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Biol Trace Elem Res (2012) 148:122–132

DOI 10.1007/s12011-012-9458-x

Determination of Distributions of Cd, Cu, and Pb


Concentrations in Sediments of a Mexican Reservoir
to Infer Their Environmental Risk
Icela Dagmar Barceló-Quintal &
Hugo Eduardo Solís-Correa & Pedro Avila-Pérez &
Edgar López-Galván & Sergio Gómez-Salazar &
Julisa García-Albortante

Received: 25 November 2011 / Accepted: 16 May 2012 / Published online: 2 June 2012
# Springer Science+Business Media, LLC 2012

Abstract The José Antonio Alzate Dam in the State of the total metals, using the criteria of EPA, Thomas and
Mexico, Mexico, receives wastewaters from domestic, Murdoch, and the Ontario Ministry of Environment for sedi-
industrial, and agricultural activities through the Lerma River. ment in water bodies. Subsequently, the risk was assessed
Chemical and physicochemical characteristics of the water using the same criteria but considering the results of sequential
were determined. Sediment has been studied in order to define extractions, where the geochemical distribution of each metal
the importance of its influence on the reservoir’s state as a allowed a better understanding of metal portions with more
whole. The quantification of the metals, Cd, Cu, and Pb in influence on the risk, in which Cu and Pb presented low risk,
total forms and the geochemical distribution and the chemical but not Cd.
mobility of these metals in sediment have been established
using a chemical sequential extraction scheme. The three Keywords Sequential extraction . Cd . Cu . Pb . Sediment
metals showed a common characteristic, being more abundant quality . Contamination
in fraction F6 (residual), but the other fractions of the geo-
chemical distribution were variable depending on the metal.
First, the contamination level was evaluated with the results of
Introduction

I. D. Barceló-Quintal (*) : H. E. Solís-Correa : The José Antonio Alzate Dam is located in the State of
E. López-Galván : J. García-Albortante Mexico, in Central Mexico, where there is temperate climate
Departamento de Ciencias Básicas, (Fig. 1). This dam is the most important water body in the
Universidad Autónoma Metropolitana—Azcapotzalco,
upper basin of the Lerma River. The reservoir is part of the
Av. San Pablo No. 180, Col. Reynosa Tamaulipas,
C.P. 02200, Del. Azcapotzalco, D.F., Mexico storage system for the control and integrated use of the
e-mail: ibarceloq@gmail.com Lerma River [1] that begins in the Almoloya lagoons [2]
and drains a large region of the high central plateau. Due to
I. D. Barceló-Quintal
e-mail: idbq@correo.azc.uam.mx
its favorable climate, intensive and diversified agricultural
activities have been developed in the region [1].
P. Avila-Pérez The bottom of this reservoir consists of lacustrine sedi-
Instituto Nacional de Investigaciones Nucleares, ment covered with a layer of organic soil of varying thick-
Gerencia de Ciencias Ambientales,
ness. The hydrogeology of the dam is an important factor in
Apartado Postal 18-1027, C.P. 11801, Cd de México, D.F., Mexico
flood control [3]. The José Antonio Alzate Dam has been in
S. Gómez-Salazar operation since 1962. There are more than 3,500 companies
Departamento de Ingeniería Química, located along this section of the river basin representing the
Centro Universitario de Ciencias Exactas e Ingenierías,
Universidad de Guadalajara,
food industry, chemical, pharmaceutical, metallurgical as
Blvd. M. García Barragán # 1451, well as the agrochemical sector, which discharge great
Guadalajara, Jalisco, Mexico quantities of polluting agents daily [4]. About 40 % of these
Cd, Cu, and Pb Concentrations in Sediments of a Mexican Reservoir 123

Fig. 1 Geographical location


of the José Antonio Alzate
Dam. A, B, and F are the zones
in this work F

industries use inorganic processes in their activities and Sedimentation may be an important factor in removing
discharge their wastewaters directly into the river, which in metals since they either tend to be adsorbed by organic and
turn transports the pollutants to the reservoir. Studies per- inorganic material [14, 15] or tend to form chemical bonds
formed by the Department of Ecology of the State of Mex- with components of the sediment. In the water phase, a large
ico considered the Lerma River basin as one of the most proportion of dissolved metals are adsorbed by particulate
highly polluted river basins in the country [5], especially in matter controlled by physicochemical conditions [15, 16].
the section located downstream of the industrial zone [6]. However, in spite of their important affinity towards
Like many of the water bodies in the region, the Lerma sediments in this body [17, 18], metals can be released and
River receives urban, industrial, and agricultural waste- undergo through a continuous exchange between sediments
waters, most of them untreated [7]. This river carries pollu- and the water column. These processes pose a risk of sec-
tion to José Antonio Alzate Dam, among the anthropogenic ondary contamination into the water column [19]. On the
wastes transported by the Lerma River are heavy metals, other hand, metals have different affinities to the solid
which accumulate in the reservoir and are therefore present phase, and its geochemical distribution in the sediment can
in the sediments within the reservoir itself [8, 9]. The level be modified when physicochemical conditions change
of contamination of the reservoir varies seasonally with the [20–22]. Some studies have shown that generally an in-
water level; however, this dam serves as a scavenger of crease in metal concentrations is positively correlated to a
contaminants from the Lerma River, although this is not its decrease in sediment particle size, an increase in the specific
principal function [2]. One of the mechanisms of water area of sediments, and to higher concentrations of organic
purification of this dam is its ability to sediment, which over matter and iron and manganese oxides [16, 23]. Several
time allows the transport of organic and inorganic pollutants studies [3, 24–26] have been performed to determine wheth-
to the bottom [3]. er the water and sediment may represent a pollution hazard
Since the sediment is the final receptor of trace metals in for the crops, soil, and human health, and even damage the
the water body [10], the metal content was determined in the autochthonous biota [23]. Heavy metals like Cd, Cu, and
sediments. As we found no specific reference in Mexico for
contaminated sediments in water bodies, in this study, sedi- Table 1 Limits of met-
ments were evaluated by three international criteria: United als in sediments (milli- Compound EPA T&M OME
gram per kilogram)
States Environmental Protection Agency (USEPA) [11], Cadmium (Cd) 6.0 1.50 1.0
accepted in sediments
Ontario Ministry of the Environment (OME) [12], and Thom- by three criteria Copper (Cu) 50 45.0 25.0
as and Murdoch (T&M) [13]. The metal concentrations ac- Lead (Pb) 60 50 50
cepted in sediments by the three criteria are shown in Table 1.
124 Barceló-Quintal et al.

Pb, which occur in the inorganic industrial waste, have Zone


polluted the Lerma River, the main influent being the Alzate A B F
0
Dam, and are known to have a strong effect on Dhapnia
pulex, principal aquatic biota [27, 28]. Total metal concen-
trations alone provide insufficient data to identify the differ- 230

Depth (cm)
ent chemical forms of metals, their reactivity, availability,
and therefore their final destiny [9, 29]. 460
The use of sequential extraction allows the determination Spring
of the geochemical distribution of metals [17, 30], which 690 Fall
describes the associations of a metal with the main organic
Winter
and inorganic constituents of the sediment [30–33]. Soluble 920
and exchangeable metal forms are considered highly mobile
and therefore available to plants and animals, which poses a Fig. 2 Depth on the sampling zones
risk of contamination due to the potential release of these
metals from the sediments to the water column under certain and stored in dark bags and cooled at 4 °C. One portion
environmental conditions [34–36]. The other geochemical (1.5 kg) of the sample was used for determining texture,
forms to which metal can be bound are carbonates, alumi- granulometric fractions, total metals, and metals by sequential
num and iron hydrated oxides, and organic matter, and can extractions. Another portion (0.5 kg) of sample was collected
present relative chemical activity or stability depending on and preserved under a nitrogen atmosphere, cooled at 4 °C,
the physical and chemical properties of the system [36]; and subjected to subsequent centrifugation to measure pH,
many of these temporary factors vary seasonally [37]. The conductivity, zeta potential (ζ), redox potential (ORP),
aims of this study were to determine in the sediment from sulfides, total organic carbon (TOC), and total carbon (TC).
Alzate Dam the Cd, Cu, and Pb distribution concentrations
and to evaluate their prevailing physicochemical character-
istics, to infer the potential risk that these metals induce in Analytical Methods
the body of water.
Physicochemical Analyses

Experimental During each sampling campaign, the following variables were


measured in situ on the surface and bottom of the water
Study Area and Sample Collection column: (1) dissolved oxygen, using a Corning multimeter
and an oxygen meter model 58 YSI [38]; (2) pH [39], with an
Three sampling zones were selected (Fig. 1) due to their electrode coupled to the Corning equipment; (3) conductivity
characteristics based on previous studies [3]. Each zone has (calibration in microsiemens [40]); (4) temperature (coupled
different conditions in the reservoir: zone A is the entry of to the Corning equipment); (5) ORP [41]; and (6) hardness,
Lerma River water to the dam which transports industrial alkalinity, and sulfides, which were detected with a HACH-
and municipal wastewater, zone B is one shallow and 2400 equipment. Of the 0.5 kg of sediment from each site,
extensive surface in which there is loss of water velocity with about 20 g was weighed and subjected to centrifugation at
respect to the input channel (zone A), and zone F is located in 12,000 rpm in a Beckman Coulter, Allegra TM21 centrifuge.
the curtain of the dam (water discharge from the dam) where pH, ORP, and conductivity in interstitial water of each sedi-
water and sediment have the best features [3]. Three sampling ment were also determined. The non-sedimented material
seasons were conducted: autumn (November 2007), winter contained in this water after centrifugation was analyzed for
(February 2008), and spring (April 2008). ζ (Zeta-Plus, Brookhaven Instruments), TOC, and TC
In each zone, we established three water sampling sites at (Analytik Jena Multi NC 300). To determine dissolved total
a depth of 20 cm during autumn (2007) and winter (2008) metals, the water samples were filtered through a filter of
and 10 cm during spring 2008 for surface water, while the 0.2 μm (HA, Millipore) and analyzed using a Thermoelemen-
sampling depth on the reservoir bottom was variable, tal Solaar M6 atomic absorption instrument.
depending on the seasonal depth (see Fig. 2). Sediments
were collected using Ekman sampler from three sites of each Physical Characterization of Sediments
zone; samples were prepared for analysis by the quartering
technique to homogenize the sediment from each zone. The X-ray diffraction (XRD) analysis was carried out using the
work was carried out in the same way in each sampling powder method. Analyses were performed on an X Siemens
period; an average of 2 kg of wet sediment was collected D-500 diffractometer under the following operating
Cd, Cu, and Pb Concentrations in Sediments of a Mexican Reservoir 125

conditions: 30 kV, 20 mA, and a 1×10 sensitivity. The methods proposed by Tessier et al. [30] and Calmano and
texture of the samples was determined using the Bouyoucos Förstner [44]. The substances used for extraction were as
hydrometer method [42]; the concentration of suspended follows: F1, 1 M ammonium acetate at pH07, for 2 h; F2,
material was measured in a settling tube by density changes 1 M sodium acetate with Suprapur acetic acid (JT Baker) at
at 25 °C. The sedimentation rate of the granulometric frac- pH05 for 5 h; F3, 10 mL of 0.1 M hydroxylamine chloride
tions (mainly sand, silt, and clay) was obtained through a in 0.01 M Suprapur nitric acid (JT Baker) at pH02 for 12 h;
series of measurements over time, and the fractions were F4, 0.2 M ammonium oxalate at pH03 for 24 h; and F5,
quantified. A sample of each sediment portion was dried in 30 % H2O2 in 0.01 M nitric acid at pH02, slowly added
the sun for 3 days. Samples were passed through U.S. Tyler until there was no effervescence, then in a water bath at 60 °
Mesh: 60, 100, 250, 325, and 400 sieves, selecting the 250/ C and 55 rpm agitation. Subsequently, 4 mL of HNO3
325 since this is the most abundant for physical character- (Suprapur, JT Baker) was added for 12 h. The sample was
ization and metal analysis. treated with 10 mL of 30 % H2O2 (JT Baker). F6 was
subjected to a microwave digestion using a mixture of
Total Metal Determination HNO3 and HF (2:1). To ensure adequate contact between
the sediment and chemical extractant, agitation was carried
In order to determine total metals, 0.5-g sediment samples out at 125 rpm and each extract was centrifuged at
were weighed, treated with 30 % H2O2 (JT Baker), heated at 3,000 rpm for 25 min. In the case of sequential extraction,
60 °C and stirred at 55 rpm in a Julabo SW23 equipment, a freeze dryer VirTis, Mod BT2K-ES, was used after each
and then subjected to acid digestion with Suprapur degree extraction; the sediment was carefully washed with deion-
HNO3 and HF acids in a CEM Mars 5 microwave oven, and ized water five times (2 mL each wash), stirred for 10 min,
diluted to 50 mL. The metal concentrations were analyzed and freeze-dried to constant weight. These procedures were
by atomic absorption spectrometry and flame graphite carried out three times for the extraction of each sediment
furnace. sample, and the analysis of each extracted fraction was
carried out by flame or graphite furnace from atomic
Sequential Extraction absorption.

Barceló-Quintal [3] developed a modified sequential extrac-


tion methodology with the combination of several available Results and Discussion
extraction methods [36, 43, 44] and identified a total of six
geochemical fractions. F1 called “exchangeable” by Tessier Water Characteristics
et al. [30] includes weakly adsorbed metal ions mostly on
hydrated oxides (colloidal material) which can be released Among the physicochemical parameters, dissolved oxygen
from the sediment surface by changes in water ionic com- may exert considerable influence on the behavior of metallic
position. F2 or “acid-soluble” fraction according to Salo- contaminant values. The averaged values for dissolved ox-
mons and Förstner [43] are metals associated to carbonates ygen per zone (three sites per zone) for three seasons are
and humic derivatives with relatively short chains, which presented in Table 2, showing very low levels regardless of
can be redissolved if there is a decrease in the pH of the time and depth in the zones.
medium. Fractions F3 and F4, “easily reducible” and “mod- The lowest value is found in all the sites of zone A,
erately reducible”, respectively, are the fractions containing whereas the rest of the samples in the sites of zones B and
the largest percentage of sequestered metals inside the nod- F for surface water showed increasing dissolved oxygen
ules or cemented particles, in the first case related to amor- concentrations throughout the reservoir. pH, ORP, alkalinity,
phous Mn oxide and in the second case metals attached to and hardness tend to increase sites for its characteristics area
poorly crystalline Fe oxyhydroxides. Both fractions are B above (section “Study Area and Sample Collection”), as
thermodynamically unstable in anoxic conditions and low to F is a deep zone with respect to each other so that these
reduction potential [30, 43, 44]. The F5 fraction, called parameters decrease within the dam. The concentration of
“oxidizable”, contains metals bound to sulfides and various sulfur (noticeable by its characteristic odor) was determined
forms of organic matter, long-chain humic material (humic in situ in each zone of the dam, being more intense during
and humin). Under oxidizing conditions, this organic matter the dry season. A higher concentration of these parameters
is transformed and can release soluble metals [36, 43, 44]. in surface water was observed (10 cm) during the dry season
Finally, the F6 fraction called “residual” or fixed can retain compared to the other seasons (20 cm in the period after the
metals in their crystal lattice. rainy season and during winter) while concentrations were
The geochemical distributions of Cd, Cu, and Pb were lower in autumn and winter. In the bottom water, slightly
determined using a combination of the sequential extraction lower values were found in all sites of the three zones; this
126 Barceló-Quintal et al.

Table 2 Averaged values of physical and chemical parameters determined in water columns in each zone for three seasons

Zone pH Conductivity ORP (mV) TOC (mg/L) DO (mg/L) HS− (mg/L) Hardness Alkalinity
(μS/cm) (mg CaCO3/L) (mg CaCO3/L)

A S 6.94±0.57 908±101 −243.12±45.40 88.62±7.91 0.20±0.01 12.71±1.55 162±51 190±21


B 6.96±1.36 948±148 −257.12±47.68 87.82±3.79 0.20±0.01 9.93±1.32 148±37 189±25
B S 7.28±0.52 785±115 −354.33±46.06 148.06±18.17 1.70±0.83 11.08±1.67 180±64 260±12
B 7.30±0.71 815±118 −422.37±63.44 145.67±19.82 0.35±0.20 8.42±1.45 169±40 268±6
F S 7.21±0.43 386±76 −258.65±32.17 53.94±8.21 2.89±1.26 6.36±0.85 165±59 258±14
B 7.24±1.37 406±51 −300.53±43.52 51.57±7.06 0.19±0.01 6.20±0.90 162±58 266±6

S surface, B bottom

indicates the release of H2S, which increases during the dry During each annual season, there was an increase in the
season, and OPR values were always negative, indicating concentration of each metal in the dry season (spring), and it
that sulfates are reduced [45]. These results, together with was reduced after the rainy season (autumn) on both the
the high organic load determined as total organic carbon surface and bottom of each water column. Zone A presented
(TOC) (see Table 2) present in the Lerma River at the the highest concentration since it is located at the Lerma
entrance to the dam, as well as inadequate ventilation, River inlet to the reservoir (Fig. 1), with a water speed of
deplete the dissolved oxygen during the oxidation of organic 0.094 m/s, where the river is the vehicle for metal contam-
matter [46], resulting in reducing conditions, mainly in zone ination. Inside the reservoir, due to its morphology, the
A, and the bottom water of each water column, especially diffusion effect predominates [16, 50]. The velocity of the
during the dry season [3, 16]. river within the dam is almost zero (0.094 m/s), allowing
The values of total metal concentrations (dissolved + greater deposition of metals adsorbed by particulate matter.
suspended) in water were compared with the environmental It is important to consider the pH of the water from the dam,
quality criteria included into The General Law of Ecological which is above 7, but less than 8, which can also cause
Equilibrium and Environmental Protection in Mexico, chemical precipitation of these three metals [51].
which allows the following limits: 10 μg/L Cd, 200 μg/L
Cu, and 5,000 μg/L Pb [47]. Table 3 shows the concentra- Sediment Characteristics
tions found for each metal. The measured levels were, in all
cases, below this Mexican Standard. Therefore, the concen- Results of the Bouyoucos method and classification of tex-
trations of Cd, Cu, and Pb do not present a legal problem in tural triangle for soils and sediments [52] used for the
the use of dam water for irrigation. Similar metal concen- classification of material in sediments are shown in Table 4.
trations were observed in surface water and at the bottom of These results indicate predominance of fine minerals
the reservoir, while significant differences were observed (<2 μm) in the dam except for the entrance where coarser
among the study zones. These spatial variations do not material was found.
appear to follow a specific pattern, which might suggest an The composition of the sediments obtained by XRD anal-
ongoing exchange of the three metals between water and ysis was observed, and the main components of the sediment
sediments, mainly through mechanisms such as adsorption, are feldspar (56 %), metahaloysite (15 %), hematite, and
because if the water is aggressive in nature [48], it should goethite (10 %). The presence of organic material, clay-like
inhibit precipitation [3, 16, 23, 49]. material, and components such as iron oxyhydroxides will

Table 3 Total concentrations of Cd, Cu, and Pb on the surface (S) and bottom (B) of the water column

Zone Cd (μg/L) Cu (μg/L) Pb (μg/L)

Fall Winter Spring Fall Winter Spring Fall Winter Spring

S B S B S B S B S B S B S B S B S B

A 1.2 1.2 4.4 3.2 9.5 6.6 50.5 44.09 23.83 23.83 68.5 53.0 38.8 27.5 10.0 7.1 42.4 39.6
B 1.2 1.2 1.3 1.2 1.6 1.4 29.36 24.42 19.4 19.4 46.7 30.1 20.9 17.3 4.0 2.4 44.0 42.2
F <bdl <bdl 1.2 1.2 1.9 1.5 43.94 32.9 7.37 7.37 58.9 31.7 45.6 18.0 4.7 3.4 25.8 16.1

S surface, B bottom, bdl below detection limit


Cd, Cu, and Pb Concentrations in Sediments of a Mexican Reservoir 127

Table 4 Classification of material in sediments activity of microorganisms and determines the species likely
Zone Sand (%) Silt (%) Clay (%) Classification to be sorbed, precipitated, or dissolved. Pérez [53] reported
that in the case of anoxic sediments, reducing and acidic
A 24.9±0.2 39.9±0.3 35.2±0.7 Sandy loam conditions favor the solubilization of sediment-associated
B 18.3±0.7 17.7±0.7 64.0±0.2 Clay metals. Zeta potential (ζ) showed seasonality, with the high-
F 18.1±0.2 13.3±0.5 68.6±0.7 Clay est values in spring and the lowest in winter. The levels of
Cd and Cu in zones A and B exceeded the limit values
recommended by the USEPA, the T&M, and the MOE
allow widespread adsorption of Cd, Pb, and Cu, while carbo- (Fig. 4a, b). Pb levels did not exceed the limits permitted
nates were not detected. by these three criteria (Fig. 4c). However, given that the
Figure 3a shows the weight loss of organic matter at sequence of sampling was winter–spring and autumn, there
temperatures of 150, 300, and 500 °C for each of the three was an improvement in the quality of the surface sediments
zones. Zone A had the highest amount of volatile organic for the three metals, probably because fine sediments are
matter contained in sediments, and most of it was lost above able to adsorb and transport various toxic pollutants, due to
300 °C. Having obtained the amount of volatile organic the hydrophobic nature of many of the toxic chemicals and
matter and the texture of the inorganic material, the sedi- their physical and chemical characteristics, including large
ment composition in percent for each zone is presented in specific areas and high ion exchange capacity [54].
Fig. 3b. Sediments can provide an area of deposition of pollutants
Zone A had the highest percentage of organic matter and and nutrients contained in the water column under the
silt, while in other zones the highest percentage was for clay. hydrodynamic forces, and consequently, the sediment may
Interstitial water, after being extracted from the sediments, act as a source of contaminants due to possible metal release
was analyzed: pH, conductivity, ORP, TOC, and ζ (the and resuspension processes [55, 56]. In this context, the dam
material contained in this water and not sedimented after appears to act as a dilution device for metals associated to
centrifugation); the values are shown in Table 5. sediments in which concentrations throughout the body of
It was not possible to measure the hardness and alkalin- water showed a general decrease in the area of zones A to F.
ity, as the low sulfur sample was not detectable by the
technique used. The range for pH, 7.32–7.69, indicates a Geochemical Distribution of Cd, Cu, and Pb
slightly basic tendency. This parameter seems to create
conditions unfavorable to significant bioavailability of met- The heterogeneity of the metal concentration values in the
als [19]. The conductivity in the interstitial water can in- dissolved phase suggests that there is a constant exchange of
crease due to the release of ions from degraded organic these metals between water and sediments. Therefore, the
matter in sediments; the highest conductivity occurs in zone release of metals from sediment to the overlying water
B where there is a shallow depth, and an expansion of area column should be included in the sediment quality criteria
which the speed is reduced, encouraging the resuspension of to allow a more precise description of the risk this could
sediments. pose to the biota [24, 26]. In the reduced sediment of the
As for the season, the highest value of this parameter was Alzate Dam, the release of metals is caused by physico-
in the spring and the lowest in the fall, which can be chemical changes in the environment created by the micro-
attributed to the increased diagenetic activity of sediments bial oxidation of organic matter [57] where Cd, Cu, and Pb
in this season [19]. The processes of oxidation and reduc- associated to the sediments can cause chemical changes with
tion, determined by the redox potential of the system, play carbonates, if present, oxyhydroxides, sulfides from the
an important role in metal mobility. At the same time, the reduction of sulfates, and other components [58], altering
redox potential affects the distribution and the metabolic their solubility and therefore its release to water [57, 59].
Fig. 3 a Loss of organic matter (a) (b)
accumulated in the sediment of 0.25
each zone at 150, 300, and 100
150°C 300°C 500°C
Sand
500 °C. b Percentage 0.20 80
% Composition
weight loss (g)

Silt
composition of sediment in
0.15 60 Clay
zones A (Lerma River channel),
OM
B (J.A. Alzate Dam), and F 0.10 40
(J.A. Alzate Dam)
0.05 20

0.00 0
A B F A B F

Zone Zone
128 Barceló-Quintal et al.

Table 5 Average values of physical and chemical parameters deter- mostly in the reducible fractions F3 and F4, with more
mined in interstitial water in sediment from each zone during three
affinity for Fe oxyhydroxides; little affinity for the oxidiz-
seasons
able material of F5 and its highest concentration in F5 was
Zone pH Conductivity ORP COT ζ (mV) on the fixed fraction. The geochemical distribution of this
(μS/cm) (mV) (mg/L) metal shows that it is a chemically mobile element and that a
A Fall 7.58 812 −64.53 21.60 21.15
large portion of cadmium can be released from sediments to
water column from the mobile fractions (F1 and F2). This
Winter 7.63 1,022 −64.21 21.80 20.42
behavior in the dam’s sediment also occurred in Polish lakes
Spring 7.69 1,210 −65.68 22.90 27.55
with similar characteristics [60].
B Fall 7.42 571 −55.76 32.54 18.78
Figure 6a shows the relationship between the three crite-
Winter 7.50 833 −56.74 31.30 17.99
ria: USEPA, Thomas and Murdoch, and OME, considering
Spring 7.56 1,960 −54.67 31.80 24.54
the fractions F1+F2, being the most mobile, where the
F Fall 7.41 525 −72.90 25.91 20.98
cadmium can be released easily, and F3+F4+F5, though
Winter 7.29 441 −72.09 25.19 20.42
less mobile, may also be susceptible as indicated above. F6
Spring 7.41 773 −72.29 25.14 24.59
was not considered because of their characteristics; it is
difficult for the metal to pass into the aqueous phase. In
This aspect of the chemical mobility of sediment-associated Fig. 6a, it can be noted that the Cd did not exceed the
metals in the dam can be explained by studying the geo- USEPA recommendations in all zones whereas the opposite
chemical distribution of Cd, Cu, and Pb during the dry occurs when considering the total metal (Fig. 5a). Accord-
seasons of 2007 and 2008 in which the highest concentra- ing to the T&M recommendation, the cadmium content is in
tion metal was observed (see Fig. 5a–c). At the same time, the borderline. On the other hand, if the OME criteria are
the ORP, pH, and temperature affect the distribution and followed, almost all the zones within the dam could pose a
metabolic activity of microorganisms and determine the relatively high risk. By eliminating F6, the values definitely
chemical species likely to be adsorbed, precipitated, or do not exceed the levels recommended by the USEPA, and it
solubilized, or the exchange anions. As indicated by Pérez should also be noted that according to T&M recommenda-
[53] in anoxic sediments, reducing and acidic conditions, tions, fractions F3, F4, and F5 are those that generate the
and in the case of the reservoir, favor the solubilization of risk. For OME, the inclusion of the fractions F1 and F2
Cd, Cu, and Pb, mainly during the dry season, where it can increases the risk.
be inferred that mobility goes in the order F1+F2>F3+F4>
F5>F6. Copper

Cadmium In the case of copper (Fig. 5b), its geochemical distribution


presented a very different behavior compared to that of
The results of the averaged geochemical distribution of cadmium, as only 10 to 15 % of the total metal was found
sediments from the Jose Alzate Dam during the dry seasons to be present in the first three fractions. The highest concen-
of 2007 and 2008 are shown in Fig. 5a, the results for trations were associated to Fe oxyhydroxides (F4) and or-
cadmium which were observed in the most mobile fractions ganic matter (F5), with higher affinity for the latter.
mainly F2. Cadmium appears to be associated to sulfides Therefore, the risk levels of this metal are significant, but
(though it does not show up in the X-ray analysis of the lower than in the case of cadmium. Although it can be
sediment). The presence of cadmium was detected from the expected that copper to be released from fraction F4, the
analysis of bottom water and reinforced by hardness and pH two fractions are thermodynamically unstable in highly
(Table 2). Bicarbonate ion and not carbonate is predominant anoxic conditions and low reduction potentials. In the case
at the bottom of the water column. Cadmium was detected of fraction F5, to which the metals are bound to different

Fig. 4 Total concentrations in (a) (b) (c)


sediment: a Cd, b Cu, and c Pb. Winter Spring Fall Winter Spring Fall Winter Spring Fall
For TEL, PEL, T&M, and 80 60 EPA
6 EPA
OME criteria, see text OME
T&M
60
[Cu] (mg/kg)

[Pb] (mg/kg)
[Cd] (mg/kg)

EPA 40
4 T&M
40
OME 20
2 20
T&M
OME
0 0 0
A B F A B F A B F
Zone Zone Zone
Cd, Cu, and Pb Concentrations in Sediments of a Mexican Reservoir 129

Fig. 5 Geochemical (a) (b) (c)


distribution of cadmium (a), F1 F2 F3
copper (b), and lead (c) on F1 F2 F3 F4 36 F4 F5 F6
4 F1 F2 F3
sediment during the dry season 32 20
F5 F6 F4 F5 F6
28
3 16

[Cd] (mg/kg)

[Cu] (mg/kg)

[Pb] (mg/kg)
24
20 12
2
16
8
12
1 8 4
4
0 0 0
A B F A B F A B F
Zone Zone Zone

forms of organic matter, this matter can be transformed and Lead


gradually release copper, although much more slowly [36,
54–56], because usually a significant fraction of copper is Lead was found mostly in fraction F6 (from 27 to 37 % of
bound to the organic fraction forming complexes well estab- the total metal). The rest of this metal was distributed
lished between copper and humic acids, as noted by Tessier between fractions F3, F4, and F5, whereas in fractions F1
et al. [30], Boyd et al. [61], and Barceló-Quintal [3]. These and F2, it was found in proportions that are very low
chelated Cu–humic complexes [62, 63] are stable, thus compared to the other fractions. This metal showed the
explaining the high affinity of copper for organic matter following affinity sequence: F6 > F3 > F5 > F4 >> F2 0F1,
and the reduction of chemical mobility, which is the and this pattern may express the high stability of Pb in these
lowest among the trace elements, according to Korte et al. sediments. This result is also consistent with studies by
[64]. Korte et al. [64], which indicate that lead is not very mobile
In the case of copper (Fig. 6b), unlike cadmium, it does in soils (less so than copper). This phenomenon is consistent
not exceed the first two criteria (EPA and T&M). On the in fractions F3, F4, F5, and F6. The high proportion in
contrary, the OME criteria were exceeded in all zones. We fraction F6 (Fig. 5c) appears to be related to the high content
note that F3+F4+F5 are the most influential (also F6 was of clay of the haloysite type and metahaloysite and Fe iron
not considered); zones A and B influence the degree of risk. oxides (hematite and goethite).
This can be compared with Fig. 4b in which the total metal There was a discrepancy with respect to the concentration
was considered and exceeded the recommended levels. The of lead from zone A (inlet of the river) and the other zones,
OME recommendation again shows the importance of cop- thus showing the anthropogenic inputs of Pb from industrial
per associated to fractions F3+F4+F5, F1+F2 contributing wastewater and transported by the Lerma River. The fact
a little, unlike cadmium. It is expected that if the majority of that the concentration decreases along the length of the dam
Cu in the sediment is present in fraction F5 (slightly mo- indicates a rapid sedimentation of the suspended matter
bile), this element would not represent high detachment risk, coming from the river. Pb accumulation in less mobile
although the association of this metal to the sediment does fractions leads us to believe that the sediments act as traps
not imply complete immobilization. This is due on the one for the metal, which means a reduced chance of being
hand to the oxidation processes of sediment and on the other released into the aqueous phase. This can be seen in the
hand to the fact that fine solid particles can be dragged to concentration of each fraction of zone B of the reservoir in
other parts of the reservoir where the physicochemical which the concentration was the highest. This zone is the
characteristics (including pH and aggressiveness of wa- lowest part of the reservoir and most prone to sedimentation
ter) may be different for the redissolution of the labile [65]. As for the three criteria for lead (Fig. 6c), this metal did
fractions. not exceed apparently any of the three criteria used.

Fig. 6 Criteria EPA, T&M, and (c)


OME to assess risk of a Cd, b (a) (b)
Cu, and c Pb F1+F2 F3+F4+F5
F1+F2 F3+F4+F5 F1+F2 F3+F4+F5
6 EPA 60
[Cd] (mg/kg)

EPA
[Pb] (mg/kg)
[Cu] (mg/kg)

5 60 EPA
4 T&M
40 T&M
3 40 OME
OME
2 20
T&M 20
1
0 OME 0 0
A B F A B F A B F
Zone Zone Zone
130 Barceló-Quintal et al.

According to geochemical distribution, it can be observed Productivos (1997) Comisión Coordinadora para la Recuperación
Ecológica de la Cuenca del río Lerma, 103–140
that concentrations of lead associated to the material of each
2. CNA, Comisión Nacional del Agua (1993) Presas de México.
fraction determined in the sediments do not represent a risk, Gerencia de Información y Participación Ciudadana, Grupo Imper-
at least during the dry season (spring), and F6 was not graf, vol. V
considered for the three criteria: USEPA, Thomas and Mur- 3. Barceló-Quintal ID (2000) Estudio de la movilidad de Ca, Cd, Fe,
Mn, Pb, y Zn en sedimentos de la presa J.A. Alzate en el Estado de
doch, and OME.
México. PhD thesis, Facultad de Ingeniería, Universidad Autón-
oma del Estado de México
4. Instituto Nacional de Ecología (2003) Diagnóstico Biofísico y
Socioeconómico de la Cuenca Lerma Chapala, Report
Conclusions 5. CNA, Comisión Nacional del Agua (2006) Estadísticas del agua en
México. Sistema Nacional de Información sobre cantidad, calidad,
The very low levels of dissolved oxygen in the dam may be usos y calidad del Agua. Subdirección General de Programación
one of the reasons for the almost complete disappearance of de CNA
6. Gobierno del Estado de México (2000) Atlas Ecológico de la
the biota in this body of water. However, the measurement of Cuenca Hidrográfica del río Lerma Tomo V: Atlas Industrial,
this parameter showed that the reservoir acts as a stabilization Comisión Coordinadora para la Recuperación Ecológica de la
pond. The low levels of dissolved oxygen and the oxygen Cuenca del río Lerma, 267–308
from compounds such as nitrates and sulfates present in the 7. Lloyd BJ, Leitner AR, Vorkas CA, Guganesharajah (2003)
Under-performance evaluation and rehabilitation strategy for
reservoir are consumed during the oxidation of organic matter waste stabilization ponds in Mexico. Water Sci Tech 48
in the three zones of the reservoir; this generates negative (2):35–43
values in the redox potential, mainly during the dry season 8. Barceló-Quintal ID, Bussy AL, Solís Correa H (2005) Metal
(spring), where the sulfates are reduced to H2S and/or HS−, S2 interactions with water and sediment in freshwaters. In: Palomar
− M (ed) Applications of analytical chemistry in environmental
, causing a part to be lost as H2S, the typical odor in the dam, research. Research Signpost, India, pp 161–188
and another part of the sulfides may react with Cd, Cu, and Pb. 9. García Aragon JA, Dìaz Delgado C, Quentin E, Avila Perez P,
Although sulfides were not detected from the XRD studies, Tejeda S, Zarazua G (2007) Caracterización de la contaminación
the odor and in situ measurements of both surface and bottom por metales pesados y reducción de la capacidad de almacena-
miento hidráulico por azolve de un embalse mexicano. Hidrobio-
water permitted their detection and confirmed their presence. lógica 17(2):127–138
The bonds formed by Cd, Cu, and Pb with the sediment along 10. Fu G, Allen HE (1992) Cadmium adsorption by anoxic sediments.
with the geochemical distribution indicated that Cd was po- Water Res 26:225–233
tentially more mobile than Cu and Pb. The three metals 11. EPA. United States Geological Survey (USGS) (2000) Prediction
of sediment toxicity using consensus-based freshwaters sediment
showed a common characteristic, being more abundant in quality guidelines. United States Geological Survey (USGS) final
fraction F6, but the rest of the geochemical distribution was report for the U.S. Environmental Protection Agency (USEPA).
variable depending on the metal. Pb showed an affinity to EPA 905/R-00/007
materials present in fractions F3, F4, and F5. Cu was concen- 12. OME, Ontario Ministry of the Environment (1976) Evaluating
construction activities impacting on water resources (Construction
trated in fractions F5 and F4, while Cd was found in fractions Handbook). Toronto, Canada
F4 and F2 (highly mobile phase). With the geochemical 13. Thomas RL, Murdoch A (1979) Small craft harbours—sediment
distribution of each metal, together with the physicochemical survey, Lakes Ontario, Erie and Lake St. Clair, 1978. Dredging
conditions of the dam and sediment composition, it was summary and protocol: report to the Great Lakes Biolimnology
Laboratory, Burlington, Ontario, Canada
possible to identify risk fractions for each of these metals 14. Walter DJ, Hurl S (2002) The reduction of heavy metals in a
providing information on the likely conditions of their release stormwater wetland. Ecol Eng 18:407–414
into the water column. Thus, low risk was observed for Cu and 15. Keyser TR, Natusch DFS, Evans CA Jr, Linton RW (1978) Char-
Pb, but not for Cd, for which the risk was highest. The acterizing the surface of environmental particles. Env Sci Tech
12:768–773
geochemical distribution of each metal allowed a better un- 16. López Galván E (2010) Determinación de la movilidad geohidro-
derstanding of metal portion that has an influence on environ- dinámica de Cd, Cu, Cr, Fe, Mn y Pb en la presa José Antonio
mental risk. Alzate en el Estado de México. PhD thesis. Instituto Técnológico
de Toluca, México
17. Zhang S, Wang S, Shan XJ (2002) Distribution and speciation of
Acknowledgments The authors gratefully acknowledge the financial
heavy metals in surface sediments from Guanting reservoir,
support of the Consejo Nacional de Ciencia y Tecnología—SEMAR-
Beijing. Env Sci Health 37:465–478
NAT (2002-C01-0504).
18. Ansari TM, Marr IL, Tariq N (2004) Heavy metals in marine
pollution perspective—a mini review. J Appl Sci 4:1–20
19. Singh BGD (2008) Evaluación de la potencialidad tóxica de
References cadmio y cobre en sedimentos de la zona ‘E’ de la presa José
Antonio Alzate, Edo. de México. MSc thesis. Universidad Autón-
oma Metropolitana-Azcapotzalco, México, 65–75
1. Gobierno del Estado de México, Atlas Ecológico de la Cuenca 20. Singh AK, Hasnain SI, Banderjee DK (1999) Grain size and
Hidrográfica del río Lerma Tomo III: Atlas de Ecosistemas geochemical partitioning of heavy metals in sediments of the
Cd, Cu, and Pb Concentrations in Sediments of a Mexican Reservoir 131

Damodar Rier a tributary of the lower Ganga, India. Environ Geol 40. Standard Method 2510A, 20th ed., American Public Health Asso-
39:90–98 ciation, Washington, D.C., 1988, EPA-600/4-79-020
21. Farmer ME, Linton RW (1984) Correlative surface analysis studies 41. Standard Method 2580, 20th ed., American Public Health Associ-
of environmental particles. Env Sci Tech 18:319–326 ation, Washington, D.C., 1988, EPA-600/4/89/032
22. Baeyens W, Dehandschutter B, Leermakers M, Bobrov V, Hus R, 42. Bouyoucos GJ (1951) A recalibration of hydrometer method for
Baeyens-Volant D (2003) Natural Hg levels in geological enriched making mechanical analysis of soils. Agron J 43:435–438
and geological active areas: case study of Katun river and Lake 43. Salomons W, Förstner U (1980) Trace metals analysis on polluted
Teletskoye, Altai (Siberia). Water Air Soil Pollut 142:375– sediments. Part 2. Environ Technol Lett 1:506–517
393 44. Calmano W, Förstner U (1983) Chemical extraction of heavy
23. Ávila-Pérez (2001) Dinámica de metales pesados no esenciales en metals in polluted river sediment in Central Europe. Sci Tot Envi-
la interacción agua-sedimento biota de la presa J. A. Alzate. PhD ron 28:77–90
thesis, Facultad de Ingeniería, Universidad Autónoma del Estado 45. Reeburgh WS (1983) Rates of biogeochemical process in anoxic
de México sediments. Ann Rev Earth Planet Sci 11:269–298
24. Håkanson L (1979) An ecological risk index for aquatic pollution 46. Kayombo S, Mbwette TSA, Mayo AW, Katima JHY, Jorgensen SE
control. A sedimentological approach. Water Res 14:975–1001 (2000) Modelling diurnal variation of dissolved oxygen in waste
25. Barceló-Quintal ID, Solís-Correa HE, González C, Avila-Perez P, stabilization ponds. Ecol Model 127:21–31
Garcia J (2000) Determination of cadmium and lead species in the 47. Diario Oficial de la Federación (1989) CE-CCA-001-89. Criterios
water column of the J.A. Alzate Reservoir, México. Water Environ Ecológicos de la Calidad del Agua. Issued December 13th, Mexico
Res 72:132–140 48. Barceló-Quintal ID, Allende AI, Solís-Correa HE, Bussy AL,
26. López-Galván E, Barceló-Quintal I, Solís-Correa HE, Bussy A-L, González MC (2002) Determinación del estado de equilibrio de
Avila-Perez P, Martínez S (2009) Calculation of the ecological risk un sistema hídrico. Revista de la Sociedad Mexicana de Química,
index in the Jose Antonio dam State of Mexico, Mexico. Biol Rev de la Soc Quím de Méx 46(2):93–104
Trace Elem Res 2010(135):121–135 49. Ubaldo EI (2008) Movilidad geoquímica de Cd, Fe y Pb en los
27. Zarazúa G (2000) Bioacumulación y toxicidad de los metales sedimentos del río Lerma antes de la entrada de la presa J A Alzate.
pesados Cr, Cu, Zn, Cd y Hg en Daphnia pulex de la presa José MSc thesis. Universidad Autónoma Metropolitana—Azcapot-
Antonio Alzate, Estado de México. MSc thesis, Facultad de Ingen- zalco, México, 59–62
iería, Universidad Autónoma del Estado de México, México 50. Márquez VM (2008) Aplicación de un modelo de dispersión
28. Ávila-Pérez P, Zarazúa-Ortega G, Barceló-Quintal ID, Díaz-Del- superficial de Cu y Cd en una sección de la presa José Antonio
gado C, Rosas Pérez I (2005) Afección a los sistemas acuáticos por Alzate. MSc thesis. Universidad Autónoma Metropolitana—Azca-
actividades antrópicas. In: Recursos Hídricos—Conceptos Básicos potzalco, México
y Estudios de Caso en Iberoamerica. Ed., RIPDA-CYTED, CIRA 51. Ringbom (1979) Formación de complejos en química analítica,
y Piriguazu, Uruguay. 2005, VIII-5, VIII41–VIII108 Edt Alhambra, España. 212
29. Merian E (1999) Metals and their compounds in the environment. 52. Coleman DC, Crossley DA Jr (1996) Fundamentals of soil ecolo-
Occurrence, analysis and biological relevance. Verlagsgesellschaft gy. Academic, San Diego, pp 10–11
mbh, Weinheim, Federal Republic of Germany 53. Pérez GG (2005) Disponibilidad de metales tóxicos en sitios con-
30. Tessier A, Campbell PGC, Bisson (1979) Sequential extraction taminados. Aplicaciones y limitaciones de la fraccionación en la
procedure for the speciation of particulate metals. Anal Chem determinación de gradientes de polución. PhD thesis, Universitat
51:844–851 Autónoma de Barcelona
31. Förstner U, Calmano W, Conradt K, Jaksch H, Schimkus C, 54. Lau YL, Krishnappan BG (1992) Size distribution and settling
Schoer J (1981) Chemical speciation of heavy metals in waste velocity of cohesive sediments during settling. J Hydraul Res 30
materials (sewage sludge, mining waste, dredge materials, polluted (5):673–684
sediments) by sequential extraction. Proceedings of the Interna- 55. Lick W, Xu Y, McNiel J (1995) Resuspension properties of sedi-
tional Conference on Heavy Metals in the Environment, Amster- ments from the Fox, Saginaw, and Buffalo Rivers. J Great Lakes
dam, CEP Consultants Eds., Edinburgh, 698–704 Res 21(2):257–274
32. Chen W, Tan SK, Tay JH (1996) Distribution fractional composi- 56. Krishnappan BG (1996) Cohesive sediment transport. In: Nakato
tion and release of sediment-bound heavy metals in tropical reser- T, Ettema R (eds) Issues and directions in hydraulics. Balkema,
voirs. Water Air Soil Pollut 92:273–287 Rotterdam
33. Shiowatana J, Tantidanai N, Nookabkaew S, Nacapricha D (2001) 57. Pedroza-Benitez S, Bussy AL, Barcelo-Quintal ID, Lopez-Galvan
A novel continuous-flow sequential extraction procedure for metal E, Avila-Perez P (2010) Organic matter biodegradation and metal
speciation in solids. J Environ Qual 30:1195–1205 behaviour in contaminated freshwater sediments. Int J Env Techn
34. Linnik PM (2000) Role of bottom sediments in the secondary Manag 12(1):85–94
pollution of aquatic environments by heavy-metal compounds. 58. Marinsky JA, Wolf A, Bunzl K (1980) The binding of trace
Lakes Reserve: Res Manag Ukraine 5:11–12 amounts of lead(II), copper(II), cadmium(II), zinc(II) and calci-
35. Chao TT (1984) Use of partial dissolution techniques in explora- um(II) to soil organic matter. Talanta 27:461–468
tion geochemistry. J Geochem Explor 20:101–135 59. Christensen TH (1989) Cadmium sorption at low concentrations:
36. Trujillo-Cárdenas JL, Saucedo-Torres NP, Zárate del Valle PF, VIII. Correlation with soil parameters. Wat Air Soil Pollut 44:71–
Ríos-Donato N, Mendizábal E, Gómez-Salazar S (2010) Specia- 82
tion and sources of toxic metals in sediments of Lake Chapala. 60. Sararek-Gwiazda E, Mazurkiewicz-Boron G (2006) Influence of
Mex J Mex Chem Soc 54(2):79–87 cadmium and lead partitioning in water and sediment on their
37. John D, Leventhal JS (1995) Bioavailability of metals. In: Prelim- deposition in the sediment of a eutrophic dam reservoir. Int J
inary compilation of descriptive geoenviromental mineral deposits Oceanogr Hydrobiol 35(2):141–157
models. US Geological Survey open file report 95-381 61. Boyd SA, Sommers LE, Nelson DW (1981) Copper (II) and iron
38. Standard Methods 4500-O, 20th ed., American Public Health (III) complexation by the carboxylate group of humic acid. Soil Sci
Association, Washington, D.C., 1988, EPA-600/4-79-020 Soc Am J 1981(45):1241–1242
39. Standard Method 4500-H+B, 20th ed., American Public Health 62. Bornemisza E, Peralta F (1981) Zinc in andosols of Costa Rica.
Association, Washington, D.C., 1988, EPA-600/4-79-020 Proc Soil Crop Sci Soc Fla 40:33–35
132 Barceló-Quintal et al.

63. Fassbenden WH, Bornemisza E (1987) Química de suelos, con 65. Barceló-Quintal ID, Avila-Perez P, Solís-Correa HE, González
enfasis en suelos de América Latina. Instituto Interamericano de C, Bussy AL (1998) Repartición geoquímica de metales pesa-
Cooperación para la Agricultura, San José, pp 381–402 dos en sedimentos superficiales de la presa J. A. Alzate en el
64. Korte NE, Skoop J, Fuller WH, Niebla EE, Alesh BA (1976) Trace Estado de México Memorias del XXVI Congreso Interamer-
elements movement, in soils. Influence of soil physical and chem- icano de Ingeniería Sanitaria y Ambiental, Lima, Perú. CD
ical properties. Soil Sci 122:350–357 ROM. 1998
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