Proceedings of the 19th IAHR-APD Congress 2014, Hanoi, Vietnam

ISBN 978604821338-1

EVALUATION OF TEMPORAL VARIATION IN PHYSICAL AND CHEMICAL CHARACTERISTICS OF WATER AND

SOIL IN OIL EXPLOITATION ZONE OF VENEZUELA

A. MRQUEZ (1), OLGUI FIGUEIRA (2), M. MURA (2) & E. GUEVARA (1)
(1)
Center of Hydrological and Environmental Researches of Carabobo University, Valencia, Venezuela
ammarquez@uc.edu.ve; eguevara@uc.edu.ve
(2)
Laboratory of Water and Soil Quality of HidroLabToro Consults, Valencia, Venezuela
figueira_cristina@hotmail.com; miguel.murar@gmail.com

ABSTRACT
To ensure the quality and quantity of soil and water resources over time is necessary to establish a continuous
monitoring system on them, which means balancing the exploitation of the resource in terms of quantity, quality and
relation to other natural resources. The characterization included sample collection water and soil in oil exploration
areas of Anzoategui, Venezuela, during the period between 2009 and 2013. In surface waters, the phosphorus and
nitrogen concentrations were below the limits set out in Article 10 of Decree 883, the suspended solids exceeded the limit
of the standard in 2009, Oils and Fats Minerals and Hydrocarbons, Biochemical Oxyen Demand and Chemical Oxygen
Demand exceeded the limit in the years between 2009 and 2013. In soils under treatment found that metals and oils and
yielded the highest concentration in 2012, concentrations of metals and hydrocarbons were higher compared to soil
samples adjacent to spills. It concludes that the temporal variability of the water is greater than that of the soil.

Keywords: Pollution, water, soil, hydrocarbons and metals.

1. INTRODUCTION Campos et al (2005) indicate that the aquatic environment

The Orinoco oil belt is a zone composed by heavy and
extra-heavy oil; which is located at the north of Orinoco
River in Venezuela. This has total and exploited areas
equal to 55.314 Km 2 and 11.593 Km 2, respectively. This
includes part of the following four states: Guarico, Delta
Amacuro, Monagas and Anzoategui. The proven oil
reserves of the Orinoco oil belt (OOB) represents 92,75%
(276.156 million of barrel) with respect to the proven
national oil reserve (297.735 million of barrel) (PDVSA,
2012). According with OPEC (2013), Venezuela is the
country with the most proven oil reserves in the world,
297,7 billion of barrel (24,8%). The OOB total production
was 2062 thousand of barrel per day of crude during
2012; what represents 98,42% of national production.
Anzoategui state is one of the most important production
region into the OOB, 687 thousand of barrel per day
during 2012; approximately 33% of the OOB production
(PDVSA, 2012).
The OOB geostrategic importance was promoted by trade
agreements with different countries since 2005 (Ministry
of Energy and Oil, 2005). During the period January-
December 2012, 405 wells were drilled in the OOB;
generating 256 thousand barrels per day of crude oil
(PDVSA, 2012). As a result of the OOB anthropic
activities, it has been necessary to implement a continue
control system about water and soil resources. Crude oil
is a complex natural mixture of hydrocarbon
combination various. The major proportion are
hydrocarbons, the rest are elements such as nitrogen,
sulfur, oxygen and some trace metals such as nickel,
vanadium, iron and copper; predominating the organic
fraction whose value varies between 50 and 98%
(Carlberg, 1980).
alteration produced by the oil and its products is an
unavoidable consequence of dependence established
between the human being and the technology based on
this resource; becoming in a strong global environmental
problem.
Among the soil contaminants; the heavy metals in small
quantities are essentials for the organism such as Fe, Mn,
Zn, B, Co, As, V, Cu, Ni and Mo; becoming noxious
when these are present in high concentrations; while that
others do not perform some biological function and are
highly toxics such as Cd, Hg or Pb (Alcala et al., 2009).
The purpose of the research is based on the study of
physical and chemical parameters of waters and soils
from OOB oil exploration wells, by statistical analysis;
including: deviations, concentration ranges, means and
variability temporal. These are essential for making
strategic decisions such as the location of projects and
reduction of monitoring costs; which may be adjusted
depending on the temporal variability found.
2. METHODOLOGY
The investigation was conducted in the oil production
area of Anzoategui state, into the OOB included in the
grid defined by the following points: P 1 64 40 26,60 W
and 8 34 53,78 N; P 2 63 36 27,02 W and 8 35 5,14
N, P3 64 40 34,8 W and 9 05 8,95 N; P 4 63 36 29,99
W and 9 05 20,99 N.
The soil component concentration is determined using
Eq. [1]:

1

[1]
Where C is the element concentration in mg/Kg, Le the
equipment reading in mg/L, V is the sample volume in
L, and P is the sample weight in Kg.
The Biochemical Oxygen Demand (BOD) is calculated
using Eq. [2]:
[2]
Where F is the dilution factor, T0 is the oxygen content
mg/L of the sample dilutions at the test beginning of the
test, T5 is the oxygen content mg/L of the sample
dilutions after 5 days incubation, DO 0 is the oxygen
content in mg/L of the dilution water at the test
beginning of the test, DO 5 is the average oxygen content
mg/L of the dilution water after 5 days of incubation.
The Chemical Oxygen Demand (COD) is calculated using
Eq. [3]:
[3]
Where A is the volume of the solution Ferrous
Ammonium Sulfate (FAS) in the blank in mL, B is the
FAS solution volume used in the sample in mL, M is the
FAS molarity in mg / L, and V is the volume of sample
in mL.
Minerals Oils and Fats and Hydrocarbons are calculated
by Eq. [4]:
[4]
Where O&F is the concentration of Fats and
Hydrocarbons and Mineral Oils in mg/L, P 1 is the weight
of the flask (free of moisture) before extraction in mg, P 2
is the weight of the flask after extraction and drying mg
and V is the volume of the filtered sample L.
The samples captured and analyzed were 3,000 for the
water and soil of the above areas during the period 2009-
2013. The surface water samples were captured in
composite form, by adding equal volumes to six liters.
Six sub-samples were taken at an average depth across
the width of the stream. The sampling points were ten as
follow: Caris river, Tigre river, San Tome river, Urupia
river, Canoa river, Moquete river, Aventazon river, La
Pea river, Carapa river, and rain water dammed in
impacted pits present in the study area. The samples
were preserved, identified with a label and refrigerated.
A blank was prepared. The pH and temperature were
measured in the field. Chains of custody and field sheets
were filled, reflecting the field measurements, the
parameters to analyze and capture process observations.
The soil samples were captured of the eight oil zone pits
following: 1)Oficina, 2)Guara), 3)Santa Rosa, 4)Nipa,
5)Merey, 6)Dacion, 7)Leona and 8)Yoaples, all of these
located into Anzoategui State.
Sediment samples were captured by selecting different
sampling points using a grid, taking the subsamples
mixed and deposited in two containers (sample and
blank) capacity 400 grams. The deposits are identified
with a self-adhesive label. A sampling protocol and chain
of custody are filled, reflecting the parameters analyzed,
preservations and observations of sampling.
To determine the concentrations of metals, a soil sample
was dried at room temperature for 3 days, then it was
sieved in a 2 mm mesh and a total of 0.5 g by adding a
mixture of HNO3 and HCl was taken. This solution was
left in a microwave vial Teflon at 60 C for two hours.
Then, this was passed to a microwave digester; diluting
the liquid extract with triple distilled water for analysis
by Inductively Coupled Plasma technique.
To determine the oil and grease, the sample was
preserved by acidifying with hydrochloric acid 1:1 to a
pH value of less than two and refrigeration at 4 C.
Determination of Oil and Grease is based on the
adsorption of fats and oils in diatomaceous earth, which
are extracted in a Soxhlet using hexane as a solvent. Once
completed the hexane extraction was evaporated and the
residue remaining in the container is weighed, and this
value content of fats and oils.
To determine the COD of water samples were collected in
glass bottles. These were preserved at pH 2 by the
addition of H 2SO4 conc. 50.0 mL of sample into a ball of
500-mL reflux. Then 25 mL of solution were added
K2Cr2O7 and mixed, then 1 g of HgSO 4 and 5.0 mL of
sulfuric acid, stirring to dissolve the added HgSO4. The
remainder of the sulfuric acid reagent (70 mL) was added
through the top of the condenser. The condenser was
cooled and rinsed from the top with distilled water. Once
the capacitor was disconnected, the sample was diluted
to twice its volume with distilled water. This was allowed
to cool to room temperature and excess K 2Cr2O7 was
graded FAS in the presence of from 0.10 to 0.15 mL of
ferroin indicator. Likewise, a blank was titrated.
To determine the BOD, a defined volume of liquid
sample was added to an opaque, complete with the
dilution water container. The pH was between 6 and 8.
The initial dissolved oxygen was measured and the bottle
was covered with a rubber cap. The sealed bottle was
introduced into a refrigerated oven at 20 C. Finally, the
dissolved oxygen subsisting after 5 days was measured.
Control test was performed, determining the oxygen
dissolved in the dilution water.
3. RESULTS
The results shown from Figures 1 to 8 and 9 to 21 reflect
the element concentration variation; considering ten
points for capturing water samples, and eight points for
capturing soil samples that have been indicated in the
methodology section, respectively. Likewise, these
figures show the element concentration variation with
respect to the time. The variation is shown using box
plots. The study period comprises from 2009 to 2013.
The most of the (N) nitrogen concentration values
measured in water into of each year vary as follow: 2009:
0 and 18 mg/L; 2010: 0 and 2 mg/L; 2011: 0 and 4 mg/L;
2012: 2 and 12 mg/L; 2013: 2 and 10 mg/L (Figure 1).
Regarding to the temporal variation of the N
concentration values; the following observations can be
made: there are extreme points (more than 3 time of the
interquartile range) from 2009 to 2011; there is more
variation in the N concentration values in 2012 with
respect to the rest years; although this variation may be
statistically insignificant because the intervals are
overlapped each other. The annual mean is
2
approximately equal to 6 mg/L. All the N concentration
values are below the limit by Decree 883 (40 mg/L).
Figure 1. Nitrogen Concentration in water during the period 2009-
2013. The black line represents the mean for all data.
The most of the (P) phosphor concentration values
measured in water into of each year vary as follow: 2009:
0 and 0,8 mg/L; 2010: 1,2 and 2,2 mg/L; 2011: 0 and 0,2
mg/L; 2012: 0 and 0,4 mg/L; 2013: 0 and 0,2 mg/L
(Figure 2). Regarding to the temporal variation of the P
concentration values; the following observations can be
made: there are extreme points; there is more variation in
the P concentration values in 2010 with respect to the rest
years; this variation may be statistically significant
because the intervals do not overlap each other. The
annual mean is approximately equal to 0,8 mg/L. All the
P concentration values are below the limit by Decree 883
(10 mg/L).
Figure 2. Phosphor Concentration in water during the period
2009-2013.
The most of the (T) temperature values measured in
water into of each year vary as follow: 2009: 25 and 38
mg/L; 2010: 28 and 33 C; 2011: 26 and 37 C; 2012: 28
and 32 C; 2013: 25 and 30 C (Figure 3). Regarding to the
temporal variation of the T values; the following
observations can be made: there are extreme points; the
variation may be statistically insignificant because the
intervals are overlapped each other. The annual mean is
approximately equal to 30C.
Figure 3. Temperature of water during the period 2009-2013.
The most of the (SS) suspended solids concentration
values measured in water into of each year vary as
follow: 2009: 0 and 200 mg/L; 2010: 0 and 0,2 mg/L;
2011: 0 and 80 mg/L; 2012: 0 and 60 mg/L; 2013: 0 and 60
mg/L (Figure 4). Regarding to the temporal variation of
the SS concentration values; the following observations
can be made: there are extreme points; there is more
variation in the SS concentration values in 2009 with
respect to the rest years; although around 75% of
observations in this year are below the limit value. The
variation may be statistically significant because the
intervals do not overlap each other. The annual mean is
approximately equal to 60 mg/L. The most of the SS
concentration values are below the limit by Decree 883
(80 mg/L).
Figure 4. Suspended Solids in water during the period 2009-2013.
The most of the pH values measured in water into of
each year vary as follow: 2009: 4 and 9; 2010: 5 and 7;
2011: 3 and 8,5; 2012: 6,5 and 7,5; 2013: 6 and 8 (Figure 5).
Regarding to the temporal variation of the pH values; the
following observations can be made: there are extreme
points; there is variation in the pH values in 2011 with
respect to the rest years; although this variation may be
statistically insignificant because the intervals are
overlapped each other. The annual mean is
approximately equal to 6,5. The most of the pH values
are into the limits by Decree 883 (6-9).
Figure 5. pH in water during the period 2009-2013.
The most of the (MOH) Minerals Oil and Hydrocarbons
values measured in water into of each year vary as
follow: 2009: 0 and 28 mg/L; 2010: 0 and 2 mg/L; 2011: 2
and 14 mg/L; 2012: 2 and 30 mg/L; 2013: 0 and 2 mg/L
(Figure 6). Regarding to the temporal variation of the
MOH values; the following observations can be made:
there are extreme points; there is more variation in the
MOH values in 2012 with respect to the rest years;
although around 75% of observations in this year are
below the limit value. The variation may be statistically
insignificant because the intervals are overlapped each
other. The annual mean is approximately equal to 6
mg/L. The most of the MOH values are below the limit
by Decree 883 (20 mg/L); with exception of some
maximum and extreme values.
3
 Figure 8. Chemical Oxygen Demand in water during the period
Figure 6. Minerals Oils and Hydrocarbons in water during the 2009-2013.
period 2009-2013.
The most of (O&F) Oil and Fast Percentage values measured
in soils adjacent to the spill zones into of each year vary as
follow: 2009: 0 and 6%; 2010: 0 and 3%; 2011: 0 and 3,5%;
2012: 0 and 5%; 2013: 0 and 0,2% (Figure 9). Regarding to
the O&F values temporal variation; the following
The most of (BOD) Biochemical Oxygen Demand values
observations can be made: there are extreme points; there
measured in water into of each year vary as follow: 2009:
is more variation in the O&F values in 2009, 2010 and
0 and 80 mg/L; 2010: 0 and 60 mg/L; 2011: 0 and 60
2013 with respect to the rest years; although this variation
mg/L; 2012: 0 and 30 mg/L; 2013: 0 and 170 mg/L
may be statistically insignificant because the intervals are
(Figure 7). Regarding to the temporal variation of the
overlapped each other. The annual mean is
BOD values; the following observations can be made:
approximately equal to 250 mg/L. Around of
there are extreme points; there is more variation in the
observations 75% in all years are above of the limit by
BOD values in 2013 with respect to the rest years;
Decree 2635 (1%).
although this variation may be statistically insignificant
because the intervals are overlapped each other. The
annual mean is approximately equal to 50 mg/L. The
most of the BOD values are below the limit by Decree 883
(60 mg/L); with exception of some maximum and
extreme values.

Figure 9. Oils and Fats in soils adjacent to the spill zones during
the period 2009-2013.

The most of (O&F) Oil and Fast values measured in soils in

treatment the spills into of each year vary as follow: 2009: 0
and 4%; 2010: 0 and 2%; 2011: 0 and 4%; 2012: 0 and 0,2%;
2013: 0 and 0,2% (Figure 10). Regarding to the O&F values
Figure 7. Biochemical Oxygen Demand in water during the period temporal variation; the following observations can be
2009-2013. made: there are extreme points; there is more variation in
the O&F values in 2009 and 2011 with respect to the rest
The most of (COD) C hemical Oxygen Demand values years; although this variation may be statistically
measured in water into of each year vary as follow: 2009: insignificant because the intervals are overlapped each
0 and 600; 2010: 0 and 300 mg/L; 2011: 0 and 200 mg/L; other. The annual mean is approximately equal to 1%.
2012: 0 and 150 mg/L; 2013: 0 and 400 mg/L (Figure 8). The most of the O&F values are below the limit by Decree
Regarding to the temporal variation of the COD values; 2635 (1%). Around of observations 75% in 2009 and 2011
the following observations can be made: there are are above of the limit.
extreme points; there are more variation in the COD
values in 2009, 2010 and 2013 with respect to the rest
years; although around 75% of observations in these
years are below the limit value. The variation may be
statistically insignificant because the intervals are
overlapped each other. The annual mean is
approximately equal to 250 mg/L. The most of the COD
values are below the limit by Decree 883 (350 mg/L);
with exception of some maximum and extreme values.

Figure 10. Oils and Fats in soils under treatment during the period
2009-2013.

The most of pH values measured in soils adjacent to the spill

zones of each year vary as follow: 2009: 4 and 7; 2010: 3

4
and 7; 2011: 3 and 7; 2012: 3 and 8; 2013: 4 and 7 (Figure
11). Regarding to the pH values temporal variation; the
following observations can be made: there are extreme
points; the variation may be statistically insignificant
because the intervals are overlapped each other. The
annual mean is approximately equal to 5,5. The most of
the pH values are into the limits by Decree 2635 (5-8);
with exception of some maximum and extreme values.

Figure 13. Arsenic in soils adjacent to the spill zones during the
period 2009-2013.

The most of (As) A rsenic values measured soils under

treatment into of each year vary as follow: 2009: 0 and 11
mg/Kg; 2010: 0 and 8 mg/Kg; 2011: 0 and 12 mg/Kg;
2012: 0 and 12 mg/Kg; 2013: 0 and 2 mg/Kg (Figure 14).
Regarding to the temporal variation of the As values; the
Figure 11. pH in soils adjacent to the spill zones during the period following observations can be made: there are extreme
2009-2013. points; the variation may be statistically insignificant
because the intervals are overlapped each other. The
The most of pH values measured in soils in treatment of each annual mean is approximately equal to 3 mg/Kg. All
year vary as follow: 2009: 3 and 9; 2010: 4 and 7; 2011: 4 observations of the As values are below the limit by
and 7,5; 2012: 4 and 9; 2013: 5 and 9 (Figure 12). Decree 2635 (25 mg/Kg).
Regarding to the temporal variation of the pH values; the
following observations can be made: there are extreme
points; the variation may be statistically insignificant
because the intervals are overlapped each other. The
annual mean is approximately equal to 6. The most of the
pH values are into the limits by Decree 2635 (5-8); with
exception of some maximum and extreme values.

Figure 14. Arsenic in soils under treatment during the period

Figure 12. pH in soils under treatment during the period 2009-
2013.
The most of (As) A rsenic values measured in soils adjacent to
the spill zones i nto of each year vary as follow: 2009: 0 and
9 mg/Kg; 2010: 0 and 8 mg/Kg; 2011: 0 and 4 mg/Kg;
2012: 0 and 18 mg/Kg; 2013: 0 and 7 mg/Kg (Figure 13).
Regarding to the temporal variation of the As values; the
following observations can be made: The variation may
be statistically insignificant because the intervals are
overlapped each other. The annual mean is
approximately equal to 3 mg/Kg. All observations of the
As values are below the limit by Decree 2635 (25 mg/Kg).
2009-2013.
The most of (Ba) Barium values measured in soils adjacent to
the spill zones into of each year vary as follow: 2009: 0 and
200 mg/Kg; 2010: 0 and 180 mg/Kg; 2011: 0 and 80
mg/Kg; 2012: 0 and 280 mg/Kg; 2013: 0 and 20 mg/Kg
(Figure 15). Regarding to the temporal variation of the Ba
values; the following observations can be made: there are
extreme points; there are more variation in the Ba values
in 2012 with respect to the rest years; although this
variation may be statistically insignificant because the
intervals are overlapped each other. The annual mean is
approximately equal to 100 mg/Kg. All observations of
the Ba values are below the limit by Decree 2635 (20.000
mg/Kg).

Figure 15. Barium in soils adjacent to the spill zones during the
period 2009-2013.

5
The most of (Ba) Barium values measured in soils under
treatment to the spill zones i nto of each year vary as follow:
2009: 0 and 200 mg/Kg; 2010: 0 and 180 mg/Kg; 2011: 0
and 80 mg/Kg; 2012: 0 and 280 mg/Kg; 2013: 0 and 20
mg/Kg (Figure 16). Regarding to the temporal variation
of the Ba values; the following observations can be made:
there are extreme points; there is more variation in the Ba
values in 2012. This variation may be statistically
insignificant because the intervals are overlapped each
other. The annual mean is approximately equal to 80
mg/Kg. The most of the Ba values are below the limit by
Decree 2635 (20.000 mg/Kg). Figure 18. Cadmium in soils under treatment during the period
2009-2013.

The most of the (Cr) Chromium values measured in soils

adjacent to the spill zones into of each year vary as follow:
2009: 0 and 30 mg/Kg; 2010: 0 and 60 mg/Kg; 2011: 0
and 60 mg/Kg; 2012: 0 and 70 mg/Kg; 2013: 0 and 50
mg/Kg (Figure 19). Regarding to the temporal variation
of the Cr value; the following observations can be made:
there are extreme points; the variation may be statistically
insignificant because the intervals are overlapped each
other. The annual mean is approximately equal to 30
mg/Kg. The most of the Cr values are below the limit by
Decree 2635 (300 mg/Kg).
Figure 16. Barium in soils under treatment during the period
2009-2013.

The most of the (Cd) Cadmium values measured in soils

adjacent to the spill zones into of each year vary as follow:
2009: 0 and 1 mg/Kg; 2010: 0 and 180 mg/Kg; 2011: 0
and 80 mg/Kg; 2012: 0 and 280 mg/Kg; 2013: 0 and 20
mg/Kg (Figure 17). Regarding to the temporal variation
of the Cd values; the following observations can be made:
there are extreme points; there are more variation in the
Cd values in 2012 with respect to the rest years; although
this variation may be statistically insignificant because
the intervals are overlapped each other. The annual mean Figure 19. Chromium in soils adjacent to the spill zones during the
is approximately equal to 1,5 mg/Kg. The most of the Ba period 2009-2013.
values are below the limit by Decree 2635 (8 mg/Kg).
The most of (Cr) Chromium values measured in soils under
treatment into of each year vary as follow: 2009: 0 and 45
mg/Kg; 2010: 0 and 50 mg/Kg; 2011: 0 and 70 mg/Kg;
2012: 0 and 65 mg/Kg; 2013: 10 and 30 mg/Kg (Figure
20). Regarding to the temporal variation of the Cr values;
the following observations can be made: there are
extreme points; the variation may be statistically
insignificant because the intervals are overlapped each
other. The annual mean is approximately equal to 30
mg/Kg. All observations of the Cr values are below the
limit by Decree 2635 (300 mg/Kg).

Figure 17. Cadmium in soils adjacent to the spill zones during the
period 2009-2013.

The most of the (Cd) Cadmium values measured in soils

under treatment into of each year vary as follow: 2009: 0
and 1,5 mg/Kg; 2010: 0 and 1 mg/Kg; 2011: 0 and 1,5
mg/Kg; 2012: 0 and 4 mg/Kg; 2013: 0 and 0,5 mg/Kg
(Figure 18). Regarding to the temporal variation of the Cd
values; the following observations can be made: the
variation may be statistically insignificant because the
intervals are overlapped each other. The annual mean is
approximately equal to 1 mg/Kg. All values of the Ba Figure 20. Chromium in soils under treatment during the period
values are below the limit by Decree 2635 (8 mg/Kg). 2009-2013.

The most of the (Pb) Plumbum values measured in soils

adjacent to the spill zones into of each year vary as follow:

6
2009: 0 and 8 mg/Kg; 2010: 0 and 14 mg/Kg; 2011: 0 and
18 mg/Kg; 2012: 0 and 20 mg/Kg; 2013: 0 and 6 mg/Kg
(Figure 21). Regarding to the temporal variation of the Pb
values; the following observations can be made: there are
extreme points; there is more variation in the Ba values in
2012 with respect to the rest years; although this variation
may be statistically insignificant because the intervals are
overlapped each other. The annual mean is
approximately equal to 8 mg/Kg. All observations of the
Pb values are below the limit by Decree 2635 (150
mg/Kg).
Figure 21. Plumbum in soils adjacent to the spill zones during the
period 2009-2013.
The most of the (Pb) Plumbum values measured in soils
under treatment into of each year vary as follow: 2009: 0
and 20 mg/Kg; 2010: 0 and 16 mg/Kg; 2011: 0 and 20
mg/Kg; 2012: 2 and 18 mg/Kg; 2013: 2 and 8 mg/Kg
(Figure 22). Regarding to the temporal variation of the Pb
values; the variation may be statistically insignificant
because the intervals are overlapped each other. The
annual mean is approximately equal to 9 mg/Kg. All
observations of the Pb values are below the limit by
Decree 2635 (150 mg/Kg).
Figure 22. Plumbum in soils under treatment during the period
2009-2013.
4. DISCUSSION OF RESULTS
By comparing of physical and chemical characteristics of
water and soil in the (Anzoategui State) OOB oil
exploitation zone, Venezuela regarding to the
international and national norms; as well as other
scientific studies, the following findings have been found
during the period from 2009 to 2013:
1) The nitrogen, phosphor and temperature values in
water are below of limits in Decree 883 (Norms for the
classification and control of quality of water bodies and
liquid effluent discharges). The most of the Suspended
Solids, pH, Minerals Oils and hydrocarbons, BOD, COD
values are below the limit by Decree 883; with exception
of some maximum and extreme values. The average
concentration of Total Nitrogen (6 mg/L), Total
Phosphor (0,8 mg/L), Suspended Solids (60 mg/L),
Mineral Oil and Hydrocarbons (20 mg/L), BOD (50
mg/L) and COD (250 mg/L) is less than the composition
of domestic wastewater considered of weak
concentration; where the concentration is as follow: Total
Nitrogen (20 mg/L), Total Phosphor (4 mg/L),
Suspended Solids (100 mg/L), Mineral Oil and
Hydrocarbons (50 mg/L), BOD 5,20C (110 mg/L) and
COD (250 mg/L) according to Metcalf & Eddy et al
(2003). The most of the pH values are into the limits by
Decree 883 (6-9); indicating that it is suitable for the
proliferation and development of suitable biological life.
The BOD / COD ratio based on the average of each
parameter is equal to 0.2, indicating that most of the
components are oxidized by chemical via instead of the
biological via (Tchobanoglous and Schoeder, 1985).
2) The As concentrations observed in soils adjacent to the
spill zones and under treatment were below the limit of
Decree 2635 (25 mg/Kg); which it can be observed in
Figures 13 and 14; however the As extreme values
occurred in 2012 (20 mg/Kg); when the observations
were approximated to the limit value. Although in the
soils under treatment, the concentrations were reduced
by comparing with the case mentioned before.
3) Some soil samples were found with acid pH values
ranging between 3,5 and 5 (Figure 11); what is in
correspondence with a trend by increasing of (Ba, Cd, Cr,
Pb) heavy metal concentrations in soils adjacent to the
spill zones shown in Figures 15, 17, 19 and 21 (Ward et al,
2010); being observed a light contrary trend in soil
samples under treatment from 2010 to 2012 (Figures 16,
18, 20 and 22). The problems associated with acidification
are well detailed in the literature, causing: inhibited plant
growth; infrastructure corrosion and; large fish kills
(White et al. 1997) as well as adversely impacting large
habitat areas such as wetlands and woodlands (van Tol et
al. 1998). Acidification may also impact the geochemical
equilibrium in soils and aquifers (Hansen and Postma
1995; Kjoller et al. 2004; Appleyard and Cook 2008).
Regarding to the soils under treatments, in an
experimental study, Adesondun and Mbagwu (2007)
found that the observed decrease in total hydrocarbons
and heavy metal concentrations with additions of organic
wastes could be attributed to the ability of these
amendments to immobilized contaminants in soil.
According with Doumet et al (2010), the
phytoremediation like a method to treat soil
contaminated with heavy metals in pilot-scale requires a
better understanding of the regulation mechanism for
transporting of complex metals from the soil into the
plants. Although; it is important to consider the impacts
mentioned above, in this field study, the most of heavy
metals concentrations founded are below limit in Decree
2635; being its impact minimum on the environment. For
example, Marquez et al (2005) made a study abut
geochemical aspects of the marine surface sediments of
the north coast of the Gulf of Cariaco, in the state of
Sucre, Venezuela; founding that the metal concentrations
presented different distributions, averaging 3548,58;
14,63; 13l,68; 11,59; 10,23; 2,29; 1,04; and 0,57 mg/g for
iron, manganese, nickel, zinc, chromium, copper,
cadmium, and lead, respectively, indicative of
contamination, especially by cadmium; influenced
probably by river-borne industrial contributions,
including the exogenous discharges running seawards
from the south coast.
7
5. CONCLUSIONS
As a result of the evaluation of temporal variation in
physical and chemical characteristics of water and soil in
oil exploitation zone of Venezuela, the following
conclusions can be made:
-The most of the Suspended Solids, pH, Minerals Oils
and hydrocarbons, BOD, COD values in water samples
are below the limit by Decree 883.
-All observations of the (Ba, Cd, Cr and Pb) heavy metals
and (As) non-metals values in soils adjacent to the spill
zones and under treatment are below the limit by Decree
2635.
-The temporal variation of physical and chemical
characteristics may be statistically insignificant because
the annual intervals are overlapped each other.
-The impact of OOB oil exploitation operations on
environment is controlled.
-Ministry of Energy and Oil, (Septiembre-Octubre 2005). Planes
Estratgicos PDVSA. Repblica Bolivariana de Venezuela,
Caracas, 3, pp.1-3.
-PDVSA, (2012) Informe de Gestin Anual 2012. Petrleos de
Venezuela, S.A., Caracas, Venezuela,
-Tchobanoglous G., and Schoeder, E. D. (1985). Water Quality:
Characteristics, Modeling, Modification, Addison-Wesley. Publishing
Company, Reading, Massachusetts.
-Van Tol G., Van Dobben H.F., Schmidt P, Klap J.M. Biodiversity
of Dutch forest ecosystems as affected by receding groundwater
levels and atmospheric deposition. Biodiversity and Conservation 7,
1998, 221-228.
-Ward J., Andersen M.S., Appleyard S., and Clohessy S. (2010).
Acidification and trace metal mobility in soil and shallow
groundwater on the Gnangara Mound, Western Australia. 19 th
World Congress of Soil Science. Australia, pp 1-4.
-White I, Melville MD, Wilson BP, Sammut J. (1997). Reducing
acidic discharges from coastal wetlands in eastern Australia.
Journal of Wetlands Ecology and Management, 5(1), 55-72.

6. ACKNOWLEDGEMENTS

The research was conducted at the Center for Water

Research and Environmental (CIHAM-UC) and
Laboratory of Water and Soil Quality of HidroLabToro
Consults, with financial support from the Ministry of
Popular Power for Science and Technology (FONACIT)
and Ministry of Popular Power for the Environment.

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