Environmental Challenges 5 (2021) 100266

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Environmental Challenges
journal homepage: www.elsevier.com/locate/envc

Water quality variables and emerging environmental contaminant in water

for human consumption in Rio Grande do Sul, Brazil
Débora Seben a, Marcos Toebe b, Arci Dirceu Wastowski a, Keli Hofstätter a, Fernanda Volpatto a,
Renato Zanella c, Osmar Damian Prestes c, Jaqueline Ineu Golombieski a,∗
a
Department of Environmental Engineering and Technology, Federal University of Santa Maria (UFSM), Linha Sete de Setembro, s/n, BR 386, Km 40 Campus,
Frederico Westphalen, RS 98400-000, Brazil
b
Department of Agronomic and Environmental Sciences, Federal University of Santa Maria, RS, Brazil
c
Department of Chemistry, Federal University of Santa Maria, RS, Brazil

a r t i c l e i n f o a b s t r a c t

Keywords: This research aimed to qualify and quantify physical, chemical, microbiological and emerging environmental
Pesticides contaminants, pharmaceuticals and pesticides in spring waters, which are used for human consumption under
Pharmaceuticals different land use and occupation conditions. These conditions were: native forests and swine farming, as well as
Spring water
soy and tobacco crops in two consecutive seasons. Due to the microbiological variables and the pH and apparent
Potability
color, the spring water studied is not potable, as it does not comply with the legislation due to the contribution of
the total coliforms found in the native forest springs. Pharmaceuticals and pesticides were found in the land use
and occupation conditions under study, which shows that land uses do not interfere with emerging environmental
contaminant variables.

1. Introduction
Groundwater has advantages when compared to surface water as it
has a wide distribution, good stability, natural regulation, good qual-
ity (Singh et al., 2013; Wang et al., 2020; Zhou et al., 2020), it needs
little treatment and has spatial availability (Loh et al., 2019). On the
other hand, aquifers are difficult to exploit and access (Gao et al.,
2020; Wang et al., 2020; Zhou et al., 2020); however, it makes them
less vulnerable to pollution (Masocha et al., 2019). The population
growth and surface water contamination cause an increase in ground-
water consumption. When compared to surface water, groundwater
has greater availability during droughts and better quality (Loh et al.,
2019) as a result of soils and rocks functioning as natural filters
(Masocha et al., 2019). However, not all types of soils perform this filtra-
tion, and contamination by pathogenic organisms from waste can occur
(Myers, 2009), in addition to interacting with the nutrients present in
the soil (Brhane, 2018). Groundwater is indispensable for economic and
human development (Li et al., 2017; Gao et al., 2020) and is used for
different activities (Brhane, 2018).
The chemical variables of groundwater quality can have high con-
centrations due to the type of soil and rocks and the formation processes
of that environment (Zhou et al., 2020), because the water interacts
with the soil rocks and organic compounds present in the environment
depending on human activities. Many dissolved mineral ions can dete-
riorate the quality of groundwater, therefore affecting its use for many
purposes (Brhane, 2018). The microbiological variables of water quality
involve the group of total coliforms that includes environmental and fe-
cal species (World Health Organization, 2017). Escherichia coli is found
in large quantities in human and animal feces and is hardly found when
there is no fecal contamination (World Health Organization, 2017), thus
being the most appropriate indicator of fecal contamination.
Pesticides and pharmaceuticals, when used or treated improperly,
can be carried through surface runoff to the water bodies causing sur-
face water contamination or can be reached by the soil, contaminating
the groundwater (Castro-Lima et al., 2020; Tien et al., 2013). The pres-
ence of chemical substances in water bodies can contribute to the risk
of diabetes, reproductive disorders, neurological dysfunction, cancer
among children and adults, as well as respiratory disorders (Rani et al.,
2020; Wu et al., 2020) due to drinking water with residues of these
pollutants. Micro-pollutants, also called emerging environmental con-
taminants (EEC), include pharmaceutical products, personal care prod-
ucts, steroid hormones, surfactants, industrial and hospital effluents and
runoff in agricultural and breeding areas for confined animals (Luo et al.,
2014).

∗
Corresponding author.
E-mail address: jaqueline.golombieski@ufsm.br (J.I. Golombieski).

https://doi.org/10.1016/j.envc.2021.100266
Received 18 May 2021; Received in revised form 8 August 2021; Accepted 1 September 2021
2667-0100/© 2021 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/)
D. Seben, M. Toebe, A.D. Wastowski et al.
Fig.1. Location of the springs evaluated in each land use and occupation condition (1: native forest, 2: swine farming, 3: soy crop and 4: tobacco crop). The cities
are described in A1–E4.
Brazil is well known worldwide for its strong agricultural poten-
tial. Rio Grande do Sul is the third state with the most swine farm-
ing (1661 thousand tons of meat) (EMBRAPA EMPRESA BRASILEIRA
DE PESQUISA AGROPECUÁRIA, 2019). In agriculture, the state stands
out in soy crops (over 18 thousand tons) (IBGE INSTITUTODEESTATÍS-
TICA, 2019). This study aims to quantify and qualify the physical, chem-
ical, microbiological, and emerging environmental contaminant (pesti-
cides and pharmaceuticals) variables found in spring water, located in
rural properties, used for human consumption, under different land use
and occupation conditions, in Rio Grande do Sul State, Brazil.
The research is innovative because these spring water collection sites
have never undergone physical, chemical and biological analyses and
neither have pesticides and pharmaceutical groups.
2. Material and methods
2.1. Study area and, land use and occupation conditions
The study area is located in Rio Grande do Sul (RS) State, Brazil
(Fig. 1). The water used for this research is from protected springs and
used for human consumption, except springs located in native forests.
The research adopted four different land use and occupation conditions
for spring water analysis: (1) a native forest area (public area), (2) a
swine farming area (perennial condition), (3) a soy crop area and, (4) a
tobacco crop area (annual) (five repetitions each).
In RS State, the climate is humid sub-tropical according to Köp-
pen (Alvares et al., 2013). According to the Brazilian Geological Sur-
vey/CPRM (2006), geological aspects in the investigated region com-
prise Serra Geral Formation, Paranapanema and Lawn Facies. In the ge-
omorphological characteristics, the domains of the water springs studied
are located in the Rio Grande Plateau (Machado and Freitas, 2005).
2
Environmental Challenges 5 (2021) 100266
2.2. Physical, chemical and microbiological analyzes
Water sample collections occurred twice in the same year - 2019:
May (season 1- crop residues) and November (season 2 - intense crop).
Temperature and pH analyzes (portable pHmeter pHEP®4 Hanna) were
performed “in loco”. In the laboratory, the analysis and methods ac-
cording to APHA, AWWA and WEF (Rice et al., 2012) were: Turbidity
(NTU), Electrical conductivity (μS/cm), Total alkalinity (mg/L CaCO3 )
and Total hardness (mg/L CaCO3 ), Total Ammonia (mg/L N-NH3 ) and
Nitrate (mg/L N-NO3 − ), True and Apparent colors (HU), Nitrite (mg/L
N-NO2 − ), Total phosphorus (P) (mg/L P), Fluoride (F− ) (mg/L F− ) and
Total iron (Fe) (mg/L Fe), Total Coliforms and Escherichia coli (MPN-
more probable number/100 mL) at Federal University of Santa Maria
(UFSM).
2.3. Emerging environmental contaminants (EEC) analysis
Twenty-six pharmaceuticals (AP: active principle) and 124 pesticides
(AI: active ingredients) were analyzed at the Pesticide Residue Analysis
Laboratory (LARP/UFSM) using solid phase extraction (SPE) for sam-
ple preparation and ultra-high performance liquid chromatography with
tandem mass spectrometry (UHPLC-MS/MS). The pesticides present in
water samples from springs were pre-concentrated using SPE with Oa-
sis HLB 60 mg cartridges based on the method described by Donato
et al. (2015). The pharmaceuticals were pre-concentrated using Strata
X 200 mg cartridge as described by de Oliveira et al. (2019). After the
sample preparation step, pesticides and pharmaceuticals were analyzed
by UHPLC-MS/MS with a triple quadruple Xevo TQ® system (Waters,
Milford, MA, USA). An Acquity UPLC BEH C18 column (50 × 2.1 mm;
1.7 μm) from Waters was used for the chromatographic separation. The
mass spectrometer was operated in selected reaction monitoring using
D. Seben, M. Toebe, A.D. Wastowski et al. Environmental Challenges 5 (2021) 100266

Table 1
Mean ± standard error and 95% confidence interval for the mean population (in parentheses) of chemical variables in water samples.

Land use(1) /Season Native Forest Swine Farming Soy Crop Tobacco Crop General Season
pH (unit)

Season 1(2) 6.46 ± 0.44abA(4) 6.66 ± 0.24aA 5.88 ± 0.12bA 6.26 ± 0.31abA 6.32 ± 0.15A
(5.24≤μ≤7.68) (6.01≤μ≤7.31) (5.56≤μ≤6.20) (5.41≤μ≤7.11) (6.00≤μ≤6.63)
Season 2(3) 6.44 ± 0.43aA 6.20 ± 0.19aA 6.00 ± 0.31aA 5.98 ± 0.44aA 6.16 ± 0.17A
(5.26≤μ≤7.62) (5.67≤μ≤6.73) (5.13≤μ≤6.87) (4.77≤μ≤7.19) (5.80≤μ≤6.51)
Land use General 6.45 ± 0.29a 6.43 ± ± 0.16a 5.94 ± 0.16a 6.12 ± 0.26a 6.24 ± 0.11
(5.80≤μ≤7.10) (6.06≤μ≤6.80) (5.58≤μ≤6.30) (5.54≤μ≤6.70) (6.01≤μ≤6.46)
Total Alkalinity (mg/L CaCO3 )
Season 1 24.93 ± 8.69bA 60.57 ± 9.31aA 21.56 ± 7.64bA 29.48 ± 6.59bA 34.14 ± 5.15A
(0.80≤μ≤49.07) (34.73≤μ≤86.41) (0.34≤μ≤42.78) (11.19≤μ≤47.77) (23.35≤μ≤44.93)
Season 2 25.81 ± 3.55bA 67.91 ± 12.21aA 20.06 ± 4.80bA 40.48 ± 19.60abA 38.56 ± 6.93A
(15.95≤μ≤35.68) (34.02≤μ≤101.79) (6.73≤μ≤33.39) (0.00(5) ≤μ≤94.90) (24.07≤μ≤53.06)
Land use General 25.37 ± 4.43b 64.24 ± 7.34a 20.81 ± 4.26b 34.98 ± 9.92b 36.35 ± 4.28
(15.35≤μ≤35.39) (47.64≤μ≤80.84) (11.17≤μ≤30.45) (12.54≤μ≤57.42) (27.70≤μ≤45.00)
Total Hardness (mg/L CaCO3 )
Season 1 17.73 ± 6.85bA 63.20 ± 7.74aA 20.40 ± 6.48bA 32.53 ± 5.64bA 33.47 ± 5.16A
(0.00≤μ≤36.76) (41.70≤μ≤84.70) (2.40≤μ≤38.40) (16.87≤μ≤48.20) (22.66≤μ≤44.27)
Season 2 25.40 ± 9.44bA 72.90 ± 13.12aA 27.10 ± 5.55bA 35.40 ± 6.80bA 40.20 ± 6.11A
(0.00≤μ≤51.61) (36.49≤μ≤109.31) (11.68≤μ≤42.52) (16.53≤μ≤54.27) (27.42≤μ≤52.98)
Land use General 21.57 ± 5.65b 68.05 ± 7.36a 23.75 ± 4.18b 33.97 ± 4.19b 36.83 ± 3.98
(8.80≤μ≤34.34) (51.40≤μ≤84.70) (14.30≤μ≤33.2) (24.48≤μ≤43.45) (28.77≤μ≤44.89)
Electric Conductivity (μS/cm)
Season 1 49.37 ± 18.77bA 154.30 ± 16.63aA 54.84 ± 14.42bA 89.43 ± 9.37bA 86.99 ± 11.86A
(0.00≤μ≤101.5) (108.14≤μ≤200.46) (14.81≤μ≤94.87) (63.42≤μ≤115.44) (62.17≤μ≤111.8)
Season 2 55.43 ± 20.36bA 162.23 ± 27.84aA 55.49 ± 13.93bA 113.51 ± 23.61ªbA 96.66 ± 14.39A
(0.00≤μ≤111.94) (84.94≤μ≤239.52) (16.82≤μ≤94.17) (47.96≤μ≤179.05) (66.54≤μ≤126.79)
Land use General 52.40 ± 13.09c 158.27 ± 15.34a 55.17 ± 9.45c 101.47 ± 12.63b 91.82 ± 9.24
(22.78≤μ≤82.02) (123.56≤μ≤192.97) (33.79≤μ≤76.55) (72.90≤μ≤130.03) (73.14≤μ≤110.51)
(1)
Land use and occupation conditions are shown in Fig. 1. (2) Season collection 1: May/2019. (3) Season collection 2: November/2019. (4) Averages followed
by the same horizontal (lowercase) and vertical (uppercase) letters do not differ significantly from each other by the t-test for independent samples (p ≤ 0.05). (5)
Confidence interval with estimated lower limit (negative value).

an electrospray ionization source. The method presented limits of quan-
tification (LOQ) from 0.010 to 0.020 μg/L and from 0.010 to 0.040 μg/L
for most of the pesticides and pharmaceuticals, respectively.
2.4. Statistical analysis
For each variable, comparisons of the averages of seasons and land
use addressed using the T-test for independent samples with a 5% prob-
ability of error and confidence intervals were constructed for the popu-
lation average with a 95% confidence level. For the cluster analysis, the
Euclidean distance matrix was used as a dissimilarity measure of UP-
GMA (Unweighted Pair Group Method with Arithmetic Mean) method
for grouping environments and variables. Statistical analyzes were per-
formed using R software (Development Core Team, 2020).
3. Results
3.1. Physical, chemical and microbiological analyzes
The pH values in the first season were higher (p ≤ 0.05) in the water
sampled in the swine farming areas than the values of water sampled in
the soybean areas (Table 1). Water pH averages in the four different land
use and occupation conditions varied from 5.88 ± 0.16 to 6.45 ± 0.29.
Total alkalinity (TA) and total hardness (TH) average, for season 1 and
2, increased significantly (p ≤ 0.05) when comparing the swine farming
area to the other land use and occupation conditions studied. TA and TH
averages in different land use and occupation conditions ranged from
20.81 ± 0.16 to 64.24 ± 0.29 and 21.57 ± 5.65 to 68.05 ± 7.36 mg/L
CaCO3 , respectively. Electrical conductivity (EC), in seasons 1 and 2,
generally in areas with the presence of swine farming were significantly
higher (p ≤ 0.05) when compared to the other land use and occupation
conditions. The EC average water in the different land use and occupa-
tion conditions ranged from 52.40 ± 13.09 to 158.27 ± 15.34 μS/cm.
The average temperature (TE) values (Table 2), in the soy crop area
were higher (p ≤ 0.05) when compared to the native forest area. TE av-
erage values between seasons 1 and 2 showed a significant difference
between them, in which values of season 2 were higher (p ≤ 0.05) than
those of season 1, in which the average water TE in different land use
and occupation conditions ranged from 19.40 ± 0.52 to 21.86 ± 1.04°C.
For the turbidity (TU) and apparent color (AC) variables in the two sea-
sons, the average values found in the native forest waters were sig-
nificantly higher (p ≤ 0.05) when compared to the waters found in
other land uses, ranging from 2.05 ± 1.15 to 14.28 ± 2.93 NTU and
11.76 ± 5.93 to 63.48 ± 14.36 HU, respectively. The native forest area
showed higher values of true color (TR) (p ≤ 0.05) when compared to
the average of the waters found close to the soy crop. However, sig-
nificantly higher values were observed in season 1, when compared to
season 2. The TR average water in different land use and occupation
conditions varied from 4.41 ± 4.33 to 21.23 ± 6.56 HU.
Total iron (TI) water in the four different land use and occupation
conditions varied from 0.35 ± 0.08 to 0.76 ± 0.19 mg/L Fe (Table 3).
The total phosphorus (TP) in season 2 was significantly higher (p ≤ 0.05)
in the water of the native forest area. The TP average in the four dif-
ferent land use and occupation conditions varied from 0.92 ± 0.31 to
1.41 ± 0.74 mg/L P.
The fluoride (FL) water collection in season 2 was significantly
higher (p ≤ 0.05) in the water of the tobacco crop area. The average FL
in different land use and occupation conditions varied from 1.20 ± 0.24
to 1.27 ± 0.31 mg/L F− . Total ammonia (AM) in season 2 was signifi-
cantly higher (p ≤ 0.05) in the water from the swine farming area that
varied from 0.08 ± 0.02 to 0.13 ± 0.03 mg/L N-NH3 . Nitrate (NA) av-
erage values in the water collection in land use was significantly higher
(p ≤ 0.05) in the swine farming area when compared to the native for-
est area. When comparing the seasons, the nitrate values of season 1
(ranging from 0.78 ± 0.38 to 2.53 ± ± 0.73 mg/L N-NO3 − ) were signif-
icantly higher than season 2. Nitrite (NI) in the four different land use
and occupation conditions varied until 0.01 ± 0.00 mg/L N-NO2 − .
The total coliform (TC) values in the water (Table 4) in native forest
areas showed significantly higher mean values (p ≤ 0.05), when com-
pared to the average values of swine farming in season 1 and soy crops

3
D. Seben, M. Toebe, A.D. Wastowski et al. Environmental Challenges 5 (2021) 100266

Table 2
Mean ± standard error and 95% confidence interval for the mean population (in parentheses) of physical variables in water samples.

Land use(1) /Season Native Forest Swine Farming Soy Crop Tobacco Crop General Season
Temperature (°C)

Season 1(2) 18.70 ± 0.72aA(4) 18.48 ± 0.86aB 19.78 ± 1.37aB 19.18 ± 0.46aB 19.04 ± 0.43B
(16.70≤μ≤20.70) (16.10≤μ≤20.86) (15.97≤μ≤23.59) (17.91≤μ≤20.45) (18.13≤μ≤19.94)
Season 2(3) 20.10 ± 0.68bA 22.82 ± 0.99abA 23.94 ± 0.90aA 22.82 ± 1.09abA 22.42 ± 0.54A
(18.20≤μ≤22.00) (20.07≤μ≤25.57) (21.45≤μ≤26.43) (19.80≤μ≤25.84) (21.30≤μ≤23.54)
Land use 19.40 ± 0.52b 20.65 ± 0.95ab 21.86 ± 1.04a 21.00 ± 0.82ab 20.73 ± 0.44
General (18.22≤μ≤20.58) (18.50≤μ≤22.80) (19.51≤μ≤24.21) (19.14≤μ≤22.86) (19.85≤μ≤21.61)
Turbidity (NTU)
Season 1 13.04 ± 3.50aA 6.89 ± 4.23abA 0.98 ± 0.28bA 2.26 ± 1.32bA 5.79 ± 1.69A
(3.31≤μ≤22.77) (0.00(5) ≤μ≤18.64) (0.22≤μ≤1.75) (0.00≤μ≤5.91) (2.25≤μ≤9.33)
Season 2 15.51 ± 5.06aA 7.23 ± 4.53aA 3.12 ± 2.30aA 2.63 ± 1.31aA 7.13 ± 2.05A
(1.48≤μ≤29.55) (0.00≤μ≤19.80) (0.00≤μ≤9.51) (0.00≤μ≤6.27) (2.84≤μ≤11.41)
Land use 14.28 ± 2.93a 7.06 ± 2.92ab 2.05 ± 1.15b 2.45 ± 0.88b 6.46 ± 1.32
General (7.65≤μ≤20.90) (0.45≤μ≤13.67) (0.00≤μ≤4.65) (0.46≤μ≤4.43) (3.80≤μ≤9.12)
Apparent Color (HU)
Season 1 74.23 ± 25.20aA 42.42 ± 18.15abA 9.33 ± 9.33bA 19.83 ± 11.10abA 36.46 ± 9.72A
(4.27≤μ≤144.19) (0.00≤μ≤92.83) (0.00≤μ≤35.24) (0.00≤μ≤50.65) (16.12≤μ≤56.79)
Season 2 52.72 ± 15.32aA 30.40 ± 24.80abA 15.66 ± 10.46abA 3.68 ± 1.52bA 25.62 ± 8.26A
(10.19≤μ≤95.26) (0.00≤μ≤99.26) (0.00≤μ≤44.72) (0.00≤μ≤7.90) (8.33≤μ≤42.90)
Land use 63.48 ± 14.36a 36.41 ± 14.63ab 12.50 ± 6.69b 11.76 ± 5.93b 31.04 ± 6.35
General (31.00≤μ≤95.95) (3.32≤μ≤69.5) (0.00≤μ≤27.64) (0.00≤μ≤25.17) (18.19≤μ≤43.89)
True Color (HU)
Season 1 25.03 ± 11.81aA 20.36 ± 11.65aA 8.67 ± 8.67aA 18.68 ± 11.44aA 18.19 ± 5.22A
(0.00≤μ≤57.82) (0.00≤μ≤52.71) (0.00≤μ≤32.76) (0.00≤μ≤50.44) (7.27≤μ≤29.10)
Season 2 17.43 ± 6.85aA 1.87 ± 0.79aA 0.15 ± 0.15aA 2.73 ± 1.59aA 5.54 ± 2.27B
(0.00≤μ≤36.43) (0.00≤μ≤4.06) (0.00≤μ≤0.57) (0.00≤μ≤7.15) (0.79≤μ≤10.30)
Land use 21.23 ± 6.56a 11.12 ± 6.31ab 4.41 ± 4.33b 10.70 ± 6.06ab 11.86 ± 2.98
General (6.39≤μ≤36.06) (0.00≤μ≤25.39) (0.00≤μ≤14.21) (0.00≤μ≤24.41) (5.83≤μ≤17.9)
(1)
Land use and occupation conditions are shown in Fig. 1. (2) Season collection 1: May/2019. (3) Season collection 2: November/2019. (4) Averages followed
by the same horizontal (lowercase) and vertical (uppercase) letters do not differ significantly from each other by the t-test for independent samples (p ≤ 0.05). (5)
Confidence interval with estimated lower limit (negative value).

in season 2. TC in the native forest was significantly larger than other
areas with different land use conditions studied. Average TC values in
different uses and general land use ranged from 8,517.04 ± 3,465.38
to 19,789.70 ± 1,583.42 MPN/100mL. Moreover, E. coli in water from
different land use and occupation conditions varied from 46.2 ± 24.2 to
562.5 ± 399.8 mg/L of MPN/100mL.
Using a cut-off point of 50% dissimilarity in the cluster analysis,
the formation of two groups of environments (Fig. 2A) and variables
(Fig. 2B) was observed. Among the environments, there was a similar-
ity in the results of the native forest in the two evaluation seasons. These
results were different from the other land use and occupation conditions
(tobacco crop, soy crop and swine farming) in the two evaluation sea-
sons. Among the variables, total coliforms (TC) differed from all other
variables, forming the isolated group. The native forest is the environ-
ment that has the highest values of total coliforms (Table 4) and this
variable was the most important in the group formation, which was
responsible for separating the native forest from other land use and oc-
cupation conditions (Fig. 2A and B).
3.2. Emerging environmental contaminant (EEC)
Pharmaceuticals were found only in season 1 of the water collec-
tion, and in all land use and occupation conditions that have a greater
quantity in soy crops, AP Paracetamol and Norfloxacin.
All AI pesticides detected in season 1, except for the Tebuconazole
fungicide, can be found in the spring water of the native forest. In this
season, 55% (11/20) of the spring water samples showed a residual ef-
fect of Atrazine herbicide, whereas in season 2, this herbicide was found
in 75% (15/20) of the samples. Clomazone herbicide was present in 95%
(19/20) of the studied spring water and in quantities greater than 0.142
μg/L, in season 1. In season 2, residues of this herbicide were found in
100% (20/20) of the water samples with a minimum concentration of
0.130 μg/L. Clothianidin insecticide residues were found in 35% (7/20)
of the samples in season 1 and 25% (5/20) of the samples in season 2.
Imidacloprid insecticide was found in the two seasons studied and in all
land use and occupation conditions except for swine farming. Picoxys-
trobin fungicide was found in 25% (5/20) of the samples in season 1 and
in 5% (1/20) of the samples in season 2. The land use and occupation
conditions that presented the greatest variety of AI in season 1 was the
soy crop with 6 of the 6 pesticides (100%) and, in season 2 it was swine
farming including 15 of the 26 pesticides that indicated a presence in
this study (57.7%).
4. Discussion
4.1. Physical, chemical and microbiological analyzes
The Brazilian legislation in force in the GM/MS Ordinance, n°. 888 of
May 4th of 2021 ( BRAZIL, 2021) establishes maximum permitted val-
ues (MPV) for the water quality variables for human consumption, and
pH values (p ≤ 0.05) must be between 6.0 and 9.5. Similarly, the World
Health Organization (World Health Organization, 2017) establishes val-
ues between 6.0 and 8.5. Thus (Table 1), only the general average for
springs located in areas close to soy crops had a pH value below that
allowed by the two legislations. pH values do not directly affect human
health, but other compounds can interact with this variable and form
secondary compounds and then be harmful to people (World Health
Organization, 2017). In a study carried out on groundwater in India
(Singh et al., 2013), pH values were found within those established by
the WHO (World Health Organization, 2017). In Ethiopia, pH values for
shallow wells ranged from 7.2 to 7.5 (Brhane, 2018).
The legislation does not establish a MPV for the variable TA for drink-
ing water. Thus, the averages for this variable ranged from 20.81 ± 4.26
to 64.24 ± 7.34 mg/L CaCO3 among the different conditions of land use
studied and 34.14 ± 5.15 and 38.56 ± 6.93 mg/L of CaCO3 respectively,
between the two seasons studied (Table 1). High values of total alka-

4
D. Seben, M. Toebe, A.D. Wastowski et al. Environmental Challenges 5 (2021) 100266

Table 3
Mean ± standard error and 95% confidence interval for the mean population (in parentheses) of chemical species variables in water samples.

Land use(1) /Season Native Forest Swine Farming Soy Crop Tobacco Crop General Season
Total Iron (mg/L Fe)

Season 1(2) 0.62 ± 0.16aA(4) 0.59 ± 0.11aA 0.41 ± 0.11aA 0.40 ± 0.10aA 0.50 ± 0.06A
(0.16≤μ≤1.07) (0.27≤μ≤0.9) (0.12≤μ≤0.71) (0.13≤μ≤0.66) (0.38≤μ≤0.63)
Season 2(3) 0.91 ± 0.36aA 0.57 ± 0.30aA 0.35 ± 0.16aA 0.31 ± 0.14aA 0.54 ± 0.13A
(0.00(5) ≤μ≤1.90) (0.00≤μ≤1.41) (0.00≤μ≤0.78) (0.00≤μ≤0.71) (0.26≤μ≤0.81)
Land use 0.76 ± 0.19a 0.58 ± 0.15a 0.38 ± 0.09a 0.35 ± 0.08a 0.52 ± 0.07
General (0.33≤μ≤1.20) (0.23≤μ≤0.92) (0.18≤μ≤0.59) (0.17≤μ≤0.54) (0.38≤μ≤0.66)
Total Phosphorus (mg/L P)
Season 1 0.44 ± 0.08aB 0.33 ± 0.08aA 0.30 ± 0.05aA 0.36 ± 0.05aA 0.36 ± 0.03B
(0.22≤μ≤0.66) (0.11≤μ≤0.54) (0.17≤μ≤0.43) (0.22≤μ≤0.51) (0.29≤μ≤0.43)
Season 2 1.44 ± 0.30aA 2.49 ± 1.37aA 2.25 ± 1.00aA 1.48 ± 0.52aA 1.91 ± 0.43A
(0.60≤μ≤2.27) (0.00≤μ≤6.31) (0.00≤μ≤5.03) (0.03≤μ≤2.93) (1.02≤μ≤2.81)
Land use 0.94 ± 0.22a 1.41 ± 0.74a 1.28 ± 0.57a 0.92 ± 0.31a 1.14 ± 0.25
General (0.44≤μ≤1.44) (0.00≤μ≤3.09) (0.00≤μ≤2.57) (0.22≤μ≤1.62) (0.64≤μ≤1.63)
Fluoride (mg/L F− )
Season 1 0.70 ± 0.37aA 0.71 ± 0.44aA 0.78 ± 0.22aA 0.61 ± 0.33aB 0.70 ± 0.16B
(0.00≤μ≤1.71) (0.00≤μ≤1.93) (0.18≤μ≤1.38) (0.00≤μ≤1.51) (0.37≤μ≤1.03)
Season 2 1.72 ± 0.43aA 1.82 ± 0.31aA 1.62 ± 0.34aA 1.94 ± 0.27aA 1.78 ± 0.16A
(0.51≤μ≤2.93) (0.96≤μ≤2.68) (0.68≤μ≤2.56) (1.19≤μ≤2.69) (1.44≤μ≤2.11)
Land use 1.21 ± 0.32a 1.27 ± 0.31a 1.20 ± 0.24a 1.27 ± 0.30a 1.24 ± 0.14
General (0.49≤μ≤1.93) (0.56≤μ≤1.97) (0.67≤μ≤1.73) (0.60≤μ≤1.95) (0.95≤μ≤1.52)
Total Ammonia (mg/L N-NH3 )
Season 1 0.12 ± 0.05aA 0.03 ± 0.02aB 0.08 ± ± 0.05aA 0.06 ± 0.03aA 0.07 ± 0.02A
(0.00≤μ≤0.26) (0.00≤μ≤0.08) (0.00≤μ≤0.23) (0.00≤μ≤0.14) (0.03≤μ≤0.12)
Season 2 0.14 ± 0.04aA 0.14 ± 0.03aA 0.17 ± 0.04aA 0.12 ± 0.03aA 0.14 ± 0.02A
(0.03≤μ≤0.24) (0.05≤μ≤0.22) (0.06≤μ≤0.27) (0.03≤μ≤0.21) (0.11≤μ≤0.17)
Land use 0.13 ± 0.03a 0.08 ± 0.02a 0.13 ± 0.03a 0.09 ± 0.02a 0.11 ± 0.01
General (0.06≤μ≤0.20) (0.02≤μ≤0.14) (0.05≤μ≤0.20) (0.04≤μ≤0.14) (0.08≤μ≤0.13)
Nitrate (mg/L N-NO3 − )
Season 1 1.26 ± 0.73aA 3.42 ± 0.80aA 1.21 ± 0.43aA 3.90 ± 1.36aA 2.45 ± 0.50A
(0.00≤μ≤3.28) (1.21≤μ≤5.63) (0.00≤μ≤2.41) (0.13≤μ≤7.67) (1.40≤μ≤3.49)
Season 2 0.31 ± ± 0.10aA 1.64 ± 1.18aA 0.57 ± 0.28aA 0.90 ± 0.41aA 0.86 ± 0.32B
(0.03≤μ≤0.60) (0.00≤μ≤4.91) (0.00≤μ≤1.36) (0.00≤μ≤2.04) (0.19≤μ≤1.52)
Land use 0.78 ± 0.38b 2.53 ± ± 0.73a 0.89 ± 0.27ab 2.40 ± 0.84ab 1.65 ± 0.32
General (0.00≤μ≤1.64) (0.87≤μ≤4.19) (0.29≤μ≤1.49) (0.51≤μ≤4.29) (1.01≤μ≤2.29)
Nitrite (mg/L N-NO2 − )
Season 1 0.00 ± 0.00aA 0.00 ± 0.00aA 0.00 ± 0.00aA 0.00 ± 0.00aA 0.00 ± 0.00A
(0.00≤μ≤0.00) (0.00≤μ≤0.01) (0.00≤μ≤0.00) (0.00≤μ≤0.00) (0.00≤μ≤0.00)
Season 2 0.01 ± 0.00aA 0.01 ± 0.00aA 0.01 ± 0.00aA 0.01 ± 0.00aA 0.01 ± 0.00A
(0.00≤μ≤0.02) (0.00≤μ≤0.02) (0.00≤μ≤0.02) (0.00≤μ≤0.02) (0.00≤μ≤0.01)
Land use 0.01 ± 0.00a 0.00 ± 0.00a 0.00 ± 0.00a 0.00 ± 0.00a 0.00 ± 0.00
General (0.00≤μ≤0.01) (0.00≤μ≤0.01) (0.00≤μ≤0.01) (0.00≤μ≤0.01) (0.00≤μ≤0.01)
(1)
Land use and occupations conditions are shown in Fig. 1. (2) Season collection 1: May/2019. (3) Season collection 2: November/2019. (4) Averages followed
by the same horizontal (lowercase) and vertical (uppercase) letters do not differ significantly from each other by the t-test for independent samples (p ≤ 0.05). (5)
Confidence interval with estimated lower limit (negative value).

linity may come from the decomposition of organic matter and a high
respiratory rate of microorganisms (World Health Organization, 2017).
In Ethiopia, alkalinity values for shallow wells ranged from 45 to 295
mg/L CaCO3 (Brhane, 2018), showing that these waters may be receiv-
ing effluents that alter their original chemical properties.
The legislation currently requires MPV of drinking water for the
variable TH of 300 mg/L CaCO3 (BRAZIL, 2021). Thus, all the sample
means, regardless of the season or the land use and occupation condi-
tions presented values within the limits permitted by the legislation used
to compare the results (Table 1). The presence of multivalent cations
in the water reflects the geology of the watershed, with high hardness
values characterizing regions with limestone formations and lower val-
ues determining sandy or clayey terrains. The high mean values of TA
(64.24 ± 7.34 mg/L CaCO3 ) and TH (68.05 ± 7.36 mg/L CaCO3 ) in
the swine farming area may come from the feed used to raise the pigs
(Golombieski et al., 2003). Calcium is one of the nutrients found in an-
imal feed. Thus, swine manure, which is commonly used in crops, in
the form of fertilization, can reach the springs, thus raising the values
(p < 0.05) of the TA and TH variables.
The legislation does not establish an MPV for the EC variable. Thus,
the averages obtained in the present study, considering the land use
conditions, are between 52.40 ± 13.09 to 158.27 ± 15.34 μS/cm and the
averages between seasons are 86.99 ± 11.86 and 96.66 ± 14.39 μS/cm
(Table 1). Higher values of this variable in swine farming can derive
from residues of pharmaceuticals used in this area. Bhrane (2018) found
a variation between 382 and 772 μS/cm in shallow wells in Ethiopian
areas that received pharmaceutical waste.
For the temperature variable, the legislation does not establish MPV.
Thus, in this work, the averages obtained, considering the land use and
occupation conditions, were between 19.40 ± 0.52 to 21.86 ± 1.04
°C and the averages of the seasons studied were 19.04 ± 0.43 and
22.42 ± 0.54 °C (Table 2). The highest average in the second season fol-
lows the ambient temperature, with season 2 (November/2019) having
higher temperatures than season 1 (May/2019). Temperature values, as
well as pH values, do not cause harm to human health, however they
can favor the occurrence of other compounds and these are harmful, as
is the case of the growth of some microorganisms at high temperatures
(World Health Organization, 2017). Temperature values ranged from 27
to 30 °C in groundwater in Malawi, Africa (Missi and Atekwana, 2020).
MPV for the turbidity variable must be less than 5 NTU. Thus, con-
sidering the land use and occupation conditions, the native forest area
and swine farming raised averages higher than the MPV (Table 2). Con-
sidering the studied seasons, season 2 had higher averages than sea-
son 1. Turbidity is related to suspended or colloidal particles that ob-

5
D. Seben, M. Toebe, A.D. Wastowski et al.
Fig. 2. Dendrogram obtained by UPGMA grouping method from the Euclidean
distance for (A) environments (native forest, swine farming, soy and tobacco
crops) and seasons (S1 = May and S2 = November) and, (B) water quality vari-
ables (chemical, physical, chemical species and microbiological).
struct the passage of light through water and may interfere with treat-
ment processes, especially in water disinfection (World Health Orga-
nization, 2017). High values of turbidity concerning the native forest
are expected, considering that these watercourses have no masonry pro-
tection, only vegetation in their surroundings. When analyzing human
consumption wells in Ethiopia (Bhrane, 2018), turbidity values found
(ranging from 1.01 to 2.17 NTU) were in line with those acceptable by
WHO.
AC has MPV in drinking water legislation of 15 HU. Water origi-
nating from native forests and close to swine farming presented higher
values than those allowed by the legislation (Table 2). In the comparison
between the seasons of the study, the two stations present values higher
than those established by the legislation. Natural and anthropic inter-
ference can modify the physical, chemical, and microbiological charac-
teristics of water, especially in the production of sediments, influencing
turbidity values.
Considering the true color of the waters studied, the legislation does
not establish an MPV. Considering the land use and occupation condi-
tions, the averages were between 4.41 ± 4.33 to 21.23 ± 6.56 HU and
between study seasons, the averages for true color were 5.54 ± 2.27
6
Environmental Challenges 5 (2021) 100266
and 18.19 ± 5.22 HU (Table 2). The color values, apparent and true, are
consistent with the high turbidity values in the two study seasons.
The MPV according to the current legislation for drinking water for
human consumption establishes values of up to 0.3 mg/L Fe, which may
be higher, but with reservations that they do not exceed 2.4 mg/L Fe
(BRAZIL, 2021). In this research, all averages that consider the land use
and occupation conditions and study seasons obtained values higher
than the MPV, but below MPVs the maximum allowed with reserva-
tions, which is 2.4 mg/L Fe (Table 3). The origin of the total Fe found
in groundwater may be due to the discharge of pollutants or natural
sources of iron (Singh et al., 2013), natural constituents of soils. The av-
erage Fe value was 0.35 mg/L in groundwater Dingbian, China, with the
maximum established by local legislation which is 0.3 mg/L (Wu et al.,
2020), a similar result to what was found in the present study.
The TP variable does not have MPV by legislation for drinking wa-
ter. The general average values among the land uses for the variable
total phosphorus varied between 0.92 ± 0.31 to 1.41 ± 0.74 mg/L P.
The averages between the studied seasons were from 0.36 ± 0.03 and
1.91 ± 0.43 mg/L P (Table 3).
The MPV for F− ion is 1.5 mg/L (BRAZIL, 2021; World Health Orga-
nization, 2017). Thus, the general averages of the land use studied were
below MPV by law (Table 3). However, only the average of the first sea-
son was within the MPV for this variable. At high concentrations, this
variable is generally associated with groundwater (World Health Orga-
nization, 2017). High values of F− originate from the water-rock inter-
action and weathering of the apatite rock, and reports show that the
highest values of F− (ranging from 0.8 to 39.5 mg/L) were found, for
example, in groundwater in Malawi, Africa (Missi and Atekwana, 2020).
Ammonia has an MPV under Brazilian legislation of 1.2 mg/L N-NH3 ,
while WHO considers that groundwater can have up to 3 mg/L N-NH3 .
The general averages by land use and by seasons of this study are lower
than the MPV by the two legislations (Table 3). Places with intensive
animal farming may have higher NH3 values (World Health Organiza-
tion, 2017) as the presence of ammonia in the water is an indicator of
possible bacterial contamination, effluents, or animal waste. The WHO
establishes that the values of ammonia for surface and groundwater are
generally below 0.2 mg/L, which is observed in the present study. In
China, 15% of the analyzed groundwater has values for this variable
higher than what is established by local legislation, originating from
local urbanization and industrialization (Zhang et al., 2019).
General averages obtained in this research for NA (by land uses and
seasons) showed values below the maximum limit established by the
current Brazilian legislation and by WHO, which is 10 mg/L N-NO3 −
(Table 3). NO3 − is a chemical pollutant commonly found in under-
ground aquifers (World Health Organization, 2017), and it is the most
harmful to human health, and may come from the leaching of efflu-
ents, fertilizers or manure irrigation (Singh et al., 2013). In India, values
higher than the limits established by WHO were found in groundwater
(Singh et al., 2013). In Lusaka, Zambia, Africa, from the eight wells ana-
lyzed, only one had nitrate values above the maximum limit of 10 mg/L
N-NO3 − (Chande and Mayo, 2019).
The legislation establishes MPV for the variable NO2 − variable of 1
and 3 mg/L N-NO2 − , respectively. Thus, all general averages obtained
in the present study are in line with the MPV by legislation (Table 3).
Nitrite is not commonly present in the environment as nitrate is, how-
ever, if ingested in high concentrations it can cause cancer in humans
(World Health Organization, 2017). NI values ranged from 0.0 to 0.5
mg/L in groundwater in northern China (Wu et al., 2020).
Legislation concerning drinking water establishes the absence of to-
tal coliform microorganisms in 100 mL of water. For this reason, no
source analyzed is suitable for human consumption, when considering
this variable (Table 4). Masocha et al. (2019) analyzed 44 underground
wells in 12 different variables and found that 57% of them were unfit
for consumption, according to the WHO, as they had high values of total
coliforms and electrical conductivity. In Zambia, out of eight wells that
were analyzed, only one was adequate in terms of drinking water for
D. Seben, M. Toebe, A.D. Wastowski et al.
Table 4
Mean ± standard error of microbiological variables in water samples.
Land use(1) /Season Native Forest Swine Farming
Total Coliforms (MPN/100mL)(2)
Season 1(3) 20222.80 ± 1107.90aA(5) 5754.80 ± 3622.32bA
Season 2(4) 19356.60 ± 3156.15aA 12008.60 ± 5095.63abA
Land use General 19789.70 ± 1583.42a 8881.70 ± 3126.07b
Escherichia coli (MPN/100mL)
Season 1 243.20 ± 127.22aA 34.20 ± 20.17aA
Season 2 881.80 ± 807.50aA 66.40 ± 51.11aA
Land use General 562.50 ± 399.78a 50.30 ± 26.45a
(1)
Land use and occupation conditions are shown in Fig. 1. (2) Most probable number in 100 mililiters. (3) Season collection 1: May/2019. (4) Season collection
2: November/2019. (5) Averages followed by the same horizontal (lowercase) and vertical (uppercase) letters do not differ significantly from each other by the
t-test for independent samples (p ≤ 0.05).
human consumption, regarding the total coliform variable (Chande and
Mayo, 2019).
The Brazil (BRAZIL, 2021) and WHO (World Health Organiza-
tion, 2017) legislation establishes that, for human consumption, there
must be an absence of E. coli organisms in 100 mL of water. Thus, all
the springs sampled are not suitable for human consumption because
of this variable (Table 4). As an indicator of fecal contamination, this
type of microorganism cannot be found in an analysis of water used for
human consumption. When examining wells in Africa, out of eight wells
analyzed, seven of them had contamination of fecal origin, and did not
comply with local legislation (Chande and Mayo, 2019).
The presence of TC in the spring water of the native forest area may
be due to the fact that there is no local protection in terms of masonry
around these places, presenting only plant protection, where water is
exposed and accessible to wild animals in these areas. In the production
areas (soy crop, and tobacco crop and swine farming), where the water is
used for human consumption, there is masonry protection, in addition
to plant protection, and animals are not allowed access to this spring
water, resulting fewer microorganisms (TC and E. coli).
4.2. Emerging environmental contaminant (EEC)
The present study found pharmaceuticals (Table 5), paracetamol,
an analgesic drug and an antipyretic drug, indicated for the relief of
headaches, muscle pain, sore throat, toothache, and fever, among others
(AGÊNCIA NACIONAL), in addition to diclofenac (Sathishkumar et al.,
2020). Analgesic drugs were found in drinking water (0.12 μg/L) in
south Germany (Kuch and Ballschmiter, 2001) and in groundwater in
Korea (6.5 × 10−4 μg/L) (Lee et al., 2019). Diclofenac was found in
drinking water in Malaysia (1.8 × 10−4 μg/L) (Praveena et al., 2019).
In surface waters in Poland, 25 APs of drugs were analyzed at different
times of the year and paracetamol was found in the winter (0.1 μg/L)
and diclofenac in the autumn (2.9 × 10−2 μg/L) (Kot-Wasik et al., 2016).
In Italy, diclofenac and trimethoprim, which were found in the present
study, were ranked as low risk regarding environmental contamination
in water (Di Nica et al., 2015).
Norfloxacin, an antibiotic indicated for the treatment of urinary
tract infections (AGÊNCIA NACIONAL), was found in water season 1
(Table 5). Antibiotics (0.2 μg/L) have been found in North Ameri-
can groundwater (USA) (Wicks et al., 2005) and in Germany in post-
treatment water (6 μg/L) (Korner et al., 2000). The norfloxacin antibi-
otic was found in rural areas in Korea, Switzerland, Italy and China
(1.3 × 10−3 , 2 × 10−3 , 0.462 and 0.5 μg/L, respectively) (Lee et al.,
2019; Lópes-Serna et al., 2013; Morasch, 2013; Tong et al., 2014).
Pharmaceutical products can be introduced into water sources
through improper disposal of sewage (in inappropriate places or drug
disposal, in large quantities, in bathrooms), as well as through the agri-
cultural runoff of animal waste. The physical and chemical characteris-
tics of the water can influence the presence of these EEC, for example
in natural degradation (World Health Organization, 2017). None of the
two legislations (BRAZIL, 2021; World Health Organization, 2017) used
7
Environmental Challenges 5 (2021) 100266
Soy Crop Tobacco Crop General Season
10747.00 ± 5568.58abA 9942.40 ± ± 4301.01abA 11666.75 ± 2198.69A
6287.08 ± 4532.61bA 8068.40 ± 4421.19abA 11430.17 ± 2308.42A
8517.04 ± 3465.38b 9005.40 ± 2924.40b 11548.46 ± 1573.52
48.40 ± 30.52aA 25.00 ± 13.04aA 87.70 ± 36.86A
44.00 ± 41.29aA 257.60 ± 194.69aA 312.45 ± 206.37A
46.20 ± 24.22a 141.30 ± 99.82a 200.08 ± 105.02
as a comparison in the present study establishes MPV for pharmaceutical
products.
In EEC pesticides, Atrazine herbicide, indicated for pineapple, sugar
cane, corn, pine, rubber, sisal and sorghum crops (AGÊNCIA NA-
CIONAL), showed residues in most water samples in seasons 1 and 2,
when compared to the other AIs found (Table 5).
Clomazone herbicide is used in cotton, rice, irrigated rice, potatoes,
sugar cane, eucalyptus, tobacco, cassava, melon, corn, peppers and soy
(AGÊNCIA NACIONAL) and was found in the present study in spring
water in all land use and occupation conditions, including areas close
to swine farming, probably due to having more than one economic
activity on the properties (Table 5). It is soluble in water (> 1g/L),
slightly volatile (9.4 × 10−5 hPa) and, depending on the value of Henry’s
constant (4.14 × 10−8 atm.m3 /mol), it remains in the water column
(Locke et al., 1996), which explains the presence of this pesticide in the
studied water samples.
Studies support the present research, showing results in China with
65 AI pesticides, Atrazine showed residual in drinking water surface
samples (Dong et al., 2019), Zhou et al. (2020) of 16 AI, Carbendazim in
100% of the water samples (0.5 μg/L) and Imidacloprid in 88% (0.4 μg
/L). e a In Canada, 18 water samples: Atrazine and Clothianidin in 100%
of these (0.8 and 0.7 μg/L, respectively), Carbendazim (0.071 μg/L),
Imidacloprid (0.9 μg/L) and Tebuconazole (0.018 μg/L) (Metcalfe et al.,
2019).
In Malaysia, 13 AI were studied in surface wastewater and found:
Imidacloprid and Tebuconazole (in 100% of water samples), Trifloxys-
trobin (60%) and Buprofezin (80%) (Elfikrie et al., 2020). In Japan, in
a study of 12 sources of water for human consumption, Diuron and Im-
idaclopride (4.6 and 25.7% of water samples, respectively), (up to 0.01
μg/L), in addition to Clothianidin and Fipronil (19.9 and 5.7%, respec-
tively) were found (Kamata et al., 2020). Samples of tap and bottled
water in Vietnam (Wan et al., 2021; Wang et al., 2020), showed the
following maximum pesticide values, respectively: Atrazine: 7.5 × 10−2
and 3.1 × 10−4 μg/L; Carbendazim: 5.8 × 10−4 and 2.4 × 10−4 μg/L;
Fipronil: 1.3 × 10−4 and 4 × 10−5 μg/L; Imidacloprid: 2.84 × 10−3 μg/L
and <LOD; Simazine: 1.6 × 10−3 and 1 × 10−5 μg/L; Terbuthylazine:
1.9 × 10−4 and 1.8−4 μg/L and finally Clothianidin and Thiamethoxam
insecticides showed <LOD results for both water sources.
In the Netherlands, among the classes of pesticides with the highest
frequency of residual effects found in water were: first of all, herbicides,
with 35% presence (15% of these products are no longer authorized) and
which represents 2/3 of the total of compounds evaluated; while 10%
of the residuals were fungicides and5% insecticides (Swartjes and Van
der Aa, 2019). In the present work, similar results were found around
35% of the total number of compounds analyzed belonging to the class
of herbicides, corroborating the work previously described. However,
for the class of fungicides (35% of the total) and insecticides (30% of
the total) both were above the values found by those authors. Regarding
other pesticides, AIs found in the present study do not have MPVs in the
two drinking water laws used to compare our results (BRAZIL, 2021;
World Health Organization, 2017).
D. Seben, M. Toebe, A.D. Wastowski et al.
Table 5
Percentage (%) and mean occurrence (μg/L) of the EEC in water samples.
(1) ∗ ∗ ∗ ∗ ∗ ∗
, , and ∗ ∗ ∗ ∗ indicate, respectively, that one, two, three or four samples presented the pharmaceuticals or pesticide, but with values lower than the LOQ. (2)
The colors indicate that, respectively, 0, 20, 40, 60, 80 or 100% of the evaluated points had pharmaceuticals or pesticide.
Not all pesticides found in this research have MPV in the studied
current legislation. The pesticides that are present in Brazilian legis-
lation (Brazil, BRAZIL, 2021) and that were found in the work are:
Atrazine (MPV=2 μg/L) Carbendazim (MPV=120 μg/L), Chlorpyrifos-
ethyl (MPV=30 μg/L), Diuron (MPV=20 μg/L), Metribuzin (MPV=25
μg/L) and Tebuconazole (MPV=180 μg/L). WHO (World Health Orga-
nization, 2017), in turn, establishes MPV for the following pesticides
that were found in the survey: Atrazine (100 μg/L), Simazine (MPV=2
μg/L) and Terbutylazine (MPV=7 μg/L). All pesticides quantified in the
survey have lower values than the MPV established by the two legisla-
tions.
5. Conclusion
This research demonstrated that the different land uses and occu-
pation conditions did not alter the drinking water quality variables in
the Rio Grande do Sul State, Brazil. In general, the spring water of
the analyzed rural properties is suitable for consumption in terms of
physical and chemical variables. However, the microbiological vari-
ables, total coliforms and Escherichia coli were not within the maxi-
8
Environmental Challenges 5 (2021) 100266
mum allowed by current legislation and are not suitable for human
consumption.
In Brazil the use of pesticides in agriculture and pharmaceuticals
in animal production are intensive and usual. Emerging environmen-
tal contaminants were found both in the pharmaceuticals and pesticide
residues in all land use and occupation conditions and occupation of the
soil studied, showing that the evaluated water sources were not affected
by any interference. It is suggested to owners of rural areas, in case of
continued consumption of this water, that specific treatment should be
carried out to eliminate pathogenic microorganisms and EEC.
Considering the results obtained from developing this research, the
researchers intend to carry out future studies to eliminate these pesti-
cides and pharmaceuticals from spring waters.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
D. Seben, M. Toebe, A.D. Wastowski et al.
Acknowledgments
J. I. Golombieski thank to Coordenação de Aperfeiçoamento de Pes-
soal de Nível Superior (CAPES) for providing research fellowship to D.
Seben and all students undergraduate who are part of the GMA (Envi-
ronmental Monitoring Research Group of CNPq) and, that participated
in this study.
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