Environmental Science and Pollution Research (2018) 25:28713–28724

https://doi.org/10.1007/s11356-018-2899-9

RESEARCH ARTICLE

Mercury contamination in the sludge of drinking water treatment plants

dumping into a reservoir in Rio de Janeiro, Brazil
Julio Cesar Wasserman 1 & Letícia de Oliveira Silva 2 & Gabriela Cugler de Pontes 3 & Evaldo de Paiva Lima 4

Received: 7 February 2018 / Accepted: 2 August 2018 / Published online: 11 August 2018
# Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
Although sludge piles from drinking water treatment plants can contain harmful substances, in many countries, their disposal
methods are still unregulated. Besides aluminum, which is a major constituent in these residues, many other contaminants—like
trace metals—can be present and may result from the quality of the raw materials used for water treatment. The application of
these chemicals for the treatment of drinking water can generate toxic sludge and contaminate the produced water. In the present
work, mercury contamination in the sludge piles of two drinking water treatment plants located along the margins of the
Juturnaíba Reservoir, Southeast Brazil, was evaluated to verify whether contaminants are incorporated during water treatment.
In the summer 2012, five cores were collected from the piles, and were analyzed for Eh, granulometry, total carbon, total nitrogen,
and total mercury. The results indicated an anoxic environment, reflecting composition of the suspended matter. Carbon and
nitrogen presented elevated concentrations, but also seemed to reproduce the characteristics of the suspended matter in the raw
water. The concentrations of mercury were extremely variable but presented unexpectedly high values in some of the layers,
reaching 18,484 ng g−1. On the other hand, concentrations ten times lower than those observed in the natural system (8 ng g−1)
could be observed. It was concluded that the only possible source for the contamination of the sludge was the chemicals used for
water treatment.

Keywords Sludge piles . Flocculation . Suspended matter . Hg . Environmentalthreat . Drinkingwatertreatmentplant . Juturnaíba

Reservoir

Introduction freshwater reservoirs constitute a serious threat, because the

Many studies have shown that, although metallic mercury is an
insoluble element, it can be oxidized to the soluble ionic form
Hg(II) and eventually to the toxic methylmercury which in
Responsible editor: Severine Le Faucheur
* Julio Cesar Wasserman
geowass@vm.uff.br
1
Programa de Pós-Graduação em Geociências (Geoquímica), and
Pós-Graduação em Sistemas de Gestão Sustentáveis, Universidade
Federal Fluminense, Av. Litorânea, Institute of Geosciences, office
406, Niterói CEP 24210-346, Brazil
2
Pós-Graduation Program in Biosystems Engineering, Niterói, Brazil
3
Department of Geoenvironmental Analysis, Universidade Federal
Fluminense, Niterói, Brazil
4
EMBRAPA-Solos, Rio de Janeiro, Brazil
extensive food chains promote biomagnification. For instance,
Aula et al. (1994) carried out an extensive study in the Tucuruí
Reservoir (Brazilian Amazon) and observed that, although mer-
cury sources were very distant, concentrations in higher links of
the food chain like predator fish species (1.3 mg kg−1) and
caimans (1.9 mg kg −1 ) were very high. These high
biomagnification rates are associated with anoxic conditions
that can develop in reservoirs, allowing physico-chemical mod-
ifications like methylation (Coquery et al. 2003; Muresan et al.
2008). This phenomenon has been observed in the Lahontan
Reservoir, which receives contaminated materials from the
Carson River in Nevada, USA, where the concentrations of
methylmercury have increased considerably (Chen et al.
1996), causing contamination of fish within the lake
(Kuwabara et al. 2007). Intensive methylation of mercury has
also been associated with the periphyton of aquatic macro-
phytes in the Amazon (Coelho-Souza et al. 2011; Correia et
al. 2012). Frequently, these macrophytes are associated with
lentic environments, where anoxic conditions may develop.
28714
The main path to mercury contamination in humans is
through consumption of fish, which in the case of the above-
mentioned Tucuruí Reservoir (in Brazil) generated mercury
concentrations in human hair in the order of 47 mg kg−1.
This level is well above the concentrations that pregnant wom-
en should avoid (Alves et al. 2017), because the transfer of the
element to their offspring through the placenta is reported to
be dangerous (Brown and Austin 2012). In a mercury model
of the food chain in the Lahontan Reservoir (Nevada), Gandhi
et al. (2007) estimated that 9% of the methylmercury released
into the water column may be withdrawn from the system
through fishing. This may be a relevant source of methylmer-
cury for fishermen in the region.
In the above-mentioned cases, the mercury was originated
from gold mining that uses mercury in the process known as
patio where metallic mercury is mixed with ground river grav-
el to separate gold amalgam (Lacerda 1997), a recent activity
(1980s) in the case of Tucuruí Reservoir and a historical ac-
tivity (1860–1890) in the case of the Carson River (Lahontan
Reservoir). Besides gold mining, Reimann and de Caritat
(1998) reported the release of mercury from the chemical in-
dustry (caustic soda and chlorine production), from discarded
batteries, thermometers, barometers and mercury-vapor
lamps, from dental amalgam, from wood impregnants, and
detonators. Furthermore, mercury can also be naturally pres-
ent in the environment, as in volcanic dust (Stracquadanio et
al. 2003) and in the soils of the Amazon (Roulet et al. 1998;
Wasserman et al. 2003), where it can harm the entire trophic
chain.
It is worth noting that these reservoirs, where mercury
shows such unique behavior, are the main sources of fresh
water for large populations, and most of them host drinking
water treatment plants along their margins. In these drinking
water treatment plants, raw natural water is pumped into the
plant, where traditional procedures are applied to remove nat-
ural suspended matter, associated pollutants (Golfinopoulos et
al. 2017), and bacterial contamination (Pestana et al. 2016).
Among these procedures, the most used is the application of
aluminum sulfate as a coagulant (Al2(SO3)4 14H2O), which
agglomerates suspended matter into microflocs, then, slow
stirring promotes flocculation of the suspended material into
larger particles that settle easily (dos Santos et al. 2017). The
formed sludge in the bottom of the reaction tank and in the
filters is a residue containing the natural suspended matter, its
associated contaminants, and large amounts of chemicals (in-
cluding the previously mentioned aluminum sulfate) that have
been applied to promote settling. For many years, this material
has been carelessly discarded into the environment, generating
contamination with alum (Muisa et al. 2011), metals (Kyncl
2014), pesticides (Soares et al. 2017), and radionuclides
(Palomo et al. 2010). In Brazil, even though the disposal of
water treatment plant sludge is recognized as negatively
impacting the environment, there are no specific regulations
Environ Sci Pollut Res (2018) 25:28713–28724
for mitigating this damage, and this residue is largely disposed
of directly into the environment (Achon et al. 2013; Reis et al.
2007). The absence of serious concern about the disposal of
water treatment plant sludge into the environment (Reis et al.
2007) originated from the knowledge that it is relatively harm-
less under normal environmental conditions of pH and redox.
Indeed, the particulate matter (the main component of the
sludge) is the same as that found in the surrounding sediment,
from normal deposition.
Calcium carbonate is added in small amounts to correct pH,
yielding harmless calcium ions and bicarbonates. Aluminum
sulfate added in the same proportion as particulate matter
(Hargesheimer et al. 1998) is also supposed to be stable in
the environment, assuming regular pH conditions (Sposito
1996). Therefore, the Brazilian Association of Technical
Standards (2004) classifies these residues as class II-B (inert
residue): Bany residue that does not present, among its
solubilizable constituents, a concentration above the regula-
tion limits for potable water….^ Nonetheless, the composition
of the commercial chemicals applied is frequently impure, and
contamination of the reagents with many pollutants—includ-
ing mercury—may be attributed to the quality of the product
and the specific production lot. Hence, this contamination
may appear in the sludge pile, sometimes constituting a seri-
ous threat to the environment.
In the present work, we evaluated mercury contamination
of sludge piles of two drinking water treatment plants in
Juturnaíba Reservoir, Southeast Brazil. Although low values
were expected, high concentrations of mercury in the sludge
may indicate that the chemicals used in the operation may bear
this contaminant, constituting a hazard for the ecosystem.
Material and methods
Study area
The Juturnaíba Reservoir is located in the eastern portion of
the state of Rio de Janeiro, within the latitudes 22° 41′ 51″ S,
22° 35′ 07″ S and the longitudes 42° 21′ 71″ W, 42° 15′ 31″ W.
The reservoir was formed by flooding 42 km2 of the basins of
the São João, Capivari, and Bacaxá Rivers (Fig. 1) after the
construction of a dam. The Juturnaíba dam was constructed in
the late 1970s, but two drinking water treatment plants had
already been operating in the margins of the ancient
Juturnaíba Lagoon since 1960 (water treatment plant 1) and
1978 (water treatment plant 2). Both drinking water treatment
plants apply conventional procedures, pumping raw water
from the Juturnaíba Lake into a Parshall flume where floccu-
lants are applied (reagents are described in Table 1).
Flocculation and decantation occurs in tubular modules,
where a polymer is applied, and the clarified water goes into
a sand filter. Decanted, flocculated, and filtered material
Environ Sci Pollut Res (2018) 25:28713–28724 28715

Fig. 1 Location of the sampling sites (numbered) in both sludge piles from the water treatment plants (WTP)

constitutes the water treatment sludge that was discharged served population and the chemicals applied and an estimation
directly into the wetlands around the lagoon. Table 1, after of the amount of sludge, produced and disposed of in the
Almeida et al. (2017), shows the flow of produced water, the sludge piles, per period.
28716 Environ Sci Pollut Res (2018) 25:28713–28724

Table 1 Mass of sludge

produced, flow of produced Start/end of operation Disposal per Flow (m3 s−1)2 Served Chemical Applied2
water, served population, and period (tons)1 population2
chemicals applied per period of
operation for both drinking water WTP 1
treatment plants in the margin of 1960/1998 37,063 0.3 129,600 Aluminum sulfate/hydrated
the Juturnaíba Reservoir. lime/potassium permanganate
Calculations based on water 1998/2004 11,704 0.6 259,200 Aluminum sulfate/hydrated
production volumes and averages lime/potassium permanganate
of suspended matter (Almeida et
al. 2017) 2004/2011 16,256 1.0 432,000 Aluminum sulfate/hydrated
lime/potassium permanganate
Total 65,023
WTP 2
1978/1998 65,650 1.1 475,200 Aluminum sulfate/polymer/lime
1998/2004 17,904 1.0 432,000 Aluminum sulfate/polymer/lime
2004/2010 11,638 0.65 280,800 Aluminum sulfate/polymer/lime
Total 95,192
1
Calculated by Almeida et al. (2017)
2
Declared by the operating companies

The Juturnaíba Reservoir is recognized as the second larg-
est water supply in the state of Rio de Janeiro, with an esti-
mated volume of around 100 Mm3 (Barcellos et al. 2012),
providing potable water for a population of over a million
people from the municipalties of Silva Jardim, Cabo Frio,
Arraial do Cabo, Armação dos Buzios, São Pedro da Aldeia,
Iguaba Grande, Araruama, and Saquarema.
The concentrations of metals in the Juturnaíba Lake were
studied by Souza and Wasserman (2015), who observed that
concentrations of Al, Cu, Fe, Mn, Pb, and Zn were within the
limits of a pristine environment. Higher concentrations were
observed in aquatic macrophyte banks and associated with
intensive erosion of the margins in some spots. Although
sludge piles show very high concentrations of aluminum rang-
ing from 50.4 to 67.3 g kg−1 (Almeida et al. 2017), this metal
did not seem to spread over the system. The authors mention
that their sampling scheme did not consider the sludge piles,
and they therefore suggested that another sampling campaign,
with samples closer to these sources, should be carried out. In
a previous work, measuring mercury concentrations in surface
sediments, Souza and Wasserman (2014) showed that the el-
ement is well distributed within the reservoir, and little or no
influence from the sludge piles could be identified. The con-
centrations ranged from 60 to 200 ng g−1 (mean shale is 180
ng g−1), showing that the environment had not yet received
any artificial contamination with mercury. Considering that in
both works the same stations were sampled, the impact of
mercury from the sludge piles could not be identified either.
Sampling and analytical procedures
Five short sediment cores were collected from stations 1–5,
depicted in Fig. 1. One sediment core per station was hand-
collected with PVC tubes, which were pushed into the sludge
by vibrations of a rubber hammer. As the PVC tube was fully
threaded into the sludge, the upper end of the tube was capped,
and the tube was carefully withdrawn to avoid any disturbance
in the sediment layers. The core was transported in a vertical
position to a field laboratory, where it was sliced every 2 cm
(in the first 4 cm) and 3 cm in the remainder. The Eh (redox
potential given in millivolt) was measured with a portable Eh
meter, by penetrating the probe into the sludge. Slices were
carefully placed in pre-cleaned polypropylene flasks and
stored in a − 20 °C freezer until analysis.
In the laboratory, samples were separated into two frac-
tions, the first for granulometric analysis and quantification
of total organic carbon (TOC in percent) and total nitrogen
(N in milligram per gram) concentrations, and the second for
total concentration of mercury. Granulometry was carried out
by humid sieving in 63-μm screens, enabling the quantifica-
tion of the silt-clay fraction (< 63 μm in percent). TOC and
total nitrogen were analyzed in freeze-dried samples with a
Perkin-Elmer CHNS/OPEZ 400 Series analyzer at
EMBRAPA-Solos, Jardim Botânico (RJ, Brazil). The proce-
dure consists of combustion at 950 °C under a pure oxygen
atmosphere, and the products were carried to an infrared de-
tector that measures concentrations of carbon dioxide and ni-
trogen oxides.
The second fraction of the sample was analyzed for total
concentration of mercury in the Water Quality Laboratory of
the Geosciences Institute at University Federal Fluminense
(Niterói, Brazil). The digestion of the humid sample was car-
ried out with a 50% aqua regia solution (HCl:HNO3; 3:1) in a
kinetic thermo-reactor (cold-finger) at 60 °C for 30 min
(Malm et al. 1989). Five-milliliter aliquotes of the extracts
were derivatized with SnCl 2% and measured in a Lumex
Environ Sci Pollut Res (2018) 25:28713–28724
Zeeman correction cold-vapor atomic absorption spectropho-
tometer (model +RA915).
The sample analyses were carried out in batches where
blank samples and standard reference materials (PACS-3
from the National Research Council of Canada) were simul-
taneously evaluated, allowing determination of the quality-
assurance and detection/quantification limits of the method.
A total of 19 blank samples were analyzed and the
detection/quantification limits were calculated by multiplying
by 3 or by 5 the standard deviation of the results respectively
(Funk et al. 2007). The standard reference material was ana-
lyzed six times falling within the limits of the certified stan-
dard deviation. The results are presented in Table 2.
Data and statistical treatment
Data were presented in graphs showing variation of concen-
trations with depth. Correlation coefficients of the different
profiles were calculated with the software Statistica®
(Statsoft). Each parameter and each core were considered as
a single variable in the calculations, so the Spearman (ranked
non-parametric) test was applied because the number of sam-
ples ranged from 8 to 11. Non-parametric statistics are consid-
ered more robust than parametric in representing environmen-
tal variations with a few number of samples (Conover and
Iman 1981). With the aim of verifying whether sludge cores
were subject to variable loads of mercury, a statistical com-
parison of means between cores was applied. The more com-
mon comparison of means applied is the t test (Student); how-
ever, the cores in the present work have not the same number
of layers and the number of values in each core is small, so a
non-parametric statistics is more adequate. The Mann-
Whitney U test (Mann and Whitney 1947) is an evolution of
the Wilcoxon rank-sum test where values are not paired (not
necessarily the same number of values per core) that is the
most adequate for the comparison of means between each
Table 2 Results of the analyses of blanks and of standard reference
material (PACS-3 from the National Research Council of Canada) carried
out simultaneously on samples
Reference material Hg concentration (ng g−1) Recovery (%)
1 3092.6 103.8
2 3205.1 107.6
3 2972.0 99.7
4 3239.4 108.7
5 2606.7 85.7
6 2789.1 91.7
Certified 3000 ± 500
Detection limit 3.9
Quantification limit 6.5
28717
core. The same statistical package was applied for this
evaluation.
Results and discussion
As stated in the introduction, the nature of the material dis-
posed of in sludge piles is suspended matter and the incorpo-
rated reagents that promote settling, so that it was expected
that the concentrations of contaminants would reflect those of
the settled sediments plus the chemicals. However, the
chemicals applied (aluminum sulfate, hydrated lime, and
small amounts of potassium permanganate and polymers)
could have been contaminated with a myriad of pollutants.
Considering the large amounts of chemicals acquired in a
drinking water treatment plant, the origin of these chemicals
is diverse and is correlated mostly with the price and the
location where the raw material was mined. Hence it is
possible that one lot of aluminum sulfate would be bought
from a local producer and another lot from a producer
somewhere in the world. Whether these chemicals are
effectively tested for a full range of contaminants is
questionable. In the literature, we found a study by Giroussi
et al. (1996) that evaluated mercury contamination in alumi-
num sulfates applied in drinking water treatment plants from
Poland. The range of concentrations observed by these au-
thors varied between 500 and 1000 ng g−1. Supposing that
this mercury does not go into the produced water (which
would be catastrophic), it would be incorporated into the
sludge, making these residues much more harmful.
Although a Brazilian Ministry of Health regulation ((Brazil
2011) establishes drinkable water quality criteria (including
mercury), monitoring is not frequent and contamination from
reagents is overlooked by companies. Further, the Brazilian
standard 15784:2017 for reagents to be applied in drinking
water treatment plants (Brazilian Association of Technical
Standards 2017) establishes limits for contaminants, but there
is no registry whether the used products were certified with
this standard.
In order to characterize the sludges, Figs. 2, 3, 4, and 5
present the profiles of Eh, granulometry, TOC, and total nitro-
gen, respectively. The Eh was expected to be negative (Fig. 2),
because the environment of the sludge is not subject to any
kind of aeration or hydrodynamic pressure. Furthermore, con-
sidering that a large portion of material composing the sludge
is suspended matter, which presents high concentrations of
carbon (Bouillon et al. 2009), any diffusion of oxygen is im-
mediately consumed by non-refractive carbon compounds
within the sludge. Sulfide concentrations were not measured
but considering the large amounts of sulfates incorporated in
the sludge and the dominant reducing conditions, it can be
safely stated that there were large conversions of sulfate into
sulfide. The presence of sulfides may severely affect the
28718 Environ Sci Pollut Res (2018) 25:28713–28724

Fig. 2 Eh in the sediment profiles

from WTP 1 (cores 1–3) and
WTP 2 (cores 4 and 5)

behavior of mercury through the bacterial formation of meth- The granulometry of the sludge was variable (Fig. 3), com-
ylated species (Benoit et al. 2001), or through the formation of posed of fine-grained material layers interleaved with coarser
mercury sulfides (Kim et al. 2004). granulometry. Although the sieving was carefully carried out,

Fig. 3 Granulometry fractions

smaller than 63 μm in the
sediment profiles from WTP 1
(cores 1–3) and WTP 2 (cores 4
and 5)
Environ Sci Pollut Res (2018) 25:28713–28724 28719

Fig. 4 TOC in the sediment

profiles from WTP 1 (cores 1–3)
and WTP 2 (cores 4 and 5)

it is possible that the ultrasound applied to disaggregate the flocculating agents. Actually, it is not likely that the
sediments was not efficient, because of the presence of the granulometry of this material would be coarse, because

Fig. 5 Total nitrogen in the

sediment profiles from WTP 1
(cores 1–3) and WTP 2 (cores 4
and 5)
28720
suspended matter normally presents a very fine granulometry,
plus organic matter and phytoplankton.
The concentrations of TOC are presented in Fig. 4. As
can be observed, the values were relatively high, ranging
around 10%, but corresponding more or less to values that
are usually encountered in suspended matter. In the Petit
Sault Lake, French Guyana, De Junet et al. (2009) ob-
served concentrations of organic carbon ranging from 2
to 40% in suspended matter composed of living and dead
phytoplankton and detritic organic matter. Wasserman
(2012) monitored concentrations of particulate organic
carbon in the water of the Juturnaíba Lake for 20 months,
at three stations (surface and bottom), and observed a
mean concentration of 25.2 ± 26.3% of carbon in the
suspended matter. Considering that the sludges were part-
ly composed of suspended matter and chemicals (particu-
larly aluminum sulfate), the values we obtained in Fig. 4
are coherent.
In Fig. 4, it can also be observed that there is little variation
with depth, showing that there was no remarkable modifica-
tion of the process over time. Although the drinking water
treatment plants are located 3.5 km apart, it is not possible to
identify any relevant differences between their sludges (cores
1, 2, and 3 were from WTP 1 and cores 4 and 5 were from
WTP2), showing that the raw water from the two plants was
probably similar (Wasserman 2012).
Figure 5 shows the variation of concentrations of total ni-
trogen in the cores from the two stations, and it is possible to
observe that the behaviors of the two elements, carbon and
nitrogen, are similar. This is corroborated by the Spearman
(non-parametric) correlation coefficients for each of the pro-
files as shown in Table 3, indicating that except for T2, all
cores had extremely high correlation (p < 0.01), and Core T2
still presents a very high correlation (p < 0.05). These high
correlations between carbon and nitrogen are probably the
result of the association of nitrogen exclusively with organic
matter, i.e., all nitrogen present in the sludges is probably
organic. The C/N ratios presented in Fig. 6 give an idea of
the nature of the organic matter. The elevated values, ranging
from 8 to 16 in all cores, show a rather lignified organic mat-
ter, with a small contribution from autochthonous producers
(Meyers and Ishiwatari 1993). These results give a good idea
of the characteristics of the sludges where concentrations of
mercury were measured and allowed us to evaluate possible
sources for this metal.
Table 3 The Spearman
correlation of nitrogen and carbon Core 1
in each of the analyzed cores
Level of significance 0.01
Spearman correlation 0.74517
n 12
Environ Sci Pollut Res (2018) 25:28713–28724
The results shown in Fig. 7 represent the profiles of con-
centrations of mercury in the cores. For all the sludge cores,
very strong variations were observed with depth, indicating
that this material is heterogeneous. This heterogenicity can be
explained by the fact that the sludges had been disposed of in
different locations over time, in such a way that every layer of
the sludge column received material from different time pe-
riods. It can also be observed from Fig. 7 that concentrations
can reach extremely high concentrations (18,484 ng g−1), and
yet very low concentrations (8 ng g−1) could also be observed.
It was expected that concentrations in the sludge would
reflect the concentrations in the sediments of the lake. In the
work of Souza and Wasserman (2014), the distribution of
mercury in the Juturnaíba Reservoir was studied, and the con-
centrations presented a very common environmental varia-
tion, ranging from 50 to 200 ng g−1. Considering that the
sludge’s principal source is suspended matter, and which is
the same suspended matter that forms the sediment of the
reservoir, it is incontrovertible that the sludge and the
sediments should have similar concentrations, except for the
incorporated chemicals. Considering that these chemicals
were used to treat drinking water, it can be expected that
they would present low contamination, following
prescriptions of Brazil (2011) and Brazilian Association of
Technical Standards (2017). However, it is probable that the
frequency of the monitoring of mercury in the produced water
is not sufficient, and not all contaminants are controlled in the
chemicals used in the process. Although the mercury can be
expected to be present in all chemicals, including lime, it is
probable that such high levels of contamination are associated
with aluminum sulfate, because it is added in greater quanti-
ties. In the work of Giroussi et al. (1996), the analysis of
mercury in commercial aluminum sulfate from Poland used
for water sanitation showed concentrations in the order of
1000 ng g−1. In the case of some layers of the sludge from
Fig. 7, the estimated concentration in the chemicals was prob-
ably much higher (perhaps reaching 36,000 ng g−1), because
dehydrated aluminum sulfate is diluted in the suspended ma-
terial in a proportion of 1:1.
Considering that the elevated concentrations can be ex-
plained by the use of mercury-contaminated aluminum sul-
fate, the use of different lots of this chemical, originating from
different industries that use different raw minerals, would ex-
plain the variation in the concentrations. For instance, the
lower concentrations of mercury observed in core 4 were
Core 2 Core 3 Core 4 Core 5
0.05 0.01 0.01 0.01
0.650459 0.981745 0.992982 0.928571
10 11 12 8
Environ Sci Pollut Res (2018) 25:28713–28724 28721

Fig. 6 Ratio of total organic

carbon to total nitrogen in the
sludge profiles from WTP 1
(cores 1–3) and WTP 2 (cores 4
and 5)

probably the result of the use of a very clean aluminum sulfate of 60 ng g−1 (Souza and Wasserman 2014) to half of this
that would dilute the suspended matter from a minimum value value. However, still lower concentrations (8 ng g−1) were

Fig. 7 Total mercury

concentrations in the sediment
profiles from WTP 1 (cores 1–3)
and WTP 2 (cores 4 and 5)
28722 Environ Sci Pollut Res (2018) 25:28713–28724

Table 4 Result of application of

the Mann-Whitney U (Mann and n1 n2 U value Critical value Z score p value Result
Whitney 1947) test for the (p < 0.01)
comparison of means of mercury
in different cores collected in the Core 1 × core 2 12 10 44 21 −1.02204 0.308 NS
sludge piles Core 1 × core 3 12 11 12 24 3.2927 0.001 S
Core 1 × core 4 12 12 15 27 3.26203 0.001 S
Core 1 × core 5 12 8 13 15 2.66173 0.008 S
Core 2 × core 3 10 11 7 18 3.34485 0.001 S
Core 2 × core 4 10 12 8 21 3.39581 0.001 S
Core 2 × core 5 10 8 7 11 2.8877 0.004 S
Core 3 × core 4 11 12 53 24 0.76932 0.441 NS
Core 3 × core 5 11 8 28 13 − 1.27987 0.201 NS
Core 4 × core 5 12 8 37 15 − 0.84867 0.395 NS

n1 number of values in the first core, n2 number of values in the second core, S similar, NS not similar

observed that should be attributed to application of lime. In a
preliminary work, Melamed and Villas-Boas (2000) sug-
gested liming as an efficient process for the reduction of the
solubility of metallic mercury (Hg0). Therefore, buffering the
raw water would promote the stripping out of part of the mer-
cury of the solution to the bottom of the reservoir, which
would not be included in the flocculated material.
In a comparison of mercury concentrations means between
cores (Table 4), applying the Mann-Whitney U test, it was
observed that there are large differences between cores 1 and
2 (WTP 1) and between cores 3 (WTP 1), 4 (WTP 2), and 5
(WTP 2). The variations in mercury concentrations in both
sludge piles can be attributed to a distribution of the sludge
in the moment of the disposal. For the whole operation of both
WTPs, the muddy/liquid sludges were disposed from a point
source, flowing through the pile like a river delta and spread-
ing the particles throughout the pile. During the periods where
the chemicals were contaminated, concentrations of mercury
would differentially increase in certain areas and layers, gen-
erating varying concentrations.
Conclusions
Regardless of the improvements in regulations, in this work,
the results show that the application of chemicals to remove
suspended matter from raw water may constitute a source of
contamination of the sludges. The inadequate disposal of these
residues in sludge piles close to raw water input systems may
threat the quality of the drinking water produced.
The sludge contents should reflect the composition of the
suspended matter, but the high levels of mercury show that a
secondary source of contamination may be associated with the
chemicals applied in the flocculation process. Commercial
aluminum sulfate is a possible source for the extremely high
values observed. On the other hand, uncontaminated
chemicals may dilute the sludges and are responsible for ex-
tremely low concentrations of mercury, also observed in some
levels of the studied cores.
As it was shown in the present study, levels of contamina-
tion in some of the commercial chemicals used in drinking
water treatment plants are an emerging issue and further stud-
ies that quantify this contamination are necessary. Presently, in
the studied drinking water treatment plants, sludges are cen-
trifuged, dried, and are disposed in sanitary or industrial land-
fills. However, the historical sludge piles constitute a liability
that has to be manage in the next few years, thereby avoiding
any risk of contamination of the lake waters.
Funding information The authors are grateful to FAPERJ for the finan-
cial support through the program Pensa-Rio (grant no. E-26/110.694/
2012). JCW is also thankful to the Brazilian Council of Scientific and
Technological Development (CNPq) for a research grant (grant no.
306714/2013-2).
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