applied

sciences
Article
Geo-Accumulation Index of Manganese in Soils Due to Flooding
in Boac and Mogpog Rivers, Marinduque, Philippines with
Mining Disaster Exposure
Cris Edward F. Monjardin 1,2,3,4 , Delia B. Senoro 1,2,3,4, * , Jeffersen James M. Magbanlac 3 ,
Kevin Lawrence M. de Jesus 1,3,4 , Carlito B. Tabelin 5 and Pablito M. Natal 3,6

1 Doctorate Program in Environmental Engineering, School of Graduate Studies, Mapua University,

Manila 1002, Philippines; cefmonjardin@[Link] (C.E.F.M.);
klmdejesus@[Link] (K.L.M.d.J.)
2 School of Civil, Environmental and Geological Engineering, Mapua University, Manila 1002, Philippines
3 Resiliency and Sustainable Development Center, Yuchengco Innovation Center, Mapua University,
Manila 1002, Philippines; jjmmagbanlac@[Link] (J.J.M.M.); pabs0205@[Link] (P.M.N.)
4 School of Chemical, Biological, Materials Engineering and Sciences, Mapua University,
Manila 1002, Philippines
5 School of Minerals and Energy Resources Engineering, University of New South Wales,
Sydney 2052, Australia; [Link]@[Link]
6 Department of Civil Engineering, Marinduque State College, Boac 4900, Philippines
* Correspondence: dbsenoro@[Link]; Tel.: +63-(2)-8251-6622

Abstract: This paper presents the effects of flooding on the accumulation of manganese (Mn) in soils





 within proximity of the Boac and Mogpog rivers in Marinduque of The Philippines. Marinduque,
Citation: Monjardin, C.E.F.; Senoro, an island province in the Philippines, experienced two catastrophic tailings storage facility (TSF)
D.B.; Magbanlac, J.J.M.; de Jesus, failures in the 1990s that released sulfide-rich tailings into the two major rivers. The Philippines
K.L.M.; Tabelin, C.B.; Natal, P.M. experiences 21–23 typhoons every year, 11 of which pass thru Marinduque that causing inundation
Geo-Accumulation Index of of floodplain areas in the province. A flood hazard map developed using LiDAR DEM was utilized
Manganese in Soils Due to Flooding for the Boac and Mogpog rivers for an accurate representation of flooding events. A portable X-ray
in Boac and Mogpog Rivers, fluorescence spectrometer (pXRF) and a Hannah multi-parameter device were used for the on-site
Marinduque, Philippines with
analyses of Mn concentration and water physico-chemical properties, respectively. Spatial grid
Mining Disaster Exposure. Appl. Sci.
mapping with zonal statistics was employed for a comprehensive analysis of all the data collected
2022, 12, 3527. [Link]
and processed. Correlation analysis was carried out on Mn concentrations in soil and surface water,
10.3390/app12073527
electrical conductivity (EC), total dissolved solids (TDS), pH, temperature, curve number (CN), and
Academic Editors: Mariagrazia flood heights. The curve number indicates the runoff response characteristic of the Mogpog-Boac
D. Emilio and Maria Ragosta River basin. The results show that 40% of the total floodplain area of Boac and Mogpog were
Received: 22 February 2022 subjected to high hazards with flood heights above 1.5 m. The Mn content of soils had a statistically
Accepted: 26 March 2022 significant moderate positive correlation with flood height (r = 0.458) and a moderate negative
Published: 30 March 2022 correlation with pH (r = −0.438). This condition suggested that more extensive flooding promotes Mn
contamination of floodplain soils in the two rivers, the source of which includes the mobilization of
Publisher’s Note: MDPI stays neutral
Mn-bearing silt, sediments, and mine drainage from the abandoned mine pits and TSFs. There is also a
with regard to jurisdictional claims in
published maps and institutional affil-
strong negative correlation between pH and Mn concentrations in surface water, a relationship attributed
iations. to the solubilization of Mn-bearing precipitates based on geochemical modeling results. Using Muller’s
geo-accumulation index, 77.5% of the total floodplain of the two rivers was identified as “moderately
contaminated” with an average Mn soil content of 3.4% by weight (34,000 mg/kg). The Mn contamination
map of floodplain soils in the Mogpog and Boac rivers described in this study could guide relevant regional,
Copyright: © 2022 by the authors. national, and local government agencies in planning appropriate intervention, mitigation, remediation,
Licensee MDPI, Basel, Switzerland.
and rehabilitation strategies to limit human exposure to highly contaminated areas.
This article is an open access article
distributed under the terms and
Keywords: flood; heavy metal geo-accumulation; manganese contamination; spatial grid; zonal
conditions of the Creative Commons
statistics; mining disaster
Attribution (CC BY) license (https://
[Link]/licenses/by/
4.0/).

Appl. Sci. 2022, 12, 3527. [Link] [Link]

Appl. Sci. 2022, 12, 3527 2 of 22

1. Introduction
The Philippines is located within the pacific ring of fire, where earthquakes, vol-
canic eruptions, and typhoons occur frequently. Agence France-Presse [1] listed ten of
the deadliest natural disasters in the country, and 5 of them were typhoon and flood-
related. According to Tropical Cyclone Information, the country is struck by an average of
20 typhoons annually, 70% of which occur from July to October [2]. The Philippine Statistics
Authority [3] released a more comprehensive record of all the major disasters in the country
from 2010 to 2019, and the results showed flooding as the most frequently experienced
disaster at 387 occurrences that induced tremendous economic losses. Data and records
proved how flood-prone the country is, and this trend is expected to worsen in the future
considering the effects of climate change [4].
Marinduque is one of the most beautiful islands in the country, located in Region IV-B
of Luzon. The province’s total land area is 952.58 square kilometers and has a total popula-
tion of 239,207 as of 2020 [5]. The island is also often visited by typhoons, as presented in
Figure 1a. Figure 1b shows that many typhoons passed the province, particularly in May,
September, and December, suggesting that these are the months when typhoon-induced
flooding events are most likely to occur in the area.

Figure 1. Typhoon Occurrences in Marinduque Province (a) Typhoon Tracks and (b) Number of
typhoons that visited the island per month from 1948 to 2017.

Last 2014, Marinduque experienced one of the strongest typhoons to hit the island,
which caused the three major rivers on the island, the Sta Cruz, Boac, and Mogpog rivers,
to overflow. The maximum flood height in Boac was 2.52 m during typhoon Glenda last
July 2014 [6]. Another typhoon event was experienced in 2020, swelling the same rivers [7]
due to intense rainfall. With these frequent and disastrous flooding events in the area, a
government project entitled Phil-Lidar 1 created hazard maps to identify flood-prone areas
and predict how extensive flooding would be regarding different rainfall return periods.
The Boac and Mogpog rivers have a watershed area of 214 km2 and 58 km2 , respectively.
About 36.1% of the municipality of Boac, and 18.4% Mogpog, are prone to flooding [6].
Another dilemma of the people in the area is the contamination of surface water and
soils by hazardous heavy metals from the abandoned open mine pits and tailings storage
facilities (TSFs) located upstream of the two rivers. Marinduque province is home to the
porphyry copper-gold-molybdenum deposit, a 372-million-ton orebody containing 0.55%
copper, 0.004% molybdenum, 0.11 g/t gold, and 0.7 g/t silver [8]. Major mining activities
commenced in 1969 and ran smoothly until 1997. The mining operation stopped after
two mining incidents that occurred in 1993 and 1996. In December 1993, the company’s
Maguilaguila TSF embankment collapsed and flooded the town of Mogpog [9]. Because of
this incident, twenty-one barangays in Mogpog were buried in tailings and toxic floodwater.
The second disaster, one of the worst mining and environmental disasters in the Philippines,
Appl. Sci. 2022, 12, 3527 3 of 22

occurred on 24 March 1996 when the concrete drainage tunnel “plug” of the Tapian pit
gave way, releasing more than 1.6 million cubic meters of toxic mine tailings into the Boac
River [10]. The Tapian pit is a decommissioned open pit, which was repurposed by the
company as an in-pit TSF from 1989 for their San Antonio mine site.
These two mining disasters contaminated the two rivers and their surrounding en-
vironments with heavy metals via two pathways: (1) release and dispersion of sulfide
minerals like pyrite (FeS2 ), chalcopyrite (CuFeS2 ), galena (PbS), and sphalerite (ZnS) found
in the tailings; and (2) formation mine drainage contaminated with heavy metals in the
abandoned mine sites. Acid mine drainage (AMD) is formed when sulfide-rich minerals in
the TSFs, waste rock dumps, and open-pits are exposed to the atmosphere with a sufficient
amount of oxygen and water [11–13]. David and coworkers [14–16], for example, reported
that the elevated heavy metals concentrations of the Boac and Mogpog rivers could be
attributed to mine drainage from the abandoned Maguilaguila TSF located upstream of
both rivers. More recently, a previous study of the authors [17] detected eight heavy metals
such as chromium (Cr), manganese (Mn), iron (Fe), lead (Pb), cadmium (Cd), zinc (Zn),
nickel (Ni), and copper (Cu) exceeding the allowable environmental limits for soils. Among
them, Mn had the highest measured concentration at 68,620 mg/kg, a 65-fold increase from
1998 measurements (~1060 mg/kg) [14,17].
Manganese is naturally occurring in soils and is necessary for the normal nutrition
and development of plants. At high concentrations, however, it is toxic to plants and
humans [18,19]. Excessive Mn exposure of humans causes damage to the central ner-
vous system exhibiting similar symptoms as lead (Pb) poisoning [20,21]. Manganese is
also a problematic contaminant because of its high solubility, similar to Cu and Zn in
the pH range of surface and ground waters (i.e., pH 6–9) [22], which makes it highly
bioavailable. Bio-accumulation of Mn in food crops, for example, has been reported in
Marinduque with rice samples harvested in Boac and Mogpog containing around 16.0 and
7.12 mg/kg of Mn [23]. Previous studies have also reported elevated Mn concentrations in
the island not only in sediments [13] and soils [16] but also in crustaceans and tilapia [24],
string beans, sweet potatoes, eggplant, and bitter melon [25], and corals [14]. United
States Environmental Protection Agency (USEPA) stated that humans could only consume
0.14 mg/kg-day of Mn to avoid toxicity. Environmental challenges related to Mn contam-
ination will also become critical due to the clean energy transition and decarbonization
because Mn, together with lithium and cobalt, is an essential metal used in rechargeable
batteries essential to renewable energy systems and clean storage technologies [26].
Previous studies have shown that flooding is a major contributor to the increase
of heavy metals content in soils [27–30]. Han et al. [27] reported higher Mn levels in
the floodplain after a major flooding event caused by Hurricane Harvey. In Poland,
Ciesielczuk et al. [28] noted that river flooding events facilitated the migration of heavy
metals from sewage treatment plants, landfill leachates, and industrial areas into arable
soils. In areas with historic mining operations, soil contamination is exacerbated during
flooding events because of overflows from upstream mining areas [29]. Ponting et al. [30]
recently reviewed how flooding affects the mobility of heavy metals in floodplain soils and
noted five key parameters: (i) soil redox potential, (ii) pH, (iii) dissolved organic matter
(DOM), (iv) Fe and Mn hydroxides, and (v) sulfate and metal sulfides. Another factor
promoting heavy metal accumulation in soils in flooded areas is the soil infiltration capacity.
Antoniadis et al. [31] demonstrated the significant relationship between the permeability
of the soil and heavy metal accumulation by developing a centrifuge infiltration setup
to quantify metal mobility in soils. Also, the curve number was the parameter used in
the study to represent permeability. This is a dimensionless number that indicates runoff
response on land-based soil type and land use. These previous studies suggest that the
accumulation of Mn in the soils near the Boac and Mogpog rivers is likely promoted by
frequent typhoon-induced flooding events.
One way to determine the extent of soil contamination is to calculate pollution indices
by comparing heavy metal contents of the study area to a reference or “background” site.
Appl. Sci. 2022, 12, 3527 4 of 22

This approach is widely used in environmental studies to identify soil contamination in

areas impacted by artisanal and small-scale mining activities [32]. Among the pollution
indices, Muller’s geo-accumulation index (Igeo ) [33] is one of the most widely used and has
been applied for heavy metals contamination studies on sediments [34] and soils [35]. One
advantage of Igeo over other pollution indices is the introduction of a constant to normalize
the variances in background levels caused by site-specific geological variations [33]. Hence,
this study investigates the effects of flooding events on the accumulation of Mn in flood-
plain soils of the Boac and Mogpog rivers. Specifically, this work aims to (i) measure the
concentrations of Mn in surface water and floodplain soils of the Boac and Mogpog rivers,
(ii) determine the extent of contamination based on Muller’s geo-accumulation index, (iii)
apply spatial interpolation to predict soil contamination around the two rivers, and (iv)
identify the role of flooding on the accumulation of Mn using geographical information
system, correlation analysis, and geochemical modeling. Geo-accumulation indices could
provide an important basis for targeted and efficient rehabilitation and remediation plan-
ning [36]. Further, it aids the government in providing information to the people about the
problem they are facing. Meanwhile, spatial interpolation, a very reliable tool for estimating
pollutant coverage in surface water [37] and soils [38,39], was applied to expand the area of
coverage of the study. Therefore, a more reliable soil contamination assessment of the target
area could be assessed [40] by combining spatial interpolation and geo-accumulation index.

2. Materials and Methods

2.1. The Study Area
Marinduque, an island province in Region IV-B of Luzon, is known to have a “heart-
shaped” boundary. The province’s total land area is roughly 953 square kilometers, divided
into six municipalities: Boac, Mogpog, Sta. Cruz, Torrijos, Buenavista, and Gasan. The
focus of this study was on the Boac and Mogpog rivers, as shown in Figure 2. Annual
rainfall in the province varies from 1700 to 2500 mm [41]. Its climate is classified as type 3
without a very pronounced maximum rain period, and a dry season during December to
February or March to May.
The total length of the major rivers in Marinduque is approximately 178 km, 40.7% of
which are attributed to the Boac River (35.71 km) and Mogpog River (35.79 km). These two
rivers are the longest in the province and are known to overflow during heavy rainfall [6].
Marinduque is the site of two major TSF failure disasters in 1993 and 1996, considered
the most extensive and worst environmental disaster in the Philippine mining industry [42].
The mining operation was stopped after the disaster, but no rehabilitation of impacted
areas, including the TSFs and open pits, were implemented. The two abandoned TSFs,
i.e., Maguilaguila and Tapian pit, are connected to Boac and Mogpog rivers. Without
rehabilitation and management, these two TSFs located upstream of the rivers will continue
to contaminate areas downstream of the mining areas, especially when flooding events and
transport of mine drainage and tailings to the floodplains of the two rivers occur.
Appl. Sci. 2022, 12, 3527 5 of 22

Figure 2. A map of the Philippines and Marinduque superimposed with surface water and floodplain
soil sampling locations and location of Boac (red) and Mogpog (blue) rivers.

2.2. Sampling, Collection, and Storage of Surface Water and Soil Samples
Two media types were collected in the study: (i) surface waters, and (ii) soils. Samples
were collected across the island, but mostly from the Boac and Mogpog rivers. Data
collection was conducted in October when frequent flooding events occur [3]. Surface
water was collected using plastic bottles following the operating protocol developed by
USEPA No. SESDPROC-201-R4 [43]. Similarly, soil samples were collected based on USEPA
No. LSASDPROC-300-R4 and stored in plastic bags [44]. Physicochemical properties of
water samples like pH, electrical conductivity (EC), and total dissolved solutes (TDS) were
measured on-site using a HANNA Multiparameter device.
Soil and surface water samples were collected in 21 and 20 sampling points, respec-
tively. The sampling locations are illustrated in Figure 2 and were selected based on the
simulated flood hazard maps of the two rivers.

2.3. Flood Hazard Mapping and Analysis

There are many available methodologies and computer software for flood hazard
modeling [45–47] but what should be considered are the methods accepted and approved
by the government agency mandated to disseminate disaster data. In the Philippines, this
mandate falls under the Mines and Geosciences Bureau (MGB), an attached agency of
the Department of Environment and Natural Resources (DENR). The flood hazard map
developed in the study of Monjardin et al. [47] was approved by the MGB and endorsed
to the public for dissemination. Similarly, this study used a flood hazard map approved
and endorsed by the MGB to ensure data reliability. In the study of Phil-Lidar 1 entitled
flood hazard mapping of the Philippines led by the University of the Philippines, flood
hazard modeling of all the principal river basins in the country was done using LiDAR
data. LiDAR or Light Detection and Ranging uses light pulses (e.g., ultraviolet, visible, or
near-infrared) to image objects at very high precision by measuring the time it takes for the
reflections to be detected by the sensor [48]. Lidar data acquisition could be airborne or
land-based. Phil-Lidar 1 program produced a flood hazard map for the Boac and Mogpog
rivers with a lidar resolution of 1 × 1 m and vertical accuracy of ±15 cm [49]. Flood hazard
Appl. Sci. 2022, 12, 3527 6 of 22

maps were produced at different return periods regarding rainfall intensities that passed
through the area historically.

2.4. Heavy Metal Detection and Testing

Olympus Vanta X-ray Fluorescence (XRF-scanner) was used in this study to measure
in situ Mn concentrations in both surface water and soil. A portable XRF was selected in
this study to address the remoteness of the sampling locations, including the unavailability
of laboratories in the area with heavy metal testing capabilities. Portable XRF scanners have
been used in many studies as portable [50,51] and reliable equipment [52] for heavy metals
detection in water [50,51] and soil [53,54]. According to Sikora [54], XRF portable scanners
measure heavy metal contents of soils on par with other laboratory techniques, provided
that the samples were air-dried and sieved. Hence, soil samples in this study were dried
and sieved. Heavy metal concentrations were measured in the study using a portable XRF
(Figure A1a), which could detect thirty-five heavy metals in a water sample. Twenty water
samples were collected and placed in a #2 plastic zipper bag for detection and analysis
of metals concentration (Figure A1b). Twenty-one soil samples from different locations
were collected to represent the current heavy metal concentrations in floodplain soils in
the Boac and Mogpog rivers. These soils were collected and placed in #2 zipper plastic
bags, as shown in Figure A1c. The X-ray fluorescence spectrometer was calibrated prior to
analysis. The calibration was carried out using the Olympus XRF calibration blank in a #2
plastic zipper bag. Comparative results of the same samples were subjected to inductively
coupled plasma optical emission spectrometer (ICP-OES) analysis.

2.5. Spatial Interpolation, Analysis, and Flood Hazard Map

The data collected in the study, such as the physicochemical properties of surface
water, hydrogeologic parameters, flood hazard, and Mn concentration of both surface
water and soil, underwent spatial interpolation. Spatial interpolation has been used in
many environmental studies [55,56] to predict values of spatial phenomena in unsampled
locations [57]. In spatial interpolation, the inverse distance weighting (IDW) method is a
deterministic method widely used by geoscientists and geographers [58]. The IDW method
assumes that the properties of an unsampled location are the weighted average of known
values in the area, and the weights are inversely correlated to the distances between the
prediction location and sampled locations. IDW was used in this study as the interpolation
method to develop spatial data in the floodplains of the two rivers. The value at the
unknown location in the floodplain was considered as the weighted sum of the values of
“N” known points, as shown in Equation (1) [59].
N
o
{

CP = a wi Ci (1)
}

i=1

1
di
wi = N
(2)
o
{

1
a di
}

i=1

where CP denotes the unknown concentration data, Ci signifies the known data, N is
the number of sampling stations, wi is the weighting of individual stations, and di is the
distance from every station to the unknown point.
The flood hazard map used in this study was developed by Phil-Lidar 1 using Lidar
technology to accurately derive elevation data and define the floodplain terrain of the area.
Flood depths identified by the hazard map were then used to identify whether these events,
specifically flood heights, affect or stimulate Mn accumulation in soils near the two rivers.
Appl. Sci. 2022, 12, 3527 7 of 22

2.6. Correlation Analysis

Considering all the collected parameters related to the elevation of Mn concentration
on soils, each correlation was computed using R-studio. The following parameters were
included in the analysis: SW pH, electric conductivity (EC), total dissolved solids (TDS),
temperature, curve number (CN), flood heights (FH), and Mn concentration in surface water
and soils. Correlation coefficient values could range from −1 to +1. A negative correlation
indicates that variables are inversely related, while a positive correlation indicates a direct
relationship. A very strong correlation could be seen in R values between 0.9 and 1,
strong correlation for 0.7 < r < 0.89, moderate correlation 0.4 < r < 0.69, weak correlation
0.1 < r < 0.39 and negligible correlation in r values of 0 to 0.1 [60]. Correlation analysis is
critical to understanding the behavior of one particular parameter. This aids in identifying
critically important variables which others depend on [61]. Equation (3) shows how to
compute correlation coefficient where “N” is the number of data sets, y1 is the data set of
one parameter, y2 is the data set of another parameter, y1 and y2 were the mean values.

∑iN=1 (y1 − y1 )(y2 − y2 )

r= q (3)
2 2
∑iN=1 (y1 − y1 ) ∑iN=1 (y2 − y2 )

2.7. Muller’s Geo-Accumulation Index

One way to identify the degree of soil contamination would be using Muller’s geoac-
cumulation. This method uses the actual metal concentration compared to the ordinary or
so-called background concentration in the area of study. Igeo is computed using Equation (4).
The following values indicate the degree of contamination in soil: Igeo o f ≤ 0 no con-
tamination, 0 < Igeo ≤ 1 no contamination to moderately contaminated, 1 < Igeo ≤ 2
moderately contaminated, 2 < Igeo ≤ 3 moderately to heavily contaminated, 3 < Igeo ≤ 4
heavily contaminated, 4 < Igeo ≤ 5 heavily to extremely contaminated and Igeo o f ≥ 5 is
considered extremely contaminated [33].
 
Cn
Igeo = log2 (4)
1.5 × Bn

where Cn is the measured concentration of the element in the environment and Bn is the
geochemical background value in soil.
Shown in Figure 3 is the research diagram of the study. The data sampling was carried
out first, followed by testing its properties using the HANNA multi-parameter and XRF
scanner. Measured data then underwent interpolation to create spatial maps using the
IDW method. These spatial maps combined with other geospatial data such as CN. Flood
hazard maps were processed and then subjected to correlation analysis to determine the
degree of relationship of the identified parameters with the continuous elevation of Mn
concentration in soil. Geo-accumulation index was also computed to determine the level of
contamination in the area by comparing the current concentration with the background
concentration of Mn in the area.
 the IDW method. These spatial maps combined with other geospatial data such as CN.
Flood hazard maps were processed and then subjected to correlation analysis to deter-
mine the degree of relationship of the identified parameters with the continuous elevation
of Mn concentration in soil. Geo-accumulation index was also computed to determine the
Appl. Sci. 2022, 12, 3527 level of contamination in the area by comparing the current concentration with the8 ofback-
22
ground concentration of Mn in the area.

Contamination
Level 𝐼

Figure 3. Research
Figure Diagram.
3. Research Diagram.

3. Results
3. Results
3.1. Flood Hazard Map
3.1. Flood Hazard Map
The LiDAR DEM used in the flood hazard map has an accuracy of 1 × 1 m pixel size,
a verticalThe LiDAR
of ± 15 cm,DEM usedbased
and was in theonflood
5, 50,hazard
and 100 map hasreturn
years an accuracy
periods.ofA1 higher
× 1 m pixel size,
return
vertical of 15 cm,
period denotes a higher intensity of rainfall but has a low likelihood of happening [Link]-
a and was based on 5, 50, and 100 years return periods. A higher
turnstudy,
In this perioda denotes a higher
5-year return intensity
period of rainfall
was selected but hasthis
because a low
kindlikelihood
of event ofhashappening
a 20%
annually. In this study, a 5-year return period was selected because
probability of happening annually [62]. Shown in Figure 4 are areas colored yellow, this kind oforange,
event has
andared
20%that
probability
illustrateof happening
low, moderate, annually
and high [62]. Shownhazards,
flooding in Figure 4 are areasAreas
respectively. colored yellow,
within
loworange,
hazardand red
areas that illustrate
experienced low,height
a flood moderate,of upand high
to 0.5 m,flooding
while thosehazards,
in therespectively.
medium
Areas within low hazard areas experienced a flood height of up to
hazard category were flooded between 0.5 and 1.5 m. High hazard areas experienced flood 0.5 m, while those in
heights greater than 1.5 m. These flood hazard classifications were based on the capability
of people to mobilize for evacuation in scenarios with those flood heights.
Appl. Sci. 2022, 12, 3527 9 of 22

Figure 4. The flood hazard map of Boac and Mogpog rivers using LiDAR DEM.

3.2. Interpolation of Spatial Data

Shown in the Appendix A, Figures A2–A6 are the interpolated spatial map for each
parameter. This interpolation used IDW to identify values in unsampled areas. The
interpolation boundary was based on the floodplain only. Limiting the boundary of data
interpolation makes it more accurate, as fewer unsampled areas are considered and the
density of available data increases [63].

3.3. Spatial Analysis Using Grids and Zonal Statistics

Spatial analysis using grids was used in the study together with zonal statistics [64]
to create a comprehensive analysis of all data collected and processed. In the study
of Xu et al. [64], they identified the most appropriate grid size for their paper using 500 m,
1 km, 2 km, and 4 km. A 500 m grid size was considered to produce the best representation
of spatial data. However, this should still be based on the needs of the specific area under
study. In this specific study, since the aim is to create a spatial map where all the mentioned
parameters will be compared, a 500 m grid size was used, and properties enclosed in each
grid were then extracted using zonal statistics representing the data sets. Grid data has
many advantages over point data as grids capture all the data enclosed in each grid, unlike
point data that present properties only of a specific point [65]. Shown in Figure 5 is the grid
map created in GIS with a size of 500 m covering the flood plain area of Boac and Mogpog
rivers. The 599 grids were formed over a 150.25 km2 area. Spatial grid data were created for
the following parameters: pH, temperature, EC, TDS, Mn concentrations of surface water
(SW), curve number (CN), flood height, and the Mn content of soils are illustrated in the
Figure 6a–h. Data of each parameter per grid were extracted and used as data sets in this
study. This method helped the researchers simplify data analysis without compromising
data quality.
Appl. Sci. 2022, 12, 3527 10 of 22
Appl. Sci. 2022, 12, x FOR PEER REVIEW 10 of 21

Figure 5. Spatial Grid map

Figure 5. map of
of the
the floodplains
floodplainsof
ofBoac
Boacand
andMogpog
Mogpogrivers.
rivers.

(a) (b)

(c) (d)

Figure 6. Cont.
 Appl.
Appl. Sci.
Sci. 2022,
2022, 12,3527
12, x FOR PEER REVIEW 11 11
of of
21 22

(e) (f)

(g) (h)
Figure 6. Spatial Grid map of (a) pH SW, (b) EC SW, (c) TDS SW, (d) Temperature SW, (e) Curve
Figure 6. Spatial Grid map of (a) pH SW, (b) EC SW, (c) TDS SW, (d) Temperature SW, (e) Curve
Number, (f) Flood hazard map, (g) Mn concentration in SW and (h) Mn content of soils with a 500
Number, (f) Flood hazard map, (g) Mn concentration in SW and (h) Mn content of soils with a 500 m
m grid size.
grid size.
[Link]
3.4. Physicochemical Properties
Properties of
of Surface
Surface Water
Water
Table 1 summarizes the physico-chemical properties
Table 1 summarizes the physico-chemical properties of surface
of surface water
water collected
collected instudy.
in the the
study.
Table 1. Physicochemical properties of surface water.
Table 1. Physicochemical properties of surface water.
PNSDW 2017
PNSDW 2017 WHO
Parameter Max Min Mean SD Guideline WHO
Parameter Max Min Mean SD Guideline Guidelines
Value Guidelines
Value
Temperature 34.5 27.4 31.2 0.972 n/a n/a
pH 8.05 Temperature
5.70 34.5 27.4
7.20 31.2 0.364
0.972 n/a
6.5–8.5 n/a
6.5–9.2
EC (µS/cm) 2430 pH 424 8.05 5.70
763 7.20 187.780
0.364 6.5–8.5
n/a 6.5–9.2
1500
TDS (mg/L) 1360 EC (μS/cm)
216 2430 424
390 763 112.526
187.780 n/a
600 1500
1200
TDS (mg/L) 1360 216 390 112.526 600 1200
All surface water collected in the study was tested using the HANNA multi-parameter
All surface
to gather water collected
physicochemical in the study
properties wasas
of water tested using the
this affects HANNA
heavy metalmulti-param-
concentration
eter to gather physicochemical properties of water as this affects
in it [56]. These parameters could aid in the analysis to identify how Mn heavy metal concentra-in
concentration
tion in it [56]. These parameters could aid
surface water and soils accumulates with time. in the analysis to identify how Mn concentration
in surface
Thesewater and soils accumulates
physicochemical propertieswith
were time.
compared with the available guidelines set
by Philippine National Standards for drinking water (PNSDW) and the World Health
Organization (WHO). The pH of the surface water ranged from 5.7 to 8.05 with an average
of 7.2, which is within the PNSDW and WHO guidelines, but the results show some
Appl. Sci. 2022, 12, 3527 12 of 22

areas in the study with acidic pH values. Figure 6a shows the spatial distribution of pH
in surface water in the study area. Most of the regions in Mogpog have acidic surface
waters, especially near the abandoned mine pit and TSFs. Meanwhile, the highest EC
measured in the area was 2430 µS/cm while the minimum was 763 µS/cm with an average
of 424 µS/cm. Electric Conductivity was correlated to the salt content of water as the
water salinity hazard is measured using this parameter. Although the average EC was
less than the WHO guidelines, some locations in the river have high EC even though they
are far from the shore (Figure 6b). These high EC samples were concentrated close to the
abandoned pit and TSFs, suggesting that the higher EC values could be attributed to mine
drainage. The highest value of TDS, a measure of inorganic salts present in solution, was
1356 mg/L which exceeds the WHO guidelines. The lowest TDS was 216 mg/L with an
average value over the whole area of 390 mg/L, which is less than the environmental limit
(Figure 6c). The TDS was also highest in the areas where EC is highest, showing the direct
relationship between these two parameters. Lastly, the temperature doesn’t have any limits
identified by NSDW and WHO. The highest surface water temperature in the area was
34.5 ◦ C, while the lowest was 27.4 ◦ C, with a mean of 31.2 ◦ C (Figure 6d).

3.5. Curve Number

Curve number is the hydrologic soil cover correlated to hydrological condition, soil
type, and land cover [66]. It indicates the runoff response characteristic of the Mogpog-Boac
River basin in this study. Soil map and land cover were provided by NAMRIA. Each soil
type corresponds to a particular value of CN, which was used in this study. Curve number
ranges from 0 to 99, with higher values denoting lower permeabilities [67]. Figure 6e
illustrates the CN distribution in the floodplains of Boac and Mogpog rivers, and the results
suggest soils in the Boac area are more permeable than those in Mogpog. Curve numbers
between 30 and 68 make up 14.4% of the total floodplain, which are classified as soils
having significant permeabilities [67]. In contrast, 85.6% were in the range of 69 to 99,
representing areas with low permeability.

3.6. Manganese Concentration in Surface Water

There were eight heavy metals—Cd, Cr, Fe, Mn, Ni, Zn, Pb, and Cu—detected in the
samples, with Mn exhibiting the highest concentrations. The highest Mn concentration
measured was 3.24 mg/L, while the lowest was 0.004 mg/L (average of 0.273 mg/L)
(Figure 6g). Both the WHO and PNSDW guidelines put the allowable limit of Mn in water
at 0.4 mg/L, so even though the average was below the standard, some areas exhibited
more than 8-fold (3.24 mg/L) higher than the allowable limit. These values must be taken
into consideration because river water in Marinduque is used as a drinking water source
with only basic treatment incapable of removing Mn. Moreover, river water is used in
agriculture on the island, which could facilitate the bio-accumulation of this contaminant
into food crops [68].

3.7. Manganese Content of Soils

The results show that the highest concentration of Mn in soils was 5.9% (59,000 mg/kg)
with an average of 3.3% (33,000 mg/kg) and lowest concentration of 0.86% (8600 mg/kg)
(Figure 6h). Based on the map, it is highly likely that the abandoned open pit and TSFs
greatly contributed to the accumulation of Mn in soils downstream of the two rivers.

3.8. Data Correlation

In this paper, seven parameters were compared to one another, including the occurring
flood heights, in the two rivers to identify their correlation to the Mn content of soils. Table 2
shows the correlation table of each parameter, particularly flood height and Mn concentration.
Appl. Sci. 2022, 12, 3527 13 of 22

Table 2. Correlation analysis of EC, TDS, pH, and Temp. of SW, Mn in SW, CN, flood height with Mn
content of soils.

EC TDS pH Temp. Mn SW CN FH Mn Soil

EC 1 0.983 ** −0.524 ** 0.206 ** 0.258 ** 0.199 ** −0.216 ** 0.196 **
TDS 1 −0.471 ** 0.223 ** 0.231 ** 0.191 ** −0.186 ** 0.186 **
pH 1 −0.107 ** −0.704 ** −0.278 ** 0.195 ** −0.438 **
Temp. 1 −0.073 0.319 ** −0.148 ** −0.300 **
Mn SW 1 0.153 ** −0.155 ** 0.381 **
CN 1 −0.213 ** 0.142 **
FH 1 0.458 **
Mn Soil 1
** Correlation is significant at the 0.01 level (2-tailed). “FH” means flood height.

Table 2 presents the correlation matrix plot of each parameter with one another. Physic-
ochemical properties of water show the following correlation with the Mn concentration in
surface water: EC (r = 0.258), TDS (r = 0.231), pH (r = −0.704) and Temp (r = −0.073). Fur-
ther, Mn concentration in soils was inversely proportional with pH (r = −0.438) and Temp.
(r = −0.3). On the other hand, this parameter was positively correlated with EC (r = 0.196),
TDS (r = 0.186), Mn in SW (r = 0.381), CN (r = 0.142) and flood heights (r = 0.458). Based
on the statistical analysis, there is a significant and moderate positive correlation between
flood heights and the Mn content of soils. In contrast, a significant and moderate negative
correlation was observed between pH and Mn content of soils. There is also a significant and
strong negative correlation between pH and Mn concentration in surface water.

3.9. Geo-Accumulation Index

Figure 7 shows the Igeo map of Mn contamination in the study area and the percentages
of land and their degrees of Mn contamination. The majority of the land in the study area
is moderately contaminated (MC) with Mn (77.5% or 11,625 ha), while uncontaminated
land only constituted 1.67% or 250 ha. These results suggest a serious Mn contamination
problem in the areas near the Mogpog and Boac rivers, which are clearly affected by
flooding events in the area. On a good note, even though the open mine pit and TSFs were
abandoned more than two decades ago, the level of contamination was still at moderately
contaminated levels. Without well-planned rehabilitation and remediation interventions,
however, heavy metal contamination in the area will worsen with time as areas close to the
abandoned mine pit and TSFs are heavily contaminated (Figure 7).

Figure 7. Boac and Mogpog geo-accumulation index map of manganese.

Appl. Sci. 2022, 12, 3527 14 of 22

4. Discussion
Based on the results, using geographical information system and data sampling on-site
provided a deeper understanding of how flooding events affect the accumulation of Mn in
soils near the two rivers. The degree of Mn contamination in floodplain soils at the two
rivers was also measured and mapped using Igeo, and areas with the highest contamination
indices were identified. In areas with heavy Mn contamination, the Mn concentration in
floodplain soils reached 5.9% by weight (~59,000 mg/kg), an amount higher than that found
naturally in soils (40–900 mg/kg) [69] and exceeds permissible limits for agricultural use [70].
These maps could guide relevant national and local government agencies in plan-
ning appropriate mitigation and rehabilitation plans to limit human exposure to highly
contaminated areas along the Mogpog and Boac rivers.
A moderate positive correlation was observed between flood height and Mn content
of soils, suggesting that more extensive flooding promotes Mn contamination of floodplain
soils in the two rivers. The most likely explanation for this correlation is the mobilization of
Mn-bearing silt and sediments from the abandoned mine pits and TSFs and their transport
and re-deposition in downstream areas during flooding events. This is also consistent
with the moderate negative correlation between pH and Mn content in soils; that is, Mn
contamination originated from geologic materials with more acidic pH, like those found in
the abandoned mine pits and TSFs (Figure 6).
The most likely carriers of Mn during these flooding events are Fe-oxyhydroxides,
which are not only more stable than Mn-oxides (Figure 8) but also more abundant in
the soils. These deductions are consistent with the moderate correlation between Fe and
Mn in floodplain soils (r = 0.542) and are supported by the Mn geo-accumulation map
shown in Figure 7. Fe-oxyhydroxides like ferrihydrite can sequester Mn from solutions via
co-precipitation and adsorption reactions, both of which are well-known processes in envi-
ronmental studies [71]. It is also interesting to note the strong negative correlation between
pH and Mn concentration in surface water, a relationship attributed to the redissolution
of Mn-bearing minerals in soils like Mn(OH)3 and Hausmannite under acidic conditions,
as explained in Figure 8b. Curve number, on the other hand, is a dimensionless number
directly correlated to the permeability of the soil that pertains to its capability to absorb
water from the surface. In the case of the Boac and Mogpog rivers, where surface water
carries Mn, this plays a vital role in how the concentration of this element increases in
soil. Frequent flooding in the area provides a course for Mn to enter the soil and increase
its concentration to a point above permissible limits and background concentration. An
increase of concentration above its background concentration then promotes an increase in
the geoaccumulation level, which is what has happened in the Boac and Mogpog rivers
over time. There are some areas, such as the USA, where a community does not frequently
experience flooding, but after one major flooding event, a significant increase of heavy
metal concentration was observed in their area [27].
Appl. Sci. 2022, 12, 3527 15 of 22

Figure 8. (a) Log activity–pH diagram of Fe-H2 O System created using the Geochemist’s Workbench®
in equilibrium with atmospheric O2 (Fugacity = 0.2), and (b) Log activity–pH diagram of Mn-H2 O sys-
tem created using the Geochemist’s Workbench® in equilibrium with atmospheric O2 (Fugacity = 0.2).
The dotted and dashed lines represent the maximum and minimum values measured for Mn concentra-
tions and pH in surface water on-site, respectively.

5. Conclusions
The objective of this study was to investigate the effects of flooding on the accumu-
lation of Mn in the floodplain soils of the Boac and Mogpog rivers. The Inverse Distance
Weighting method was used as an interpolation technique to aid in the spatial analysis of
the area. Mn concentration in surface water ranged from 0.004–3.33 mg/L with an average
of 0.273 mg/L. The average Mn concentration of surface water in the area is still within the
standards (0.4 mg/L). However, some surface water samples recorded Mn concentration
beyond the reference guideline limits of the USEPA and the International Labour Organiza-
tion. Mn concentration in soil ranged from 8584–59,206 mg/kg, above the WHO allowable
limit of 4000 mg/kg.
Marinduque, like other areas in the Luzon Island and other parts of the country,
experiences extreme typhoon events that cause floods in the area, especially in the Boac
and Mogpog rivers. We discovered that 40% of the total area considered in the study is
subject to high hazards, experiencing flood heights of above 1.5 m based on the available
Lidar data.
Correlation analysis and geochemical modeling identified flood height to have a
moderate positive correlation with Mn accumulation in the soil, while pH had a moderate
negative correlation. This indicates that flooding carries more Mn-bearing materials from
the abandoned mine pit and TSFs to floodplains downstream. The correlation result of
pH emphasized the effect of acidic mine drainage from the abandoned mine site. These
contribute to higher geo-accumulation of Mn with time. Finally, a strong positive-negative
correlation between pH and Mn concentrations in surface water, a relationship to be
expected because Mn-bearing precipitates like Mn(OH)3 and Hausmannite become more
soluble under acidic conditions.
Contamination levels of Mn in floodplain soils of the two rivers were identified us-
ing Muller’s geo-accumulation index. The abandoned open pit and TSFs for the last
two decades have moderately contaminated 77.5% of the total area (1 < Igeo ≤ 2) while
those close to the abandoned open pit and TSFs were moderately to heavily contaminated
(2 < Igeo ≤ 3). These results suggest that intervention, remediation, and rehabilitation
strategies should be carried out by the national and local governments immediately, espe-
Appl. Sci. 2022, 12, 3527 16 of 22

cially around the abandoned mine pit and TSF. This could limit the further spread of heavy
metal contaminants downstream of the Mogpog and Boac rivers.

Author Contributions: Conceptualization, D.B.S.; methodology, D.B.S. and C.E.F.M.; software,

C.E.F.M.; validation, J.J.M.M., P.M.N. and K.L.M.d.J.; formal analysis, P.M.N., C.E.F.M. and C.B.T.;
investigation, D.B.S., P.M.N., J.J.M.M. and C.E.F.M.; resources, D.B.S.; data curation, D.B.S., C.E.F.M.
and J.J.M.M.; writing—original draft preparation, D.B.S., C.B.T. and C.E.F.M.; writing—review and
editing, D.B.S., C.B.T. and K.L.M.d.J.; visualization, C.E.F.M. and C.B.T.; supervision, D.B.S.; project
administration, D.B.S.; funding acquisition, D.B.S. All authors have read and agreed to the published
version of the manuscript.
Funding: This research was funded by the Department of Science and Technology-Philippine Council
for Health Research and Development (DOST-PCHRD), D-HIVE 4B Capital Research Project.
Data Availability Statement: All data are contained in the manuscript.
Acknowledgments: This is to acknowledge the support-in-kind of Mapua University, Marinduque
Local Government Units, University of the Philippines LiDAR Portal for Archiving and Distribution,
Marinduque State College, and the National Mapping and Resource Information Authority.
Conflicts of Interest: The authors declare no conflict of interest.

Appendix A

Figure A1. Setup of heavy metal testing of surface water and soil using the portable XRF. (a) is the
portable XRF, (b) water samples, and (c) soil samples.
Appl. Sci. 2022, 12, 3527 17 of 22

Figure A2. Spatial map for pH.

Figure A3. Spatial Map for TDS.

Appl. Sci. 2022, 12, 3527 18 of 22

Figure A4. Spatial map for EC.

Figure A5. Spatial map for Temperature.

Appl. Sci. 2022, 12, 3527 19 of 22
Figure A5. Spatial map for Temperature.

FigureA6.
Figure A6. Spatial
Spatial mapmap forconcentration
for Mn Mn concentration
in Surfacein Surface
Water. Water.

Figure A7. Spatial map for Mn concentration in Soil.

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