2023.08.03.124
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Assessment of pollution with some heavy metals in agricultural soils near Qayyarah oil fields, southern Mosul

Ibrahim Mahmoud Ibrahim 1*,
Khaled A. Khaled 2 and Moath Abdullah 3
1 Soil Sciences and Water
Resources Dept., College of Agriculture and Forestry, University of Mosul, Iraq
2 Soil Sciences and Water
Resources Dept., College of Agriculture and Forestry, University of Mosul, Iraq
* Correspondence: [email protected].
Available from. http://dx.doi.org/10.21931/RB/2023.08.03.124
ABSTRACT
To assess soil contamination in the
Qayyarah sub-district of Nineveh Governorate with elements (Pb, Cr and Ni), the
study area was divided into three areas depending on the distance of the land
from the oil fields. The results showed an increase in the total concentration
of heavy metals, Ni in all locations exceeded the maximum permissible limit of
50 mg.kg-1 according to WHO (World Health Organization) and FAO
(Food and Agriculture Organization), which ranged in concentration (61.15 -
221.4) mg.kg-1. While the total soil content of pb ranged between
(32.33 - 103.88) mg.kg-1, location (2) exceeded the maximum
permissible limit in the soil of (100)mg.kg-1.The total Cr content
ranged between (17.76 - 71.08) mg.kg-1. Enrichment factors pb, Cr
and Ni ranged from (1-2.8)(0.8-2.7) and (1.8-4.2), respectively, in the surface
soils affected by residues oil field when compared with the control soil CS 16. It was found through the spatial distribution that the
concentrations of Lead were the highest in the soils of region A, which are
located inside the oil fields. They decrease as we move away from the polluted
source, specifically in areas B and C, and this confirms the role of liquid,
solid and gaseous oil residues thrown from those oil wells to those soils and
agricultural lands, which caused an increase in the total content of Lead. Chromium
was found to have a different soca from Lead, and the highest concentrations
appeared in the C region, far from the oil fields, with slight variation from
the A and B regions. The results of the spatial distribution of Nickel also
showed that it had a similar behavior to Chromium. Significant increases in
concentration were shown in the soils of area C, which reinforces the assertion
that the geological structure of the study area had an impact on the high
values of Nickel and Chromium, particularly in the areas far from the oil
fields. The results of the correlation analysis showed a significant negative
relationship between the studied heavy metals with sand and a positive
correlation with clay. The effect of this relationship was shown in Site 3,
which is located within Zone A, which showed low concentrations of heavy metals
due to the nature of its sandy texture, in addition to an essential positive
relationship between heavy minerals, which confirms that it resulted from the
same pollutant source.
Keywords:
heavy metals, Pollution, Soils
INTRODUCTION
Soil pollution refers to any
chemical substance in soil that exceeds normal levels that causes adverse
effects on plant growth as well as on animal and human health through its entry
into the food chain and its impact on soil quality and the entire ecosystem 1, presence some
pollutants may also lead to nutrient imbalances and soil acidification, which
are important issues in many countries 2; therefore it is a
chemical degradation causes a partial or complete loss of soil functions. Soil
productivity is affected, as well as the organisms in polluted soil; when these
pollutants exceed the permitted levels, the soil becomes functionally dead, adversely
affecting the growth of plants in those soils 3, and soil is the central
basin for those pollutants emitted by environment 4.
Due to the rapid economic
development and severe industrial activities, pollutants are considered one of
the most critical human problems in the world, especially in recent years,
which has high levels of pollutants are released, which led to their
accumulation in the soil, which reached alarming levels 5, Therefore, some
locations near the oil manufacturers have become contaminated by the
distinctive activities of these businesses and their organic and inorganic
pollutants, including heavy metals 6, Soil pollution with
heavy metals is a serious global environmental issue and not less dangerous
than water and air pollution because it harms the plant growth and adversely
affects on soil microbial processes through its harmful effects on soil microorganisms
such as bacteria, earthworms and other soil organisms that live in the soil
7, Whereas, high
concentrations of heavy metals lead to a significant inhibition of soil
respiration, because the severe pollution of heavy metals weakens soil
microbial activity, which poses a serious threat to the function of the soil
ecosystem 8, Also Soil
contamination is directly related to the soil physical properties. Therefore,
In highly contaminated soils, surface hardening processes take place that
increase soil bulk density, degrade soil porosity, and significantly reduce
water permeability 9; as a result of this
adverse effect, many countries around the world have adopted national soil
protection and pollution treatment regulations, and research on soil pollution
assessment and treatment has increased 10.
Qayyarah is an Iraqi town located
south of the city of Mosul. It is characterized by the presence of many oil
fields nearby as it contains large oil reserves, which led to attracting many
international private investing companies to explore for oil, in addition to
the presence of an oil refinery in it, and because of the lack of commitment of
these companies operating in The field of the oil industry and the lack of
respect for the environment, which led to significant pollution of the soil and
air as a result of the release of liquid waste into the soil without treatment,
in addition to the burning of fuel and the release of gases into the
atmosphere, which led to the deterioration of the soil system in particular by
affecting the crops grown near the oil fields in These agricultural lands and
the ecosystem in general. Therefore, the current study aims to assess the
pollution with lead, chromium and nickel elements in those lands close to the
oil fields and compare them with lands and soils far from the source of
pollution by relying on the enrichment factor and some global determinants of
the World Health Organization and the International Food and Agriculture
Organization.
MATERIALS
AND METHODS
Study Area
The study area is located 60 km
southern of Mosul, which is represented by agricultural lands in Qayyarah
district of Nineveh Governorate, which lines between longitudes (43°20'55.87"E-43°6'2.66"
E) and latitudes (35°55'30.42"N - 35°34'36.56" N) (Figure 1), Where
the study area was divided into three parts depending on the distance of the
agricultural lands from the oil fields from all directions, part (A) represent
lands close to the fields, which are located under the influence of solid,
liquid and gaseous oil wast, at a distance of (400-800) m, (B) lands about (1500-2000)
m away from center, and (C) area about (4000-5000) km from the oil fields.
Because wind movement and direction play an essential role in the distribution
of pollutants, in addition to the comparison sample (CS), located about 6000 m
northeast of the oil fields, 16 surface soil samples are included at a depth of
0-30 cm. All soil samples were dried upon collection and sieved through with a
diameter of (2) mm, thus becoming ready for the following physical and chemical
analyses.
Figure 1. Study area in the
Qayyarah district.
Soil Sampling and Analysis
Particle size distribution was
determined using the hydrometer method 11, Soil pH was determined
by a pH meter, Soil EC was determined by using the (EC meter), Organic matter
and Calcium carbonate were determined according to the method by 12, Cations Exchange
Capacity was determined according to the method by 13.
Determine Heavy Metals in soil.
Soil samples were digested using
royal water (acidic method) 14 to estimate the total
amount of heavy elements (Pb, Ni, Cr) in the soil. (2) gm of each soil sample
was added to a conical flask with (15) ml of royal water consisting of a 3:1
ratio of hydrochloric and nitric acids and left for 24 hours. Then, it is heated
for digestion to 120°C; after two to three hours of heating (when the color
turns brown to colorless), leave the mixture to cool, then use Whatman filter
paper and fill into 50 ml distilled water. Heavy metal concentrations in the
extracts were estimated using a German-made Atomic Absorption
Spectrophotometer, model Analytika jena 350A.
Enrichment Factor (EF)
The enrichment factor assesses soil
pollution and seeks to know the natural or human inputs and their impact on the
soil. The most common reference elements used in determining the EF value are
Aluminum (Al), Tin (Sn), Iron (Fe), and Manganese (Mn) 15; in the current study,
(Fe) was selected as a reference element because of its high concentration in
study area soils, where Fe is stable in soil and is characterized by the
absence of vertical movement within the soil. In addition, its concentration does
not change in human terms 16. Enrichment factor
values were calculated according to the following equation 17:
EF
= (Cm/CFe)sample / (Cm/CFe)Background
where
(Cm
sample)= Heavy metal Concentration in a soil sample.
(CFe
sample) = Total Iron concentration in the same sample.
(Cm
Background) = Heavy metal Concentration in comparison to soil.
(CFe
Background) = Iron concentration in comparison to soil.
Seven
categories have been identified to classify the results of the enrichment
factor as described by 18, as shown in Table (1).
Table
1. Interpretation Levels of Enrichment Factor
RESULTS
The Physicochemical Properties of
Soil
It is evident from Table 2 that the
proportion of separated (clay, sand and silt) was different for the soil of the
study area, as it ranged between (224.5-387) g.kg-1 for clay, and
the percentage of silt ranged between (125-460) g.kg-1, while it was
The sand ratio ranged between (212-603) g.kg-1, and the electrical
conductivity EC values ranged between (0.6-8.6) ds.m-1. As for the
pH values, they ranged between (7.38-7.92), and the results showed that the
organic matter ranged between (6.87-20.63) g.kg-1. The content of
the soils of the study area of calcium carbonate ranged between (45-370) g.kg-1.
The results show that the cation exchange capacity of CEC was between
(9.56-23.48) centimole (+).kg-1.
Total Content of Heavy Metals
When heavy metals are found in
large quantities in soil, this may be due to the accumulation of chemicals
containing heavy metals that are discharged into the soil due to oil
exploration and production activities 19.Table .3
The results of Table 3 indicate
that the concentrations of the total content of Lead in the study soils ranged
between (32.33-103.88) mg.kg-1, and it is clear from Figure 1 that
the highest values of Lead were in the
sites located within Zone A close to the source of pollution, specifically Sample 2 (Q2), then the concentrations start
decreasing gradually as we move away from the oil fields in areas B and C until
it reaches the lowest value of Lead in the control soil CS, while the results
showed that the total chromium concentrations ranged between (19,56-71.08)
mg.kg-1, and Figure 2 shows that there is a discrepancy in the total
chromium concentration of the studied sites between highs and lows within one
region, as the results showed varying concentrations within region A, where the
lowest value of Chromium was recorded in sample 3 (Q3), then return to To rise in sites belonging to region B and C
with a little difference from region A, as for Nickel, the results of the total
content indicated that it ranged between (54,2-221,4) mg.kg-1, and
it was shown by Figure 2 that the variation in the total content of Nickel in
the soil It was clear and the highest
values were in the southeastern part of
the study area within area A, specifically in sample 2, while in sample 3 It decreases suddenly, but in areas B and C
it rises again significantly, precisely sample 12 and 13.
The results were less than what 20 found, which indicated
an increase in total lead concentration in agricultural soils in Baghdad
Governorate, which ranged between (56.73- 714.87) mg kg-1 and
attributed this to the power stations' impact and oil facilities such as Aldora
Refinery, and higher than the results reached by 21 in agricultural soils
close to industrial facilities as a result of the waste they pose and decrease
the farther away from the source of pollution, as they noted an increase in
lead concentrations, which ranged between (9.6 - 44.79) ) mg kg-1
Table 2. Physical and chemical
properties of the studied soil
Table
3.
Heavy metal analysis of study soils (mg.kg-1)
Figure 2. (a) Total content of Lead
in the studied soils; (b) Total chromium content in the studied soils; (c) The total nickel content in the studied
soils.
The enrichment factor
was calculated from the concentration of heavy metals in 15 samples surrounding
the oil fields of the study area, and the concentration of heavy metals in
sample 16 (comparison soil) was used as a standard concentration to assess the
contamination with heavy metals for those soils 22.
Table 4. Higher, lower value
and enrichment factor rate for heavy elements in the study soils.
The results indicate
that the values of the enrichment factor for heavy metal pollution are
different for the study area soil. The average values increase in the order Ni
> Pb > Cr, where the values for Lead ranged between (1 - 2.8) and fall
within the range of little enrichment 1> EF>3, and ranged between (0.8 -
2.7) for Chromium which also falls within the range of little enrichment 1>
EF>3 except for site 3 it was low within the range of no enrichment EF <
1, while Nickel ranged between (1.9 - 4.2), where most of it falls within low
enrichment range 1> EF>3 except for samples 1, 2, 5, 9, 12 and 13 that
were within the moderate enrichment range 3> EF>5 according to 18,
usually when the value of the enrichment factor is close to or less than 1,
this reflect that the primary source of heavy metals is from a natural source.
Still, if the enrichment factor exceeds 1, the primary source is human
activities 23. Some opinions suggest
that enrichment factor values of 1.5 or more indicate human influence, which
was determined by 24. According to this
suggestion, the sources of heavy metals are considered human in most of the
study's soil sites, and what confirms this is the spatial variation of the EF
values, which exceeded the critical limit mentioned by 24.
Figure (3) shows that
the highest values of Lead were in samples close to the oil fields, precisely
samples 1, 2, 3, 4, 5, 6, 7 and 9, which exceeded the critical limit (1.5). For
Chromium, the enrichment factor values in samples 1, 2, 4, 5, 9, 12 and 13 were
greater or equal to (1.5). However, Nickel shows a significant increase in
enrichment factor values, as the values of the enrichment factor in all the 24
study soil sites exceeded the critical value of 1.5, where it reached 4.2.
Figure 3. Enrichment
factor value for Lead, Chromium and Nickel.
Correlation Matrix
Describe the
relationship between the total concentrations of heavy metals and the physical
and chemical properties of the soil. It was done by the Pearson correlation
coefficient Table 4.
**. Correlation is significant at
the 0.01 level (2-tailed).
*. Correlation is significant at
the 0.05 level (2-tailed).
Table 5. Pearson correlation matrix
between heavy metals and the chemical and physical properties of the soils of
the study area.
The results showed a
significant positive correlation between Lead and CEC (0.64**), and a weak
positive correlation with clay (0.47), CaCO3 (0.30) and pH (0,22), with a
negative correlation of Lead with sand ( -0.33) and organic matter (-0.07),
while Chromium showed a significant positive correlation with CEC (0,50*),
organic matter (0.49*), pH (0,53*), and a weak positive correlation with clay
(0.36) and CaCO3 (0.38), while the correlation of Chromium with sand was
significantly negative (-0.65**), and the results showed a significant positive
correlation of Nickel with CEC (0,62**) and organic matter (0,52*). Moreover,
there was a weak positive correlation with clay (0.35), CaCO3 (0.39) and pH
(0.32), while the correlation of Nickel with sand was a significant negative
correlation (-0.67**).
The relationship between
heavy metals was evaluated to determine the common source of these elements in
the study area. It was found that there were significant positive correlations
between heavy metals, as Lead showed a significant positive correlation with
nickel (0.60*). The relationship between Chromium and Nickel also showed a
significant positive correlation (0,81**), but it was a weak positive between Lead
and Chromium (0,49).
DISCUSSION
Discussion of the
Chemical Properties of Soil
It is clear from these
results that most of the soils are average soils whose salinity was (less than
4) dSm -1, with an increase in electrical conductivity in sample 14
observations whose conductivity values exceeded 4 dSm -1; they
appear as saline for plates 25. This results from
several factors, the most important of which are low rainfall, high surface
evaporation, weathering of salt rocks, saline irrigation, and poor agricultural
practices 26, indicating that the
study area soils were of a neutral to slightly alkaline reaction degree. The
reason for the high degree of soil interaction is due to the nature of the soil
formation conditions in terms of climate and the origin material rich in
calcium carbonate, as the presence of carbonates affects the degree of soil
interaction, as carbonate soil is characterized by having a pH greater than 7
27. It is clear that there
is a discrepancy in the values of the organic matter between the soils, and in
general, it appears that there is a decrease in the values of the organic
matter in all soils due to the nature of the dry climatic conditions, with the
exposure of these Areas of lower rainfall and higher temperatures result in
less input of organic matter and nutrients from external sources 28. The reason for the
high values of calcium carbonate in most of the sites may be attributed to the
fact that the nature of the origin material for the soils of the study area is
mainly rich in calcium carbonate, which is also due to the geological formations
of these The area, which was rich in these carbonate minerals, and the lack of
rainfall It works on the accumulation of calcium carbonate in the sub-surface
horizons 29. The cation exchange
capacity (CEC) is one of the essential properties of soil and a primary
criterion for its quality and the ability to remove environmental pollution,
which affects the adsorption of heavy elements such as copper, zinc and lead
30.
Heavy Metals Content and
Soil Pollution.
The highest Lead
concentrations were in the sites located within the (A) area close to the
source of pollution, where it was highest in Sample 2 (Q2); the reason for the
high lead concentration due to its proximity to the oil fields and resulting
from the solid, liquid and gaseous wastes that have contaminated these soils
and agricultural land near oil wells, and the alkaline pH depositing Lead in
the arable soil layers in carbonate and phosphates form at pH greater than 6.5.
Thirty-one
indicates that Lead is significantly associated with organic matter and metal
oxides at 26 % of the total amount.
The results show a
discrepancy in the total concentration of Lead for all sites in the study area,
as we notice a significant decrease in lead values for some samples in (A)
part. Despite their proximity to the oil fields, the sample (Q3), which is
located to the west of the oil fields, compared to the rest of the samples
located at the same distance as the polluting source; this is due to its low
content of clay and organic matter, which catch and fixation lead and the rest
of the heavy metals. On the other hand, it has a high content of sand, as the
clay soil retains a high amount of heavy metals compared to sandy soil 32. The results obtained
showed that all samples are considered to have a high concentration of Lead.
However, they are within the permitted limits in the soil, except for sample
Q2, which exceeded the maximum limit of (100) mg kg-1 according to the WHO and
the FAO 33.
The result Chromium
there was a variation in the study area, as the highest concentration appeared
in (C) Area, which is 3 km away from the oil fields, precisely sample 12. which
is explained by the wind speed and direction, which works to transfer pollutants
and their Chromium from the source of pollution to further areas and then are
deposited on the surface of the soil in those locations, as weather conditions
play an essential role in the distribution of heavy metals in the air 34. Alternatively, it is
due to the original material, since soil chromium is inherited from the mother
rocks, as the chromium content increases in soils formed from mafic rocks and
stone sediments 35. Thirty-six
noted that the increase of Chromium in Iraqi soils resulted from the transfer
of calcareous deposits from weathering processes in northern and northeastern
Iraq. The lowest concentration of total Chromium is upper in the sample (3)
despite its proximity to the source of pollution due to the low percentage of
clay and the prevalence of sand, as sandy soils have a weak ability to adsorb
heavy elements 37. According to 33,
the results of the total chromium content in all sites are considered within
the permitted limits in soil, which is less than 100 mg kg-1, which are
approved by standard regulatory bodies such as (WHO) and (FAO), which do not
cause risks to Soil and plant system.
The spatial distribution
of high nickel concentrations may be associated with oil combustion and
agricultural activities such as phosphate fertilizers 38, as the variation in
the total nickel content was apparent. The highest values were in the
southeastern part of the study area, where the highest concentrations in sample
2 (Qayyarah 39), due to their proximity to the oil fields and solid, liquid and
gaseous wastes posed by these oil wells, in addition to their high content of
clay. The other far locations, specifically (Q12 and Q13), which are located in
the same direction, were also highly concentration due to the predominance of
northwest winds in the region, which transfer these pollutants and the elements
they contain and deposit them in those sites. Ni can be released into the
atmosphere through industrial activities, accumulating on the surface after
precipitation reactions 39. All sites exceeded the
maximum allowable limit for nickel components set by the World Health
Organization and the Food and Agriculture Organization of (50) mg kg-1, which
threatens the soil, plants and human system 40.
Nickei, it has been
found that there is a noticeable increase in the total content of Nickel in
most locations compared to the rest of the heavy metals due to the high ability
of Nickel to adsorb on The surfaces of clay minerals, as clays have a high
cation exchange capacity and therefore have a more remarkable ability to
stabilize heavy metals 38, Montmorillonite is the dominant mineral
in arid and semi-arid region. It may also be attributed to increased sediments
and fragments transported from the northern and northeastern regions, which
contain pyroxene, olefin and chlorite minerals rich in Nickel.
These high values of Lead,
Chromium and Nickel in the areas mentioned above are an explicit confirmation
of human activity, which means that the enrichment of these elements results
from industrial inputs such as liquid oil residues that flow from those oil
wells or emissions of pollutants into the air, This is due to the burning operations
of the oil wells that enriched the soils of the region, especially the nearby
ones, with heavy elements as a result of smoke and ash emitted from it and the
mineral and organic pollutants it contain, which eventually reach the soils of
the neighboring lands either through sedimentation or by rain.
It appears in the rest
of the locations that the values of the enrichment factor for Lead and Chromium
decreased below 1.5 until it reached the lowest value of Chromium, which is 0.8
in sample 3 (Fig. 1), due to the total chromium concentration at that point was
slightly due to the nature of the sandy texture poor in clay minerals,
It facilitates the
movement and washing of heavy elements and thus reduces their amounts in soil,
as well as the calculation of the enrichment factor index with the total iron
concentration; whenever the Iron content is high, there is a decrease in
enrichment factor 21.
The close positive
correlations between heavy metals, which emerged through Pearson correlation
analysis, indicate that heavy metals may be produced from the same polluting
source, which in our study represents oil fields 41, where the wind works
to transfer gaseous emissions containing these heavy metals to agricultural
lands. Near the oil fields, which led to an increase in the total content in
the soil, and the geological composition of the area may contribute to the rise
in the total concentration of Nickel and chromium elements, especially in places
far from pollution sources (oil fields) 42.
CONCLUSIONS
The region's soil was
contaminated with Nickel, as it exceeded the maximum allowable limit according
to FAO and WHO. The Lead and Chromium concentrations in soils were within the
permitted extent, except in sample 2 (Qiyarat 39), where Lead exceeded the
upper limit allowed in the soil. The values of the enrichment factor explain
that the enrichment of these heavy metals results from industrial inputs such
as oil residues and emissions of pollutants into the air, which are deposited
on agricultural lands adjacent to the polluted source.
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Received: 25 June 2023/ Accepted: 26 August 2023 /
Published:15 September 2023
Citation: Ibrahim,
I.M.; Khaled, K.A.; Abdullah, M. As-sessment of pollution with some heavy
metals in agricultural soils near Qayyarah oil fields, southern of Mo-sul.
Revis Bionatura 2023;8 (3) 124 http://dx.doi.org/10.21931/RB/2023.08.03.124