resources
Article
Study and Evaluation of Surface Water Resources Affected by
Ancient and Illegal Mining in the Upper Part of the Milluni
Micro-Basin, Bolivia
Paola Andrea Alvizuri-Tintaya 1,2 , Marco Rios-Ruiz 3 , Jaime Lora-Garcia 4 , Juan Ignacio Torregrosa-López 4 and
Vanesa G. Lo-Iacono-Ferreira 1, *






Citation: Alvizuri-Tintaya, P.A.;
Rios-Ruiz, M.; Lora-Garcia, J.;
Torregrosa-López, J.I.; Lo-Iacono-
Ferreira, V.G. Study and Evaluation
of Surface Water Resources Affected
by Ancient and Illegal Mining in the
Upper Part of the Milluni
Micro-Basin, Bolivia. Resources 2022,
11, 36. https://doi.org/10.3390/
resources11040036
Academic Editors: Elena Rada and
Antonio A. R. Ioris
Received: 16 February 2022
Accepted: 28 March 2022
Published: 31 March 2022
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
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iations.
Copyright: © 2022 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Resources 2022, 11, 36. https://doi.org/10.3390/resources11040036
1 Project Management, Innovation and Sustainability Research Center (PRINS), Alcoy Campus,
Universitat Politècnica de València, Plaza Ferrándiz y Carbonell, s/n, 03801 Alcoy, Spain;
palvizuri@ucb.edu.bo
2 Centro de Investigación en Agua, Energía y Sostenibilidad, Universidad Católica Boliviana “San Pablo”,
La Paz, Bolivia
3 Departamento de Ingeniería Medio Ambiente, Universidad Católica Boliviana “San Pablo”,
La Paz, Bolivia; marcoriosruiz7@gmail.com
4 Research Institute for Industrial, Radiophysical and Environmental Safety (ISIRYM), Alcoy Campus,
Universitat Politècnica de València, Plaza Ferrándiz y Carbonell, s/n, 03690 Alcoy, Spain;
jlora@iqn.upv.es (J.L.-G.); jitorreg@iqn.upv.es (J.I.T.-L.)
* Correspondence: valoia@upv.es
Abstract: One of the factors with the most significant impact due to pollution caused by mining
activities is water. Surface water resources are limited, and in many cases, they are the primary
water source for consumption; thus, its quality is a fundamental subject of study. The traditional
way of studying water quality is to measure parameters and compare the results with tables of
values established in the regulations. The quality of drinking water is characterized and controlled.
However, this traditional comparison method may be subjective and insufficient to classify water
quality as safe. Therefore, it is necessary to develop and complement the conventional monitoring,
linking physicochemical analysis with remote perception. The different variables analyzed can be
integrated and result in much more complete water quality indices, achieving the evolution of the
monitoring programs of the water quality of the surface bodies. This research combines remote
sensing with traditional monitoring to obtain a more robust and affordable indicator, resulting in a
study of the central water bodies of Milluni. The main finding—the alarming contamination in the
Milluni Chico and Milluni Grande lagoons—provides more accurate information to decision-makers
to improve water management in Bolivia.
Keywords: water quality monitoring; remote sensing; geographic information systems; safe water;
heavy metals
1. Introduction
The sustainable and affordable supply of clean, safe, and adequate quality water is
one of the world’s most challenging problems [1]. As is known, the relationship between
mining and sustainability is complex and controversial [2]. That is why many developing
countries whose main economic activity is mining are highly vulnerable to the negative
impacts on different environmental factors, especially water. According to the World
Health Organization, diseases associated with the lack of drinking water, adequate sanitation,
and hygiene continue to be one of the leading causes of mortality for millions of developing
countries [3]. The current water problem is reflected as a priority in Goal 6, “Clean Water and
Sanitation,” within the Sustainable Development Goals (SDG), which frame the 2030 agenda [4].
Water resources in developing regions of the world have high social and ecological
value, and many vulnerable human communities depend on these resources for their
https://www.mdpi.com/journal/resources
Resources 2022, 11, 36 2 of 16

livelihoods [5]. In this sense, the quality of surface water bodies represents an aspect of
great relevance that should be a fundamental object of study for its preservation [6,7].
There are various tools to analyze the state of the quality of water bodies; among these, a
reasonably conventional one that is frequently applied is the Water Quality Index (ICA).
This index (ICA) indicates the degree of contamination of a water body for a given use and
is related to the anthropic activities that cause it [8].
Likewise, there are emerging tools such as the Normalized Chlorophyll-a Index
(NDCI) [9–11]. Through methodologies related to remote sensing, this index focuses
on the measurement of the organic load in a body of water as an indicator of eutrophication
processes, in addition to the presence of a turbidity level, by identifying a specific pigment
(chlorophyll-a) [12–14]. Geographic information systems and remote sensing applied to the
management of water resources allow us to study various biophysical factors, such as the
delimitation of basins, identification of bodies of water, and their characterization, among
other fundamental aspects [15].
The marked water deficit that exists in the semi-arid areas of the Bolivian Altiplano
exposes the need to protect the water sources in the region [16]. The first step is to estimate
water quality in terms of spatial and temporal variability to use these resources sustain-
ably [17]. During and after mining, the environment is being negatively impacted [18].
This study takes the upper part of the Milluni micro-basin as the study area. The Milluni
lagoons, which come from natural snowy mountains, are very close to illegal, exploited,
and abandoned mines, which compromises the quality of their waters [19]. The main
water problem caused by mining operations is contamination with heavy metals at toxic
levels, particularly copper, lead, cadmium, zinc, and arsenic, which are naturally found
in traces in the natural environment [20,21]. This makes Milluni highly vulnerable to the
contamination of its water resources, which are natural drinking water sources that supply
two cities with a high population density in Bolivia.
This research aims to proposes a combined monitoring system to complement the
traditional monitoring designed for Milluni [22] with the remote sensing of pollutants. The
latter was obtained using remote sensing methodologies and programming on the “Google
Earth Engine” platform [23]. As a result, more information on water quality in Milluni
would be accessible to decision-makers in water management. This could help improve the
monitoring of water resources in Bolivia and worldwide.

2. Materials and Methods

In this section, a description of the study area is presented, which is followed by a
description of the methodology used in this study.

2.1. Description of the Study Area

Milluni is approximately 4600 m.a.s.l., it has an area of 40 km2 and is part of the
Altiplano basin system. This micro-basin presents extreme climatic conditions typical
of the region [24]. Mining activity developed in this area from 1940 to 1990. Although
mining activities stopped approximately 20 years ago, the impact of mining waste on water
quality remains a severe national environmental problem. Another issue that affects water
quality in this area is small-scale and illegal mining activities for which there is no precise
information [19]. There are four lagoons in the upper part of the Milluni micro-basin; their
names are Pata Khota lagoon, Jankho Khota lagoon, Milluni Chico lagoon, and Milluni
Grande lagoon; a brief detail of these lagoons is presented below [25].
• Pata Khota: A natural lagoon of irregular shape that receives water from the glacier of
the Huayna Potosí. It is located at 4665 m.a.s.l.
• Jankho Khota: Located at 4560 m.a.s.l., an irregular-shaped natural lagoon that receives
water from the Pata Khota lagoon.
• Milluni Chico: An artificial lagoon at an altitude of 4550 m.a.s.l., having an irregular
shape and receiving water from natural springs, Jankho Khota lagoon, and mines.
Resources 2022, 11, x FOR PEER REVIEW 3 of 16

• Milluni Chico: An artificial lagoon at an altitude of 4550 m.a.s.l., having an irregular

shape and receiving water from natural springs, Jankho Khota lagoon, and mines.
Resources 2022, 11, 36 3 of 16
This artificial lagoon aims to capture the acid drainage of the mines to prevent it from
entering the Milluni Grande lagoon.
• Milluni Grande: Located at 4530 m.a.s.l., the Milluni Grande lagoon receives effluents
Thisnatural
from artificial lagoonmines’
springs, aims todrainage,
capture theandacid
thedrainage of the lagoon,
Milluni Chico mines tospecifically
prevent it from
lo-
entering the Milluni Grande lagoon.
cated 2.7 km from this lagoon; it also receives water from the Jankho Khota lagoon
• through
MilluniaGrande: Located There
bypass system. at 4530ism.a.s.l.,
a waterthe Milluni
storage damGrande lagoon
for public receives
supply effluents
in this la-
from natural springs, mines’ drainage, and the Milluni Chico lagoon,
goon, which has a high probability of contamination by heavy metals due to its trib- specifically
located 2.7 km from this lagoon; it also receives water from the Jankho Khota lagoon
utaries.
through a bypass system. There is a water storage dam for public supply in this lagoon,
The upper part of the Milluni micro-basin is relevant because its lagoons are a source
which has a high probability of contamination by heavy metals due to its tributaries.
of water for the public supply. This area has a high probability of contamination by heavy
metals,The
whichupper
waspart of thein
exposed Milluni micro-basin
the study is relevant
in 2008 [19] and wasbecause
ratifiedits
in lagoons
2019 [26].are a source
This last
of water for the public supply. This area has a high probability of contamination by heavy
study carried out a review of historical data on water quality in the area, where the pres-
metals, which was exposed in the study in 2008 [19] and was ratified in 2019 [26]. This last
ence of heavy metals such as arsenic, cadmium, iron, zinc, and manganese was identified,
study carried out a review of historical data on water quality in the area, where the presence
which were found with concentrations higher than those values established in Bolivian
of heavy metals such as arsenic, cadmium, iron, zinc, and manganese was identified, which
Standard 512 for drinking water [27]. For this reason, the Milluni area must be closely
were found with concentrations higher than those values established in Bolivian Standard
monitored to avoid risk to public health. For this purpose, a monitoring program for sur-
512 for drinking water [27]. For this reason, the Milluni area must be closely monitored
face water bodies was designed, which considers the Milluni area’s specific characteristics
to avoid risk to public health. For this purpose, a monitoring program for surface water
[22].
bodies was designed, which considers the Milluni area’s specific characteristics [22].
The Water Quality Monitoring Program (WQMP) for Milluni was based on two in-
The Water Quality Monitoring Program (WQMP) for Milluni was based on two
ternational standards: the UNEP/WHO monitoring program design guide [28] and Boliv-
international standards: the UNEP/WHO monitoring program design guide [28] and
ian Norm NB, which adopts ISO 5667-1[29], the latter specific to bodies’ surface water.
Bolivian Norm NB, which adopts ISO 5667-1 [29], the latter specific to bodies’ surface
The objective
water. of the WQMP
The objective of theisWQMP
to determine the quality
is to determine ofquality
the the water of Milluni
of the water oftoMilluni
becometo
a become
control program
a control program that generates representative data and contributes to theman-
that generates representative data and contributes to the water water
agement of
management the of
place. There There
the place. were three
were designated monitoring
three designated points;points;
monitoring their locations can
their locations
becan
seen in Figure 1, and the image of each of them can be seen in Figure
be seen in Figure 1, and the image of each of them can be seen in Figure 2. 2.

Figure
Figure1. Distribution of the
1. Distribution of Milluni lagoons
the Milluni and location
lagoons of monitored
and location points. points.
of monitored Source: Own elabo-
Source: Own
ration, 2022. 2022.
elaboration,
(a) (b) (c)
Figure 2. Sampling points in Milluni. (a) Point 1: Pata Khota lagoon, beginning of the lagoon sys-
Resources 2022, 11, 36 4 of 16
tem; (b) Point 2: Laguna
Mulluni Chico, seriously impacted by mining; (c) Point 3: Laguna Milluni
Resources 2022, 11, x FOR PEER REVIEW 4 of 16
Grande, where the water storage dam that supplies two cities in Bolivia is located.

(a) (b) (c)

(a) (b) (c)
Figure 2. Sampling points in Milluni. (a) Point 1: Pata Khota lagoon, beginning of the lagoon sys-
Figure
tem; Sampling
(b)2.Point pointsMulluni
2: Laguna in Milluni. (a) seriously
Chico, Point 1: Pata Khota by
impacted lagoon, beginning
mining; (c) Point of3:
the lagoonMilluni
Laguna system;
Grande,
(b) Point where the water
2: Laguna storage
Mulluni Chico,dam that supplies
seriously impactedtwoby cities
mining;in Bolivia
(c) Pointis3:located.
Laguna Milluni Grande,
Point 1 (E: where the
592549; N: water storage
8197635) dam
has thatpurpose
the supplies two
of cities in Bolivia isthe
determining located.
reference condi-
Point 1 (E: 592549; N: 8197635) has the purpose of determining the reference condi-
tions in the watercourse system; for this reason, it isthe
located in the headwaters of the la-
tionsPoint
in the1 watercourse
(E: 592549; N:system;
8197635) has
for purpose
this reason, it of
is determining
located in thethe reference conditions
headwaters of the la-
goon system in thegoon
inPata Khotainlagoon.
thesystem
watercourse the system;
Point
Pata Khota
2lagoon.
(E:reason,
for this 589887;
Point
N:
it is 8193022)
located
2 (E: in the
589887;
seeks to identify
headwaters
N: 8193022) of the
seeks lagoon
to identify
any sign of deterioration
system in
in the
the quality
Pata Khota of the water
lagoon. in
Point the
2 (E:water
589887; system
N: due
8193022) to anthropo-
seeks
any sign of deterioration in the quality of the water in the water system due to anthropo- to identify any
sign
genic activities andgenic ofactivities
deterioration
is located inand inlocated
the quality
the isMilluni Chico of the water
lagoon. in the
Finally, water system
Point 3 (E:due to
589147;anthropogenic
in the Milluni Chico lagoon. Finally, Point 3 (E: 589147; N: N:
activities
8190424) aims to expose
8190424) and istolocated
whether
aims the
expose in
body the
of Milluni
whetherwater Chico
in
the body theoflagoon.
course
water in Finally,
system Point
meets
the course 3 (E:
systemthe589147;
desired
meets N:
the8190424)
desired
aims to
quality expose
standards whether
when the body
located inof
a water
storage in the
dam. course system meets the desired quality
quality standards when located in a storage dam.
standards when located in a storage dam.
2.2. Methodology
2.2. Methodology 2.2. Methodology
The study was carried out in 3 stages, as shown in Figure 3, and developed in the
The study was The study
carried out inwas3 carried
stages,out
as in 3 stages,
shown in as shown
Figure 3,inand
Figure 3, and developed
developed in the in the
following sections.
following sections.following sections.

Figure 3.
Figure The methodology
3. The methodology applied
applied in
in the
the study.
study.

2.2.1. Climatological Analysis

2.2.1. Climatological Analysis
The hydrological analysis is essential for monitoring the quality of water resources [30,31].
Figure 3. The methodologyThe hydrological
applied analysis is essential for monitoring the quality of water resources
in the study.
Through the climatological analysis of the area of interest, it will be possible to know the
[30,31]. Through the climatological analysis of the area of interest, it will be possible to
distribution of dry and wet seasons by month in a hydrological year (July–June). The above
know the distribution of dry and wet seasons by month in a hydrological year (July–June).
2.2.1. Climatological Analysis
is used to interpret the incidence of hydrological behavior on contamination levels in the
The above
central is used
bodies to interpret
of water the incidence
in the Milluni of hydrological
micro-basin. behavior onof
For the development contamination
this analysis,
levels in the central bodies of water
the following procedure was carried out: in the Milluni micro-basin. For the development of
this analysis, the following procedure was carried out:
1. Compilation of meteorological information from the Alto Achachicala station of SEN-
1. Compilation
HAMI for theofclimatological
meteorological information
analysis from the (mm)
[32]: precipitation Alto and
Achachicala station of
evapotranspiration
SENHAMI
(mm) with afor the climatological
return rate of 18 yearsanalysis [32]: in
(1999–2018), precipitation (mm)
the framework of aand evapotranspi-
hydrological year;
ration (mm) with a return rate of 18 years (1999–2018), in the framework of a hydro-
logical year;
Resources 2022, 11, 36 5 of 16

2. Statistical processing of the information collected to obtain total data and averages
per month of the precipitation and evapotranspiration parameters;
3. Generation of a graph with monthly data of total precipitation, mean, and total
evapotranspiration parameters;
4. Analysis of the results obtained to identify dry and wet seasons.

2.2.2. Study of Water Quality of the Milluni Lagoons

This section presents the two parts developed for the Milluni water quality study. The
first part is traditional monitoring, and the second is remote sensing of contaminants.

Traditional Field Monitoring

Fieldwork to monitor Milluni was completed in 2019 following the designed WQMP.
The monitoring frequency was determined according to the temporality of the study area.
The samplings were carried out three times in the dry season and three times in the rainy
season with intervals of 1 month between samples. Fundamental in situ control parameters
(pH, dissolved oxygen, conductivity, turbidity, and temperature) were measured with an
HQ40D—Hach Handheld Multimeter and Hach 2100Q Handheld Turbidimeter. Ex situ
parameters (heavy metals) were analyzed with an Agilent Model 7700x Inductively Coupled
Plasma Mass Spectrometer (ICP-MS). The sampling protocol adopted was ISO 5667-4:2016
Water quality—Sampling—Part 4: Guidance on sampling of lakes, natural and artificial [33].

Remote Sensing
This part applied sequential processes developed based on remote sensing through
the Google Earth Engine platform. Thanks to its adequate spatial resolution, the satellite
images selected for this purpose were captured by the Sentinel-2 satellite. The temporality
that was handled was monthly during 2019; it was fitted to the availability of images
captured by the satellite and the monitoring dates in the field.
To study the water quality in the central water bodies of the Milluni micro-basin, the
manipulation of satellite bands was carried out using scripts in Java language within the
Google Earth Engine platform. Two leading indicators were obtained: the Normalized
Water Index (NDWI) and the Normalized Chlorophyll-a Index (NDCl). It should be noted
that the NDCI is an indicator of the presence of eutrophication. The equations to determine
the values for the indices are presented below.
• NDWI. To obtain the pixels that represent water, the work was carried out with two
spectral bands, green and shortwave infrared (SWIR), following Equation (1).

green − SWIR
NDWI = (1)
green + SWIR
• NDCI. To obtain the pixels representing water, the work was completed with two
spectral bands, Red edge one and Red, following Equation (2).

Red edge1 − Red

NDCI = (2)
Red edge1 + Red
It was possible to identify the representative pixels of areas with water coverage and
their quality level. Figure 4 details the sequence of processes that have been followed in
this phase of the investigation.
Resources 2022, 11, x FOR PEER REVIEW 6 of 16
Resources 2022, 11, 36 6 of 16

Figure 4. Normalized Chlorophyll-a Index (NDCI) flow chart.

Figure 4. Normalized Chlorophyll-a Index (NDCI) flow chart.
The satellite images obtained from the previous process are presented in Section 3.2.2.
The satellitewill
The lagoons images
show obtained from
three colors the previous
related process arelevels
to the concentration presented in Section
determined for the
3.2.2. The lagoons
NDCI. will show
It is essential threethe
to analyze colors
threerelated tothe
levels of theindicator
concentration levels
to assess the determined
risk of eutroph-
for the NDCI.
ication It is essential
in each to analyze
lagoon. Low the threerepresented
concentration, levels of theby
indicator
yellow,to assesslittle
means the risk of of
chance
eutrophication in each lagoon. Low concentration, represented by yellow, means
eutrophication. The medium concentration implies a moderate risk of eutrophication with little
chance of eutrophication.
an orange The medium
coloration. Finally, concentration implies
a high concentration, presenteda moderate risk ofaeutroph-
in red, suggests high risk of
ication with an orange coloration. Finally, a high concentration, presented in red, suggests
eutrophication.
a high risk of eutrophication.
2.2.3. Analysis and Interpretation of Results
2.2.3. Analysis
The last and Interpretation
phase of Results
of this research interprets the correlation of the results obtained from
The last
remote phaseand
sensing of this
theresearch interprets
values obtained the correlation
through of the the
implementing results
firstobtained from
year of the Water
remote sensing
Quality and theProgram
Monitoring values obtained
(WQMP), through implementing
where in theparameters
situ and ex situ first year of the measured.
were Water
Quality Monitoring Program (WQMP), where in situ and ex situ parameters were meas-
3. Results
ured.
In this section, the results will be presented for the different stages of the study.
3. Results
3.1. Climatological Analysis
In this section, the results will be presented for the different stages of the study.
Information was collected from SENHAMI meteorological stations on precipitation
3.1. Climatological Analysis from 1999 to 2018 [32]. Table 1 below shows the average data for
and evapotranspiration
all months of the year in terms of total rainfall and total and mean evapotranspiration.
Information was collected from SENHAMI meteorological stations on precipitation
and evapotranspiration from 1999 to 2018 [32]. Table 1 below shows the average data for
all months of the year in terms of total rainfall and total and mean evapotranspiration.

Table 1. Average precipitation and evapotranspiration data from 1999 to 2018 for the Milluni area.

Total Precipitation Total Evapotranspiration Mean Evapotranspi-

Month
(mm) (mm) ration (mm)
July 7.54 61.62 30.81
August 12.10 72.26 36.13
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Table 1. Average precipitation and evapotranspiration data from 1999 to 2018 for the Milluni area.
September 25.16 78.05 39.03
Total Precipitation Total Evapotranspiration Mean Evapotranspiration
Month
October 42.92 93.12 46.56
(mm) (mm) (mm)
November
July 41.09
7.54 98.06
61.62 49.03
30.81
December
August 94.67
12.10 100.49
72.26 50.24
36.13
September 25.16 78.05 39.03
January
October
128.06
42.92
92.43
93.12
46.22
46.56
February
November 109.71
41.09 79.00
98.06 39.50
49.03
December 94.67 100.49 50.24
March 83.67 81.25 40.63
January 128.06 92.43 46.22
April
February 37.92
109.71 71.17
79.00 35.59
39.50
March
May 83.67
13.95 81.25
66.55 40.63
33.27
April 37.92 71.17 35.59
June
May 9.52
13.95 58.44
66.55 29.22
33.27
Note: Total precipitation and total evapotranspiration are referred to as the full water considered
June 9.52 58.44 29.22
through these
Note: Total climatic and
precipitation processes in a given period,
total evapotranspiration are such as atomonth
referred or water
as the full year. considered
Mean evapotranspira-
through these
climatic
tion processes
refers to the in a given data
average period, such as a from
calculated monthall
or the
year.data
Mean evapotranspiration
collected in a certainrefers to the
period; average
for data
example,
calculated from all the data collected in a certain period; for example, by collecting daily data, we can obtain an
by collecting daily data, we can obtain an average in a particular month. Source: Data from
average in a particular month. Source: Data from SENAMHI, 2021.
SENAMHI, 2021.

With the
With the data
data in
in Table
Table 1,
1, Figure
Figure 55 was
was made,
made, and
and this
this area’s
area’s dry
dry and
and humid
humid periods
periods
can be appreciated. On the one hand, the dry period starts in May and last until October.
can be appreciated. On the one hand, the dry period starts in May and last until October.
On the
On the other
other hand,
hand, the
the wet
wet period
period begins
begins inin November
November and
and ends
ends at
at the
the end
end of
of April.
April.

140

120

100
Volume (mm)

80

60

40

20

Total Precipitation TotalEvapotranspiration MediumEvapotranspiration

Figure
Figure 5.
5. Climatological
Climatological analysis.
analysis. Source:
Source: Own
Ownelaboration,
elaboration, 2022.
2022.

From
From the
the climatological
climatological analysis
analysis of the
the Milluni
Milluni area,
area, itit is
is observed
observed that
that the
the maximum
maximum
precipitation
precipitation peak
peakoccurs
occursduring
duringthethemonth
monthofof January.
January.This cancan
This cause thethe
cause lagoons to in-
lagoons to
crease volume
increase volume and thethe
and pollutant
pollutantdilution phenomenon
dilution phenomenon to tooccur naturally.
occur In In
naturally. addition, it
addition,
it should
should be be considered
considered thatthat
thethe driest
driest months
months are are
JuneJune
and and July.July.
In theIndry
the period,
dry period,
a con-a
concentration
centration of pollutants
of pollutants could
could occur
occur duedue
to to reducing
reducing the
the volumeofofwater
volume waterininthe
thelagoons.
lagoons.
The months of January,
The January,June,
June,and
andJuly
Julyshould
shouldbe becarefully
carefullyexamined
examinedlater when
later when interpreting
interpret-
the the
ing results.
results.

3.2. Study
3.2. Study of
of the
the Water
Water Quality
Quality of
of Milluni
Milluni Lagoons
Lagoons
This section presents the results of traditional
This section presents the results of monitoring where
traditional monitoring where physicochemical
physicochemical
control parameters
control parameters were
were measured
measured and and the
the results
results were
were obtained
obtained by
by remote
remote sensing
sensing of
of
contaminants.
contaminants.

3.2.1. Results of Traditional Field Monitoring

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3.2.1. Results
In the threeofpoints
Traditional Field
defined by Monitoring
the Water Quality Monitoring Program for the upper
part ofIn the three
Milluni, points
4 in defined parameters
situ control by the Waterand
Quality
33 exMonitoring
situ controlProgram for the
parameters upper
were mon-part
of Milluni,
itored. 4 in situ
The results control
of the parameters
in situ and
and ex situ 33 ex situ are
parameters control parameters
presented were monitored.
below.
The results of the in situ and ex situ parameters are presented below.
Results of In-Situ Parameters
Results of In-Situ Parameters
The pH and conductivity are related to the presence of metal ions and dissolved ox-
The pH and conductivity are related to the presence of metal ions and dissolved oxy-
ygen, and turbidity is directly associated with NDCI, which is an indicator of eutrophica-
gen, and turbidity is directly associated with NDCI, which is an indicator of eutrophication.
tion. As for the four parameters measured in situ, point 1 is the only one with values below
As for the four parameters measured in situ, point 1 is the only one with values below what
what is stipulated in the Bolivian standard 512 [27], indicating that it is free of contamina-
is stipulated in the Bolivian standard 512 [27], indicating that it is free of contamination.
tion. However, points 2 and 3 are negatively impacted by anthropogenic activities in the
However, points 2 and 3 are negatively impacted by anthropogenic activities in the area,
area, presenting acidic pH values, conductivities above 700 uS/cm, and high turbidity in
presenting acidic pH values, conductivities above 700 uS/cm, and high turbidity in January
January for point 2 and October for point 3. Figure 6 shows the measured values for the
for point 2 and October for point 3. Figure 6 shows the measured values for the in situ
in situ parameters at the three monitored points.
parameters at the three monitored points.

Figure 6. Parameter values in situ. Source: Own elaboration, 2022.

Figure 6. Parameter values in situ. Source: Own elaboration, 2022.
These four parameters will be correlated with the indicator of the presence of eutroph-
These
ication in four parameters
Section 3.3. will be correlated with the indicator of the presence of eu-
trophication in Section 3.3.
Results of Ex Situ Parameters
ResultsAtofthe
Ex same
Situ Parameters
time, 33 heavy metals were monitored. Seven metal ions were found with
concentrations outside
At the same time, 33 theheavy
current environmental
metals regulations:
were monitored. arsenic,
Seven metalcadmium,
ions wereiron, zinc,
found
manganese,
with nickel, outside
concentrations and aluminum. Some
the current of these metalsregulations:
environmental were also identified in previous
arsenic, cadmium,
studies
iron, zinc,[19,22]. In this
manganese, study,
nickel, only
and three of these
aluminum. Some will be analyzed
of these due also
metals were to their toxicity
identified
Resources 2022, 11, x FOR PEER REVIEW 9 of 16
Resources 2022, 11, 36 9 of 16

in previous studies [19,22]. In this study, only three of these will be analyzed due to their
toxicity (arsenic),
(arsenic), theirconcentration
their high high concentration
(zinc),(zinc), and persistence
and their their persistence
in theinarea
the(manganese).
area (man-
ganese). Figure 7 shows the attention of the three metals
Figure 7 shows the attention of the three metals analyzed. analyzed.

Figure 7. Parameter values ex situ. Source: Own elaboration, 2022.

Figure 7. Parameter values ex situ. Source: Own elaboration, 2022.
From the graphs presented above, we can see that point 1 continues to be the point
From heavy
without the graphs
metalpresented above, However,
contamination. we can seepoints
that point 1 continues
2 and to be the point
3 are contaminated by the
without heavystudied.
three metals metal contamination. However,
It should be noticed points
that point 2 is2the
and 3 are
most contaminated
affected. The threebymetals
the
three metals studied. It should be noticed that point 2 is the most affected. The three
were previously exposed. These parameters will also be correlated with the indicator of themetals
were previously
presence exposed. These
of eutrophication parameters
in Section 3.3. will also be correlated with the indicator of
the presence of eutrophication in Section 3.3.
3.2.2. Results of Remote Sensing
3.2.2. Results of Remote
The satellite images Sensing
selected for the study include the months of February, April, June,
The
July, satellite
August, images selected
September for January
2019, and the study include
2020. The the months
months of February,
of January, March,April,
May,
June, July,November,
October, August, September 2019, 2019
and December and January
could not2020. The months
be considered dueoftoJanuary,
the low March,
visibility
May, October,
caused by the November,
dense cloudsand December
of those months. 2019 could
Figure not be considered
8 presents the satellitedue to of
views the low
Milluni.
visibility caused by the dense clouds of those months. Figure 8 presents the satellite views
of Milluni.
Resources 2022, 11, x FOR PEER REVIEW 10 of 16
Resources 2022, 11, 36 10 of 16

Figure 8. Satellite views of the surface water bodies of Milluni. Source: Own elaboration, 2022.
Figure 8. Satellite views of the surface water bodies of Milluni. Source: Own elaboration, 2022.

From Figure 8, it can be seen that there are no high concentrations of NDCI in any of
the months studied, which shows that the risk of extreme eutrophication in the surface
water bodies of Milluni is low. However, the medium concentrations of the NDCI are
prevalent in some months, such as February, June, and August 2019, and January 2020.
Resources 2022, 11, x FOR PEER REVIEW
Resources 2022, 11, 36 11 of 16

climatological analysis, which would indicate that an increase or decrease in precip

From Figure 8, it can be seen that there are no high concentrations of NDCI in any of
would not affect the medium concentration prevalent in the Milluni lagoons. This
the months studied, which shows that the risk of extreme eutrophication in the surface
imply that time
water bodies does is
of Milluni not fully
low. influence
However, the presence
the medium of organic
concentrations pollutants
of the NDCI are in the M
lagoon system.
prevalent in some months, such as February, June, and August 2019, and January 2020.
February 2019 and January 2020 are months in the wet season according to the area’s
climatological
3.3. analysis,
Analysis and which would
Interpretation of indicate that an increase or decrease in precipitation
the Results
would not affect the medium concentration prevalent in the Milluni lagoons. This would
implyThe
thatcorrelation
time does notof theinfluence
fully resultstheof presence
the parameters
of organic monitored
pollutants in in
thesitu, ex situ, a
Milluni
NDCI
lagoon for each lagoon belonging to the upper part of the Milluni micro-basin is
system.
below.
3.3. Analysis and Interpretation of the Results
The correlation of the results of the parameters monitored in situ, ex situ, and the NDCI
3.3.1. Pata
for each Khota
lagoon Lagoon
belonging to the upper part of the Milluni micro-basin is shown below.
The Pata Khota Lagoon is the first lagoon of the water system, with waters c
3.3.1. Pata Khota Lagoon
from the natural glacier called Huayna Potosí. Monitoring point 1 was located in
The Pata Khota Lagoon is the first lagoon of the water system, with waters coming
goon. Point
from the 1 isglacier
natural the least polluted
called Huayna according to the contrast
Potosí. Monitoring point 1 wasof located
the in in
situ
thisand ex s
rameters with
lagoon. Point 1 isthe
theBolivian Regulation
least polluted according512. The
to the dynamics
contrast ofsitu
of the in theand
Pataex Khota
situ lago
based on the climatological analysis where wet and dry times are denoted. The o
parameters with the Bolivian Regulation 512. The dynamics of the Pata Khota lagoon are
basedbased
load on the on
climatological analysis where
what is registered wet and
by the NDCIdryistimes are denoted.
in the functionTheof organic
the season. F
load based on what is registered by the NDCI is in the function of the season. Figure 9
shows concentrations of NDCI in the lagoon.
shows concentrations of NDCI in the lagoon.

Figure 9. NDCI concentrations in the Pata Khota lagoon. Source: Own elaboration, 2022.
Figure 9. NDCI concentrations in the Pata Khota lagoon. Source: Own elaboration, 2022.
When comparing the predominant chlorophyll-a concentration in the Pata Khota
When
lagoon, whichcomparing
is the low one,thewith
predominant chlorophyll-a
the turbidity and concentration
dissolved oxygen in the Pata Kh
values, they showed
that there would not be a pollutant increasing the organic load
goon, which is the low one, with the turbidity and dissolved oxygen values, of the lagoon. On the they s
contrary, if the dissolved oxygen values decrease and the turbidity values rise, a eutrophi-
that there would not be a pollutant increasing the organic load of the lagoon. On t
cation process would occur in the Pata Khota lagoon, and the predominant concentration
trary, if the dissolved
of chlorophyll-a would beoxygen
medium values decrease
or high range. and the
In addition, theturbidity
monitoredvalues rise,
point 1 has a a eutro
tion process
neutral pH and would occur in the
a low conductivity Pata Khota
throughout lagoon,
the year andbeing
without the predominant concentra
affected by the dry
or wet season. This
chlorophyll-a wouldwould beindicate
medium the or
absence
highofrange.
metal ions, which is confirmed
In addition, by the point
the monitored
heavy metals’ low concentrations.
neutral pH and a low conductivity throughout the year without being affected by
In summary, the results of the monitoring and what can be seen in the satellite images
or wet season.
indicate ThisKhota
that the Pata would indicate
lagoon wouldthe
notabsence of metal
be negatively ions,
affected which is confirmed
by contamination
heavy metals’
from human low concentrations.
activities. The water in this body of surface water is of sufficient quality and
can be
In summary, theconsumption.
used for human results of the monitoring and what can be seen in the satellite
indicate that the Pata Khota lagoon would not be negatively affected by contam
from human activities. The water in this body of surface water is of sufficient qual
can be used for human consumption.
 Resources 2022, 11, 36 12 of 16

3.3.2. Jhanko Khota Lagoon

Resources 2022, 11, x FOR PEER REVIEW 1
This lagoon was not monitored because, visually, it is very similar to the first Pata
Khota lagoon. However, satellite images show that its water quality is different from the
first lagoon. In the months of January and February, belonging to the wet season according
This
to theexposes the existence
climatological of a polluting
analysis carried agent
out, the most thatdifferences
notable would be arealtering theThis
presented. water qua
exposes the existence of a polluting agent that would be altering the water
this lagoon, the source of which must be studied. Figure 10 reveals the concentratquality of this
lagoon, the source of which must be studied. Figure 10 reveals the concentrations of NDCI
NDCI in the second lagoon.
in the second lagoon.

Figure 10. NDCI concentrations in the Jhanko Khota lagoon. Source: Own elaboration, 2022.
Figure 10. NDCI concentrations in the Jhanko Khota lagoon. Source: Own elaboration, 2022
3.3.3. Milluni Chico Lagoon
3.3.3.The second
Milluni monitored
Chico point was located in the Milluni Chico lagoon. According to
Lagoon
the monitored parameters, point 2 is the most visually and analytically contaminated point.
This The secondtomonitored
is attributed the mining point
activitywas located
around it, andinthe
the MilluniofChico
indicators lagoon.
the presence of Accord
the monitored
heavy parameters,
metals corroborate it. Thepoint
Milluni2Chico
is the mosthas
lagoon visually and analytically
an acid character throughoutcontam
point. This is attributed to the mining activity around it, and the indicators
the year without being affected by the time. It also has conductivities above 700 uS/cm, of the pr
which suggests the presence of metal ions in the water. The lowest
of heavy metals corroborate it. The Milluni Chico lagoon has an acid character conductivities occur in throu
the season with the most significant precipitation, which would present the dilution effect
the year without being affected by the time. It also has conductivities above 700
of pollutants. The concentration of metal ions (As, Zn, and Mn) is outside the permissible
which
limits. suggests
Likewise, the presence
there of metal
is a decrease ions ininthe
in turbidity water.
May, which The lowest conductivities
is congruent with the o
the season
decline with
in the the most
average significant
concentration precipitation,
of the which would
Normalized Chlorophyll-A present
Index the dilution
in Milluni
Chico. Regarding the dissolved oxygen values, it can be said that
of pollutants. The concentration of metal ions (As, Zn, and Mn) is outside the perm they are acceptable,
with a tendency to decrease from May when the dry season begins. Figure 11 shows the
limits. Likewise, there is a decrease in turbidity in May, which is congruent with t
concentrations of NDCI in the lagoon.
cline Figure
in the11average concentration
reveals that of the
the Milluni Chico Normalized
lagoon has a moreChlorophyll-A
significant amount Index
of in M
Chico. Regarding the dissolved oxygen values, it can be said
chlorophyll-a in medium concentration in February. This decreases throughout the year,that they are acceptabl
awith a minimum
tendency peak in September.
to decrease from MayContrary
when the to the
drylow chlorophyll-a
season begins. concentration,
Figure 11 shows th
which has its most down season
centrations of NDCI in the lagoon. in February, it tends to rise throughout the year with a
maximum growing peak in September. It denotes that the dynamics of organic pollutants
in this lagoon are not related to the dry or wet season detected in Milluni.
 limits. Likewise, there is a decrease in turbidity in May, which is congruent with
cline in the average concentration of the Normalized Chlorophyll-A Index in M
Chico. Regarding the dissolved oxygen values, it can be said that they are acceptabl
a tendency to decrease from May when the dry season begins. Figure 11 shows t
Resources 2022, 11, 36 13 of 16
centrations of NDCI in the lagoon.

Resources 2022, 11, x FOR PEER REVIEW

maximum growing peak in September. It denotes that the dynamics of organic pol
in this lagoon are not related to the dry or wet season detected in Milluni.

3.3.4. Milluni Grande Lagoon

The third monitored point is located in the water storage dam located in the M
Figure 11. NDCI concentrations in the Milluni Chico lagoon. Source: Own elaboration, 2022.
Grande
Figure 11. lagoon. The water at this
NDCI concentrations point
in the should
Milluni Chicobelagoon.
of highSource:
quality, Ownconsidering
elaboration, that
2022it
from a natural glacier and is used for public supply. Milluni Grande has an acid ch
3.3.4. Milluni Grande Lagoon
Figure
throughout
The 11
thirdthe reveals
monitored thatisthe
year without
point Milluni
being
located the Chico
affected
in lagoon
bystorage
water the wetdamhas a more
orlocated
dry season.
in thesignificant
The conduc
Milluni amo
Grande lagoon.
chlorophyll-a
are above 1000inuS/cm.The water
medium at
Once this point
concentration should
again, the lowest be of high
in February. quality, considering
This decreases
conductivity that
occurs at throughout it
the time of m th
comes from a natural glacier and is used for public supply. Milluni Grande has an acid
with a minimum
nificant precipitation, peak in September.
denoting Contrary
the dilution effectto of the pollutants
low chlorophyll-a
present. This concen
is c
character throughout the year without being affected by the wet or dry season. The
which
orated has
withits
conductivities most
high
are down seasonduring
conductivities
above 1000 uS/cm. in February,
Once the it
the dry
again, tendsconductivity
season.
lowest to risethe
Both throughout
pH and
occurs thecondu
the
at the year
suggested
time of mostthe presence
significant of metaldenoting
precipitation, ions inthe thedilution
water,effect
which is pollutants
of the confirmed by the con
present.
tions of arsenic, zinc, and manganese outside the permissible limits. Inthethis sen
This is corroborated with high conductivities during the dry season. Both the pH and
conductivity suggested the presence of metal ions in the water, which is confirmed by the
verified that this water body would be negatively impacted by the mining in the a
concentrations of arsenic, zinc, and manganese outside the permissible limits. In this sense,
Regarding
it is verified turbidity,
that this water body it would
is observed that impacted
be negatively this decreases in thein rainy
by the mining the area.season a
creases from May, which exposes the effect of dilution of pollutants
Regarding turbidity, it is observed that this decreases in the rainy season and increases generated by t
in water
from May,in the dam.
which exposesThe
the dissolved oxygen
effect of dilution values at
of pollutants this point
generated by theare acceptable,
rise in water with
in the dam. The dissolved oxygen values at this point are acceptable,
dency to decrease from May when the dry season begins. Figure 12 presents the c with a tendency to
decrease from May when the dry season begins. Figure 12 presents the concentrations of
trations of NDCI in the last lagoon.
NDCI in the last lagoon.

Figure 12. NDCI concentrations in the Milluni Grande lagoon. Source: Own elaboration, 2022.
Figure 12. NDCI concentrations in the Milluni Grande lagoon. Source: Own elaboration, 20
Figure 12 shows that the low and medium concentrations of chlorophyll-a in Milluni
Grande vary throughout
Figure 12 shows the
thatyear
thewithout
low anda direct relationship
medium with the region’s
concentrations dry or wet
of chlorophyll-a in M
Grande vary throughout the year without a direct relationship with the region’s
wet season. This could suggest that the factor influencing the low and medium c
trations of chlorophyll-a is independent of the Milluni season.
Resources 2022, 11, 36 14 of 16

season. This could suggest that the factor influencing the low and medium concentrations
of chlorophyll-a is independent of the Milluni season.

4. Discussion
Many previous studies have shown that mining is one of the activities with the most
significant negative impact on the environment, especially on water. The ecological problem
generated by unsustainable mining has been seen worldwide, but developing countries
currently have the most significant vulnerabilities. This is due to many factors but in
particular to the lack of resources to carry out complete controls and to be able to identify
the sources and the degree of contamination.
Access to safe water is the current challenge for humanity, since it is directly linked
to public health. This initial study exposes the water quality of the lagoons located in the
upper part of the Milluni micro-basin. On the one hand, the first lagoon of the system
(P1) does not present contamination according to international water quality standards,
which implies that its water could be suitable for consumption after simple treatment. On
the other hand, the Milluni Chico (P2) and Milluni Grande (P3) lagoons show alarming
contamination. For P2 and P3, the measured pH values are around three and have high
conductivities. In addition, toxic heavy metals were found for both points with values
outside the permissible limits by the EPA and the WHO, exposing significant health risks if
the water is used for public supply. The problem of water with compromised quality must be
addressed in the first instance by reinforcing the monitoring of water bodies and subsequently
seeking treatment alternatives to guarantee access to safe water for the population.
Although the traditional monitoring program designed for Milluni is functional and
the results of its first year of implementation revealed the contamination of its lagoons,
there are parameters within the permitted limits that are not a problem. However, over
time, these parameters, heavy metals, could bioaccumulate and biomagnify within living
organisms, leading to an ecological or public health disaster. Thus, this study exposes a
future problem to be considered by decision-makers within water resources management.

5. Conclusions
The study presented the first approximation to the quality of surface water bodies
in the upper part of the Milluni micro basin, which is the area affected by ancient and
illegal mining. This is by correlating the results of the first year of the water quality
monitoring program with satellite images obtained through remote sensing methodologies
and programming on the “Google Earth Engine” platform. The four lagoons in the studied
water system presented different qualities. Based on this, it can be seen that anthropogenic
activities are not negatively impacting the first part, but they are affecting the second.
The part without contamination includes the first two lagoons, Pata Khota and Jhanco
Khota. Still, as an important finding, the quality of the Pata Khota and Jhanko Khota
lagoons do not have similar organic compositions (Figure 8). This would mean that a
control point should be added within the Jhanko Khota lagoon for future monitoring to
obtain adequate control of its quality. As for the most polluted part of the system, it was
observed that it is the Milluni Chico lagoon, and the Milluni Grande lagoon is receiving its
effluents. This compromises the water quality inside the water storage dam located at the
end of the Milluni Grande lagoon, presenting a risk to public health.
Finally, combining the remote sensing tool with traditional monitoring was a more
robust and affordable indicator of water quality. It is possible to constantly monitor surface
water bodies without requiring additional financial resources because several remote
sensing methodologies use resources such as free software or platforms. In addition, it was
seen that remote sensing served to observe the bodies of water in a given period in a global
manner, reducing the risk of error when evaluating the quality of surface water bodies that
depend on a single control point.
Future research related to the analysis of surface water quality should consider the
application of contaminant remote sensing methodologies as a mechanism to validate
Resources 2022, 11, 36 15 of 16

their results. In addition, monitoring programs looking for optimization could incorporate
remote sensing as was mentioned above; these methodologies would not represent extra
costs for the program but would help to carry out a constant and global control of surface
water bodies.

Author Contributions: Conceptualization, P.A.A.-T. and M.R.-R.; methodology, P.A.A.-T. and M.R.-
R.; software, M.R.-R.; validation, P.A.A.-T. and M.R.-R.; formal analysis, P.A.A.-T. and M.R.-R.;
investigation, P.A.A.-T. and M.R.-R.; resources, P.A.A.-T.; data curation, M.R.-R.; writing—original
draft preparation, P.A.A.-T., M.R.-R. and V.G.L.-I.-F.; essay—review and editing, P.A.A.-T., M.R.-
R. and V.G.L.-I.-F.; visualization, P.A.A.-T. and M.R.-R.; supervision, J.L.-G. and J.I.T.-L.; project
administration, J.L.-G. and J.I.T.-L.; funding acquisition, J.I.T.-L. and P.A.A.-T. All authors have read
and agreed to the published version of the manuscript.
Funding: This research was funded by The Universidad Católica Boliviana-Academic Unit of La Paz, and
PROGRAMA ADSIDEO-2018 Development Cooperation Center of the Universitat Politècnica de València.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: The research has been carried out with the support of the Center for Research in
Water, Energy and Sustainability (CINAES) of the Environmental Engineering career of the Universi-
dad Católica Boliviana—Sede LaPaz and The Project Management, Innovation and Sustainability
Research Center (PRINS), Alcoy Campus, Universitat Politècnica de València.
Conflicts of Interest: The authors declare no conflict of interest.

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