located It must
in the beLima
city of considered in themining
and reaching case ofsites
Peruinthat the environmental
regions takes a long
authorities are located in the city of Lima and reaching mining sites
time due to the complex topography of the country and long distances to travel by in regions takes
car aonlong
time due
highways. to the complex topography of the country and long distances to travel by car
on highways.
Figure 5. Area affected by tailings spill—Huancavelica Department (Modified from [45]).
As observed by residents, the waters of the rivers had a leaden and reddish color,
estimating that 10% of the tailings from tailings storage facility A were mobilized, releas-
ing a discharge of 57,000 m3 of mining tailings [45].
Figure5.5.Area
Figure Areaaffected
affected by tailings spill—HuancavelicaDepartment
tailings spill—Huancavelica Department (Modified
(Modified from
from [45]).
[45]).
As observed by residents, the waters of the rivers had a leaden and reddish color,
estimating that 10% of the tailings from tailings storage facility A were mobilized, releas-
ing a discharge of 57,000 m3 of mining tailings [45].
Water 2022, 14, 3057 10 of 30
FeS + the
As observed by residents, O waters
+ H O →ofFe the + 2SO had
rivers + 2H (1)
a leaden and reddish color,
estimating that 10% of the tailings from tailings storage facility A were mobilized, releasing
Fe + O + H → Fe + H O (2)
a discharge of 57,000 m3 of mining tailings [45].
The spilled tailings
FeStraveled
+ Fe through
+ 8H O → the15Fe
riverbed, reaching
+ 2SO + 16Hup to 10 m in height
(3)
in some sections of the bed, lowering the flow very quickly and violently. The most
Fe +
serious thing is that these rivers are3Htributaries
O → Fe OHof the s +Urubamba
3H (4)
and Mantaro rivers,
which flow into the Amazon River through the department of Ucayali [46]. Water and
Pyrite oxidation by ferric ion in tailings is accelerated by microbial activity (Acidithi-
sediment samples were taken from rivers upstream and downstream of the tailings spill
obacillus or Leptospirillum), particularly at low pH. Under abiotic conditions, the rate of
site. Additionally, sampling of the soils that were affected by the spill was carried out.
oxidation of pyrite by ferric ion is controlled by the rate of oxidation of ferrous ion, which
decreases rapidly with decreasing pH. For values below of pH 3, the oxidation of pyrite
5.1.4. Environmental Impacts on the Physical Environment—Water
with the oxidizing agent iron III is 10–100 times faster than with oxygen O2 [8].
The rivers
Finally, affected by
considering thethe tailings spill
conceptual are of
model used bycontaminated
sites the population as water
with tailingssources,
pre-
where
sented above (Figure 3), it is possible to mention the following characteristics to
40% of the towns in that area lack a drinking water system, equivalent more
that than
affect
4120 peopleenvironment
the natural who live on the
calledbanks of those
water: rivers.
(i) source Considering this
of contamination background,
(mine samplings
tailings), (ii) iden-
were carried out on the waters of the river Escalera, considering that the main
tification of contaminants of interest (Zn, Fe, As, Cd, Mn, and Pb), (iii) mobilization mech-use of river
water in the sector is for agricultural use and drinking water. This approach
anisms (surface and underground water courses), (iv) routes of exposure (aquatic envi- has been
compared with standards applicable to these uses, together with the recommendations
ronment), and (v) existing potential receptors (fish, mammals and people who drink wa-
of the WHO [47]. Figure 6 and Table 2 show the sampling location and the measured
ter).
parameters, respectively.
Figure 6. Water Monitoring Points in Tailings Spills—Huancavelica Department (Modified from [45]).
Figure 6. Water Monitoring Points in Tailings Spills—Huancavelica Department (Modified from
[45]). According to the analyzes carried out at the indicated sampling points, the following
can be concluded: (i) all the parameters far exceed the values of the regulations for the
receiving bodies, even
5.1.5. Environmental these results
Impacts would not
on the Physical meet the discharge limits. (ii) In the river
Environment—Soil
Escalera,
The environmental impact has affected soils andFe,
the concentrations of metals, such as Zn, As, Cd, Mn,
agricultural andsince
crops, Pb, heavy metals
the tailings
that
in some sectors have entered irrigation channels through intakes located on the edge very
can cause toxic risk to the biota, are very high. (iii) Regarding the pH, this is of
low and is an indicator
the riverbeds. of reason
It is for this the potential presence
that soil of has
sampling acidbeen
drainage from
carried out the tailings. This
as indicated in
confirms that there is contamination in the receiving body of the Escalera River, with the
potential to affect the aquatic flora and fauna. In this case, no studies have been carried out
on the chemical quality of the underground water in the area affected by the spill.
Water 2022, 14, 3057 11 of 30
Table 2. Water Monitoring in the Escalera River—Compared to Water Standards [48–51].
Total Parameters (mg/L) (*)

Sample Points Water/Water Standards C. E.
Zn Fe As Cd Mn Pb (µS/cm) pH
E-01 (Tailings Spillage Point in Escalera River) 54.86 234 110 0.225 7.87 0.95 3546 2.5
A-02 (Chipchilla River) downstream Spillage Point 40.22 215 101 0.200 7.45 0.90 2658 2.8
A-03 (Huachocolpa River) downstream Spillage Point 36.45 40.03 86 0.175 7.02 0.76 2812 3.0
A-04 (Atoccomarca River) downstream Spillage Point 29.66 4.12 65 0.135 6.26 0.63 3362 2.5
A-05 (Huachocolpa and Atoccomarca river union) 23.89 2.48 49 0.109 5.14 0.45 2717 3.2
ECA Drinking Water Quality Category 1 A1 2008 (Peru) 3.00 0.30 0.01 0.003 0.10 0.01 1500 6.5–8.5
ECA Water Quality Irrigation Category 3 2008 (Peru) 2.00 1.00 0.05 0.005 0.20 0.05 2000 6.0–9.0
NCh 1333 Water Standard for Irrigation (Chile) 0.20 0.30 0.10 0.01 0.02 5.00 1500 5.5–9.0
NCh 409 Drinking Water Standard (Chile) 3.00 5.00 0.01 0.01 0.01 0.05 - 6.5–8.5
WHO Drinking Water Guide (2006) 3.00 - 0.01 0.003 0.50 0.01 - 6.5–9.5
Note(s): (*) Sampling carried out by a certified laboratory Inspectorate Service Perú S.A.C. and OEFA by EPA
method, and by ICP Spectrometry.
The presence of low pH and dissolved ions together with high electrical conductivity
confirms the presence of acid rock drainage (ARD). The most common sulfide mineral
in tailings in Peru is pyrite (FeS2 ), which oxidizes to form meta-stable products, such
as Ferrihydrite and Hematite. The oxidation of the pyrite present in the tailings is car-
ried out by: (i) the oxidation of sulfide in the presence of atmospheric O2 (Equation (1)),
(ii) the oxidation of the ferrous ion (Equation (2)), and (iii) the hydrolysis and precipitation
of ferric complexes and mineral species (Equations (3) and (4)) [10]:
7
FeS2 + O2 + H2 O → Fe2+ + 2SO24− + 2H+ (1)
2
1 1
Fe2+ + O2 + H+ → Fe3+ + H2 O (2)
4 2
1
FeS2 + Fe3+ + 8H2 O → 15Fe2+ + 2SO24− + 16H− (3)
4
Fe3+ + 3H2 O → Fe(OH)3 (s) + 3H+ (4)
Pyrite oxidation by ferric ion in tailings is accelerated by microbial activity
(Acidithiobacillus or Leptospirillum), particularly at low pH. Under abiotic conditions, the
rate of oxidation of pyrite by ferric ion is controlled by the rate of oxidation of ferrous ion,
which decreases rapidly with decreasing pH. For values below of pH 3, the oxidation of
pyrite with the oxidizing agent iron III is 10–100 times faster than with oxygen O2 [8].
Finally, considering the conceptual model of sites contaminated with tailings presented
above (Figure 3), it is possible to mention the following characteristics that affect the natural
environment called water: (i) source of contamination (mine tailings), (ii) identification
of contaminants of interest (Zn, Fe, As, Cd, Mn, and Pb), (iii) mobilization mechanisms
(surface and underground water courses), (iv) routes of exposure (aquatic environment),
and (v) existing potential receptors (fish, mammals and people who drink water).
5.1.5. Environmental Impacts on the Physical Environment—Soil

The environmental impact has affected soils and agricultural crops, since the tailings
in some sectors have entered irrigation channels through intakes located on the edge of the
riverbeds. It is for this reason that soil sampling has been carried out as indicated in Table 3
and Figure 7, where the results are compared with local and international regulations:
Table 3 and Figure 7, where the results are compared with local and international regula-
tions:
Water 2022, 14, 3057 12 of 30
Table 3. Soil Quality and Tailings Monitoring Compared to Soil Standards [45].
Sample Points Soils/Soil Parameters (mg/Kg) (*)

Standards Table 3. Soil
NiQuality andCu Tailings Monitoring
Zn Compared
As to Soil
Pb StandardsFe[45]. Hg Free CN
S1-A (Toropampa Area) 9.34 30.21 215 72 158 25,385 - -
Parameters (mg/Kg) (*)
S2-A (Toropampa
Sample Area) Standards 10.03
Points Soils/Soil 191 704 244 936 30,818 - -
S3-A (Toropampa Area) 15.38Ni 290Cu Zn
1790 As
299 Pb
1131 Fe
46,125 Hg - Free- CN
S1-A (Tailings
M-R1 (Toropampa Area)
Sample) 7.189.34 30.21
546 215
1725 72
497 158
1195 25,385
44,048 -0.33 -
0.30
S2-A (Toropampa Area)
M-R2 (Tailings Sample) 7.38 10.03 406191 704
2357 244
822 936
581 30,818
45,558 -0.21 -
0.07
S3-A (Toropampa Area) 15.38 290 1790 299 1131 46,125 - -
M-R3 (Tailings Sample)
M-R1 (Tailings Sample) 6.18 7.18 464546 5526
1725 467
497 765
1195 29,870
44,048 0.16
0.33 0.38
0.30
ECA
M-R2Agricultural Soils (Peru) 2010
(Tailings Sample) - 7.38 -406 -
2357 50.00
822 70.00
581 45,558- 6.60
0.21 0.90
0.07
M-R3 (Tailings
Canada QualitySample)
Guide 2003 (PEL) 6.18 464 5526 467 765 29,870 0.16 0.38
- 197.00 315.00 17.00 90.00 - 6.60 0.90
(**)
ECA Agricultural Soils (Peru) 2010 - - - 50.00 70.00 - 6.60 0.90
Canada
Dutch Quality Guide
Standard VROM 2003 (PEL) (**)
1983 - - 197.00
500.00 315.00
3000 17.00
- 90.00
600.00 - -6.60
10.00 0.90
-
Dutch Standard VROM 1983 Note(s): (*) Sampling
- 500.00 3000 - 600.00 - 10.00 -
carried out by a certified laboratory Inspectorate Service Peru S.A.C and OEFA
by EPA (*)
Note(s): method, and
Sampling by ICP
carried outSpectrometry. (**) PEL (Probable
by a certified laboratory Effect
Inspectorate Level),
Service Probable
Peru S.A.C and Effect
OEFA byLevel:
EPA
method, and byabove
concentration ICP Spectrometry. (**) PEL
which adverse (Probable
biological Effectare
effects Level), Probablefound.
frequently Effect Level: concentration above
which adverse biological effects are frequently found.
Figure 7. Monitoring Points in Tailings Spill Soils—Department of Huancavelica (Modified from [45]).
Figure 7. Monitoring Points in Tailings Spill Soils—Department of Huancavelica (Modified from
[45]).
The results of the analysis indicate that the soil samples present high concentrations
of Ni, Cu, Zn, As, Pb, and Fe, which are altering the quality of the soil, exceeding the
The results of the analysis indicate that the soil samples present high concentrations
environmental quality standards of Peru (ECA) in the case of As and Pb, and exceeding
of Ni, Cu, Zn, As, Pb, and Fe, which are altering the quality of the soil, exceeding the
international standards in Cu, Zn, As, and Pb. Regarding the tailings samples, it can
environmental quality standards of Peru (ECA) in the case of As and Pb, and exceeding
be seen that they are materials with high concentrations of heavy metals, together with
international standards in Cu, Zn, As, and Pb. Regarding the tailings samples, it can be
concentrations of CN and Hg that do not exceed the mentioned standards.
seen that they are materials with high concentrations of heavy metals, together with con-
centrations of CN and Hg that do not exceed the mentioned standards.
environment called soil: (i) source of contamination (mine tailings), (ii) identification of
contaminants of interest (Ni, Cu, Zn, As, Pb, and Fe), (iii) mobilization mechanisms (natural
soils, crop fields, and irrigation channels), (iv) routes of exposure (terrestrial environment),
and (v) existing potential receptors (mammals that they feed on vegetation).
Water 2022, 14, 3057 13 of 30
environment called sediments: (i) source of contamination (mine tailings), (ii) identifica-
tion of contaminants of interest (Pb, Cu, Zn, As, and Cd), (iii) mobilization mechanisms
On the
(surface andother hand, Figure
underground 8 and
water), (iv)Table 4 show
routes the sampling
of exposure points
(aquatic and the results
environment), of
and (v)
sediment samplingreceptors
existing potential carried out in the
(fish, bed of the
mammals, andEscalera
people river, respectively,
who drink water). values that are
compared with the standards of local regulations and international regulations:
8. Tailings Spill
Figure 8. Spill Monitoring
Monitoring Points—Sediments—Department
Points—Sediments—Department of Huancavelica
Huancavelica (Modified
(Modified
[45]).
from [45]).
5.1.6. 4.
Table Environmental Impacts
Sediment Monitoring onRiver
in the the Physical Environment—Air
Bed of the Escalera Compared with Soil Standards [45,52].
Mine tailings particles can be resuspended by wind and human activity, where par-
ticles < 10 μm, and especially those < 2.5 μm, with metallic species in colloids that can
Sediments Samples/Soil Standards Free
cross the Cr defenses CNof theNirespiratory
Pb Cu
system andFeenter theZn lungs [53]. Hg OneAs of the Cd most
harmful
S-1 (sediments Point.1 Escalera river) effects
8.96 of tailings
0.04 deposits
8.60 adjacent to towns
1242.27 596.11 42,002.36 in Peru is
3095.77 the inhalation
0.13 of particles
413.51 17.07
with heavy
S-2 (sediments Point 2 Escalera river) 24.73metals0.04such11.31
as lead,1724.52
with children and animals
440.70 41,065.57 being the0.15
5787.80 most vulnerable
608.03 28.94 re-
S-3 (sediments Point 3 Escalera river)
ceptors [53].9.75 No 0.03 9.09 by
air pollution 1134.12 324.80 material
particulate 36,973.65 has2459.91 0.11
been documented 370.72
in this21.42
spill
S-4 (sediments Point 4 Escalera river) 16.05 0.02 17.69 329.50 104.49 30,380.42 1278.47 0.06 126.73 7.46
case, since
S-5 (sediments Point.5 Escalera river) most of
16.59 0.04the particulate
7.92 material
1520.40 390.96was deposited2790.29
28,731.73 in the riverbed0.14 and the rest
443.44 19.11re-
S-6 (sediments Point.6 Escalera river) 26.51
mained suspended 0.04in the
13.45
water1470.85
column 376.94
[45]. 28,386.48 2862.32 0.12 408.85 16.91
37.07
S-7 (sediments Point 7 Escalera river)
Copper and0.02 20.82 939.57 238.12 26,656.76
gold tailings 1830.00
have a typical particle size distribution 0.04 246.49 10.37
according to Figure
ECA Agricultural Soils (Peru) 2010 0.40 0.09 - 70.00 - - -
9, where 25% of the total particles correspond to PM10 and 12% to PM2.5. Considering 6.60 50.00 1.40
that
Canada Quality Guide 2003 (PEL) (**) 90.00 - - 91.30 197.00 - 315.00 0.50 17.00 3.50
Dutch Standard VROM 1983 tailings have - a dry- density- of 1.5 tons/m
600.00 3, this means
500.00 - that for 1.5 tons10.00
3000 of tailings - deposited
20.00
there is(*)
Note(s): anSampling
averagecarried
concentration of 100 × 10and
out by an Inspectorate
6 μgr/m3 particles vulnerable to being emitted
OEFA certified laboratory by EPA method, and by
by wind.
ICP Spectrometry. (**) PEL (Probable Effect Level), Probable Effect Level: concentration above which adverse
biological effects are frequently
Considering found.
the conceptual model of sites contaminated with tailings presented
above (Figure 3),toitwhat
According is possible to mention
is indicated in Table the 4,
following characteristics
heavy metals are present thatinaffect the nat-
the samples
ural environment called air: (i) source of contamination (mine tailings),
taken from the sediments of the Escalera River with high concentrations, mainly of Pb, Cu, (ii) identification
of contaminants
Zn, of interest
As, and Cd, according to (particulate matter it contains
Canadian regulations. Regarding Pb,local
Cu,regulations,
Zn, As, andthere Cd),were
(iii)
mobilization mechanisms (winds and air breezes), (iv) routes of exposure
exceedances in Cr, Pb, As, and Cd. It is important to mention that, in the case of sediment (aerial environ-
ment), and
analysis, (v)necessary
it is existing potential
to consider receptors (mammals
physicochemical and
and people who
biological need
factors of tothebreathe).
behavior
of the sediment in time and space, as well as the hydrodynamics of the flow, which is
outside the scope of this investigation. The cited standards allow us to have a reference to
evaluate the need to carry out additional investigations or remediation with respect to the
specific use of a soil. In this sense, from the analysis of the indicated results, alterations to
the quality of the receiving bodies are evidenced, such as the superficial waters, soil, and
Water 2022, 14, 3057 14 of 30
sediments of the Escalera River, which were caused by direct contact with the tailings from
the tailings storage facility A.
Finally, considering the conceptual model of sites contaminated with tailings pre-
sented above, it is possible to mention the following characteristics that affect the natural
environment called sediments: (i) source of contamination (mine tailings), (ii) identification
of contaminants of interest (Pb, Cu, Zn, As, and Cd), (iii) mobilization mechanisms (surface
and underground water), (iv) routes of exposure (aquatic environment), and (v) existing
potential receptors (fish, mammals, and people who drink water).
5.1.6. Environmental Impacts on the Physical Environment—Air

Mine tailings particles can be resuspended by wind and human activity, where parti-
cles < 10 µm, and especially those < 2.5 µm, with metallic species in colloids that can cross
the defenses of the respiratory system and enter the lungs [53]. One of the most harmful
effects of tailings deposits adjacent to towns in Peru is the inhalation of particles with heavy
metals such as lead, with children and animals being the most vulnerable receptors [53].
No air pollution by particulate material has been documented in this spill case, since most
of the particulate material was deposited in the riverbed and the rest remained suspended
in the water column [45].
Copper and gold tailings have a typical particle size distribution according to Figure 9,
where 25% of the total particles correspond to PM10 and 12% to PM2.5 . Considering that
tailings have a dry density of 1.5 tons/m3 , this means that for 1.5 tons of tailings deposited
there is an average concentration of 100 × 106 µgr/m3 particles vulnerable to being emitted
by wind.
Figure9.9.Typical
Figure Typicalgranulometric
granulometriccurves
curvesofofcopper/molybdenum
copper/molybdenumand
andgold
goldmining
miningtailings
tailings[54].
[54].
Consideringthe
Considering theconceptual
scientific literature
model of sitesapplied to this casewith
contaminated of tailings
tailingsspill, a study
presented car-
above
(Figure
ried out3),[55]
it ishaspossible
concludedto mention
that theretheisfollowing characteristics
an association that affect the
between continuous naturalto
exposure
environment
PM10 and PMcalled 2.5 (withair: (i) source
metallic of contamination
contents (mine
of Cu, Fe, As, Zn, Cn,tailings), (ii) Mo)
Pb, As, Hg, identification
from mining of
contaminants
tailings and the of interest (particulate
effects on matter health
the respiratory it contains
of the Pb,population
Cu, Zn, As, ofand Cd), (iii) mobi-
neighboring cities.
lization
Table 5mechanisms (windsofand
shows the results theair
PM breezes), (iv) routes
2.5 monitoring of exposure
carried out on an (aerial environment),
abandoned tailings
and (v) existing
deposit potentialliability)
(environmental receptorsin(mammals
the city of and peopleChile
Chañaral, who between
need to breathe).
2012 and 2013:
Considering the scientific literature applied to this case of tailings spill, a study carried
out [55]5. has
Table concluded
Chañaral that
Tailings there is Matter
Particulate an association
comparedbetween
with Air continuous
Standards [55].exposure to PM10
and PM2.5 (with metallic contents of Cu, Fe, As, Zn, Cn, Pb, As, Hg, Mo) from mining
Air Monitoring Point (2012–2013)/
tailings and the effects on the respiratory Parameter
healthPMof 2.5
the(µg/m 3N) 24 h
population of neighboring cities.
Air Standards Mínimun P25 Mean P75 Maximun
E-01(Tailings Beach of Chañaral) 0.01 7.88 17.15 60.08 172.50
ECAs DS 003-2008-MINAM (Perú) 25.00 25.00 25.00 25.00 25.00
Ministry of Environment MMA Chile (*) 50.00 50.00 50.00 50.00 50.00
WHO (2006) 25.00 25.00 25.00 25.00 25.00
Note(s): (*) Decree 144 of the Ministry of Health of 1961 and Resolution 1215 of the Ministry of
Water 2022, 14, 3057 15 of 30
Table 5 shows the results of the PM2.5 monitoring carried out on an abandoned tailings
deposit (environmental liability) in the city of Chañaral, Chile between 2012 and 2013:
Table 5. Chañaral Tailings Particulate Matter compared with Air Standards [55].
Air Monitoring Point (2012–2013)/ Parameter PM2.5 (µg/m3 N) 24 h

Air Standards Mínimun P25 Mean P75 Maximun
E-01(Tailings Beach of Chañaral) 0.01 7.88 17.15 60.08 172.50
ECAs DS 003-2008-MINAM (Perú) 25.00 25.00 25.00 25.00 25.00
Ministry of Environment MMA Chile (*) 50.00 50.00 50.00 50.00 50.00
WHO (2006) 25.00 25.00 25.00 25.00 25.00
Note(s): (*) Decree 144 of the Ministry of Health of 1961 and Resolution 1215 of the Ministry of Health of 1978.
The results indicate the average levels per minute, as well as the average of 24 h for
PM2.5 . PM2.5 levels per minute showed a range from 0.01 to 172.50 µg/m3 . The graph in
Figure 10 shows a time series for the 24-h (every day) average of PM2.5 concentrations and
wind speed, as well as the 25th and 75th percentiles (P25 , P75 ) of daily PM2.5 measurements
these variables throughout the study period.
As can be seen, the 24-h average of PM2.5 exceeded the Chilean norm of 50 µg/m3 N
only once. It is important to mention that when analyzing P75 and the maximum value,
during times of the day there are PM2.5 concentrations that are equivalent to approximately
25% of the measurements that exceed the cited standards (MMA, WHO, and Peru), which
is a risk to health, since each increase in 10 µg/m3 N of fine particles in the air determines a
4% increase in general mortality, an 8% increase in cardiopulmonary diseases, and a 6%
increase in cancer mortality pulmonary [56,57].
These results can be considered and taken into account for the case of the spill in the
Escalera River where there are polymetallic tailings, as well as for decision-making on
measures to protect people’s health, such as the use of masks for a certain period of time
while the environmental emergency passes in the area.
5.1.7. Environmental Impacts on the Physical Environment—Flora and Fauna

Since the occurrence of the tailings spill, the possibility of using the waters of the
Escalera/Huachocolpa/Lircay/Opamayo rivers has been annulled, as their waters are
contaminated with heavy metals and chemical reagents. Consequently, agricultural activity
has been reduced to crops that await only the rainy season (November–April), this being a
critical point since the event occurred in the dry season (May–October). Pollution has dam-
aged the flora and fauna, affecting in the short term the aquatic ecosystem that lives in the
riverbed, where hundreds of trout and aquatic plants have died [46]. Due to this, thousands
of animals and plants have been left without a water source, affecting 3300 head of cattle,
including cattle, horses, sheep, llamas, and alpacas, as well as 40 hectares of crops of peas,
wheat, alfalfa, vegetables, and prickly pears [45,46]. Figure 11 shows some of the effects
and impacts generated in the bed of the Escalera river due to the mining tailings spill.
5.1.8. Environmental Impacts on the Physical Environment—Humans

There are no studies of the effect on human health for the present case study. However,
there are studies in Peru that indicate that the populations surrounding mining tailings
have high levels of lead and arsenic contamination tested in blood and urine [53,58–62].
Therefore, it is not recommended that populations inhabit these areas due to the health risks
that this implies [53], causing the bioaccumulation of Pb and As in children in Peru, vulner-
able due to malnutrition, affecting their health with: (i) high rates of morbidity–mortality,
cases of lead anemia, and neurodevelopmental disorders in children [53]. Figure 12 shows
some of the effects and impacts generated in the bed of the Escalera river due to the mining
tailings spill, including some tasks of cleaning and control of the spill, such as fish mortality
in the riverbed.
Water 2022, 14, x FOR PEER REVIEW 17 o
Water 2022, 14, 3057 16 of 30
Figure 10.Monitoring
Figure 10. Monitoring Study
Study PMPM 2.5 Tailings
2.5 Tailings Deposit
Deposit Chañaral
Chañaral Chile [55].
Chile [55].

Since the occurrence of the tailings spill, the possibility of using the waters of
Escalera/Huachocolpa/Lircay/Opamayo rivers has been annulled, as their waters are c
taminated with heavy metals and chemical reagents. Consequently, agricultural activ
has been reduced to crops that await only the rainy season (November–April), this be
thousands of animals and plants have been left without a water source, affecting 3300
head of cattle, including cattle, horses, sheep, llamas, and alpacas, as well as 40 hectares
of crops of peas, wheat, alfalfa, vegetables, and prickly pears [45,46]. Figure 11 shows
Water 2022, 14, 3057 17 of 30
some of the effects and impacts generated in the bed of the Escalera river due to the mining
tailings spill.

Figure 11. Effects of the flow of tailings spilled in the Escalera and Huachocolpa rivers [45,46].
Figure 11. Effects of the flow of tailings spilled in the Escalera and Huachocolpa rivers [45,46].
5.1.8. Environmental Impacts on the Physical Environment—Humans

There are no studies of the effect on human health for the present case study. How-
ever, there are studies in Peru that indicate that the populations surrounding mining tail-
ings have high levels of lead and arsenic contamination tested in blood and urine [53,58–
62]. Therefore, it is not recommended that populations inhabit these areas due to the
health risks that this implies [53], causing the bioaccumulation of Pb and As in children in
Peru, vulnerable due to malnutrition, affecting their health with: (i) high rates of morbid-
ity–mortality, cases of lead anemia, and neurodevelopmental disorders in children [53].
Figure 12 shows some of the effects and impacts generated in the bed of the Escalera river
due to the mining tailings spill, including some tasks of cleaning and control of the spill,
such as fish mortality in the riverbed.
Finally, Figure 13 shows the impact of the mining tailings spill on crops and irrigation
channels. It is also possible to observe cattle in the riverbed drinking water from the river
affected by the spill, as well as the installation of fences to prevent the entry of animals to
drink water from the Escalera River.
Figure 12. Tailings removal by community and miners, impacts on aquatic biota [45,46].
Finally, Figure 13 shows the impact of the mining tailings spill on crops and irrigation
channels. It is also possible to observe cattle in the riverbed drinking water from the river
affected by the spill, as well as the installation of fences to prevent the entry of animals to
drink water from the Escalera River.
Water 2022, 14, 3057 18 of 30
Figure13.
Figure 13.Impacts
Impactson
on agricultural-livestock
agricultural-livestock activities,
activities,installation
installationofof
fences forfor
fences livestock [46].
livestock [46].
5.2. Gold Tailings in Las Palmas Creek, Pencahue, Maule Region—Chile

5.2.1. Description of the Characteristics of the Site and Its Physical Environment
The commune of Pencahue is located in the eastern part of the Cordillera de la Costa
in the Maule region, with the main watercourses being Los Puercos Creek and Las Palmas
Creek, which are tributaries of the Maule River. The flow of these creeks varies between
0.05 (m3 /s) and 1.0 (m3 /s), in the dry and wet seasons, respectively. The average width
of its beds is equivalent to 4 m and the slopes are in the range of 0.5% and 3.0% [63].
In the Pencahue sector, there is an elevation of 125 m above sea level, the average an-
nual temperature is 15 ◦ C, presenting average maximum and minimum temperatures of
29 ◦ C (dry season—January) and 4.9 ◦ C (wet season—July). The average annual rainfall is
696 mm, with a maximum of 123 mm in June.
The main activities in the area are agriculture, livestock, and wine vineyards, with the
mining activity highlighted in the 1980s and 1990s. This is how in the 1980s gold mining
was outlined where gold mining was carried out. In 1980, the Cominor company, owned
by the Grupo Francisco Javier Errázuriz mining holding company, acquired and developed
the Minera Las Palmas (MLPS) property [64].
The gold mineralogical composition of the materials mined by MLPS consisted of:
blende (zinc sulphide, ZnS), galena (lead sulphide, PbS), auriferous pyrite (iron sulphide,
FeS2 ), chalcopyrite (copper iron sulphide, CuFeS2 ), and specularite (specular hematite,
Fe2 O3 ) [63], processing 350 tons/day in 1988. The metallurgical process used was counter-
current decanting and leaching with cyanide-activated carbon. During its operation, MLPS
generated tailings from its process as waste, which was stored in a site adjacent to its plant
in the Los Ladrones creek. Its work ceased in 1999, with voluntary closure plan carried out
by the mining company [64].
5.2.2. Causes of the Tailings Spill Event

On 27 February 2010, an earthquake measuring 8.8 on the Richter scale shook southern
Chile, producing a tsunami that flooded and destroyed the coastline. In the small valley
current decanting and leaching with cyanide-activated carbon. During its operatio
MLPS generated tailings from its process as waste, which was stored in a site adjacent
its plant in the Los Ladrones creek. Its work ceased in 1999, with voluntary closure pl
carried out by the mining company [64].
Water 2022, 14, 3057 5.2.2. Causes of the Tailings Spill Event 19 of 30
On 27 February 2010, an earthquake measuring 8.8 on the Richter scale shook sout
ern Chile, producing a tsunami that flooded and destroyed the coastline. In the small va
of Las Palmas,ley in of Las Palmas,
Pencahue, in Pencahue,ofa five
a community community
houses of fivelocated
was houses inwas located
the in the
vicinity of vicinity
the abandoned MLPS mining site. Nobody suspected that the hill next to the mine was amine was
the abandoned MLPS mining site. Nobody suspected that the hill next to the
tailings deposit.tailings deposit.
The seismic The seismic
waves passedwaves
throughpassed throughdeposit,
the tailings the tailings deposit,
violently violently causin
causing
its physical destabilization, which meant that this mineral waste deposit behaved asbehaved
its physical destabilization, which meant that this mineral waste deposit if it as if
were a
were a fluid (Figure 14).fluid (Figure 14).
Figure
Figure 14. Collapsed 14.of
area Collapsed areatailings
Las Palmas of Las Palmas
storagetailings
facility.storage facility
A basal liquefaction in the dam and reservoir of the tailings deposit (mud flow)
increased due to the flow of underground water from a non-visible spring (aquifer). The
latter, which probably appeared after the closure of the tailings deposit, caused the collapse
of the structure [65,66]. Consequently, the tailings flowed for around 3–4 Ha, clogging
the Las Palmas and Los Ladrones creeks with tailings, and four members of the Gálvez
Chamorro family were buried [67].
5.2.3. Identification of the Area of Influence by Pollution

The strong earthquake caused 2.5 Ha of the Las Palmas tailings deposit to collapse
on approximately 11 Ha of surrounding land, blocking the Las Palmas, Los Ladrones,
and Los Puercos streams. The area of the northwest zone of the deposit did not collapse,
but it did present a serious risk of collapse [63]. The total volume collapsed represented
approximately 200,000 m3 . The obstructions of the channels (tacos) were estimated at
23,000 m3 for two obstructed areas of the Las Palmas creek and 42,000 m3 for the Los
Ladrones creek. The collapsed material is made up of tailings and in part by the soil
cover originally laid over the tailings for the mine closure process. Locally, the collapsed
tailings contain objects washed away during the event, including machinery and structural
remains [63]. Figure 15 shows the area affected by the collapse and spillage of tailings at
the Las Palmas mine. Samples were taken from the water and sediments of the creeks
3 days after the tailings spill event, both upstream and downstream from the tailings spill
site. In addition, sampling of closure cover solids, material from the tailings deposit, and
solid material near the mining process plant was carried out.
5.2.4. Environmental Impacts on the Physical Environment—Water

Due to the fact that a large part of the collapsed tailings was spilled in part of the Las
Palmas creek, and Los Ladrones creek, blocking its normal course, a sampling was carried
out in both receiving bodies, to analyze the chemical quality of their waters (Table 6). In
addition, a sampling was carried out at Los Puercos creek, where the waters of the previous
channels converge. Figure 16 shows the sample points of water considered.
laid over the tailings for the mine closure process. Locally, the collapsed tailings contain
objects washed away during the event, including machinery and structural remains [63].
Figure 15 shows the area affected by the collapse and spillage of tailings at the Las Palmas
mine. Samples were taken from the water and sediments of the creeks 3 days after the
tailings spill event, both upstream and downstream from the tailings spill site. In addition,
Water 2022, 14, 3057 20 of 30
sampling of closure cover solids, material from the tailings deposit, and solid material
near the mining process plant was carried out.
Figure 15.
Figure Area affected
15. Area affected by
by mining
mining tailings
tailings spill
spill in
in Las
Las Palmas
Palmas Creek
Creek (Modified
(Modified from
from [63]).
[63]).
Table 6. Results of Chemical Analysis of Water Samples compared with Water Standards [51,63].
Total Parameters (mg/L) (**)

Sample Points of Water/Water
Standards Free C.E.
Pb Zn Fe Cu Mn As (*) Hg (*) CN O2 pH (µS/cm)
M-809 (Los Ladrones Creek) 0.01 0.11 4.00 0.03 3.06 <LOD <LOD 0.59 - - -
M-829 (Las Palmas Creek) 1.16 33.70 1.74 0.06 2.53 <0.006 <0.001 <0.05 9.37 7.2 1088
M-831 (Los Puercos Creek) 0.02 0.92 1.63 0.02 1.26 <0.006 <0.001 <0.05 8.89 7.6 202
ECA Potable Water A1 2008 (Peru) 0.01 3.00 0.30 2.00 0.10 0.01 0.001 - - - 1500
ECA Water for Irrigation 2008 (Peru) 0.05 2.00 1.00 0.20 0.05 0.001 0.10 ≥4.00 6.5–8.5 2000
NCh 1333 Water for Irrigation (Chile) 5.00 0.20 0.30 0.20 0.02 0.10 0.001 0.20 ≥5.00 - 1500
NCh 409 Potable Water (Chile) 0.05 3.00 5.00 2.00 0.01 0.01 0.001 0.05 - - -
WHO 0.01 3.00 - 2.00 0.50 0.01 0.001 0.07 - - -
Note(s): (*) Measured by TXRF method; LOD: limit of detection. (**) Sampling carried out by DICTUC and DGA
certified laboratory by EPA method, and by ICP Spectrometry.
The results of Table 4 indicate that the water samples from the Las Palmas creek have
high concentrations above the standards for Pb, Zn and Mn. The Los Puercos creek has
high levels of Mn. The situation of the Los Ladrones stream, which has high levels of Mn
and free CN above the regulation, is of concern. Since the use of water in the area is for
irrigation, livestock and the use of drinking water, it is necessary to carry out a remediation
of this water streams. No underground water studies were conducted to measure chemical
quality.
environment called water: (i) source of contamination (mine tailings), (ii) identification
of contaminants of interest (Pb, Zn and Mn), (iii) mobilization mechanisms (surface and
ECA Water for Irrigation 2008
0.05 2.00 1.00 0.20 0.05 0.001 0.10 ≥4.00 6.5–8.5 2000
(Peru)
NCh 1333 Water for Irrigation
5.00 0.20 0.30 0.20 0.02 0.10 0.001 0.20 ≥5.00 - 1500
(Chile)
NCh Water 2022, 14, 3057
409 Potable Water (Chile) 0.05 3.00 5.00 2.00 0.01 0.01 0.001 0.05 - - 21 of 30
-
WHO 0.01 3.00 - 2.00 0.50 0.01 0.001 0.07 - - -
Note(s): (*) Measured by TXRF method; LOD: limit of detection. (**) Sampling carried out by DIC-
underground water courses), (iv) routes of exposure (aquatic environment), and (v) existing
TUC and DGA certified laboratory by EPA method, and by ICP Spectrometry.
potential receptors (fish, mammals, and people who drink water).
Figure
Figure 16.16. Area
Area affected
affected byby mining
mining tailingsspill
tailings spillLas
LasPalmas
Palmascreek,
creek, water
water sampling
sampling (Modified
(Modified from
from
[63]). [63]).
5.2.5. Environmental Impacts on the Physical Environment—Soil

According to the available information, this tailing corresponds to gold mining, char-
acterized by the use of toxic substances (e.g., cyanide) and the generation of residues with a
high potential to produce negative environmental impacts [63,68]. Considering antecedents
of the mine’s geology and the metallurgical process used (cyanidation), this allows us to
expect that the spilled tailings contain potentially important concentrations of Zn, Pb, Cu,
and Fe, in addition to the cyanide residue generated by the mineral processing [64]. Table 7
shows the results of a sampling of solids from the area affected by the event and Figure 17
shows the monitoring points considered.
Table 7. Result of Chemical Analysis of Soil Samples compared with Soil Standards [63].

Sample Point Soils/Soil Standards
Mn Fe Cu Zn Mg Pb As
M-821 (Original Soil) 1265 54,707 29 390 0.15 40.89 <0.006
M-814 (Tailings in Las Palmas Creek) 751 37,406 612 11,389 0.20 7192 <0.006
M-815 (Tailings in Los Ladrones Creek) 251 32,420 611 1267 0.16 8023 <0.006
M-827 (No Collapsed Tailings) 635 47,074 1350 2512 0.32 10,460 <0.006
M-812 (Process Plant Dust) 1016 25,051 783 48,034 0.38 9874 <0.006
Water 2022, 14, 3057 22 of 30
Table 7. Cont.

Sample Point Soils/Soil Standards
Mn Fe Cu Zn Mg Pb As
ECA Agricultural Soils (Peru) 2010 - - - - - 70.00 50.00
Canada Quality Guide 2003 (PEL) (**) - - 197.00 315.00 - 91.30 17.00
Dutch Standard VROM 1983 3000 - 500.00 3000 - 600.00 -
Water 2022, 14, x FOR PEER REVIEW Note(s): (*) Sampling carried out by DICTUC and DGA certified laboratory by EPA method, and 24 by
of ICP
32
Spectrometry. (**) PEL (Probable Effect Level), Probable Effect Level: concentration above which adverse
biological effects are frequently found.
Figure
Figure17.
17.Area affected
Area byby
affected mining tailings
mining spillspill
tailings in Las
in Palmas creek,creek,
Las Palmas soil sampling (Modified
soil sampling from
(Modified
[63]).
from [63]).
5.2.6. The
Environmental Impacts
results of the onsoil
original the sampling
Physical Environment—Air
(solids used in the closure cover of tailings
storage
Air facility),
pollutioncollapsed tailings
has not been (present in
documented inthe
thiscreeks), non-collapsed
case study tailings,
but considering theand dust
mining
present with
activity in the metallurgical
cyanide process
in the sector, is plant indicate,significant
undoubtedly when compared withdisposal
due to the international
of its
standards,
tailings thatthat for the
contain sample
traces of soil covering
of cyanide, thethe
as well as closure of the
emission ofdeposit,
materialall the parameters
particulate mat-
are met except for Zn. Regarding tailings, Mn and As parameters are met,
ter once the tailings lose moisture and dry out. According to the scientific literature, while foritZn,
is
Cu, andtoPbmention
possible the values
that exceed the of
in the case regulations, for processes
metallurgical which remediation is required.
that use cyanide, It is
the most
worth
used mentioningare
compounds that Chileand
NaCN currently doesFree
KCN [69]. not have a decontamination
cyanide or soil remediation
refers to the concentration of CN-
regulation.
and a weak acid HCN in solution, which dissolve in water according to (Equations (5)–
(7)): Finally, considering the conceptual model of sites contaminated with tailings presented
environment called soil: (i) source of NaCN → Na + CN(mine tailings), (ii) identification(5)
contamination of
contaminants of interest (Zn, Cu, and Pb), (iii) mobilization mechanisms (natural soils,
KCN → K + CN (6)
CN + H O → HCN + OH (7)
The state of the reversible reaction noted above is critical in the gold cyanide extrac-
tion process. At pH greater than 10.3, free cyanide in the process water or leach fluid will
Water 2022, 14, 3057 23 of 30
crop fields, and irrigation channels), (iv) routes of exposure (terrestrial environment), and
(v) existing potential receptors (mammals that they feed on vegetation).
5.2.6. Environmental Impacts on the Physical Environment—Air

Air pollution has not been documented in this case study but considering the mining
activity with cyanide in the sector, is undoubtedly significant due to the disposal of its
tailings that contain traces of cyanide, as well as the emission of material particulate matter
once the tailings lose moisture and dry out. According to the scientific literature, it is
possible to mention that in the case of metallurgical processes that use cyanide, the most
used compounds are NaCN and KCN [69]. Free cyanide refers to the concentration of CN-
and a weak acid HCN in solution, which dissolve in water according to (Equations (5)–(7)):
NaCN → Na+ + CN− (5)
KCN → K+ + CN− (6)

− −
CN + H2 O → HCN + OH (7)
The state of the reversible reaction noted above is critical in the gold cyanide extraction
process. At pH greater than 10.3, free cyanide in the process water or leach fluid will be
in the CN-form. When the pH falls below 8.5, then HCN is the dominant species. This is
because its lower boiling point and its high available vapor pressure allow it to be lost from
solution through volatilization into air (gas). It is known that cyanide has a peculiar smell,
similar to almonds, and it is a high risk for the biota to inhale this substance for prolonged
periods of time [36].
Considering the conceptual model of sites contaminated with tailings presented above
(Figure 3), it is possible to mention the following characteristics that affect the natural
environment called air: (i) source of contamination (mine tailings), (ii) identification of
contaminants of interest (particulate matter containing Zn, Cu, Pb, and gas such as HCN),
(iii) mobilization mechanisms (winds and air breezes), (iv) routes of exposure (aerial envi-
ronment), and (v) existing potential receptors (mammals and people who need to breathe).

The effects on flora and fauna in the tailings spill sector have not been documented
for this case. However, according to studies carried out on tailings spills that occurred
at the El Teniente mine, the toxic effects of Mo and Cu are known in agricultural crops,
presenting a bioaccumulation of these heavy metals in flora and fauna [70]. Although
cyanide reacts rapidly in the environment and degrades or forms complexes and salts of
varying stabilities, it is toxic to many living organisms, even at very low concentrations.
There are certain bacteria, algae and fungi that naturally produce cyanide. Moreover, many
species of the plant world naturally produce cyanide, such as coffee beans, fruits (apple
and pear seeds), almonds, roots, among others.
Fish and marine invertebrates are especially sensitive to cyanide exposure, for con-
centrations between 5.0 and 7.2 µg/L, reducing swimming ability and reproduction. At
concentrations above 200 µg/L, the toxic effect is rapid for most aquatic species. Algae and
aquatic plants are able to tolerate cyanide concentrations even higher than those tolerated
by fish and invertebrates. Aquatic plants appear immune to cyanide even at concentra-
tions above 160 µg/L, which is fatal to most freshwater aquatic fish and invertebrates.
Meanwhile, for terrestrial birds and mammals, the toxic levels of cyanide inhalation due to
the food chain are 0.7 mg/kg and 2.0 mg/kg in relation to body weight, respectively [68].
Figure 18 shows some images of the collapse of the tailings deposit, where it is possible to
appreciate the spilled volume and the presence of water as an underground water level
within the tailings storage area.
senting a bioaccumulation of these heavy metals in flora and fauna [70]. Although cyanide
reacts rapidly in the environment and degrades or forms complexes and salts of varying
stabilities, it is toxic to many living organisms, even at very low concentrations. There are
certain bacteria, algae and fungi that naturally produce cyanide. Moreover, many species
Water 2022, 14, 3057 of the plant world naturally produce cyanide, such as coffee beans, fruits (apple and24pear of 30
seeds), almonds, roots, among others.
Fish and marine invertebrates are especially sensitive to cyanide exposure, for con-
centrations between 5.0
5.2.8. Environmental and 7.2
Impacts on μg/L, reducing
the Physical swimming ability and reproduction. At
Environment—Humans
concentrations above 200 μg/L, the toxic effect is rapid for most aquatic species. Algae and
Without a doubt, the most serious impact in the short term produced by the collapse
aquatic plants are able to tolerate cyanide concentrations even higher than those tolerated
of the Las Palmas tailings deposit was the death of four people living in a nearby house.
by fish and invertebrates. Aquatic plants appear immune to cyanide even at concentra-
This event also had an impact on people’s activities, such as the use of water from the
tions
creeksabove
for both160irrigation
μg/L, which is fatal to most
and residential freshwater
use, due aquatic fish
to the obstruction and
with invertebrates.
tailings material
Meanwhile, for terrestrial birds and mammals, the toxic levels of cyanide
from the nearby Los Ladrones and Las Palmas creeks. Along with this, the dispersion inhalation due
to the food chain are 0.7 mg/kg and 2.0 mg/kg in relation to body weight, respectively
of tailings in surrounding soils caused damage to local agriculture. Studies carried out [68].
Figure
indicate18that
shows some
there areimages
no highofconcentrations
the collapse of the tailingsthat
of metals deposit, where
indicate it is possible or
contamination to
appreciate
direct health thedamage
spilled in
volume and term,
the short the presence of water
due to the as an
exposure ofunderground
heavy metalswater level
that could
within the tailings storage area.
have been dispersed in this event, but traces of CN in soils must be taken into account [71].
Figure 18. Collapsed

Figure 18. Collapsed area
area of the Las
of the Las Palmas
Palmas tailings
tailings deposit
deposit [66].
[66].
The most toxic form of CN is gaseous hydrocyanic acid (HCN). The upper threshold
limit for HCN in the workplace was set by the North American Conference of Governmental
Industrial Hygienists (ACGIH) at 4.7 ppm. At concentrations of 20–40 ppm HCN in air,
some respiratory distress may be observed after several hours. Death occurs within a few
minutes at HCN concentrations above about 250 ppm in air. For potassium or sodium
cyanide, the lethal dose in humans by ingestion or inhalation varies between 0.050 and
0.2 g of cyanide, corresponding to about 3 grains of rice [69]. No HCN-affected people or
animals were reported in the area.
Considering that the mining exploitation between 1980 and 1990 could cause a system-
atic incorporation of metals in the area would explain the high levels of heavy metals in the
soil. It is emphasized that, after the spill, the collapsed tailings were safely disposed of and
that no adverse effects have since been observed, which does not guarantee the absence
of harmful effects on people caused by heavy metals in the medium and long term [71].
Figures 19 and 20 show some images of the collapse of the tailings deposit, where it is
possible to appreciate the material that obstructed the surrounding creeks and the presence
of machinery used to excavate in the area where the four deceased people were buried.
in the soil. It is emphasized that, after the spill, the collapsed tailings were safely disposed
of and that no adverse effects have since been observed, which does not guarantee the
absence of harmful effects on people caused by heavy metals in the medium and long
term [71]. Figures 19 and 20 show some images of the collapse of the tailings deposit,
where it is possible to appreciate the material that obstructed the surrounding creeks and
Water 2022, 14, 3057 25 of 30
the presence of machinery used to excavate in the area where the four deceased people
were buried.

Figure
Figure 19.
19. Tailings spill in
Tailings spill in Los
Los Ladrones
Ladrones creek,
creek, and
and rescue
rescue of
of people
people [32].
[32].
Figure
Figure 20.
20. Tailings
Tailings spill in Las
spill in Las Palmas
Palmas creek
creek and
and collapsed
collapsed tailings
tailings stratigraphy
stratigraphy [63].
[63].
Mitigation of
6. Mitigation of Pollution Due to Mining Tailings Spills
The mitigation measures for contamination due to spillage of mining tailings applied
Caudalosa (Peru)
in the cases of the tailings deposit of Minera Caudalosa (Peru) and
and the case of the Las
Palmas tailings
Palmas tailings deposit
deposit (Chile)
(Chile) are
are presented
presented below. When
When the existence
existence of a potentially
contaminated site
contaminated site is determined
determined due
due to an accident related to operating activities with
mining tailings or environmental liabilities, the project owner, together with the compe-
tent authority, must present a soil decontamination plan (SDP).
The SDP determines the corresponding remediation actions, based on the character-
ization studies of the contaminated site, in relation to the concentrations of the parameters
regulated by the regulations. In the event that the levels of heavy metals in a site naturally
Water 2022, 14, 3057 26 of 30
mining tailings or environmental liabilities, the project owner, together with the competent
authority, must present a soil decontamination plan (SDP).
The SDP determines the corresponding remediation actions, based on the characteri-
zation studies of the contaminated site, in relation to the concentrations of the parameters
regulated by the regulations. In the event that the levels of heavy metals in a site naturally
exceed the corresponding regulations, this level will be used as the target concentration for
remediation [72].
Depending on the severity of the risk generated by a tailings spill, in some cases,
it is necessary to implement quick-apply control actions (short term), which consider:
(i) installation of signage, (ii) perimeter closures, (iii) implementation of simple containment
techniques (earth dams or sandbags), (iv) collection of tailings from the river bed and from
affected soils, for their adequate and safe disposal, (v) rehabilitation of affected soils and
pastures by tailings, (vi) inventory of animals affected by lack of safe water for consumption,
(vii) protection of cattle and llamas in the area, to prevent them from drinking water from
the affected rivers, (viii) construction of drinking troughs, water supply and fodder for
cattle, (ix) monitoring of the evolution of the chemical quality of the water in rivers, and (x)
health care for the inhabitants of affected localities.
People should also be told not to drink water from wells or rivers until the alert ends.
In the meantime, they should drink bottled water or water from a cistern truck. Protective
clothing, gloves, boots, and filter masks must be provided for everyone who performs
tailings collection and remediation work, avoiding direct contact with tailings.
In severe cases and large spilled volumes, the application of some
physical–chemical–biological technology for the remediation of sites could be necessary as
a medium-term mitigation measure, in order to reduce the risk to the health of the inhabi-
tants. Pollution source modification options include: (i) coverage with a low-permeability
media, (ii) use of chemicals to neutralize acidity, or (iii) immobilize heavy metals and toxic
elements, (iv) tailings dredging, or (v) relocation of the tailings deposit. The reengineering
of the contaminant transport route could include: (i) the construction of structures or
civil works such as reactive barriers and/or wetlands, which would be used to modify
the acidity condition and control the potential for oxidation of contaminated water, thus
immobilizing contaminants dissolved in the water, or (ii) a change in tailings dewatering
technology, or relocation of people and animals.
That is why this article argues for taking a step forward in the management of mining
tailings to develop greater awareness of the environmental importance of such disposal
and manage mine tailings in accordance with the sustainability principles described as
follows by Frank et al. [73]:
• “Mining and mineral processing wastes should be managed so that they remain
physically, geographically, hydrologically, chemically, and radiologically stable”.
• “Mining and mineral processing of wastes that interact with the environment should
be inert, i.e., equivalent (in form, concentration, location, volume, time, and rate) to
materials and chemicals in the same ecosystem”.
• “Mining and mineral processing wastes that are not inert should be isolated, as inert
as practicable, and in a form that is compatible with the adopted waste management
technique and the sensitivity of the ecosystem and the social context”.
• “Mining and mineral processing wastes should be contained, i.e., geographically
bounded, exhibit a minimal footprint in a location of acceptably low ecological and
social values, and be in physical and chemical forms that limit interaction with the
surrounding environment”.
Long-term measures must be applied to create a culture of safety and knowledge in
the population, promoting the use of the best available technologies (BATs) for tailings
management, which requires generating public policies that consider: emergency plans for
contingency events, environmental inspection of tailings deposits, definition of the risk or
threat area, as well as environmental and risk education for the population, among others.
Water 2022, 14, 3057 27 of 30
7. Conclusions
There is no doubt that the most visible impacts of mining are made, among others,
by mining tailings in operation and abandonment, generating acid rock drainage (ARD),
which in turn generates effects as a source of dispersion of heavy metals on the environment.
Mining impacts the physical environment (removal of material, change in the landscape),
emits particulate matter and gases, and discharges uncontrolled effluents into watercourses,
inducing socio-cultural changes.
Tailings spill accidents still occur in the world, e.g., Mount Polley case in Canada
(2014), Fundao Samarco case in Brazil (2015), Corrego do Feijao Brumadinho case in Brazil
(2019) and Jagersfontain case in South Africa (2022). Failures of tailings deposits occur
mainly due to: (i) causes of human origin (e.g., failure of dams, inadequate management
of tailings/water, etc.) and (ii) natural causes (e.g., floods, earthquakes, mudflows, etc.),
which indicates that for these hazardous wastes there is still no degree of safety that allows
to provide confidence to vulnerable communities and ecosystems. This has meant that
tailings transport and storage activities today represent a matter that requires adequate
environmental management and responsible management.
As a consequence of these disasters, the international community, institutions, and
global groups, such as the ICMM (International Council on Mining and Metals), UN
environment program, and the Principles for Responsible Investments (PRI), developed a
“Global Tailings Management Standard for the Mining Industry” launched in August 2020,
with the aim of regulating the operation throughout the entire life cycle of tailings deposits,
including closure and post-closure (perpetuity), considering zero harm to people and the
environment and zero tolerance for human fatalities. ICMM advocates that the application
of appropriate design and management standards and good practices allow tailings storage
facilities to be safe. ICMM members are committed to preventing catastrophic failures of
tailings deposits, with continuous improvement in the design, construction, and operation
stages of these facilities. This organization urges mining companies to improve their
management by adopting the Global Industry Standard on Tailings Management, taking
advantage of technological innovation and continuous improvement.
The sedimentation of mining tailings in aquatic environments due to spill accidents
allows the storage of different chemical species, both metals and other types of pollutants,
influencing the composition of surface water. In addition to the movement of particulate
matter through the water column, it also causes a flux of chemical species from the sed-
iments into the natural solution. Sediments can be mobilized into the water column by
changes in environmental conditions, such as pH, redox potential, and dissolved oxygen.
Of the total concentration of the metal, only certain chemical forms are toxic to organisms,
including free ions and fat-soluble metals, which is why, in the event of a tailings spill,
the population should be put on alert and apply an immediate contingency plan to avoid
impacting the ecosystem (flora and fauna) and people.
Considering the current level of development of tailings management technology in
Chile and Peru, environmental protection is of primary concern for human health and
environmental safety. It is necessary to adopt responsible and safe practices to provide
protection against the loss of life caused by tailings dam failures and impacts on the envi-
ronment. Moreover, it remains important to maintain tailings (operation and abandonment
stage) and prevent mining process waters from coming into contact with continental and/or
marine waters.
Author Contributions: Conceptualization, C.C. and D.C.; formal analysis, C.C.; investigation, C.C.;
resources, D.C.; writing—original draft preparation, C.C.; writing—review and editing, C.C.; visu-
alization, C.C.; supervision, D.C. All authors have read and agreed to the published version of the
manuscript.
Funding: The research is funded by the Research Department of Catholic University of Temuco, Chile.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Water 2022, 14, 3057 28 of 30
Conflicts of Interest: The authors declare no conflict of interest.
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Academic Editors: Margarida 1. Introduction

Water 2022, 14, 3057. https://doi.org/10.3390/w14193057 https://www.mdpi.com/journal/water

determined by local seismic activity, process water clarification requirements, tailings

3. Socio-Environmental Context of Mining Tailings

4. Conceptual Model for Sites Contaminated by Mining Tailings Spills

Figure 3. Conceptual Model ofModel

From a conceptual model perspective, the catastrophic erosion or collapse of a tailings

Table 1. Potentially Mobile Chemical Species in Tailings Slurries [21].

5. Mine Tailings Spill Case Studies

5.1.2. Causes of the Tailings Spill Event

Water 2022, 14, x FOR PEER REVIEW 10 of 32

Figure 4. Breaking of the Tailings Dam A—Caudalosa Mine [42,43].

Figure 5. Area affected by tailings spill—Huancavelica Department (Modified from [45]).

Table 2. Water Monitoring in the Escalera River—Compared to Water Standards [48–51].

Total Parameters (mg/L) (*)

5.1.5. Environmental Impacts on the Physical Environment—Soil

Sample Points Soils/Soil Parameters (mg/Kg) (*)

Water 2022, 14, 3057 13 of 30

5.1.6. Environmental Impacts on the Physical Environment—Air

Air Monitoring Point (2012–2013)/ Parameter PM2.5 (µg/m3 N) 24 h

5.1.7. Environmental Impacts on the Physical Environment—Flora and Fauna

5.1.8. Environmental Impacts on the Physical Environment—Humans

5.1.7. Environmental Impacts on the Physical Environment—Flora and Fauna

Water 2022, 14, x FOR PEER REVIEW 19 of 32

5.1.8. Environmental Impacts on the Physical Environment—Humans

5.2. Gold Tailings in Las Palmas Creek, Pencahue, Maule Region—Chile

5.2.2. Causes of the Tailings Spill Event

5.2.3. Identification of the Area of Influence by Pollution

5.2.4. Environmental Impacts on the Physical Environment—Water

Total Parameters (mg/L) (**)

5.2.5. Environmental Impacts on the Physical Environment—Soil

Parameters (mg/Kg) (*)

Parameters (mg/Kg) (*)

5.2.6. Environmental Impacts on the Physical Environment—Air

NaCN → Na+ + CN− (5)

KCN → K+ + CN− (6)

5.2.7. Environmental Impacts on the Physical Environment—Flora and Fauna

Figure 18. Collapsed

Water 2022, 14, x FOR PEER REVIEW 27 of 32

Conflicts of Interest: The authors declare no conflict of interest.

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