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Modeling Earth Systems and Environment (2023) 9:4539–4555

https://doi.org/10.1007/s40808-023-01753-y

ORIGINAL ARTICLE

A Monte Carlo simulation approach for the assessment of health risk


from NO−3 ‑N perturbation in groundwater
George Y. Afrifa1 · Theophilus Ansah‑Narh2 · Kwabina Ibrahim1 · Yvonne S. A. Loh1 · Patrick A. Sakyi1 ·
Larry Pax Chegbeleh1 · Sandow M. Yidana1

Received: 14 November 2022 / Accepted: 18 January 2023 / Published online: 21 March 2023
© The Author(s), under exclusive licence to Springer Nature Switzerland AG 2023

Abstract
As a prerequisite towards sustainable management of an aquifer system, it is critical to reveal and quantify the relationship
between NO−3 –N and human health in order to delineate health-risk zones. The various sources of NO−3 –N in an environ-
ment as well as the interaction of natural and anthropogenic processes, present considerable obstacles when considering
a technique to estimate health risk. Another constraint on health risk estimation is choosing right technique. This research
applied deterministic and MC approaches coupled with finite mixture model to evaluate the sources and concentrations
of NO−3 –N in groundwater, and appraise the hazard risks associated with various exposure groups in the Densu Basin in
Southern Ghana. The Monte Carlo approach was applied to the data with due cognizance of the various identified sources
of NO−3 –N, and a hypothetical single source (HSS). The results suggest that the probability of risk for identified NO−3 –N
sources (human-induced) fall within the ranges of 0.16-−0.39, 0.15-−0.30, and 0.12-−0.24 respectively for infants, children,
and adults. The MC technique applied to the HSS concentration recorded a relatively low probability of risk, presenting
0.07-−0.17, 0.02-−0.05, and 0.01-−0.04 for infants, children, and adults respectively. It, therefore, goes without saying that
the health hazard caused by the human-induced sources of NO−3 –N on exposure groups is comparatively higher than the
single sources. The MC simulation based on identified NO−3 –N sources appears to have performed better compared to the
HSS and the deterministic approach.

Keywords Monte Carlo simulation · Anthropogenic activities · Groundwater nitrate · Health risk assessment ·
Non-carcinogenic · Densu Basin

Introduction the hydrological system (through industrial, municipal, and


agricultural practices). The effect of this problem can have a
Naturally, groundwater is fresher and more unperturbed to significant impact on human health, as well as the ecosystem
drink without prior treatment than surface water because (Li et al 2021).
the topsoil serves as an environmental filter for discarding In Ghana, the Densu river basin has been cited as one of
undesirable particles (both solid and gaseous) from air and the catchments with variable pollution sources (Commis-
water (Singer and Sojka 2002; Parr et al 1992), hence, mak- sion et al 2007). Earlier studies (Attua et al 2014; Amoako
ing groundwater free of microorganisms. However, ground- et al 2011; Abass et al 2010; Fianko et al 2010; Tay and
water can become contaminated through naturally occur- Kortatsi 2008) have reported high NO−3 –N concentrations of
ring processes (e.g., geogenic, natural disasters, climate groundwater in certain parts of the basin and attributed this
change, soil/matrix) and/or anthropogenic activities with to different sources. For instance, Tay and Kortatsi (2008)
reported that NO−3 –N concentration in some parts of the
* Yvonne S. A. Loh basin falls between the interval (0.1, 106) mg/L and traced
sloh@ug.edu.gh the concentration level to mainly the use of ammonia and
1
compost in the farming communities. Amoako et al (2011)
Department of Earth Science, University of Ghana, Legon,
also recorded groundwater NO−3 –N as high as 34 mg/L and
P.O. Box LG 25, Accra, Ghana
2
ascribed it to the use of fertilizers. These high levels of
Ghana Space Science and Technology Institute, Ghana
NO−3 –N concentration in groundwater of the Densu basin
Atomic Energy Commission, P. O. Box LG 80, Accra, Ghana

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are of grave concern as several studies have linked long- are expected to change in order to capture the intrinsic
term exposure of NO−3 –N to various human diseases such as behaviour of the contamination.
methemoglobinemia1 (also known as a blue baby syndrome) As a prerequisite towards sustainable management of an
(Gao et al 2020; Maghanga et al 2013; Gulis et al 2002), aquifer system, it is critical to reveal and quantify the rela-
gastric cancer (Majumdar and Gupta 2000; Rademacher tionship between NO−3 –N and human health, and for delin-
et al 1992), thyroid disorder diabetes (Fabro et al 2015; Wu eating health-risk zones, especially in rapidly developing
et al 2017; Hord 2011), and spontaneous abortions (Almasri areas like the Densu Basin. The Monte Carlo simulation
2007; Dan-Hassan et al 2012). technique will be employed in this study to examine the
Due to the human health risk associated with the con- risk levels for infants, children, and adults while taking into
sumption of groundwater with high NO−3 –N concentration, account the following scenarios:
international bodies such as the US Environmental Protec-
tion Agency (USEPA), Global Environment Monitoring Sys- i. consider a deterministic approach for measuring the
tem Database, and World Health Organization have set out a health risk;
contaminant level of 10 mg∕L (Cotruvo 2017; Shamsuddin ii. assume that the observed NO−3 –N data distribution is
et al 2016; He et al 2011). These agencies have also outlined symmetric (thus, originating from a hypothetical single
environmental health hazards that are caused by deleterious source) and then evaluate the risk level using different
elements like NO−3 –N. So far, research on human health risks confidence intervals (CI) (for 1𝜎 , 2𝜎 and 3𝜎),
in the Densu basin (Fianko et al 2011) has solely focused on iii. take into account that the NO−3 –N dataset is multi-
a deterministic approach where the outcome of an event is modal and also estimate the risk level on the same
directly computed from a fixed model. Meanwhile, in deter- confidence intervals as in (ii).
ministic models, it is impractical to model different combi- iv. perform a comparative analysis of these schemes.
nations of values for different inputs to observe the effects of
different cases. There is also the possibility to overestimate To achieve the scenario listed in (iii), we propose an unsu-
or underestimate the potential risk since the model does not pervised algorithm to learn the finite mixture component in
quantify the likelihood of each outcome. Recent studies by the NO−3 –N dataset. This technique is capable of selecting
Mukherjee et al (2019, 2020) in risk assessments indicate the components as well as the relevant input parameters nec-
that using deterministic techniques to perform sensitivity essary for the Monte Carlo simulation. The findings of this
analysis, becomes difficult to determine which factors have study would serve as a repository of NO−3 –N information,
the greatest influence on the result. To overcome these draw- that can be counted on to manage the aquifer sustainably.
backs and account for the potential risk, we adopt the Monte
Carlo method in this work. During the Monte Carlo simula-
tion process, a random sequence of events is drawn from Study area
an appropriate probability distribution of a given variable.
The results are gathered and analysed statistically in order Location and climate
to arrive at a probability distribution of the potential out-
comes of the work and to estimate the various risk measures. The Densu River Basin is located in the southern part of
The technique has been applied in numerous types of risk Ghana, between latitude 5◦ 30′–6◦ 20′ N and longitude 0◦ 10′
analysis such as investment appraisal (Platon and Constan- –0◦ 35′ W (refer to Fig. 1). Details of the morphology of the
tinescu 2014; Hacura et al 2001), seismic hazard assessment basin have been copiously captured by Kusimi et al (2008);
(Musson 2000), and even human health risk assessment (Liu Amoako et al (2011); Commission et al (2007). The North-
et al 2022; Yang et al 2022; Jiang et al 2021; Ramesh et al ern part of the basin is found within the Eastern Region of
2021; Kaur et al 2020; Mukherjee et al 2019). The previous Ghana which covers about 72%. Additionally, 5% falls within
works on health risk assessment considered the probabil- the Central Region whiles the remaining 23% falls within the
ity distribution of groundwater pollution to be symmetric Greater Accra Region (Nyamekye et al 2016). The Densu
which means the contamination is coming from a common River Basin is characterized by a bi-modal climatic and
source. The situation is however not the same when the con- rainfall regime. The upper part of the basin is described by
tamination is coming from heterogeneous sources which is the wet semi-equatorial climate, while the dry equatorial
exactly what we are investigating in this research. In this climate is experienced in the south-eastern portion of the
case, the input parameters for the Monte Carlo simulation basin (Dickson et al 1988; Tay and Kortatsi 2008). Details
of the climatic conditions in the basin are well documented
(Commission et al 2007; Amoako et al 2011; Nyamekye et al
1
This disease is the result of a reduction in the capacity of blood to 2016; Abass et al 2010).
transmit oxygen in nurslings who are mostly under 6 months of age.

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Modeling Earth Systems and Environment (2023) 9:4539–4555 4541

.00000
760000.000000 770000.000000 780000.000000 790000.000000 800000.000000 810000.000000 820000.000000 830000.000000 840000.000000

700000
B
A

Ü
ills

Vo
.000000

.000000
aH
Ate Basin

lta
690000

690000
wa

Ba
si
EAST AKIM
im

n
.000000

.000000
Bir
680000

680000
NEW JUABEN
.000000

.000000
SUHUM
670000

670000
.000000

.000000
AKWAPEM NORTH
660000

660000
Legend
AYENSUANO
AKWAPEM SOUTH Sampling location
Ayensu Basin
.000000

.000000
Burkina Faso
C

Republic of Benin
Rivers
650000

650000
Geology
NSAWAM ADOAGYIRI
.000000

.000000
UPPER WEST AKIM Dyke (Mesozoic)
640000

640000
in
Accraian Group

Republic of Togo
Bas

GA WEST
.000000

.000000
Voltaian Supergroup
Okradu Basin

Cote D'Voire
630000

630000
aw

Togo Structural Unit


Od

GA SOUTH
Eburnean Plutonic Suite
.000000

.000000
AWUTU SENYA WEST GA CENTRAL
620000

620000
'Tamnean' Plutonic Suite

Tarkwaian Group
.000000

.000000
610000

610000
Birimian Supergroup
0 5 10 20 km Faults/lineaments Gulf of Guinea
760000 770000 780000 790000 800000 810000 820000 830000 840000
.000000 .000000 .000000 .000000 .000000 .000000 .000000 .000000 .000000

Fig. 1  A geological map of the catchment area showing the sampling points

Land use the Birimain Supergroup. At the southern tip of the study
area outcrops the sedimentary rocks of the Accraian (Fig. 1).
The area is noted for the cultivation of both cash and food Tamnean Plutonic Suite covers about 70% of the catchment
crops. Maize, cassava, yam, plantain, banana, and cocoyam with the other seven lithologies occupying 30% of the catch-
are examples of food crops produced in the area. Other ment area. The granite complex is composed of a sequence
cash crops cultivated in the area include oil palm, pine- of granitic to quartz-diorite gneisses. The gneissic rocks are
apple, cocoa, papaya, mango, and orange (Amoako et al interrupted by both acidic and basic igneous rocks, which
2011), vegetable farming also takes place along the Densu include white and pink pegmatite, aplites, granodiorite and
River banks (Afful et al 2010). One of the fastest-growing dykes (Abass et al 2010). The dykes trend southwest to the
activities is the building of housing units, animal farming, northeast of the basin within the Tamnean Plutonic Suite.
sand winning, and salt mining. These ongoing events have The granite composite is made up of a group of assorted
severely exhausted the vegetative shelter of the basin, lead- rocks deposited in the north-western part of the Akwapim
ing to serious implications of flooding, excessive evapora- North and portions of Akwapim South Districts (Amoako
tion, soil erosion, and siltation of the river channel. et al 2011). The bulk of the granite is characterized by mus-
covite quartz, albite and orthoclase. The texture of the gran-
Geology and hydrogeology ite ranges from well-sorted to moderate-grained, with strati-
fied biotite quartz diorite gneiss to hornblende-quartz diorite
The catchment is underlain primarily by the Birimian Super- gneiss (Adomako et al 2011). Rocks of the Birimian meta-
group, however, its northwestern, northeastern, and south- sediments underlie the north-western parts of the landscape
eastern boundaries are occupied by the Tarkwaian Super- (Junner 1940; Yidana et al 2018). They are predominantly
group, Voltaian Supergroup, and the Togo Structural Unit of chemical sediments, greywackes, phyllites, argillites,
respectively (Fig. 1). The Birimian Supergroup includes the dacitic volcaniclastics intercalated with metamorphosed tuff,
Tamnean Plutonic Suite, Birimian metasedimentary rocks, and lava. The lavas are principally composed of tholeiitic
Eburnean and Plutonic Suite. Mafic dyke swarms cut across basalts with inserted volcaniclastics, pyroclastic lavas, and

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hypabyssal basic thrusting inward. Eburnean plutonic suite the suggestion that aquifer units may be uninterrupted or
also comprises undifferentiated granitoids such as granites, disjointed, depending on the predominant geological for-
granodiorites and gneiss. The Tarkwaian Supergroup is a mation in the area (Ganyaglo et al 2012). The groundwater
Proterozoic supracrustal system overlying the Birimian. It occurrence in the fractured zone aquifers within the basin
trends in the north-western part of the basin and is made up is largely controlled by the amount of splintering and the
of mainly sandstones, conglomerates, argillites, arkoses, and nature of groundwater accumulation (Commission et al
detrital sediment. The Togo Structural Unit (also known as 2007). Consequently, the aquifer materials do not exhibit
the Akwapim-Togo Range) is located in the south-eastern constant homogeneous physical characteristics. Examination
parts. It is a highly pleated and interconnected geological of borehole data in the geological terrain of the Tamnean
material. Marbles, sandstones, quartz schists, quartzites, Plutonic suite, Birimian Supergroup, and Togo Structural
shales, phyllites, and some talc mica schists are predomi- Unit (see Fig. 1) suggests many variations in the borehole
nant in the Togo Structural Unit (Amoako et al 2011; Yidana depth in the ranges [9.1-−103.0, 23.0-−40.0, 28.0-−97.0] m,
et al 2018). The Votaian Supergroup covers about 4% of the weathered zone thickness ranges from [1 –32, 5–27, 3–36]
total land mass of the basin and trends from the southwest m, respectively. Static water level for various formations in
through the west to northwest of the basin. It is underlain by the basin range [0.1-−13.5, 0.8-−16.9, 1.1-−17.8] m, and
basal sandstones consisting mainly of quartz-sandstone, peb- borehole yield [0.1–30, 0.7-−9.0, 0.6-−6.0] m (Commission
bly grits, shale, mudstone, siltstone, sandstone, arkose, and et al 2007; Yidana et al 2018)
conglomerate (Dapaah-Siakwan and Gyau-Boakye 2000).
The Accraian rocks are made up of quartz grits gently folded
sandstones, shales and mudstones. It occurs along the coast- Methods and material
line within the southeastern part of Ghana. The various rock
types in the basin lack primary porosities and permeabilities. Data acquisition
This means it has very minute pore spaces existing between
the grains of the rocks and is dominated by little or no prin- Water samples were collected from boreholes and hand-dug
cipal porosity and permeability. Thus, the original porosity wells in the catchment which is mainly for domestic use. A
is less and groundwater occurrence is a result of second- total of 95 groundwater samples were collected during the
ary porosities. These porosities are caused by weathering, dry season (in January 2020). At each sample site, purging
fracturing, jointing and faulting, which creates access for was done for about two minutes by flushing the stall water
groundwater flow, accumulation, and storage. The granitic out. This was to ensure that the water sampled accurately
rock which covers the largest part of the basin is the least represented the status of the community groundwater. The
fractured and weathered. Additionally, a large portion of the samples collected were filtered through 0.45 mm pore space
gneisses is characterised by low to moderate groundwater filter paper into a pre-cleaned 500 mL polythene bottle and
occurrence though the northern portions of the granitic area kept under a temperature below 4 ◦C. It was then transferred
have relatively productive aquifer zones (Commission et al to the Ecological Laboratory of the University of Ghana,
2007). The Togo Structural Unit to the southeast of the basin Legon2 for analysis—using the hydro-chemical standard
is characterised by extremely pleated, interconnected, and guidelines proposed by Tomovska et al (2016). The con-
fissured rocks. The contact zone between the Togo Struc- centration of NO−3 –N was measured using a spectroquant
tural Unit and the granitic rocks in the Tamnean plutonic Pharo 300 spectrophotometer.
suite offers good conditions for groundwater build-up in the
aquifer system in addition to the existence of springs. The Health risk assessment and characterization
Birimian metavolcanic formation located in the far-flung
northwest of the basin is largely deep-weathered, pleated, Exposure to polluted water through ingestion and dermal
and fractured. Therefore the occurrence of groundwater in contact can pose a severe hazard to human life (USEPA
the area underlain by the Birimian rocks is rated high in 2001). Due to this, a holistic model for human health haz-
terms of yield. The secondary porosity is found to be the ard valuation was offered by the United States Environmen-
major conduit leading to the accumulation of groundwater tal Protection Agency (USEPA) (USEPA 2001). Zhai et al
in the basin. Two different aquifer types exist in the Basin, (2017) describe it as a “kind of valuation process that links
notably the weathered zone aquifers and the fractured zone the risk of water resource pollution with human health to
aquifers. The former is mostly observed at the base of the determine the extent of risk of the human body in the envi-
weathered layer. The type of rocks and climatic conditions rons of contaminated water. This is done through diverse
are factors that significantly determine the thickness of the
weathered zones. Groundwater occurs in a fractured zone
where the weathered zone in the basin is thin. This supports 2
http://​iess.​ug.​edu.​gh/​proje​cts/​insti​tutio​nal/​enreca-​ecolab-​proje​ct.

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Modeling Earth Systems and Environment (2023) 9:4539–4555 4543

Table 1  Input parameters of the Parameters Adults Children Infants Unit References
risk model
Exposure frequency (EF) 365 365 365 days Mohammadi et al (2017)
Exposure duration (ED) 30 12 180 (days) years
Ingestion rate (IR) 3.4 1.6 1.034 L/day Egbi et al (2020)
Average exposure (AT) 10950 4830 182.5 days (Egbi et al 2020)
Average body weight (BW) 64.34 30.02 4.85 kg (Egbi et al 2020)
Oral reference dose for NO−3 –N 1.6 1.6 1.6 mg/kg/day
NO−3 –N concentration (C) C C C mg/L NA

exposure pathways, so as to come up with conforming rec- is the exposure duration (year); BW is the body weight (kg);
ommendations and control measures for the health of the AT is the average exposure time (days).
human body”. It consists of measuring the magnitude of the The expected values of IR, EF, ED, AT and BW pre-
health effect of human contact with chemical species (con- sented in Table 1. Average body weights (BW) for children
taminants) in water. This model has gained prominence in (30.02 ± 20.49 kg), adults (64.36 ± 17 kg) and infants (4.85
its practicability and usage around the world (Li et al 2015; ± 0.93 kg ) were also obtained from a survey done by Egbi
Wu et al 2012; Wu and Sun 2016; Chen et al 2017; Zhai et al et al (2020) in the Lower Volta Basin of Ghana. These values
2017). Four phases are recognized in the assessment, namely were adopted for this study considering the fact that both
risk identification, amount-response assessment, exposure geographical locations are in the southern part of Ghana.
assessment, and hazard classification (Anornu et al 2017; The corresponding average ingestion water rates from the
Akber et al 2020). same survey (Egbi et al 2020) were 1.6 ± 0.4 L/day and
In the first phase, NO−3 –N in drinking groundwater was 3.4 ± 1.0 L/day for children and adults respectively. This
identified for the risk assessment due to its prevalence in is consistent with ingestion rate values (1.7 and 3.3 L/day
the basin. Reconnaissance appraisal from preceding research respectively) obtained by Craig et al (2015) in the Northern
work identified substantial loading of NO−3 –N in certain part of Ghana, which indicates that regardless of the setting,
parts of the study area (Tay and Kortatsi 2008; Amoako et al the average daily water consumption in Ghana has less vari-
2011; Yidana et al 2018). Additionally, high NO−3 –N con- ation and may be attributed to relatively homogeneous influ-
sumption has also been thought to have long-term chronic ences such as meteorological conditions and frequency of
effects in humans, especially babies (Yu et al 2020). activities. For infants, the average ingestion rate of 1034 ml/
The second and third phases of risk assessment, amount- day was adopted based on recommended ingestion rate for
response and exposure assessment, are based on estimat- infants (including feeding) from USEPA (2001).
ing the health risk by taking into account its frequency and The concluding phase of the hazard evaluation of ground-
the magnitude of the exposure. This assessment takes into water contamination is risk characterization, which assesses
consideration the exposure conduit, which is the point of the possibility of negative health effects in people exposed
access for the contaminant into the body. Previous studies to a specific contaminant (Zhai et al 2017). At this stage,
have shown that ingestion and skin contact is the primary the nature and occurrence or absence of danger are based
exposure pathway to NO−3 –N health hazards, with consump- on discussions in relation to assumptions, uncertainties and
tion being two to three times greater than skin contact (Wu limitations. It discusses the extent to which these conclu-
and Sun 2016; Li et al 2015; Anornu et al 2017). For this sions are supported by data (USEPA).3 Non-carcinogenic
reason and due to the paucity of data for skin contact, the hazard risk characterization is estimated by the Hazard Quo-
current investigation only focused on the hazard caused by tient (HQ) (Eq. 2).
ingestion for adults (above 18 years), children (1–17 years)
CDI
and babies (3–6 months) in the study area. HQnitrate = , (2)
RfD
The exposure dose through oral ingestion was calculated
using Eq. (1) (USEPA 2001) where RfD is the reference dose for non-carcinogenic haz-
C × IR × EF × ED ard classification, which is 1.6 mg∕kg∕day for NO−3 –N. An
CDI = , (1) estimated HQ value of < 1 means there are no negative
BW × AT
where CDI is the chronic dose intake from absorption in
drinking water (mg/kg/day); C is the NO3−–N concentration
in drinking groundwater (mg/L); IR is the water ingestion 3
https://​www.​epa.​gov/​envir​onmen​tal-​topics/​land-​waste-​and-​clean​up-​
rate (L/day); EF is the exposure frequency (days/year); ED topics.

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Fig. 2  Conceptual model of the


Monte Carlo simulation

non-carcinogenic characteristics present; by contrast, a nega- [ ]


1 1
ℵ(x|𝜇j , 𝜎j ) = √ exp − (zi − 𝝁𝜆 )T 𝜎j−1 (zi − 𝝁j )
tive non-carcinogenic risk is expected when HQ value is > 1. 2 (4)
|2𝜋𝜎j |

The following stages, using some initial Gaussian distribu-


Finite mixture model
tions, can be used to maximize the probability distribution
mentioned above for all points in the entire data set under
A finite mixture model is a statistical framework that
the premise of finite Gaussian distributions:
presupposes the existence of latent classes (unobserved
groups) within a larger population. It is possible to fit a
i. Find the Gaussian probability that is most likely to
function for each latent class identified. A popular finite
generate each point from ℵ(x|𝜇j , 𝜎j ). Here, the simi-
mixture strategy for clustering data produced by multi-
larity for each component in the data is measured by
modal distributions is the Gaussian mixture model
Eq. (4).
(GMM). For the purpose of this study, we employed the
GMM model due to possible variations in the NO−3 –N ii. Estimate the parameters (𝜇j , 𝜎j ), for each 1 < 𝜆 < Λ ,
dataset. The GMM can compare parameter estimates using the data points for each cluster.
between classes for a particular model. It can also fore-
cast the probabilities that the observations in our sample Since the GMM is nonlinear, it should be noted that the
belong to each latent class as well as the percentage of the Maximum Likelihood Estimation (MLE) method cannot be
population that belongs to each latent class. computed directly. In order to estimate the model parameters
The GMM presented in Eq. (3) is a parametric probability in Step ii above for this work, the Expectation–Maximization
density function defined as the weighted sum of Gaussian— (EM) approach described in Vu et al (2019) was employed.
each recognized by j ∈ 1, 2, … , C , where C is the number
of sub-populations in the dataset.
Monte Carlo simulation
C

p(x|𝚯) = 𝜔j ℵ(x|𝜇j , 𝜎j ), (3) Conventionally, risk assessment outcomes are expressed as
j=1
point estimates, leading to a high level of uncertainty (Dinis
here, x denotes the NO−3 –N concentration in D-dimension, and Fiúza 2010). However, the most precise way to perform
𝚯 = (𝜔1 , 𝜇1 , 𝜎1 ;𝜔2 , 𝜇2 , 𝜎2 ; … ;𝜔C , 𝜇C , 𝜎C )T assembles all the risk analysis is to use the Monte Carlo simulation (MCS).
hidden parameters, 𝜔j represents the mixture kernels such The technique employs a stochastic approach to draw sam-
∑C ples from a probability distribution and use them to estimate
that j=1 𝜔j = 1, and ℵ(x|𝜇j , 𝜎j ) are the mixture components
of Gaussian densities defined as, the characteristics. In our case, we adopted the MCS method
depicted in Fig. 2 to assess the health risk in this work.
The following algorithms describe the concept presented
in Fig. 2:

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Modeling Earth Systems and Environment (2023) 9:4539–4555 4545

Table 2  Deterministic values of principal statistical parameters of


NO−3 –N concentration, HQinfants, HQchildren , and HQadults
Statistical NO−3 –N (mg/L) HQinfants HQchildren HQadults
parameters

Count 95.0 95.0 95.00 95.00


Mean 6.30 0.86 0.220 0.210
std 5.90 0.81 0.200 0.190
Mini 0.02 0.003 0.0009 0.0008
25% 1.40 0.20 0.051 0.049
50% 4.30 0.59 0.051 0.140
75% 8.90 1.22 0.313 0.299
Max 25.70 3.43 0.882 0.841

i. Identifying multi-modal distributions in the NO−3 –N Fig. 3  Violin plot showing the respective distributions of the NO−3 –N
concentration. data set. The white dot in the violin plots represents the median. The
ii. Generating random values (1000) from each modal broad black line in the interior denotes the inter-quartile range and the
thin black bar represents the rest of the distribution. On each side of
distribution in step i. Here, the random samples for the grey line is a kernel density estimation to show the spectra distri-
the two clusters are computed as the probability of bution of the data. The wider section of the plot represents the higher
observing DNBL , if DNBL came from the NBL compo- population density, conversely, the skinnier sections represent a lower
nent: probability

P(DNBL |CNBL ) = N(𝜇CNBL , 𝜎C2 ) (5) observed standard deviation of 5.9 mg∕L depicts some vari-
NBL

ation in the NO−3 –N data set.


also, the probability of observing DHI , if DHI came
This is confirmed by the violin plot in Fig. 3 which syner-
from the human-induced component:
gistically blends the box plot and the density trace (smoothed
P(DHI |CHI ) = N(𝜇CHI , 𝜎C2 ) histogram) into a single display that exposes the morphology
(6)
HI
making up the NO−3 –N data set. The plot shows that there
additionally, the probability of observing DHS , if DHS is more than one sub-population in the distribution, sug-
came from the hypothetical single source: gesting significant lateral disparity in groundwater NO−3 –N
loading in the area. This variation could be attributed to the
P(DHS |CHS ) = N(𝜇CHS , 𝜎C2 )
HS
(7) underlying geology, periodic precipitation pattern, ground-
water recharge rate and evapotranspiration process. Other
Note that these generated random samples are consid- natural factors that may account for the spatial differences
ered to mimic the values of the NO−3 –N concentration in NO−3 –N contamination may include the soil type, soil
for each cluster and the hypothetical single cluster. grain size, soil water holding ability, rainfall intensity, well
iii. Using the random samples for the two clusters and the depth, aquifer physical properties, etc. (Shalev et al 2015;
assumed single source in step ii the respective HQs Buvaneshwari et al 2017; Minet et al 2017; Nakagawa et al
were computed. 2017; Re et al 2017; Ahada and Suthar 2018). That not-
iv. All the values of HQ > 1 in step iii were counted and withstanding, anthropogenic activities due to industrializa-
divided by the sampling size to estimate the probabil- tion and unregulated fertilizer application can also play a
ity risk for actual (both natural and human-induced) major role in this variation since most parts of the basin
as well as hypothetical single source concentration. are noted for the production of cash and food crops. The
indiscriminate disposal of solid and liquid waste in the area
is another issue. It is therefore instructive to suggest that the
Results and discussion NO−3 –N concentration in the study area may be coming from
multiple sources. A critical observation of the violin plot
Morphology and sources of the NO−3 –N (3) shows that the first modulation with a wider section of
the plot represents a higher population density, suggesting a
Table 2 shows that NO−3 –N concentration varies between higher likelihood that a selected member will fall within this
[0.01, 25.7] mg/L, while the 25th, 50th and 75th percentiles range of values. It is also the distribution with a relatively
were estimated as 1.4, 4.3 and 8.9 mg∕L , respectively. The lower concentration compared to the WHO permissible limit

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4546 Modeling Earth Systems and Environment (2023) 9:4539–4555

Fig. 4  A histogram distribution superimposed on a Gaussian mixture


model of the NO−3 –N dataset. The red curved line shows the best-
fit Gaussian mixture model. The green curved dash line shows the
first cluster in the mixture model identified as NBL and the yellow
curved dash line also depicts the second cluster of the mixture model
described as human induce (HI) sources

(10 mg/L) for drinking water (Marmolejo-Ramos and Tian


2010). Conversely, the skinnier section of the plot represents
a lower probability and is also associated with a cluster of
high concentration. The violin plot has the ability to identify
Fig. 5  Spatial demarcation of NO−3 –N in groundwater in the study
sub-clusters in a dataset, but distinguishing them becomes area. The red legend represents the concentration above the permis-
a graphical task. sible limit (10 mg/L)
For this work, we adopt a finite GMM probability distri-
bution to fit the NO−3 –N concentration to fortify the limita-
tions of the violin plot. The robustness of the GMM lies in for consumption and domestic needs. The USEPA health
its capacity to cluster and estimate each segregated param- hazard evaluation model was adapted to estimate the non-
eter (Psutka 2015; Reynolds 2009; Madenova and Madani carcinogenic effects on infants (< 1 year), children (1–18
2021) which is exactly what has been demonstrated in Fig. 4. years), and adults (> 18 years) who consume groundwa-
The expected value of the first component in the plot is esti- ter as their daily source of drinking water. The health risk
mated at 1.7 ± 1.3 mg/L. The low concentration value in this assessments of different age groups were performed using
component was considered as the natural background and the deterministic approach based on the parameters above,
we suspect that this is due to atmospheric deposition and with the most significant parameters being NO−3 –N, body
organic materials in the aquifer system. This component weight (BW) and ingestion rate (IR) considering the oral
forms about 54% of the groundwater samples collected in ingestion. It was assumed that groundwater consumers did
the area, hence, suggesting a fairly good status for domestic not travel out of their location within the study area and that
use. The second component estimated at 8.32 ± 3.13 mg/L, they consumed the groundwater all year round so 365 days/
originates from human-induced (HI) activities such as indus- year was considered as the exposure frequency. Additionally,
trial, domestic-oriented, and agricultural activities. Using using such exposure frequency will help compute the worst-
different thresholds in terms of 68%, 95% and 99% confi- case scenario risk (Opoku et al 2020).
dence intervals for the estimated values, we simulate the
range of possible outcomes to aid in decision-making. Here, Deterministic assessment of HQ
the Monte Carlo simulation is used to calculate the expected
risk of NO−3 –N exposure in human health. Table 2 presents the range of values for the determinis-
In the catchment area, the population mostly belonging tic approach of assessing non-carcinogenic health risks.
to the low-income class, especially from the middle to the ­HQinfants of the NO−3 –N ranges from [0.003, 3.42] with
northern part of the study area (mostly rural or semi-urban a mean of 0.85. The values of ­HQchildren also vary from
areas) (Fig. 5), are unable to afford mineral water (packaged [0.0009, 0.88] with an associated average of 0.22. A range of
water) from the market and as a result, rely on groundwater [0.0008, 0.84] with a mean of 0.21 was obtained for H
­ Qadults.

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Modeling Earth Systems and Environment (2023) 9:4539–4555 4547

for this study. About thirty-seven percent ( 37.2%) of the


infant population are at medium risk within the range of
[1, 4], 46% are at low risk within the range of [0.1, 1] and
16.8% are at negligible risk (< 0.1). This reveals that there is
a non-carcinogenic hazard for NO−3 –N associated with oral
ingestion exposure for infants in some parts of the basin.
Current and previous studies have shown that high NO−3 –N
is intensely correlated with various chronic diseases.
For children and adults, 38.9% and 38.5% of the samples
were below the classification, having negligible non-carci-
nogenic risk. 61% and 61.5% of the samples were found in
the low non-carcinogenic risk for children and adults respec-
tively. The results indicated that the ­HQchildren and ­HQadults
Fig. 6  Bi-plot showing safe and risk levels among various age classes were lower than a unit (HQ < 1) (Fig. 6). This suggests that
in the study area based on hazard quotient(HQ). HQ < 1—safe for children and adults exposed to this level of concentrations
drinking, HQ > 1—hazardous for drinking
of NO−3 –N recorded in the groundwater of the study area are
safe from non-carcinogenic risk hazards.
Epidemiological evidence submits that NO−3 –N expo-
sure is intensely correlated with numerous health condi-
tions, such as methemoglobinemia (blue baby syndrome) in
infants. This occurs as a result of a reduction in the ability of
blood to carry oxygen in babies below 6 months (Gulis et al
2002; Gao et al 2012; Maghanga et al 2013). Besides blue
baby syndrome, it has been observed that the oral ingestion
of water polluted with NO−3 –N may also lead to multiple
sclerosis, non-Hodgkin lymphoma, thyroid gland hypertro-
phy, mutagenesis, and teratogenesis, among other health
disorders in grownups, of which the severity depends on
the consumed dose (Wu et al 2017). In past investigations,
there have also been instances of gastric cancer, thyroid
issues, diabetes, and spontaneous miscarriages (Almasri
2007; Dan-Hassan et al 2012). Nursing mothers consuming
Fig. 7  Box plot showing the distribution of HQ for each exposure age water containing high loads of NO−3 –N, may considerably
group. ­HQinfants shows relatively much variation in its distribution
increase the quantity of NO−3 –N in breast milk. However,
there is inconclusive evidence of the occurrence of
Table 3  Variation of deterministic chronic risk assessment and blue-baby syndrome attributed to NO−3 –N in breast milk.
respective proportions for infants, children and adults Nevertheless, it may be advisable for nursing mothers
% of sample to eschew drinking water that has more than 10 mg∕L of
NO−3 –N in it (WDNRBDWG).4
Risk level HQ Chronic risk Infant Children Adults

1 < 0.1 Negligible 16.8 38.5 38.9 Stochastic risk assessment of HQ


2 ≥ 0.1 < 1 Low 46.0 61.0 61.5
3 ≥1<4 Medium 37.2 – – The embryonic stage in the MCS is to test the algorithm in
4 >4 High – – – step i and GMM was efficient at doing that. Figure 8 shows
the results of the MC simulation predicting the risk of
infants exposed to NO−3 –N concentration based on the iden-
Figures 6 and 7 show that there is much variation in H ­ Qinfants tified components (Fig. 4) and various confidence intervals
relative to H
­ Qchildren and H
­ Qadults. This is attributed to the (CI). The results show that the background concentration
body weight and the daily ingestion rate. In general, the HQ (first cluster) of the NO−3 –N predicted probability risk for
values were high for corresponding elevated NO−3 –N concen- CI (68.27%, 95.45% and 99.73%) ranges from 0.00 to 0.04.
tration, suggesting its major influence on HQ determination.
Table 3 shows the scale of chronic risk assessment used
by (Rahman et al 2020) and (Egbi et al 2020) and adopted 4
https://​www.​dhs.​wisco​nsin.​gov/​water/​index.​htm.

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4548 Modeling Earth Systems and Environment (2023) 9:4539–4555

Table 4  Comparative analysis HSS (%) NBL (%) HI (%)


of the methods used for health
risk of infant and the estimated Methods 1𝜎 2𝜎 3𝜎 1𝜎 2𝜎 3𝜎 1𝜎 2𝜎 3𝜎
error factor
MCS 0.07 0.12 0.17 0.00 0.00 0.04 0.16 0.31 0.39
DT 0.37 0.37 0.37 0.37 0.37 0.37 0.37 0.37 0.37
Error 0.30 0.16 0.20 0.37 0.37 0.33 0.21 0.06 0.02
a
Deterministic approach
b
Hypothetical single source

Table 5  Comparative analysis NBL (%) HI (%)


HSS a (%)
of the methods used for
health risk of children and the Methods 1𝜎 2𝜎 3𝜎 1𝜎 2𝜎 3𝜎 1𝜎 2𝜎 3𝜎
estimated error factor
MCS 0.02 0.03 0.05 0.02 0.03 0.07 0.15 0.23 0.31
DT b 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Error 0.02 0.03 0.05 0.02 0.03 0.07 0.15 0.23 0.31

Table 6  Comparative analysis HSS (%) NBL (%) HI (%)


of the methods used for health
risk of Adults and the estimated Methods 1𝜎 2𝜎 3𝜎 1𝜎 2𝜎 3𝜎 1𝜎 2𝜎 3𝜎
error factor
MCS 0.01 0.02 0.04 0.03 0.05 0.07 0.12 0.18 0.24
DT 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Error 0.01 0.02 0.04 0.03 0.05 0.07 0.12 0.18 0.24

DT Deterministic approach, HSS hypothetical single source

Additionally, the human-induced (second cluster) NO−3 –N A comparative assessment of health risk estimation
concentration predicted a probability risk in the range of
0.16-−0.39 for the various CI. The predicted risk based on Using the MCS, Tables 4, 5, and 6 shows the range of prob-
random sampling for the observed combined NO−3 –N con- ability risk values for the hypothetical single source (HSS),
centration, assuming it is from a hypothetical single source, NBL and HI sources for infants, children and adult respec-
ranges from 0.07 to 0.17 for the same range of CI. tively for various intervals. The range of values for the natu-
Figure 9 presents the results of the simulation predict- ral background source concentration is generally low due to
ing the risk of NO−3 –N exposure for children based on the the low NO−3 –N concentration from that source. Also, HSS
various clusters and CI. The predicted probability of non- probability risk values for infants (0.07-−0.17) especially
carcinogenic risk from the first cluster (NBL) ranges from for the purpose of this discussion, are too low compared to
0.03 to 0.07. The second cluster and the hypothetical single the ones estimated by the segregated HI source (0.16-−0.39)
distribution (assumed symmetric) also estimated a range of with an error margin of 0.09-−0.22. This observation is due
0.15 to 0.31 and 0.02 to 0.05, respectively. to the skewness of the probability distribution obtained from
Figure 10 displays the results of the model predicting the hypothetical single source, which was assumed to have a
the probability of non-carcinogenic risk of NO−3 exposure normal distribution. The GMM identified two distributions
to adults based on various components and CI. The risk in the NO−3 –N dataset, making it far more challenging for the
of adult exposure to concentration from the natural source HSS data set to accurately predict the health risk. This sug-
ranges from 0.03-−0.07. Additionally, the second compo- gests that when performing an MCS, employing a hypotheti-
nent (HI) and the hypothetical single distribution recorded cal symmetric distribution for an observed dataset without
the probability ranges of risk of 0.12-−0.24 and 0.01-− taking into account the dataset’s morphology could lead to
0.04, respectively. The data suggest that, comparatively, the erroneous risk characterization. The error margin (0.09-−
anthropogenic source of NO−3 –N has a greater non-carci- 0.22) can be utilized as a corrective factor when MCS is
nogenic health hazard for exposure groups than the natural applied to a multi-modal data set without taking the mor-
background and the hypothetical single sources. This is due phology of the distribution into account. Monte Carlo simu-
to the relatively high NO−3 –N concentration obtained in the lation for risk characterization is extremely useful when the
second cluster compared with the first. observational data is symmetric. However, the distribution

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Modeling Earth Systems and Environment (2023) 9:4539–4555 4549

Fig. 8  Results of the Monte Carlo simulation predicting risk of ond row (D, E, and F) represents the risk exposure of human-induced
infants exposed to NO−3 –N based on the identified clusters and vari- concentration (second cluster). The third row also exhibits the pre-
ous confidence intervals shaded in cyan (68.27%, 95.45%, and dicted risk based on the combined NO−3 –N distribution and various
99.73%). The first row (A, B and C) represents the risk in the NO−3 –N confidence intervals
exposure of natural background concentration (first cluster). The sec-

of the data set and sample size has a significant impact on takes worst-case scenarios into account, this will provide a
the efficiency of this strategy. In the majority of cases, outli- better estimation.
ers are eliminated before using MCS in order to assume a The deterministic and stochastic risks indicate that infants
normal distribution status. This can only be achieved when are the most susceptible to non-carcinogenic health risks,
the number of outliers being removed is negligibly small which is due to their lower body weight. The deterministic
in relation to the total sample size. The MCS taking into technique percentage risk assessment for all exposure groups
account HSS cannot be performed efficiently in areas where for CI 68% is high compared with that estimated by MCS,
data has a multi-modal distribution, such as the Densu basin. which takes into account the worst-case scenario. While
It is more acceptable to use a mixture model technique, such the MC simulation, which took into account the worst-case
as the Gaussian and Gamma prior to MCS, which is much scenario for HI concentration, offered a credible estimate as
more robust when dealing with a skewed multi-modal and high as 31% for both children and adults, the probability of
uni-modal data set. The study suggests that using MCS exceeding the limit (HQ = 1) for the exposure groups of chil-
techniques for health risk estimation is data-dependent. In dren and adults was “null” for the deterministic approach.
conclusion, the analysis of the morphology of the data set With less data, the Monte Carlo simulation-based probabil-
to identify the distributions is the first step in estimating istic approach can produce more thorough results and dis-
the health risk of a chemical specie utilizing MCS. Since it play the probability of various simulation values in a more

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4550 Modeling Earth Systems and Environment (2023) 9:4539–4555

Fig. 9  Results of the Monte Carlo simulation predicting risk of chil- (D, E, and F) represents the risk exposure of human-induced concen-
dren exposed to NO−3 –N based on the identified clusters and various tration (second cluster). The third row also exhibits the predicted risk
confidence intervals shaded in bisque (68.27%, 95.45%, and 99.73%). based on combined NO−3 –N distribution and various confidence inter-
The first row (A, B and C) represents the risk in the NO−3 –N exposure vals
of natural background concentration (first cluster). The Second row

comprehensible manner compared with the deterministic hand-dug wells, which are prone to anthropogenic activi-
approach. According to Rivera-Velasquez et al (2013), the ties. The very high NO−3 –N concentration located in the
MC simulation technique can provide greater precision to Eastern part of the basin results from boreholes sunk in
the risk estimation values within an interval with a specified swamp areas and in farming communities (D36, D42,
probability than the deterministic risk estimation method. D86). Nitrogen fertilizer application is responsible for
To provide visualization of the NO−3 –N concentration such loads of NO−3 –N. Others were also located close to
and to identify safe and risk zones in the study area, an wastewater channels (D45, D70, D71) and are attributed
inverse distance weighting (IDW) spatial model in GIS to domestic waste effluent. However from Figs. 5 and 11,
software was used. This spatial distribution analysis was relatively high NO−3 –N and its corresponding HQ levels
conducted to delineate the health risk zones of NO−3 –N were located predominantly along the eastern flanks of
exposure of infants, children and adults in the study the study region notably the Akuapem South, Akuapem
region. Figure 5 shows the spatial variation of the NO−3 –N North, and New Juaben Municipal. There were also some
in the study area. Some of the samples with a high con- packets of high HQ as well as high NO−3 –N in Upper West
centration of NO−3 –N from observation were partially due Akim, Ayensuano and Suhum Municipal. The southern
to open wells which were located within 100 m of damp and northern parts of the basin showed very low NO−3 –N
sites (D4, D5, D6, D7, D31 and D34). These are shallow concentration corresponding to low HQ in all the age

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Modeling Earth Systems and Environment (2023) 9:4539–4555 4551

Fig. 10  Results of the Monte Carlo simulation predicting risk of The second row (D, E, and F) represents the risk exposure of human-
adults exposed to NO−3 –N based on the identified clusters and vari- induced concentration (second cluster). The third row also exhibits
ous confidence intervals shaded in antiquewhite (68.27%, 95.45%, the predicted risk based on combined NO−3 –N distribution and vari-
and 99.73%). The first row (A, B and C) represents the risk in the ous confidence intervals
NO−3 –N exposure of natural background concentration (first cluster).

groups, suggesting a high correlation between HQ and Analysis of uncertainty


NO−3 –N. The results indicate that the non-carcinogenic risk
level of all the vulnerable populations varied in the order NO−3 –N loading and their associated non-carcinogenic health
of adults < children < infants. This suggests that infants risk assessments in the basin are recorded coupled with the
in some parts of the catchment are potentially exposed identification of health risk-prone zones and safe zones. This
to non-carcinogenic risks more than children and adults. notwithstanding, every risk evaluation has some degree of
Similar results were obtained by other studies (Chen et al uncertainty. A one-time water sample was taken for analysis
2017; Adimalla 2019; He and Wu 2019). The lesser body in this investigation. Seasonal fluctuations in groundwater
weight of infants situates them at higher health risks as hydro-chemical concentrations had previously been reported
put forward by earlier scientists (Adimalla 2019; Adimalla by researchers. Furthermore, despite rigorous adherence to
and Qian 2020; Aslani et al 2019; Chen et al 2017). Also, quality control methods during operation, there may be some
the distinct biological features and behavioural traits of unavoidable errors during the data gathering and analysis
infants put them at greater risk, because at this early stage procedures. Every geographic interpolation approach has its
there is an increase in gastrointestinal absorption of certain own set of restrictions, which might have an impact on the
materials, which makes them more susceptible to external spatial prediction of dangers and safe zones. In addition, due
pollutants. to the lack of accurate data for the people of the research

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4552 Modeling Earth Systems and Environment (2023) 9:4539–4555

Fig. 11  Spatial map showing the variation in the risk zones for (A) infants (B) children and (C) adults

region, the parameters utilized in the HHRA model were and policymakers better understand and manage groundwa-
derived directly from USEPA reference values and earlier ter resources in the study area.
work done in similar terrain. Finally, due to a lack of data,
the study only investigated drinking water channels for risk
assessments, ignoring other highly probable paths such as Conclusion
dermal contact through swimming and bathing.
Despite these challenges, the study findings are useful The study evaluated the levels of NO−3 –N in groundwater
and significant. The findings agree with previous research in for domestic use and assessed the non-carcinogenic health
similar terrains. This research will provide an initial assess- risk effects using USEPA human health risk assessment
ment of the basin’s groundwater ingestion health for the models coupled with deterministic and probability assess-
basin. This research will help water managers, stakeholders, ment techniques using the Monte Carlo model. This study

13
Modeling Earth Systems and Environment (2023) 9:4539–4555 4553

is a preliminary investigation of NO−3 –N hazards in the sub- Centre (NCERC) of the Ghana Atomic Energy Commission, and the
region using a probability health risk assessment model, of Carnegie Corporation of New York.
this kind in an environment with multiple sources of ground- Funding This work was partially supported by the Building and New
water NO−3 –N. Based on a mixture model the study revealed Generation of Academics in Africa (BaNGA-Africa), through funds
the morphology of the NO−3 –N distributions, which were provided by the Carnegie Corporation of New York.
classified as NBL and human-induced sources. The follow-
Data availability The datasets generated during and/or analysed during
ing conclusions were drawn from the study: the current study are not publicly available since is an on-going project
but are available from the corresponding author on reasonable request.
i. The deterministic technique evaluated the non-car-
cinogenic risk (HQ > 1) as a percentage to be 39% Declarations
(0.39) for infants and reported null values for both
Conflict of interest The authors declare no competing interests.
children and adults, indicating that children and adults
are likely free from non-carcinogenic risk based on the
current NO−3 –N exposure.
ii. Assuming that there is just one source of NO−3 –N, the References
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