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Mercury in the Waters of the Jundia River,

SP, Brazil: The Role of Dissolved Organic


Matter
Enelton Fagnani, Jos Roberto
Guimares & Pedro Srgio Fadini

Aquatic Geochemistry
ISSN 1380-6165
Volume 18
Number 5
Aquat Geochem (2012) 18:445-456
DOI 10.1007/s10498-012-9169-0

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Aquat Geochem (2012) 18:445456
DOI 10.1007/s10498-012-9169-0
ORIGINAL PAPER

Mercury in the Waters of the Jundia River, SP, Brazil:


The Role of Dissolved Organic Matter
Enelton Fagnani Jose Roberto Guimaraes Pedro Sergio Fadini

Received: 12 November 2010 / Accepted: 20 April 2012 / Published online: 26 May 2012
 Springer Science+Business Media B.V. 2012

Abstract Many developing countries have regions of high demographic density, where
untreated residuary waters from different sources are often discharged into rivers, streams
and other water bodies. This paper discusses the reducing action of organic matter of
anthropic origin on the mercury redox cycle in the Jundia River impacted by discharged
wastes, and on the Pira River, a non-impacted water body. The total mercury concentrations in these locations vary from 1.7 to 32 ng L-1 in the former and from 0.6 to
10.6 ng L-1 in the latter. Dissolved organic carbon concentrations of up to 68.3 and
6.5 mg L-1 were observed, confirming the higher impact on the Jundia River. It was
found that an inverse correlation between the concentration of dissolved organic carbon
and total mercury was stronger in the Jundia River, given that it receives higher organic
loads, suggesting that organic matter exerts a reducing action on mercury, which is
released as gas into the atmosphere. This correlation was not observed in the Pira River,
where the organic matter of natural origin is probably not sufficiently labile to act intensely
upon the Hg redox cycle, favoring the metal transport.
Keywords

Mercury redox cycle  Jundia River

1 Introduction
Mercury is a chemical element known for its toxicity and ability to bioaccumulate and
biomagnify (Drott et al. 2008), presenting a complex biogeochemical cycle which is not
fully understood (Ravichandran 2004; Fitzgerald et al. 2007). The various chemical species

E. Fagnani  J. R. Guimaraes
Faculdade de Engenharia Civil, Arquitetura e Urbanismo, Universidade Estadual de Campinas
(UNICAMP), POB 6021, Campinas, SP 13083-852, Brazil
P. S. Fadini (&)
Departamento de Qumica, Universidade Federal de Sao Carlos (UFSCAR), POB 676, Sao Carlos, SP
13565-905, Brazil
e-mail: psfadini@ufscar.br

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of mercury include elemental mercury, Hg (0), the inorganic forms, Hg(II) and Hg(I),
mainly chlorides and sulfates, and the inorganic forms such as methylmercury, MeHg.
Methylmercury is formed mainly in anoxic waters and sediments (Covelli et al. 2008),
and its presence in water is controlled by methylation and demethylation process (Morel
et al. 1998). In some animals, MeHg is retained in fatty tissues, but liposolubility does not
explain the bioaccumulation in fish muscles. In this case, the intestine wall is responsible
by the absorption (Boudou and Ribeyre 1997).
In sulfidic sediments, Hg(II) complexes with sulfur and enters the cellular membrane as
soluble neutral HgS where it undergoes methylation (Benoit et al. 1999). Once methylmercury is formed, its solubility is facilitated in large quantities of dissolved organic matter
(DOM), increasing its concentration in the aqueous phase (Ravichandran 2004), and it can
subsequently be destroyed (demethylation) by both abiotic and biotic processes (Morel
et al. 1998).
In aquatic environments, mercury fluxes occur at the water/atmosphere and water/
sediment interfaces. In the atmosphere, mercury exists predominantly in gaseous form as
Hg(0), but also as divalent reactive gaseous mercury (RGM) or as particulate mercury,
which is RGM adsorbed in particles suspended in the air, such as soot, dust and marine
aerosols. The passage of mercury from air to water may be the result of dry deposition
(Fang et al. 2010), wet deposition or invasive fluxes of Hg(0) that occur when water is
undersaturated in relation to the atmosphere (Jardim et al. 2010; Silva et al. 2006, 2009a,
b). A contribution of mercury in aquatic environments may also occur through silting
processes (Liu et al. 2008).
Intercompartmental mercury fluxes are affected by natural phenomena such as volcanism, rainfall, wind velocity, solar intensity and temperature, and by anthropic interventions linked to industrialization, mining and the use of fossil fuels, among others. These
phenomena, in turn, cause changes in pH, redox conditions and in the concentrations of
sulfides, organic matter, oxyhydroxides and carbonates in the water column and sediments,
influencing strongly and impacting the benthic and microbial community (Hatje et al.
2009; Hung et al. 2009; Zhong and Wang 2008).
At the water/atmosphere interface, solar ultraviolet (UV) radiation can induce photochemical modifications in mercury speciation (Peters et al. 2007), an action that is variable
during the day (Garcia et al. 2005a, b; Jardim et al. 2010). Humic and fulvic acids, the
predominant forms of aquatic organic carbon (De Oliveira et al. 2007), are able to reduce
Hg(II) to Hg(0), and the latter is carried easily from the water column to the atmosphere,
decreasing the methylation and bioaccumulation potential of the water body as was
observed in rivers of the Amazon region and described by Jardim et al. (2010). On the
other hand, organic matter contains acid sites, such as carboxylic and phenolic acids, which
are able to complex metals and, particularly in the case of mercury, thiols, sulfides and
other reduced sulfurated groups, rendering the metal unavailable for chemical redox
reactions and anchoring it in the water column (Barringer et al. 2006; Chadwick et al.
2006), thereby increasing the bioaccumulation potential.
Dissolved organic matter is the most important phase related with the transportation of
mercury in water. Its complexing capacity is due mainly to reduced sulfur functional
groups such as thiols, which are present in minor quantities but which act as strong metal
ligands (Haitzer et al. 2003). The type and lability of dissolved organic matter may imply
complexation mechanisms of adsorption and even interfere in the mercury redox cycle
through the formation of H2O2, which can both oxidize and reduce mercury species
depending on the pH. In an acid medium, the proton competes for the acid sites of DOM,
causing it to lose much of its metal-complexing potential and leaving the Hg free to

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undergo methylation, since the pKa of the thiol groups is higher than the pH values
frequently found in acid waters (Haitzer et al. 2003).
Methylation is favored (Bisinoti et al. 2007) by microbiological growth in more labile
and degradable DOM. However, if sufficiently labile, this same organic matter can act
directly upon mercury, reducing it chemically and preventing it from remaining in the
water (Lalonde et al. 2004; Silva et al. 2009a, b; Jardim et al. 2010). Hence, speciation
processes are governed not only by the quantity but also by the type of DOM (Han et al.
2006). That is why several methodologies involving molecular fluorescence have been
proposed to elucidate the composition and formation kinetics of HgDOM complexes in
the environment, using three-dimensional techniques and fluorescence quenching titration
(Wu et al. 2004; Fu et al. 2007).
When positive correlations are found between Hg and DOM concentrations in a water
body (Dennis et al. 2005), this usually means that the Hg originates from floodable areas
and soils rich in organic matter and leaches into the water body under study (Akerblom
et al. 2008). However, when Hg comes predominantly from atmospheric sources, this
correlation with organic matter is not always unequivocal (He et al. 2007).
In waters containing high concentrations of mercury comparatively to humic acids, the
latter usually promote the chemical reduction of the metal. Conversely, when the concentration of humic acids is very high, three important events occur. The first of these
events is inhibition of the photochemical reduction of Hg due to the lower penetration of
the solar radiation as a result of the dark color of the water; the second is the ability of
humic acids to complex the metal (ODriscoll et al. 2006); and the third is that the direct
oxidation of DOM by UV radiation may also produce hydroxyl radicals (OH) that are able
to oxidize Hg(0) into Hg(II) (Whalin et al. 2007).
Because the behavior of the HgDOM system varies in each region, studies were
conducted in the Jundia River watershed in the state of Sao Paulo, Brazil, to looking for
insights into the linkage between DOM and Hg in this location. The present study therefore
focused on the Jundia River, several stretches of which are impacted by domestic and
industrial effluents, and the Pira River, an important tributary that supplies water for
human consumption (Fadini et al. 2004), pointing out for a hypothesis that the organic
matter of anthropic origin have a reductor agent role over the mercury on its cycle.

2 Methods
2.1 Area Descriptions
The Jundia River, which is approximately 110 km long and drains an area of 1,114 km2, is
located in a highly industrialized region of the state of Sao Paulo (PCJ 2007). This intense
industrialization will soon make it imperative to find alternative sources of water supply for
the cities located in this hydrographic basin, which is home to approximately one million
people.
In this context, the Jundia River stands out as a strategic water resource. However, at
the moment, it is the recipient of industrial and urban wastewaters from innumerable
sources, often without any type of treatment.
The National Environmental Agency, a Brazilian federal legislative body, classifies
water bodies into four categories, where class 1 indicates non-impacted waters and class 4
indicates waters highly impacted by humans (CONAMA 2005). Due to its high level of
contamination, the Jundia River is classified according to this index as class 4 along most

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of its length and independently of the time of year. On the other hand, the Pira River, a
tributary of the Jundia River and also an object of study, can be classified as class 2 due to
the quality of its waters.
2.2 Sampling
Three (03) water sampling sites were selected in the Jundia River and one (01) in the Pira
River, its main tributary. The abbreviations and coordinates of the four sampling sites are,
respectively, CLP (S = 238 12.3800 ; W = 468 47.0190 ), downstream from a metal workshop in the city of Campo Limpo Paulista; DIST (S = 238 8.1550 , W = 478 12.6740 ), an
industrial district in the city of Indaiatuba; SALTO (S = 238 12.6150 , W = 478 17.5300 ), at
the mouth of the Jundia River in the city of Salto; and PIRAI (S = 238 11.0170 , W = 478
14.7860 ), which is close to the mouth of the Pira River in the city of Indaiatuba.
The CLP site is marked by strong human occupation, both domestic and industrial,
notably by the presence of a metal workshop. The DIST site is characterized by a high
diversified and active industrial park. The SALTO sampling site shows a strong presence
of domestic sewage and industrial effluents, including effluents from timber beneficiation,
and paint and varnish factories. PIRAI is the most well-preserved site in terms of vegetation and intensity of sewage disposal.
Field sampling was based on protocols described in the literature by Fadini and Jardim
(2000, 2001), which provide guidelines on clean procedures for the collection, preservation, transportation and storage of samples.
To determine the dissolved organic carbon (DOC), the water samples were collected in
glass jars with polyethylene lids, which were previously washed in a solution containing 20
volume % of sulfuric acid, rinsed in ultrapure water and dried. The jars containing water
samples were then double-bagged and stored on ice in thermal boxes until the moment of
analysis, which occurred within no more than 48 h. Duplicate samples were collected at
each sampling site.
2.3 Determination of Total Mercury (THg)
During all the time, clean techniques were used, including gloves use, extractions inside
class 100 fume hood, samples storage in double plastics bags, blanks control, and carrying
out of analytical calibration curves at each analysis session and sample determinations in
triplicate, where the standard deviations were in the range of 5 %. Preparation of the water
samples for total mercury determination involved oxidizing all the Hg species into Hg2?,
using BrCl, as described by Bloom and Crecelius (1983) and by Fadini and Jardim (2001).
The samples were allowed to settle for 2 h, and the clarified supernatant was injected into
the equipment. In an extractor, the Hg2? was reduced with stannous chloride, purged with
N2 and amalgamated in a quartz column packed with gold-coated sand. Quantification was
performed by two-stage amalgamation and thermal desorption, followed by detection in
the Cold Vapor Atomic Fluorescence Spectrometry, CVAFS (Brooks Rand mercury
detector).
2.4 Determination of Dissolved Organic Carbon (DOC)
Carbon was quantified in a Shimadzu TOC-5000A total organic carbon analyzer, which
operates under the principle of high temperature catalytic oxidation (HTCO) at 680 C.

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The samples were allowed to settle for 2 h, and the clarified supernatant was injected into
the equipment. Results with standard deviation minor than 2 % were obtained.

3 Results and Discussion


The variables of total mercury (THg) and dissolved organic carbon (DOC) were quantified
and monitored at the various sampling points during the period of August 2007December
2008. Figure 1 and Table 1 show the THg results.
As can be seen from the data in Fig. 1 and Table 1, the samples collected in the Pira
River presented the lowest HgT contents, as well as the lowest amplitude of variation
among the results. This finding suggests that Hg contamination is lower and predominantly
of diffuse origin, characterizing the region as less impacted. The Jundia River presented
consistently higher concentrations of THg than the Pira River at all its sampling sites.
In the period between January and April 2008, water samples collected in the region of
the Industrial District of Indaiatuba (DIST) presented a peak in the values of THg on one
Table 1 Minimum, maximum and mean concentrations of THg in waters between August 2007 and
December 2008
THg (ng L-1)

Site

Max

Mean

SD and RSD

CLP

2.0

22.5

8.2

6.4 (78 %)

DIST

1.7

32.0

7.0

6.6 (95 %)

SALTO
PIRAI

2.1

17.2

5.2

3.6 (70 %)

0.6

10.6

2.1

1.9 (88 %)

34
32
30
28
26
24
22
20
18
16
14
12
10
8
6
4
2
0

CLP
SALTO
DIST
PIRAI

22

/0
8
14 /07
/0
9/
25 07
/1
0
21 /07
/1
1
09 /07
/0
1
20 /08
/0
2
25 /08
/0
3
30 /08
/0
4
04 /08
/0
6
07 /08
/0
7
20 /08
/0
8
15 /08
/0
9
13 /08
/1
0
24 /08
/1
1/
08

Total Hg (ng L-1)

Min

Sampling date
Fig. 1 Concentration of THg in water samples between August 2007 and December 2008

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occasion, characterizing pointwise discharges of effluents containing the metal in question,


whose source was not identified.
No clear and systematic correlation was identified between the seasons of the year and
the values of total mercury found in the water bodies under study, probably due to the
anthropic influence that mischaracterizes the possible natural relations that might be
observed (Caron and Lucotte 2008).
Figure 2 and Table 2 show the DOC findings.
The highest concentrations of dissolved organic carbon (DOC) were found close to the
mouth of the Jundia River in the municipality of Salto, SP (SALTO). This region is highly
urbanized and has a large industrial park, which are factors that directly influence the
composition of the Jundia River in terms of organic matter. The lowest DOC concentrations were found in the Pira River (PIRAI). The DOC concentrations were usually
found in the following increasing order: PIRAI \ CLP \ DIST \ SALTO, a relationship
that is valid for any time of the year.
In an attempt to gain an understanding of how DOC may interact with THg in the waters,
correlations between these two variables were tested for each sampling site throughout the

70
60
CLP
SALTO
DIST
PIRAI

DOC (mg L-1)

50
40
30
20
10

28
/0
8/
05 07
/1
0/
08 07
/1
1/
06 07
/1
2/
22 07
/0
1/
07 08
/0
3/
08 08
/0
4/
20 08
/0
5/
26 08
/0
6/
28 08
/0
7/
01 08
/0
9/
29 08
/0
9/
03 08
/1
1/
08

Sampling date
Fig. 2 Concentration of DOC in water samples between August 2007 and December 2008

Table 2 Minimum, maximum and mean concentrations of DOC in water samples between August 2007
and December 2008
Site

DOC (mg L-1)


Min

Max

Mean

CLP

4.6

10.5

7.1

DIST

5.1

13.3

9.4

2.2 (23 %)

SALTO
PIRAI

7.8

68.3

28.6

17.7 (62 %)

1.7

6.5

3.3

1.2 (35 %)

123

SD and RSD
1.5 (21 %)

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period of this study. Figures 3, 4, 5 and 6 illustrate how the variables of THg and DOC
correlated.
There is a positive correlation between THg and DOC in the PIRAI site, as illustrated in
Fig. 3. Because the site is relatively well preserved, it is assumed that the humic and fulvic
acids originating from the degradation of natural organic matter may basically present two
distinct effects on THg: complexation or chemical reduction (Ravichandran 2004). At the
PIRAI site, as in other water bodies rich in humic and fulvic acids (Dong et al. 2009;
Khwaja et al. 2010), the organic matter can complex mercury. Thus, the metal will have a
strong tendency to remain in the water column, acquiring good mobility along the river
course, rather than a transfer between the compartments waterair (volatilization and
photochemical reduction) or watersediment (sulfide precipitation and/or adsorption).
12

Fig. 3 Variation in the


concentration of THg as function
of DOC in the samples from the
PIRAI sampling site (September
2007December 2008).
Significant correlation at
p = 0.05 was observed

Total Hg (ng L-1)

10

r = 0.577

0
1

DOC (mg L-1)

Total Hg (ng L-1)

20

15

r = 0.05
10

0
4

10

11

DOC (mg L-1)


Fig. 4 Variation in the concentration of THg as function of DOC in the samples from the CLP sampling site
(September 2007December 2008). No significant correlation was observed

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35

Fig. 5 Variation in the


concentration of THg as function
of DOC in the samples from the
DIST sampling site (September
2007December 2008).
Significant correlation at
p = 0.10 was observed

30

r = - 0.338

Total Hg (ng L-1)

25
20
15
10
5
0
4

10

12

14

DOC (mg L-1)


18
16

Total Hg (ng L-1)

14
12
10

r = - 0.352
8
6
4
2
0
0

10

20

30

40

DOC (mg

50

60

70

L-1)

Fig. 6 Variation in the concentration of THg as function of DOC in the samples from the SALTO sampling
site (September 2007December 2008). Significant correlation at p = 0.10 was observed

Sampling data from the region of the CLP site presented slightly positive or null
correlation coefficients, suggesting that the concentration of THg is not affected systematically by the concentration of DOC. This weak correlation between THg and DOC is
probably due to competition between the reducing action of the organic matter (OM) of
anthropic origin and the complexing capacity of OM of natural origin (Jardim et al. 2010).
The CLP sampling site did not show a clear correlation between DOC and THg,
probably because this site is little impacted and lacks sufficient contents of labile organic
matter to trigger a significant process of Hg reduction and its release into the atmosphere.
Several types of industrial and domestic wastewaters are discharged into the Jundia
River in the region of the industrial district of Indaiatuba (DIST). What is noteworthy is the
inverse correlation from the one found in the Pira River, that is, the higher the content of

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organic matter, the lower the amount of mercury found. Based on an analysis of these data,
it seems feasible to suggest that the nature of the organic matter found in the region of the
industrial district differs considerably from that found in the Pira River because, rather
than concentrating mercury in the water compartment, it appears to effect a phase transfer,
probably into the atmosphere, in the form of elemental Hg via reduction of the Hg2?
cations. In this case, the complexing capacity of the natural organic matter is supplanted by
the reducing capacity of the organic matter of anthropic origin.
An analysis of the results obtained from monitoring the samples collected at the mouth
of the Jundia River in the municipality of Salto (SALTO) revealed a mercury dynamics in
the presence of organic matter analogous to that found in the industrial district of Indaiatuba (DIST). This finding is an indicator that the organic matter in this region plays a
similar role to that found in the industrial district, chemically reducing mercury and
releasing it into the atmosphere. This correlation followed the same trend during the entire
study, that is, an increase in DOC corresponded to a lower concentration of THg.
Data obtained in previous works presented and published in 24th Brazilian Meeting of
Sanitary and Environmental Engineering (Fadini and De Lima 2007), revealed the tendency of waters from Jundiai River to photoreduce dissolved mercury to elemental state.
Dissolved gaseous mercury (DGM) measurements were carried out in waters displaced in
transparent bottles spiked with Hg in pH ranged from 3.7 to 8.2. The organic matter was
responsible for the Hg reduction, corroborating to our main hypothesis.
This set of data on correlations between THg and DOC allows us to put forward the
hypothesis that, in a practically non-impacted environment such as that of the Pira River,
the organic matter appears in the form of large complex and stable molecules, that is,
humic and fulvic acids of natural origin, which are able to anchor mercury in the water
column. At sites strongly impacted by human activities, such as industrial parks, as is the
case of the Jundia River in the industrial district of Indaiatuba, as well as at its mouth in
the city of Salto, the more labile organic matter possesses reducing properties that are
responsible for releasing mercury from the water column into the atmosphere in the form
of Hg0. This, therefore, is evidence of the fact that organic matter plays an important and
differentiated role, depending on the characteristics of the contributions upstream from the
sample collection site.
Within the scenario of complexity of the biogeochemical cycle of mercury, the information presented in this paper highlights the fundamental role not only of organic matter
but also, and particularly, of its origin. DOM may or may not be responsible for keeping
mercury in the water column, influencing the global cycle of this metal, since, if it is
released into the atmosphere, Hg0 will have a mean residence time of 1 year in this
compartment, and hence, will be the object of intercontinental transport (Schroeder and
Munthe 1998). The results found in this study are consistent with those observed for DOM
of natural origin and with differentiated lability that exists in the Negro River, in the
Brazilian Amazonian region (Jardim et al. 2010).
Table 3 summarizes the correlations found between DOC and THg at the various
sampling site in the Jundia River basin, as well as a suggestion of the probable mechanisms of interaction between the metal and organic matter present at those sites.

4 Conclusions
The correlations between dissolved organic carbon (DOC) and total mercury (THg) in the
waters of the Jundia River basin observed in this study indicated that dissolved organic

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Table 3 Correlations between DOC and THg obtained from the waters of the Jundia and Pira rivers
Sampling
site

Correlation
THg 9 DOC

Probable THg dynamics

PIRAI

DOC :, THg :

Complexation with dissolved organic matter in the waters (humic and


fulvic acids)

CLP

Inconclusive

DIST

DOC :, THg ;

Chemical reduction of Hg2? to Hg0, with resulting release into the


atmosphere

SALTO

DOC :, THg ;

Chemical reduction of Hg2? to Hg0, with resulting release into the


atmosphere

matter (DOM) plays differentiated roles with respect to mercury dynamics, as a function of
the anthropic impact at each sampling site. Although an increment was found in the
organic load from upstream to downstream of the Jundia River, the DOM exhibited a
differentiated reducing action on the mercury in stock. In the Pira River, which is less
impacted, the DOM promotes chemical complexation of THg in the water column, facilitating its transport along the watercourse. In contrast, in the Jundia River, in the industrial
district of Indaiatuba and close to its mouth (SALTO), the DOM plays the role of chemical
reducer, transforming Hg(II) into Hg(0) and favoring its evasive flux at the water/air
interface. A weaker correlation was observed at the sampling site located in Campo Limpo
Paulista (CLP), probably due to the lower lability of the organic matter at this point, which
receives a low load of OM of anthropic origin.

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