BASELINE OF Ca, Mg, Fe, Mn AND Al CONCENTRATIONS IN

CATATUMBO RIVER SURFICIAL SEDIMENTS

HILDA LEDO
1
, ZULAY RIVAS
2
, JANIO GUTIRREZ
1
,
ELIZABETH GUTIRREZ
1
, JESS OJEDA
1
and HENDRIK AVILA
2
1
Laboratorio de Qumica Ambiental, Facultad Experimental de Ciencias, Universidad del Zulia,
Mdulo 2. Maracaibo, Estado Zulia, Venezuela;
2
Instituto para el Control y la Conservacin de la
Cuenca del Lago de Maracaibo (ICLAM), Maracaibo, Venezuela
(

author for correspondence, e-mail: hild@cantv.net, Fax: 58 261 7598125)

(Received 19 March 2002; accepted 11 December 2003)
Abstract. Ca, Mg, Fe, Mn and Al were determined in surcial sediment samples from Catatumbo
River (including sediments from major tributaries) a binational basin shared by both Venezuela and
Colombia in approximately 30% and 70%, respectively. The global mean concentration of the metals
was Al > Fe > Mg > Ca > Mn (0.376; 0.304; 0.063; 0.042; 5.9 10
4
mmol g
1
dry weight).
The objectives of this investigation were (1) to establish metal-concentration baselines, and (2) to
determine spatial distribution of Ca, Mg, Fe, Mn and Al concentrations, in bed sediment samples
from Catatumbo River (including sediments from major tributaries). As Catatumbo River is the
main tributary to Lake Maracaibo system (South Americas largest inland lake), its impact on the
eutrophication process of Lake Maracaibo due to the formation of metal/phosphorus complexes is
discussed.
Keywords: baseline, Catatumbo River, eutrophication, Lake Maracaibo, metals, phosphorus, sedi-
ment
1. Introduction
The total load of metals in the rivers depends upon the geological and ecological
condition of their basin as well as the human activities being developed along their
beds. Sediments can be considered as the result of the integration of all processes
occurring in the aquatic ecosystem (Esteves, 1988; Frstner and Wittmann, 1981)
and they are indicators of the chemical history of the body of water. Furthermore,
the sediment allows to know seasonal changes related to the use of oxygen and the
accumulation of organic matter which determine the form of the iron compounds
as well as their mobilization. This is similar for other metals (Margalef, 1977).
Sediments act as a trap for different elements due to precipitation, exchange and
absorption reactions which occur within their structure (Bortleson, 1971). Metals
can also be found in water, particulate matter and the ecosystem organisms (Anmar
et al., 1993).
There are several physical-chemical factors participating in the precipitation or
immobilization of phosphorus in aquatic environments (Bianchi et al., 1990) such
Water, Air, and Soil Pollution 155: 117135, 2004.
2004 Kluwer Academic Publishers. Printed in the Netherlands.
118 H. LEDO ET AL.
as concentrations of iron, aluminum, sulfate as well as organic compounds, pH,
temperature and redox conditions. Moreover, the oxidation state of iron is the most
important factor since it controls changes in the equilibrium between sediments
and solution. The absorption of phosphorus on iron hydroxide occurs in aerobic
soils, more than in anaerobic ones (Esteves, 1988; Bianchi et al., 1990; Teasdale et
al., 2003). P is immobilized in oxygenated sediments due to retention with Fe(III).
Under reducing conditions P, is released from sediments following reduction of
Fe(III) to Fe(II) and the associated disruption of solid Fe(III)-PO
4
forms. The ratio
Fe/P > 1.8 was stated by Chambers and Prepas (1994) as an important indicator of
phosphorus absorption by the sediment. When such ratio becomes lower than 1.8,
desorption can occur. Manganese has a high absorption surface, therefore it re-
tains phosphorus leading the precipitation of the complex manganese-phosphorus
with iron as Fe-Mn-P complex (Esteves, 1988). On the other hand, when the ratio
Ca/P = 3.18 phosphorus is forming complexes (Staudinger et al., 1990) such as
Ca
3
(HCO
3
)
3
PO
4
and dolomite, CaMg(CO
3
)
2
, is formed when ratio Mg/Ca > 0.6
(Moore et al., 1991).
This work is the rst study of Catatumbo River sediments to estimate the Mn,
Al, Mg, Fe and Ca content and to establish the baseline values. Additionally, the
relation between phosphorus and metals mentioned above was studied, due to the
relevant role of sediments acting as a trap for different elements and with the know-
ledge of the formation of phosphorous complexes which limit its release to the
water column, and their relation with phosphorus content in both Colombian and
Venezuelan sides along the river bed until its outlet in Lake Maracaibo (Venezuela).
The objectives of this investigation were:
To provide baseline concentrations of Ca, Mg, Fe, Mn and Al in bed sediment
of the Catatumbo River streams;
To describe the spatial distribution of Ca, Mg, Fe, Mn and Al concentrations
in bed sediment and correlate total phosphorus, orthophosphate and metals for
all samples; and
To discuss the ratio metal/phosphorus as an indicative of the complexes form-
ation.
2. Region under Study
2.1. CATATUMBO RIVER
The hydrographic system Catatumbo River is a binational basin shared by both
Venezuela and Colombia in approximately 30 and 70%, respectively. It is located
between the coordenates 72

00

and 73

26

19

of eastern length and 7

46

30

and 9

31

05

of northern latitude. Its area is 25 563 km

2
and a mean yearly ow of
1147 m
3
sec
1
. It is one of the main tributaries to Lake Maracaibo (Venezuela) with
SURFICIAL SEDIMENT SAMPLES FROM CATATUMBO RIVER 119
load of 70% of fresh water discharged to the lake. This Lake is a central location
in Venezuelas oil production.
Limestones mines are located in both Colombian and Venezuelan areas belong-
ing to the Catatumbo River system. These limestones are used as construction
material and ornament, agricultural limestone and for the production of cement.
There are also phosphoric rock mines in the area owing on the main river bed and
located at approximately 254 and 234 km. Phosphorus also comes from several
others sources including human disturbance of the land and its vegetation, human
waste, sewage from septic tanks and animal waste. Soil erosion also contributes
with phosphorus and the excessive use of fertilizers for crops and lawns results in
a higher amount of phosphorus going into Catatumbo River. Also, iron industry is
developed near the shore of the Catatumbo.
Venezuela is one of the worlds top oil producers and an OPEC member. Fre-
quently, the dynamiting of the Cao Limon pipeline, in Colombia, set off alarms
in Venezuela. These events cause large spills crude oil into Catatumbo and Tarra
Rivers which ow into Lake Maracaibo (Venezuela). This situation limits the ef-
forts for sampling trips to the region.
There is not a reported project for a similar study in the zone, especially in the
higher zone of the river, and the present study is the only information available at
the moment.
2.2. LAKE MARACAIBO SYSTEM
Lake Maracaibo, the largest lake in Latin America, is a large hypereutrophic estuar-
ine lake in north-western Venezuela which has suffered severe pollution problems
caused by inputs of excessive nutrients, petroleum products from a major pet-
rochemical industrial park and other contaminants. The lake is considered to be
naturally eutrophic, however, the current state of hypereutrophy is mainly caused
by excessive inputs of nutrients from treated and untreated sewage water and in-
dustrial wastes, riverine and agricultural sources as well as air pollution. Strong
petroleum activity has developed in the colombian territory of the river, which is
aggravated by the sabotage of oil pipelines (guerrilla activity) which is numerous
during the year and affect mainly the river bed and therefore Lake Maracaibo basin.
Catatumbo River brings approximately 70% of the fresh water to the lake, which
could indicate a signicant contribution to its eutrophication (Rivas, 2000).
Previous monitoring of the Lake showed a content of total phosphorus in the
water between 0.03 and 0.10 mg L
1
in the surface and between 0.20 and 0.30 mg
L
1
in its maximum depth. Dissolved oxygen varied from 100% of saturation in
the surface to less than 10% at 15 m below, in the center of the Lake. 1% of the
incident light penetrated to a maximum of 6 m. Chlorophyll values were between
610 mg L
1
(Parra-Pardi, 1979).
In 1994, ESCAM carried out a study in Lake Maracaibo, nding dissolved
oxygen concentrations between 68 mg L
1
in the epilimnion and lower than
120 H. LEDO ET AL.
1 mg L
1
in the hypolimnion. Total phosphorus concentrations oscillated between
0.030.61 mg L
1
in the surface and between 0.063.45 mg L
1
at the bottom.
Transparency values varied between 1 and 3.5 m.
3. Materials and Methods
A total of 22 sampling stations were located close to the shore from the Colombian
side until its outlet in the Lake including bed sediments from the major tributaries
to the river. Figure 1 shows the sampling sites and the location of Catatumbo River
in the Lake Maracaibo system. The dotted line is the geographic limit of both
countries, and the dark line shows the main bed of the Catatumbo River. From
each location a sample of sediments of approximately 1 kg was manually collected
giving a total of 44 samples during three periods: OctoberNovember 1993 (rainy
season); FebruaryMarch 1994 (dry season) and AugustSeptember 1994 (rainy
season). All stations could not be sampled in the three periods, since during dry
season some stations were completely dry and, in rainy season, episodes of ood
occurred, which impeded to sample other stations.
Samples were frozen until experiments were performed. Total phosphorus was
analyzed with the following method: 2.5 g of sediment were ignited for 2 hr in a
furnace at 550

C, allowed to cool for 1 hr before adding 10 mL of 1 N HCl and
boiled for 1 hr. The sample was then ltrated, completed to 10 mL with deionized
water and analyzed as orthophosphate using the standard ascorbic acid method
(APHA, 1992). Orthophosphate was analyzed in the following way: 2.5 g of wet
sediment were dissolved in 100 mL of the acid mixture H
2
SO
4
-HCl 1 N, stirred for
2 hr, ltrated and analyzed by the standard ascorbic acid method (APHA, 1992).
For metals determination samples were lyophilized before acid digestion in a Parr
type bomb at 105

C. The nal solution was analyzed by ame atomic absorption
spectroscopy using a Perkin Elmer 3100 instrument.
4. Data Analysis
For data analysis, graphics and tables were processed with all available information
to know the distribution of metals, by sampling and stations.
A simple Cluster analysis was used in order to clarify the differences between
sampling sites, sampling period and metal contents in the sediments of the area.
Classication was performed using 1-Pearson coefcient as the measure of dissim-
ilarity. The UPGMA (Unweighted Pair-Group Method using Arithmetic Averages)
clustering method was applied.
Analysis of variance (ANOVA) was carried out to compare the levels of metals
on different cluster sites.
Linear regression was performed between all elements studied with p < 0.05.
SURFICIAL SEDIMENT SAMPLES FROM CATATUMBO RIVER 121
Figure 1. Location of the sampling sites in Catatumbo River. Main river bed: (4) Limones sewer,
64 km; (8) Before Zulia River conuence, 120 km; (10) Before Tarra river conuence, 153 km;
(11) Ecuador bridge, 194 km; (13) Las Delicias, 229 km; (14) Puerto Barco, 234 km; (15) La Gabarra,
241 km; (17) Before San Miguel river conuence, 247 km; (18) Before Brandy river conuence,
254 km; (20) Filogringo, 303 km; (21) Aserrio, 345 km; (22) San Pablo, 355 km. Tributaries:
(5) Guasimales sewer; (6) Bravo River; (7) Zulia River; (9) Tarra River; (12) Oro River; (16) San
Miguel River; (19) Brandy River. Catatumbo River mouth in Lake Maracaibo: (1) Boca Norte;
(2) Boca Sur; (3) Congo Mirador.
122 H. LEDO ET AL.
TABLE I
Phosphorus and metals in sediments in the Catatumbo River bed
Sampling Distance Station Country
a
Total Mn Mg Ca Fe Al
date to Lake (See phospho-
Maracaibo Fig. 1) rus (TP)
(km) (mmol g
1
dry weight)
11/19/1993 254 18 2 0.018 0.0011 0.165 0.227 0.380 0.708
11/19/1993 241 15 2 0.008 0.0006 0.088 0.037 0.294 0.410
11/19/1993 229 13 2 0.009 0.0005 0.042 0.008 0.016 0.194
11/19/1993 194.1 11 1 0.002 0.0001 0.075 0.054 0.195 0.147
11/19/1993 153 10 1 0.012 0.0005 0.030 0.003 0.124 0.157
03/01/1994 355 22 2 0.034 0.0003 0.064 0.035 0.188 0.281
03/01/1994 345 21 2 0.032 0.0006 0.059 0.033 0.200 0.284
03/01/1994 303 20 2 0.024 0.0007 0.055 0.031 0.211 0.288
02/25/1994 247 15 2 0.007 0.0005 0.058 0.049 0.180 0.333
02/26/1994 234 14 2 0.010 0.0009 0.098 0.116 0.366 0.479
02/26/1994 229 13 2 0.001 0.0004 0.047 0.042 0.154 0.328
03/07/1994 194 11 1 0.014 0.0004 0.020 0.046 0.111 0.235
03/08/1994 120 8 1 0.007 0.0006 0.051 0.027 0.284 0.274
08/02/1994 254 18 2 0.017 0.0010 0.156 0.214 0.359 0.668
08/18/1994 247 17 2 0.011 0.0006 0.091 0.021 0.232 0.282
08/04/1994 241 15 2 0.015 0.0012 0.129 0.077 0.397 0.762
08/11/1994 234 14 2 0.005 0.0004 0.028 0.003 0.127 0.278
09/08/1994 229 13 2 0.012 0.0007 0.045 0.057 0.222 0.335
09/07/1994 153 10 1 0.005 0.0005 0.047 0.078 0.168 0.391
09/07/1994 120 8 1 0.009 0.0007 0.063 0.041 0.301 0.305
a
1 = Venezuela, 2 = Colombia.
5. Results and Discussion
Previous size particle analysis showed a homogeneous distribution in size particle
composition in sediments from the Catatumbo River within the river basin. Aver-
age results showed that 89% of the sediment has a particle size around 150 m,
which means that the sediment is classied as ne sand. No relationship was
found between the P-concentration and metals with the particle size. Hence, sedi-
ment transportation, availability, presence and distribution of P and metals are not
inuenced by particle size distribution in this sediment.
SURFICIAL SEDIMENT SAMPLES FROM CATATUMBO RIVER 123
TABLE II
Phosphorus and metals in sediments from tributaries to the Catatumbo River
Sampling Tributary Station Country
a
Total Mn Mg Ca Fe Al
date river (See phospho-
Fig. 1) rus (TP)
(mmol g
1
dry weight)
11/19/1993 San Miguel 16 2 0.009 0.0005 0.046 0.007 0.171 0.215
11/19/1993 Bravo 6 1 0.006 0.0009 0.110 0.018 0.458 0.363
02/25/1994 Brandy 19 2 0.025 0.0008 0.161 0.129 0.288 0.542
03/07/1994 Oro 12 1 0.011 0.0004 0.026 0.002 0.144 0.190
03/08/1994 Tarra 9 1 0.008 0.0004 0.024 0.001 0.105 0.119
03/08/1994 Zulia 7 1 0.006 0.0004 0.027 0.008 0.184 0.169
03/08/1994 Limones 4 1 0.030 0.0003 0.048 0.004 0.340 0.263
sewer
03/08/1994 Bravo 6 1 0.017 0.0005 0.021 0.014 0.152 0.203
03/09/1994 Guasimales 5 1 0.016 0.0003 0.034 0.002 0.180 0.198
sewer
08/02/1994 Brandy 19 2 0.002 0.0005 0.028 0.020 0.135 0.263
08/12/1994 San Miguel 16 2 0.007 0.0006 0.025 0.046 0.207 0.339
09/01/1994 Tarra 9 1 0.008 0.0004 0.025 0.004 0.209 0.495
09/01/1994 Oro 12 2 0.010 0.0005 0.048 0.107 0.192 0.395
09/07/1994 Zulia 7 1 0.012 0.0007 0.064 0.032 0.358 0.343
09/08/1994 Guasimales 5 1 0.006 0.0012 0.089 0.043 0.129 0.744
sewer
09/08/1994 Bravo 6 1 0.016 0.0003 0.045 0.002 0.208 0.427
a
1 = Venezuela, 2 = Colombia.
5.1. BASELINE CONCENTRATIONS OF Ca, Mg, Fe, Mn AND Al IN BED
SEDIMENT OF THE CATATUMBO RIVER STREAM
The mean concentrations found along the river bed were in the following order Al >
Fe > Mg > Ca > Mn (0.357; 0.226; 0.070; 0.060; 6 10
4
mmol g
1
dry sediment).
Phosphorus showed higher values at 254 km on the main river bed, probably due
to the presence of phosphoric rocks mines owing into the river in the area located
between 254 and 234 km approximately as can be seen in Table I. It was found that
Fe and Al concentrations were higher than the other element concentrations. The
high values for iron and aluminum probably show the characteristics of the soils in
this region which were characterized as tertiary and quaternary (M.E.M., 1995).
Table II shows metals concentrations found in sediments of tributary rivers.
The mean concentrations found in the rivers were Al > Fe > Mg > Ca> Mn (0.329;
124 H. LEDO ET AL.
0.211; 0.051; 0.028; 5.42 10
4
mmol g
1
dry sediment) being slightly higher in
the Colombian side.
The mean concentration for the metals in the river outlet was in the following
sequence Fe > Al > Mg > Ca > Mn (0.802; 0.563; 0.070; 0.018; 6.9 10
4
mmol
g
1
dry sediment), as can be seen in Table III. The magnitude of these values was
expected since the zone belongs to the type referred as accumulation of elements.
Sediments are deposited in areas of quiet, slow moving water (the mouth of the
river in the opening to Lake Maracaibo) and are picked up and carried on further
downstream when ows increase. Much sediment transport occurs during rainy
events. Deeper parts of the lake, on the other hand, act as basins where sediments
accumulate.
Additionally, Figure 2 presents the log concentration (mmol g
1
dry weight) of
P, Mn, Mg, Ca, Fe and Al, along the river bed, of the surface samples taken over 3
separate eld sampling times in relation to the distance from Lake Maracaibo and
the evaluated Colombian and Venezuelan territories.
Values of metals found in sediments of the river show levels below minimum
values in other ecosystems. These metals are associated with rocks, ne-grained
mineral structure, and biogenic sediments. A list of the results for another ecosys-
tems is given in Table IV.
An attempt to evaluate the quality of the sediment data, was done by com-
paring it to the sediment background values in other ecosystems worldwide. The
background values can be used as a point of reference to establish the Catatumbo
River sediment baseline, as can be seen in Table V. No enforceable USA Federal
or State Sediment Quality Standards exist for the elements under study except iron
and manganese with values of 0.36 and 0.0084 mmol g
1
of dry sediment, respect-
ively (Persaud et al., 1993). Venezuela has no national criteria for any elements in
sediments.
The natural metal/aluminum relationships shown in Table V were used to de-
velop guidelines for distinguishing natural from contaminated sediments for a num-
ber of metals and metalloids commonly released to the environment due to an-
thropogenic activities. Aluminum was chosen as a reference element to normalize
sediment metals concentrations since: it is the most abundant naturally occurring
metal; it is highly refractory; and its concentration is generally not inuenced by
anthropogenic sources. Additionally, aluminum is the second most abundant metal
in the earths crust, being silicon the most abundant (Windom, 1988).
Most metals transported by rivers are tightly bound in the aluminosilicate solid
phases. As a consequence, during the weathering, there is very little fractionation
between the naturally occurring metals and aluminum. It has long been assumed
that in freshwater sediments, hydrous manganese and iron oxides provide import-
ant adsorbing surfaces being probably responsible for trace metal transport in redox
sensitive environments (Morfett et al., 1988).
Since much of the natural constituents of metals in estuarine sediments are
chemically bound in the aluminosilicate structure, the metals are generally non-
SURFICIAL SEDIMENT SAMPLES FROM CATATUMBO RIVER 125
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126 H. LEDO ET AL.
Figure 2. Metals and phosphorus concentrations in Catatumbo River sediments. (A) Octo-
berNovember 1993; (B) FebruaryMarch 1994; (C) AugustSeptember 1994.
SURFICIAL SEDIMENT SAMPLES FROM CATATUMBO RIVER 127
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r
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a
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7
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r
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s
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h
i
s
W
o
r
k
a
N
R
=
N
o
t
r
e
p
o
r
t
e
d
.
128 H. LEDO ET AL.
T
A
B
L
E
V
C
o
m
p
a
r
i
s
o
n
s
o
f
m
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t
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l
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c
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W
o
r
l
d
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.
V
a
l
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b
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w
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p
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t
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d
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r
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M
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1
d
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l
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)
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o
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,
1
9
9
9
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a
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b
a
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1
6
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2
3
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0
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T
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o
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t
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l
.
(
1
9
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)
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e
r
s
a
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t
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l
.
,
1
9
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3
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a
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0
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o
r
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w
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t
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t
a
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,
1
9
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m
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0
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2
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(
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(
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h
i
s
w
o
r
k
a
N
R
=
N
o
t
r
e
p
o
r
t
e
d
.
SURFICIAL SEDIMENT SAMPLES FROM CATATUMBO RIVER 129
Figure 3. Classication of variables (metals and phosphorus content) in the sediment samples.
labile. The adsorbed anthropogenic or pollutant component is more loosely bound.
Metals in the anthropogenic fraction, therefore, may be more available to estuarine
biota and may be released to the water column when sediments are disturbed (e.g.,
by dredging or storms). Due to the fact that the levels of the studied metals in
samples of surcial sediments in Catatumbo River and the ratios metal/aluminum
are very low when compared with values established as background and crusts in
other ecosystems, these results could be considered as baseline levels.
5.2. SPATIAL DISTRIBUTION OF Ca, Mg, Fe, Mn AND Al CONCENTRATIONS IN
BED SEDIMENT OF THE CATATUMBO RIVER STREAM AND CORRELATION
AMONG TOTAL PHOSPHORUS, ORTHOPHOSPHATE AND METALS
Figure 3 presents the classication of variables (metal concentrations and phos-
phorus content) in the sediment, by means a simple cluster analysis, using Pearson
correlation coefcients (UPGMA) as a measure of similarity. According to this
dendogram, four main clusters with geochemical signicance appear to exist:
(a) The Ca group: The presence of naturally occurring Ca in this group suggests
natural origin.
(b) The Mg and phosphate group: It shows a stronger association between phos-
phate and magnesium than between phosphate and other metals.
130 H. LEDO ET AL.

Figure 4. Classication of the stations using as variables the concentrations of metals and phosphorus
in the sediments.
(c) The Al, Fe and Mn group. The fact that Fe and Mn appear in the same group
with Al, suggests that weathering of natural rocks may play an important role
in the distribution of those metals in the sediments of the study area. Fe and
Mn oxides probably play an important role in this distribution. There are iron
reserves in Colombia which could explain the high amount of iron.
(d) Total Phosphorus forms a separated group, which shows a different distribution
process compared to the metals. Probably, ferlilizers could be the main source
of phosphorus.
Pearson product-moment correlations between each pair of variables were used,
and p-values below 0.05 indicate statistically signicant non-zero correlations at
the 95% condence level. There is a very poor correlation between total phos-
phorus and the studied metals. It is also shown a positive correlation between the
metals and orthophosphate which indicates that orthophosphate is the main specie
interacting with the metals. Correlations among metals are high and positive which
show their interaction to form multiple complexes such as Fe-Mn-P, Fe-Ca-P and
Mn-Ca-P.
SURFICIAL SEDIMENT SAMPLES FROM CATATUMBO RIVER 131
A simple Cluster analysis was used to nd the differences between sampling
sites, sampling period and metal contents in sediments of the area as appears in
Figure 4. The concentration of metals and phosphorus were used as variables. It
was found no clear groups in the dendrogram depicting cluster analysis. With the
exception of some stations that cluster together, there is no homogeneous pattern
to describe the clustering and sites are not signicantly different from each other.
It should be noted that this study was performed on near-shore sediments rather
than on deeper areas of the river where sediment accumulation might occur. The
fact that no metal concentration was related to distance downstream in this river
may be related to the low level of metal contamination.
5.3. RATIO METAL/PHOSPHORUS AS AN INDICATIVE OF THE COMPLEXES
FORMATION
In general, when dissolved metals from natural or anthropogenic sources come in
contact with saline water, they are quickly absorbed to particulate matter and are
removed from the water column to bottom sediments. Thus, metals from both nat-
ural and anthropogenic sources are ultimately concentrated in estuarine sediments,
not the water column. When the ground water rich on trace elements contacts less
acidic surface water (the union Catatumbo River with Lake Maracaibo waters),
substantial amounts of dissolved Fe and Al will precipitate as ne grained Fe
oxides or aluminium hydroxides. In turn, these substrates can scavenge and con-
centrate other dissolved trace elements (e.g., Cu, Zn). Finally, these trace elements
could accumulate in the bed sediments of Lake Maracaibo. That is to say, that
although the concentrations of metals are very low, and are included as part of the
ground, they can inuence later in the metal accumulation in sediments of the water
body where they are transported. This can be the case of the outlet of Catatumbo
River in Lake Maracaibo, specially the formation of compounds with phosphorus
which can inuence the eutrophication process of the Lake Maracaibo.
Metal and total phosphorus concentrations were used to determine the molar
ratio in the Catatumbo River bed, in its tributaries and its mouth in Lake Maracaibo.
The global mean ratios for these areas are shown in Table VI. Additionally, this
table shows the global mean ratios calculated from P and metal concentrations for
three sediment samples from Lake Maracaibo taken near the mouth of Catatumbo
River. These could suggest that Al, Fe, Mg, and Ca form complexes with phos-
phorus, therefore, they control the phosphorus release to the water column. The
molar ratios found (Al/P; Fe/P; Ca/P and Mg/Ca) are higher than the minimum re-
quired values for the formation of the mentioned complexes (Chamber and Prepas,
1994; Moore et al., 1991; Dannen-Louwerse et al., 1993; Staudinger et al., 1990).
Consequently, it can be stated that the metal complexes could be present in the
analyzed sediment samples, existing the Mg/Ca complex as Dolomite (Moore et
al., 1991). The complex Fe-Al-P could be predominant because Fe and Al have in
a higher ratio with phosphorus as compared to the other metals. Additionally, it was
132 H. LEDO ET AL.
T
A
B
L
E
V
I
M
e
a
n
m
o
l
a
r
r
a
t
i
o
f
o
r
t
h
e
s
t
u
d
i
e
d
m
e
t
a
l
s
i
n
s
e
d
i
m
e
n
t
R
a
t
i
o
C
a
t
a
t
u
m
b
o
T
r
i
b
u
t
a
r
i
e
s
C
a
t
a
t
u
m
b
o
R
i
v
e
r
L
a
k
e
M
a
r
a
c
a
i
b
o
L
i
t
e
r
a
t
u
r
e
R
e
f
e
r
e
n
c
e
R
i
v
e
r
b
e
d
o
u
t
l
e
t
i
n
t
h
e
(
n
e
a
r
C
a
t
a
t
u
m
b
o
M
a
r
a
c
a
i
b
o
L
a
k
e
R
i
v
e
r
m
o
u
t
h
)
A
l
/
P
5
0
.
9
6
4
1
.
2
6
1
8
.
9
7
5
4
.
9
7
3
.
1
3
D
a
n
e
n
-
L
o
u
w
e
r
s
e
e
t
a
l
.
(
1
9
9
3
)
F
e
/
P
3
1
.
6
2
2
4
.
6
5
2
3
.
4
7
5
3
.
0
3
1
.
8
0
(
a
)
C
h
a
m
b
e
r
s
e
t
a
l
.
(
1
9
9
4
)
6
.
6
6
(
b
)
D
a
n
e
n
-
L
o
u
w
e
r
s
e
e
t
a
l
.
(
1
9
9
3
)
M
g
/
P
9
.
8
4
5
.
8
1
2
.
7
4
1
4
.
2
2
N
R
a
N
R
a
C
a
/
P
8
.
0
9
3
.
0
9
0
.
5
0
2
0
.
0
8
3
.
1
8
S
t
a
u
d
i
n
g
e
r
e
t
a
l
.
(
1
9
9
0
)
M
g
/
C
a
1
.
2
2
1
.
8
8
5
.
4
8
0
.
7
1
>
0
.
6
M
o
o
r
e
e
t
a
l
.
(
1
9
9
1
)
M
n
/
P
0
.
0
8
0
.
0
7
0
.
0
2
0
.
0
6
N
R
a
N
R
a
a
N
R
=
N
o
t
r
e
p
o
r
t
e
d
i
n
t
h
e
l
i
t
e
r
a
t
u
r
e
.
SURFICIAL SEDIMENT SAMPLES FROM CATATUMBO RIVER 133
found that the mean pH value and dissolved oxygen values in sediments overlying
water were 7.0 and 5.0 mg L
1
, respectively (Gutirrez, 1995) which indicates
the aerobic nature of the sediments. This fact is favorable for the formation of
phosphorus and metals complexes such as Al, Fe and Ca present in the sediments.
6. Conclusions
The present work provides baseline data for future impact assessment and in-
formation on existing environmental alterations for one of the most important
river in the binational South American region.
The present investigation provides primary eld data metals in sediments from
Catatumbo River. The global mean concentration of the metals was Al > Fe >
Mg > Ca > Mn (0.376; 0.304; 0.063; 0.042; 5.9 10
4
mmol g
1
dry weight).
The metal/P ratios found with the oxygen levels in the river, suggest the form-
ation of metal-P complexes, especially with Fe, Al and Ca. This indicates that
once the sediments arrive to the anoxic center of Lake Maracaibo, a phosphorus
source can be developed.
Acknowledgements
The authors wish to thank the INTEVEP- Gerencia de Ecologia y Ambiente, es-
pecially to Dr. Jorge Rodrguez, Ivan Galindo and Enrique Abreu, for providing
facilities to obtain samples sediment and nancial partially this study.
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