Spatial distribution of metals in topsoil

of Islamabad City, Pakistan

DEFINING THE PROBLEM:

The soil is chief component of an ecosystem and is the most endangered due to influence of
various human activities related to industrial, agricultural, urban development and determine the
quality of the urban environment. Urban areas are expanding all over the world utilizing more
and more agricultural and natural areas. Land use drew attention towards possible impacts on
soils and becomes an important source controlling metal distribution in urban catchments.
Modern land use practices have given increased supplies of material goods but undermined many
ecosystem services in the long term. Due to land use changes, soil pollution has become
important environmental issue in developing countries. Additional input of waste materials,
landscaping, and rapid change of land use also contributes towards an unpredictable modification
of soil properties such as increasing concentrations of heavy metals.
Urban soils act as a sink for heavy metals and other pollutants which are mainly caused by
anthropogenic activities such as vehicular emissions, wastewater sludges, and industrial wastes.
Heavy metal contents in soil are highly dependent on geochemical nature of parent material and
their accumulation is of considerable importance because they are persistent and
nonbiodegradable. Like other metropolises, Islamabad also faces a rapid urban and industrial
growth resulting in degradation of soil ecosystem. There is a need to better understand the
relationship between land use and environmental change that drive them, say scientists. Status of
urban soils and heavy metal contamination in Pakistan in terms of is not predominantly focused,
and an attempt to produce an extensive survey using a systematic sampling strategy of urban
soils has been limited.
An understanding of the modifications of soil characteristics and their spatial variation in
Islamabad is needed to combine traditionally based soil survey approach and associated soil
interpretations. GIS-based approach refines and confirms geochemical interpretation of statistical
output. Analysis of the effects of land use on metal concentrations in soils is critical for the
making of policies aimed at reducing metal inputs. The aims of the present work were to
measure the total (acid extractable) and available (water soluble) physicochemical properties in
topsoil of three land use.

DESIGNING THE ANALYTICAL METHOD:

Systematic grid-based sampling was used to collect surface soils from three land cover types,
1. built-up area (area inside city including residential, commercial, industrial, etc.),
 2. drain sides (small drains passing through whole of the city which are actually tributaries
of river Soan and Kurang)
3. and green area (constituting parks, open green spaces, and green belts within the city
area).
Equal-sized grids of 0.25 Km2 were laid within the total area of 100 Km2 across the whole city
which aggregated into a total of 308 grids.

SAMPLNG AND SAMPLE STORAGE:

Surface soils were collected from two to three random places with quadrat size of 100 m2 at a
depth of 9 in. from each grid, and a total of 834 surface soil samples were collected from three
land cover types. From each quadrat, composite soil samples comprised of three to five
subsurface samples were collected, placed in air-tight polythene bags, labeled, and brought to the
laboratory for further analysis. The geographical coordinates of each quadrat were recorded with
a Garmin (Geko 301) GPS.

SAMPLE PREPARATION:
Soil samples were air-dried at room temperature and sieved through 2-mm sized sieve to remove
coarse particles, stones, and debris. Soil samples were analyzed for particle size, i.e., sand, silt,
and clay, and soil textural classes were determined by using the textural triangle. OM was
determined by Tyurin’s method. The soil pH, EC, and TDS were determined in soil solution in a
ratio of 1:10 using Milwaukee SM802 Smart combined meter with a glass electrode.
Soil acid digests were prepared using CEM 630W closed vessel microwave digestion system
(USEPA 1998: Method 3051A) for the determination of elemental concentration Each soil
sample was weighed (0.5 gm) and placed in a prewashed Teflon vessel, and the soil samples
were digested in 9 ± 0.1 ml concentrated nitric acid and 3 ± 0.1 ml concentrated hydrochloric
acid. The microwave unit was calibrated to power and temperature. Ramping of temperature was
adjusted to 220 ± 5◦C, and a power of 1,200W was provided (USEPA 1998:Method 3051A).
After cooling, the contents of the vessel were filtered with Whatman filter paper no.42 and
diluted to volume of 50 ml. Metal concentrations of the major elements: Ca, Mg, Na, K, Fe, and
trace metals: Cd, Co, Cu, Ni, Pb, and Zn in the solutions were measured using atomic absorption
spectrometer (Varian FSS-240). For quality control, reagent blanks, standard samples, and
replicate samples were simultaneously performed to assess contamination and precision in the
samples. Standard reference materials NISTSRM- 2709 (1992) and BCR-CRM-142R (1989)
were used for quality control procedures of major (Ca, Mg, Na, K, and Fe) and minor soil metals
(Cd, Cu, Co, Ni, Pb, and Zn). The recovery rates for most of the major elements were between
90% and 128% and for heavy metals in the international standard, reference material was
between 75% and 135%.
ANALYSIS:
Analytical results were compiled to form a multielement database using EXCEL and
STATISTICA prior to multivariate analysis. Descriptive statistics such as mean, standard error,
minimum, maximum, standard deviation, and variance were carried out Spatial variation
between land cover types based on metal properties was explained using discriminant function
analysis (DFA) to discriminate factors which bring variations amongst three land cover types.
Metal chemical parameters were considered as dependent variables while land cover types
constituted independent variables.
Principal component analysis based on factor analysis was applied for source identification of
metals input in urban soils. Raw dataset of three land cover types was dealt separately to evaluate
pattern of relationship between the soil parameters and to illustrate the factors that influence each
other. Factor loadings with a VARIMAX rotation were used. Input data matrices included
variables vs sites (11 × 173), (11 × 354), and (11 × 307) for drain side, green area, and built-up
area, respectively. Heavy metal concentrations were used as the input data to predict distribution
of metals in urban soils. Spatial interpolation technique such as kriging was used which utilizes
the coregionalization structure of soil properties and provide unbiased estimates and minimum
variance underlying the kriging model. Metal concentrations showed normal distribution except
acid extractable Pb content which showed skewed distribution and was log-transformed prior to
statistical analysis and kriging.
Enrichment Factor (EF) was calculated for individual elements in soils of each of the quadrat of
three land use types to assess most likely source of contamination after using,

“where, EFM is the enrichment factor of metal, (Cx/CFe)sample is the ratio of the concentration
of a test element to that of Fe at each sampling site, and (Cx/CFe)ref is the same ratio of the
concentration with respect to a reference soil”
Shale values of Turekian and Wedepohl (1961) in the earth’s crust were used as a reference soil.
Aluminum is frequently used as a reference element assuming the ease of determination of this
element. Al was substituted by Fe and used as reference element in this study. The focus was on
the comparison between the concentrations obtained and the concentrations of the elements in
the earth crust because soil is a part of the surface layer of the Earth’s crust, and its chemical
composition is related to one of the crusts. Due to the considerable influence of anthropogenic
transformations, soil contamination in three land use types was also evaluated using the
percentage enrichment factor, using

“Where, C is the mean total concentration in the soil, Cmin is the minimum concentration
determined during the study period, Cmax is the maximum concentration determined during the
study period.”
EF can give an insight into differentiating an anthropogenic source from a natural origin. Five
contamination categories are recognized on the basis of the enrichment factor, where EF < 2 is
deficiency to minimal enrichment; EF 2–5 is moderate enrichment; EF 5–20 is significant
enrichment; EF 20–40 is very high enrichment, and EF > 40 is extremely high enrichment.
Basically, as the EF value increases, the contribution from non-crustal sources also increases. A
quantitative measure of the degree of pollution was also developed in late 1970s and has been
widely used in heavy metal studies. The Index of geo-accumulation was calculated by using

“Where, Cn is the concentration of a given element in the soil tested, while Bn is the
concentration of the element in the crust” The constant 1.5 factor is used due to possible
variations in baseline data attributable to lithogenic effects Descriptive classification for the
index of geoaccumulation given by Frostner et al. (1990) is used:<0 = practically unpolluted; 0–1
= unpolluted to moderately polluted; 1–2 = moderately polluted; 2–3 = moderate to strongly
polluted; 3–4 = strongly polluted; 4–5 = strongly to very strongly polluted and >5 = very
strongly polluted. The overall metal contents of soils of each of the quadrat at three land use
types in this study was compared using the MPI using

MPIn=(Cf1×Cf2×. . . . . . . . . . . . . . . . . . . . . . . × Cfn)1/n . . . . . . . . . . . . , (4)

“Where C fn is the concentrations of the metal n in the sample”

ASSESSING THE DATA:

Mean metal concentration of Cd, Co, Cu, Fe, Ni, Pb, and Zn ranged from 0–8.4, 1.2–32.7, 1.1–
33.4, 24,401–74,782, 45.4–193.9, 81–338, and 740–3,255.9 μg g−1, respectively, in soils of
built-up area whereas their concentration in soils of drain side was 0–8, 0.8–32.1, 3–30.7,
17,368–69,551, 35.9–171, 87–332, and 802.8–3,135.1 μg g−1, while mean concentrations for
these metals in soils collected from green area ranged between 0.7–8.6, 1.1–37.6, 3.2–41.6,
19,723–79,606, 2.7–219, 69–973, and 101.6–3,206 μg g−1 Acid extractable content of the
metals in the soils explains the total amount of physicochemical parameters available to soils for
plant growth. Urban soils showed higher nutrient concentrations of Ca, Mg, Na, and K along
drain sides which receive untreated sewage and industrial effluents from the city. Higher
concentrations of Fe, Ni, Pb, and Zn were recorded in current study as compared to the surface
soils from other cities such as Xuzhou, Aviles, and Bangkok Concentration of Ni (185 μg/g)
reported in Torino was within range recorded in the current study. Eikmann and Kloke in
Germany estimated that in 75% of the topsoil sampled, the content of at least one metal exceeds
the threshold values if the land is in multifunctional use. Pb concentrations were measured higher
in built-up area as compared to other land cover types. This can be due to its closeness to
roadsides. Similarly, EF (%) of Pb was 49.91% in built-up area. This is related to its use in
gasoline. Almost 95% of the Pb emitted to the environment is associated with human activity.
Zhang (2005) reported greater concentrations of Cu, Pb, and Zn in urban soils of Galway in
comparison to present study, whereas lower concentrations of Pb (17 and 3.6 μg g−1) were
found in surface soils of Damascus and Vietnam. Soil samples collected along the roadsides in
urban areas had higher values for Pb concentrations indicating input from anthropogenic sources.
Pb is nondegradable and toxic element. Pb inputs in urban soils probably come from vehicles
that use gasoline additives. Lowest values of Pb were found in the green areas and near drain
sides.
Heavy metals, viz., Cu, Pb, Ni, and Zn showed positive correlation. Similar associations were
also reported in other surface soil studies. Zn was recorded high in green areas. Zinc is readily
adsorbed by clay minerals and carbonates Possible reason for Zn concentration being higher is
due to its association with sewage pollution. Cu is both an essential and potentially toxic element
It forms major part of vehicle engine wear showing the utilization of these sites for this purpose.
Cu is retained in soils through exchange and specific adsorption mechanisms. The results showed
that EF (%) of Cu, Cd, and Co was greater in soil samples collected from drain sides as
compared to other land cover types. However, measured mean concentrations of Cu in the
current study were lower (Table 4) to those recorded in topsoil of Torino (171 μg g−1);
Guangdong (576.5 μg g−1); Palermo (82.27 μg g−1); and Amman (93 μg g−1). The results
indicated relatively lower concentrations of metals like Cd, Ni, and Zn as compared to those
Higher concentrations of these heavy metals in

METHOD VALIDATION
urban soils of the current study can be attributed to increased urban activities related to land
clearing, road construction, and formation of housing schemes. EF% of these metals indicated
extreme contamination of surface soils. Ni concentration is due to industrial and vehicular
emissions, and its lower EF in the urban surface soils leads to the assumption that Ni originated
partly from the parent material. Higher EF values of Pb (13) and Zn (21) in built-up area, while
Cd (15.01) soils samples from drain side were recorded, highlighting serious soil contamination
due to specific pollution sources. Higher EF values for Pb and Zn in the built-up area can be
attributed to the vehicular emissions, manufacturing of goods and their use in industrial activities
in the city. Zn distribution in all three land use types indicated its common origin mainly from
vehicular emissions. The minimum EF values, i.e., <5, implied moderate soil enrichment, and the
maximum EF values pointed to significant enrichment with Pb and Cd while for Zn, very high
enrichment values were found in three land use types of the city. Higher concentration of Cd was
found in southwestern part of the in-surface soils of other cities such as Beijing, Oklahoma,
Xuzhou city which is mostly undergoing different construction and developmental activities. Cd
emissions arise from the manufacture, use, and disposal of products utilizing Cd such as Cd
batteries, Cd pigmented plastics, ceramics, glasses, paints, and enamels, most of which are
extensively used in constructions. Presence of Cd in soil can also be related to sewage sludge
application Industrial area on the southwestern part of the city showed high levels of Co and Zn
concentrations especially in sectors I-9, I-10, and I-11. Co is a naturally occurring earth element
present as trace element in soils. The toxicity of Co in soil is generally very low as compared to
other metals. It usually occurs in association with other elements such as Ni. Co and Ni showed
similar trend. In soils, Ni is usually present in the organically bound form, which increases its
bioavailability and mobility Fe concentrations were high mainly in green and built-up areas
pointing towards its natural source. The soils in built-up areas are less polluted by heavy metals.
Along roadsides and drain sides, soils are heavily contaminated explaining a strong effect of
urbanization processes and anthropogenic activities.

DOCUMENTATION
The results will provide a base for future management practices. Soil contamination,
rearrangement of traffic flow should be a part of future plan. Measures should be taken to avoid
further clearing of land in order to avoid further contamination of soils in the city which is
evolving rapidly into a megacity.