CHAPTER 2

REVIEW OF LITERATURE
Changing scenario with economic development of the society to large scale
urbanization and industrialization during the 20th century have noticeably increased the
demand for metals that lead to high anthropogenic emissions into environment
(Antosiewicz, 1992; Vangronsveld and Cunningham, 1998). This emission via
atmospheric deposition (Antosiewicz, 1992), application of metal contaminated effluents
for crop production (Jaffer and Saleem, 1987; Salt et al., 1995; Wang and Qin, 2006),
phosphate fertilizers (Chen et al., 1997; Basta et al., 2001; Zhou, 2003) and agro
chemicals may contaminate soil and water resources to the extent that adversely affects
environment and human health. A common feature of heavy metals, despite of whether
they are biologically essential or not, are that these might cause toxic effects at low
concentrations (Adriano, 2001; Kabata-Pendias, 2001).
More than 40% world population in 80 countries has become deficient in water
supply (Qadir et al., 2003). Slow but sure decline in availability of fresh water
necessitates agricultural use of city effluents. In addition to nutrient supply, city effluent
irrigation may cause buildup of heavy metals in soil that is a natural sink where toxic
metals undergo a number of transformations and become part of the cycle that affects all
forms of life directly or indirectly (Brady and Weil, 2002). In crops, either grown on these
soils or irrigated with untreated raw effluent, there is a tendency of bio-accumulation of
metals in their tissues without showing signs of toxicity or decreased crop yield.
Conversely, elevated levels of metals in crops can be harmful or even fatal to consumers.
Metals uptake in plants varies with plant age, plant species, genotypes and soil condition.
Most soils of Punjab, Pakistan have < 10 mg kg-1 available P (Rashid and Memon,
2001). Phosphorus levels in soil influence availability of Cd, Zn, Cu and other metals to
plants. The interactive effect of metals may be synergistic, antagonistic, independent, or
additive in nature (Kabata-Pendias, 2001). Heavy metal solubility, mobility and
availability in soils are controlled by reactions between metals and soil constituents which
depend upon level of contamination, origin and speciation of the metals and physical as
well as chemical properties of soils (Harter and Naidu, 1995). The following section
7

reviews especially Cd, Cu and Zn accumulation in soils and plants irrigated with effluent
or contaminated water or grown in metal contaminated soils under management of P
fertilizer.
2.1 Cadmium, zinc and copper in soil-plant system
Cadmium, Cu and Zn are the members of heavy metal groups which are highly
persistent in soils with residence times in the order of thousands of years (McGrath,
1987). Many terms including trace metals, transition metals, toxic metals and heavy
metals have been used to describe metals on the basis of density, atomic number, atomic
weight, chemical properties or toxicity (John, 2002). More acceptably, heavy metals
cover all metals with an atomic density of 5 Mg m

-3

and with metallic properties and

atomic number > 20 (Wild, 1996). Heavy metal elements are naturally present in soils in
very low concentration (Zhenli et al., 2005) when their concentration exceeds due to
anthropogenic activities, heavy metals are viewed as dangerous pollutants (Adriano,
2001).
Cadmium, Zn and Cu have similarities in many properties for example, ionization
potential of Cd, Cu and Zn is 9.0, 9.4 and 7.7 while electro-negativity is 1.69, 1.60 and
1.90, respectively. Due to chemical similarities these metals interact in soil plant-system
and affect bioavailability of each other and hence were selected for study and briefly
reviewed in detail below.
Cadmium is one of the most toxic metals that have adverse effects on soil
biological activity, plant metabolism and human and animal health. Cadmium, a transition
metal, is largely found associated with ores of Zn, Pb and Cu (Elinder, 1992). Common
range of Cd for soil is 0.06-1.10 mg kg-1 with an average of 0.53 mg kg-1 (Kabata-Pendias,
2001). In soils, about 1% of total Cd is located in the soil solution (Farrah and Pickering,
1977; Christensen and Huang, 1999). Cadmium can form precipitates with CO32-, S2-,
PO43- and OH- in the soil. However, in most arable soils, high redox potential and low pH,
Cd and anion concentration restrict the formation of Cd-precipitates (Christensen and
Huang, 1999). Therefore, Cd is most likely controlled by sorption processes in the soil
and not by precipitation of Cd minerals (Farrah and Pickering, 1977; Soon, 1981). Most
of the Cd was associated with CO32- (Renella et al., 2004) in calcareous soils and free
Cd2+ and CdHCO3+ were estimated to 35% to 45%, respectively (Hirsch and Banin, 1990;
Zhao and McGrath, 2002).
8

Cadmium and its compounds, compared with other heavy metals, are relatively water
soluble. Many Cl-, SO42-, and acetate of Cd are soluble in water, while O2- and S2- have a
low solubility and are insoluble species of Cd (Sarkar, 2002). In soil, Cd2+, CdSO4,
CdCl+, CdHCO3+ are dominant chemical speciation while Cd2+, CdS, CdCO3, Cd(OH)2
are prevalent in the water (Sposito, 1989).
Cadmium is taken by plants as divalent cation (Cd2+) and its concentration in
normal plants ranged from 0.1-2.4 mg kg-1 (Alloway, 1995) and at higher concentration it
adversely affected plant growth and dry matter yield. The lowest level of Cd in plant
tissues at which it has toxic effects is 5 mg kg-1 (Macnicol and Beckett, 1985). Several
elements are known to interact with Cd uptake by plants. Cadmium interaction with Zn,
Mg, Cu, Fe, Se, Ca, Mn and P in soil and plants has been reported in many studies (Page
et al., 1981; Kabata-Pendias, 2001).
Zinc is crucial for the normal healthy growth and reproduction of plants. In
normal soils, Kabata -Pendias (2001) reported a typical range of 3-770 mg kg-1 Zn with an
average of 64 mg kg-1. In the arid and semi-arid soils of Asia, a mean value of 59 mg kg-1
(ranging from 20 - 89 mg kg-1) of total Zn has been observed (Katyal and Vlek, 1985).
AB-DTPA extractable Zn < 1.5 mg kg-1 is considered high (Rashid and Memon, 2001).
Zinc is found in environment as Zn2+, ZnSO4, Zn-Org, ZnCO3, ZnHCO3-, ZnOH+, Zn2+,
ZnS, ZnCO3 and ZnSiO3 forms (Sposito, 1989). About 0.004 to 0.270 mg L-1 Zn is
present in the soil solution (Kabata-Pendias, 2001). Zinc is taken up as divalent cation but
at high pH it is most likely absorbed as a mono-valent form (ZnOH). In normal soils,
Kabata Pendias (2001) reported a typical range of 3 to 770 mg kg-1). Zinc is associated
with above ions via adsorption, surface complexation formation, ion exchange,
incorporation into crystal lattice (Jenny, 1968; Shuman, 1991). Zinc solubility is highly
pH-dependant and decrease by a factor of 100 for each unit pH increase (Lindsay, 1979).
Normal range of Zn in plants is 20 to 100 mg kg-1 while more than 100 mg Zn kg-1 is
generally regarded as excessive, and above 400 mg kg-1 is suggested as toxic for some
crops (Katyal and Randhawa, 1983).
Despite its essentiality, Cu is toxic to plants at more than 25 mg kg-1 concentration
(Macnicol and Beckett, 1985). Copper is linked with a number of metallo-proteins and
play a role in metabolism, photosynthesis, respiration, N fixation and many other
enzymatic activities. Soils usually contain 2 to100 mg kg-1 of Cu with an average of 30
mg kg-1 (McBride, 2001), however, according to Kabata-Pendias (2001) mean level for
9

Cu vary from 13-24 mg kg-1. Copper < 0.5 mg kg-1 AB-DTPA extractable is considered
high. Common oxidation states of Cu in the soil are Cu+ (the less stable state) and Cu2+
(the more stable state). Soil chemical properties mainly control Cu speciation and total
soil Cu may not be a useful indicator of potential toxicity to plants (McBride, 2001).
Copper occurs in soil and water as Cu in organic form and CuCO3 (Sposito, 1989).
Copper accumulates in top soil horizons due to high affinity with organic matter. Copper
is slightly less abundant in soil than Zn (Lindsay, 1979). In Pakistan, Cu deficiency is less
common. High level of N or P can contribute to Cu deficiency (Rashid and Memon,
2001).
Copper is actively taken up by plant roots and is not readily transported to shoots,
so high concentration of Cu accumulates in roots (Fernandes and Henriques, 1991; Ahsan
et al., 2007). Copper in plants generally varies from 5 to 20 mg kg-1. The Cu contents of
many edible plant parts (corn grains, alfalfa leaves) was not correlated to the amount of
soil copper (Babilla- Ohlbaum et al., 2001; Nan and Cheng, 2001; Mantovi et al., 2003).
2.2 Health risks associated with effluent irrigation and heavy metals
Untreated raw effluent also contains a variety of pathogens like viruses, bacteria,
protozoa and helminthes that may cause diseases in human on exposure (Peasey et al,
2000; Toze, 2006). The risk from these pathogens depends on factors like pathogen
number and dispersion in water, the infective dose required and the susceptibility of an
exposed population and doses of preventive treatment taken (Hogervorst et al., 2007).
Public and commercial concern does exist regarding pathogens through reuse of water on
cereal crops (Crute et al., 2004).
Ingestion of contaminated food or drinking of contaminated water can lead to
metals accumulation in humans and animals. When metals reach to a toxic level, they
induce tumor and mutations, cause genetic damage to germ cells and act as cumulative
toxins which through biomagnification in plants affect human health (Wagner, 1993).
Specific health problems associated with Cd are diarrhea, stomach pains, severe vomiting,
bone demineralization, reproductive failure and infertility, damage to the nervous system,
immune system and DNA, psychological disorders (Godt et al., 2006). On the other hand,
excess Zn causes stomach cramps, skin irritations, vomiting, nausea and anemia, metal
fever. Copper is reported to cause irritation of nose, mouth and eyes, headaches,
dizziness, vomiting and diarrhea, liver and kidney damage and even death.
10

2.3 Toxic effects of metal in plants

Higher concentrations of heavy metals in surface soil have been reported to inhibit
nutrient uptake, physiological and metabolic processes (Barcelo et al., 1998; Ahsan et al.,
2007) or reduce plant growth (Boussama et al., 1999) also cause chlorosis due to interfere
with photosynthesis and respiration (Sandalio et al., 2001; Ekmekci et al., 2008), damage
to cell membrane (Cunha et al., 2008) and to root tips (Sheldon and Menzies, 2005),
reduced water and nutrient uptake and damage to enzymes (Sanita di Toppi and Gabbrielli, 1999; Balestrasse et al., 2001). Heavy metals also induce increased antioxidant
enzyme activities in plants (Rodriguez-Serrano et al., 2006).
2.4 Bioavailability of metals
The bioavailability of metals in soils depends on their solution concentration
which in turn is dependent on the soil processes like cation exchange, specific adsorption,
precipitation and complexation (Harter and Naidu, 1995; Basta et al., 2005; CarrilloGonzales et al., 2006).
Many factors like total concentration and speciation of metals, soil mineralogy,
pH and CEC (Basta et al., 2005), total soil organic content (Harter and Naidu, 1995), soil
moisture percentage and biological influence (Harter and Naidu, 1995) govern the
bioavailability of metals. Many of these factors vary seasonally and temporlly, and are
interrelated and also inhibit prediction of metal bioavailability. So changing one factor
may affect several others. The differential response of species and varieties to
environmental changes also contributes to differences in uptake of heavy metals from
soil.
2.4.1 Effect of soil chemical and physical characteristics on metal bioavailability
Pollutants are released in soil where they are partitioned between solid and liquid
phases and further sub-partitioning occur among ligands as determined by ligand
concentrations and metal-ligand bond strengths. Partitioning is affected by already given
factors. Carrillo-Gonzales et al. (2006) suggested that solubility and mobility of Cd, Cu
and Zn in soils and their sequestration in carbonates or phosphates is controlled by
sorption or coprecipitation mechanisms which attenuate their phytoavailability.
High soil organic carbon forms soluble complexes with metals like Cd, Cu and Zn
(Sauve et al., 2000). Conversely, in a field trial with 146 samples, there was no significant
correlation between the organic matter content of soils and the Cd extracted by
11

ammonium nitrate or DTPA (He and Singh, 1993). At pH 6-8, organic matter increased
solution Cd concentration because Cd was complexed by soluble organic substances
(Brummer and Herms, 1983).
Cadmium in soil solution also forms soluble ion-pair complexes with Cl- that
increased its mobility (Smolders and McLaughlin, 1996; Weggler et al., 2004). This
appeared the primary reason for increased Cd absorption by plants irrigated with high Clirrigation water (McLaughlin et al., 1995; Smolders and McLaughlin 1996; Norvell et al.,
2000; Chien et al., 2003).
2.4.2 Effect of plant factors on metal bioavailabilty
Plant genetics, physiology and morphology can also control the bioavailability of
heavy metals. But these effects might be variable and require deep study. It is concluded
that metals bioavailability is modified by soil processes, genetic and environmental
factors. These effects may be exerted either through the root or shoot or through the
whole plant. Soils irrigated with tubewell, canal or effluent water differ in ionic
composition and other properties; similarly plants grown on these soils may have variable
metal composition.
2.5 Effluent irrigation and environmental concern
In Pakistan, like other developing countries, industrial wastes and raw municipal
effluents are used for crops production in and near urban centers or discharged un-treated
into the canals, rivers, along roadsides or in the vicinity of industrial establishments and
cities. Although wastewater reuse for agricultural irrigation seems to be a positive mean
of recycling water but it is characterized by a complex heterogeneous composition
depending upon its origin and subsequent dilution (Toze, 2006; Ghafoor, 2004).
In almost all towns of Pakistan that have a sewage system, the raw effluent is
directly used for irrigation. Authenticated and comprehensive figures about effluent
irrigated area are lacking. Available total estimate of effluent irrigated area in the main
cities is 32500 hectares (Ensink et al., 2004). A negligible proportion of this effluent is
treated and no clear regulations exist on crops that can be irrigated with city effluents.
Effluents generated in small towns and cities may be suitable for recycling in
agriculture without any concern while urban sewage represents a blended mixture of
sewage and industrial waste effluents which gets contaminated with heavy metal and
12

other pollutant materials that leads to environmental pollution (Reiman and Caritat,
1988).
Raw effluent often contains significant quantity of organic and inorganic
nutrients, such as N, P, many toxic wastes, microorganisms and human pathogens (Toze,
2006). High concentration of nutrients in effluent irrigation contributes to high crop
yields. Khouri et al. (1994) observed yield increases between 28 and 51% in wheat, rice,
mung beans, cotton and potatoes compared with fresh water irrigation plus application of
commercial fertilizers. Among toxic wastes, heavy metals were found in appreciable
amount (Feign et al., 1991; Brar et al 2000; Yadav et al, 2002; Rattan et al., 2005;
Ahmad, 2007) and their concentration varied according to source. Raw effluent generally
contain low concentration of heavy metals but long term use of raw effluents on
agricultural lands often results in the elevated levels of metals in surface soils (Ghafoor et
al., 2004; Murtaza et al., 2008) that leads to changes in soil physical, chemical and
biological properties (Nan et al., 2002; Chen et al., 2004).
2.6 Sewage system of Faisalabad
Sewage system of Faisalabad has been divided into the Eastern and Western zones
which are separated by Rakh Branch Canal and the Railway Line. The effluent generated
at Eastern side is almost from household sources and drains into Madhuana drain and
Western side is from industrial sources and disposed off into the Paharang drain. The
average daily wastewater production is about 450 thousand m3 and out of which, 140.23
thousand m3 is used for irrigation purposes; 82.1 thousand m3 on eastern and 58.1
thousand m3 on western side (Munir et al., 2005).
2.7 City effluent suitability and metal composition
Water quality standards established for crop irrigation with fresh water (Ayers and
Westcot, 1985) are considered best available criteria for effluent use at present. Sewage
effluent usually has 200-400 mg L-1 more salt than the municipal input water (Bouwer
and Idelovitch, 1987). Among the available useful water quality guidelines for irrigated
agriculture, none has been found entirely satisfactory because of the wide variability in
field conditions. Water quality or suitability for use is judged on the potential severity of
problems that can be expected to develop in long-term use. The problems that result vary
both in kind and degree, and are modified by soil, climate and crop, as well as by the skill

13

and knowledge of the water user. As a result, there is no set limit on water quality; rather,
its suitability for use is determined by the conditions of use.
Many countries have developed guide lines and criteria for reuse of water and
these guide lines mainly focus on the human health or environmental risk from microbial
pathogens, nutrient, total soluble salts, SAR and RSC and toxic metals (Toze, 2006).
Maximum limits of 0.01, 0.2 and 2.0 mg L-1 for Cd, Cu and Zn, respectively for long term
irrigation have been recommended (Bouwer and Idelovitch, 1987) while EC, SAR and
RSC permissible limits were advocated as 1.0 dS m-1, 10.0 and 2.5 mmolc L-1 (Ayers and
Westcot, 1985). An element at a given concentration in water may be immediately toxic
to a crop or it may require a number of years to accumulate in the soil before it become
toxic.
Most of the research work conducted in Pakistan showed that effluents either from
domestic or industrial origin, have elevated concentration of metals and soluble salts
compared with canal or ground water.
The mean values of pH, EC, SAR and RSC in effluent of various industries
(dying, printing, tannery and textile) in Faisalabad ranged from 6.19-12.75, 4.14-68.0 dS
m-1, 13.96-157.0 and 0.93-188.5 mmolc L-1, respectively (Ahmad, 2007). Likewise,
effluent of main drains (Paharang and Madhuana) and its surrounding industrial units in
Faisalabad was found unfit for irrigation with respect to EC, SAR and RSC (Ghafoor et
al., 1994, 1996). However, the concentration of metals (Cu, Fe, Mn, Pb, Ni, and Zn) was
within limit proposed by Ayers and Westcot (1985). Comparable results were for
effluents collected at Ghulam Muhammadabad, Satiana road, Jaranwala road and Jhang
road effluent pumping stations in Faisalabad (Ibrhim and Salmon, 1992).
Nearly all the studies pointed out the elevated level of heavy metals in effluents
although their concentration was widely variable and lower than upper critical limits in
some cases. In effluents at Faisalabad, metal abundance was followed the order Fe > Mn
> Cu > Zn > Cd > Co (Sadiq, 1999). While Ahmad (2007) found the order as Cu > Cr >
Mn > Ni > Zn > Pb > Cd with a mean concentration of 0.384, 0.305, 0.195, 0.106, 0.095,
0.021 and 0.007 mg L-1, respectively in 11 industrial effluents of Faisalabad, Pakistan.
Hussain (2000) reported mean concentration of Cd (0.004 mg L-1), Zn (0.034 mg L-1) and
Cu (0.055 mg L-1) in effluent used as irrigation at Uchkera village, Faisalabad. In close
proximity, Khan et al. (1994) observed concentration range of Cd, Fe, Cu, Pb and Mn
14

between 0.051-0.054, 1.78-1.85, 0.34-0.58, 0.39-0.6 and 0.18-3.07 mg L-1 in mixed

effluents used for irrigating fields at Chak 219, 220, 224 and 279 RB of Faisalabad.
Temporal variation in composition of city effluent was also recorded (Ahmad, 2007) but
the above concentrations were relatively higher than previous studies.
Butt et al. (2005) recorded significant amount of heavy metals like Fe, Cu, Zn,
Mn, Ni and Pb in industrial effluents of ghee mill, flour mill, textile industries and
hosieries at Faisalabad which drain into main drain system. The mean concentration of
Cd, Cr and Co was found above the permissible limits recommended for irrigation at
Gandakhue, Mulkhanwala, Awanwala and Kanuwala along Satiana road drain, Faisalabad
(Farid, 2003).
High concentration of metals in effluents, diverted for irrigation purposes in other
cities for example Islamabad (Gulfraz et al., 2003), Lahore (Bashir et al., 2006); Haripur
and other cities of North West Frontier Province (NWFP) (Midrar-ul Haq et al. 2005; Sial
at el., 2006), Attock, Rawalpindi and Abotabad (Chattha et al., 2005) and Karachi
(Midrar-ul Haq et al., 2003) has also been reported. Significant amount of heavy metals
like Fe (0.51-2.57 mg L-1), Cu (0.21-4.41 mg L-1), Zn (0.31-5.18 mg L-1), Mn (0.15-1.94
mg L-1), Ni (0.37-5.21 mg L-1), Cd (0.12-3.42 mg L-1) and Pb (0.01-6.11 mg L-1) in
effluents of various industries of Rawalpindi and Islamabad were detected by Gulfraz et
al. (2003). Sewage water at Lahore was unfit for irrigation due to high Mn, Zn and Cd
(Bashir et al., 2006). Extensive use of this effluent for irrigation resulted in increased
concentration of metals in soils and crops compared with canal irrigated. Range of pH,
EC and RSC of effluents of Hattar industrial estate of Haripur district, used for irrigation,
was 7.20-10.35, 1.00-8.14 dS m-1 and 0.5-27.1 mmolc L-1, respectively. Mean
concentration of Fe, Zn, Cu and Pb in effluents used as irrigation was 2.64, 0.215, 1.2 and
0.002 mg L-1 which was 4.9, 40.0, 3.0 and 4.0 times more than concentration in ground
water, respectively.
Total toxic metals (Cd, Cu, Cr, Pb, Hg, Se, Ni and Ag) load in effluents of textile
and ghee industry and city was above the limit of National Environment Quality
Standards (NEQS) Pakistan, i.e. 2 mg L-1 (Anonymous, 1993). Copper and Fe in effluent
of textile and city, and Mn and Fe in effluent of ghee industries were above while Ni and
Pb were below the NEQS (Sial et al., 2006; Gulfraz et al., 2003). Chattha et al. (2005)
evaluated effluent quality used for irrigation of vegetables production in the districts of
Attock, Rawalpindi and Abbotabad. Heavy metals concentration was in the range of Zn
15

(0.43-0.083), Cu (0.21-0.84), Cd (0.012-0.046) and Pb (0.24-0.84) mg L-1. Cadmium and

Cu were above the maximum permissible limits of FAO (1998) that is 0.2, 0.01, 0.2 and
0.10 mg L-1, respectively. Similar results were reported by Midrar-ul Haq et al. (2005)
who found significantly high concentration of heavy metals in effluent irrigated soils of
NWFP compared with their back ground levels.
On an average sewage effluents contained 5.5, 3.6, 2.6, 6.4 and 1.3 times higher
amounts of Zn, Cu, Fe, Mn and Ni, respectively compared with ground water in India as
observed by Rattan et al. (2005). Indiscriminate use of such industrial effluent for
irrigation has aggravated the salinity, sodicity and or metals as well (Chattha et al., 2005;
Kumar et al., 1998 and Bernal et al., 2006).
It is inferred from the preceding review that effluent waters normally contain high
concentration of soluble salts and all essential and toxic metals than ground water or canal
irrigation water. So soils around urban and industrial establishments are becoming
increasingly polluted with heavy metals as a result of irrigation with raw effluent.
Concentrations of metals in most studies differed widely and are difficult to correlate with
each other due to variable study conditions. At field outlet metals and salts might be
diluted in down stream due to domestic effluents. Therefore, it is desirable that irrigation
quality of sewage waters must be assessed not only for EC and RSC and compared with
ground water used for irrigation but also for metal ions before their soil application to
protect and sustain the agricultural production and preserve agro- environment.
2.8 Heavy metal buildup and distribution pattern in soils
Metal buildup in soil due to effluent irrigation has been reported by many
researchers in Pakistan (Murtaza et al., 2008;, 2007; Butt et al., 2005; Midrar-ul-Haq et
al., 2003; Ghafoor et al., 1996 and 2004) and in India (Sutapa and Bhattacharyya, 2008,
Rattan et al., 2005; Yadav et al. 2002; Kumar et al., 1998; Kuhad et al., 1989).
Movement of metals through soil profile is considered a slow process and the
surface soil accumulate higher concentrations than lower horizons (Murtaza et al., 2008;
Salmasi and Tavassoli, 2006; Lamy et al., 2006). However, downward movement to
lower horizons has also been reported by Richard et al. (1998), Haiyan and Stuanes
(2003) and Van Oort et al. (2006). The problem of vertical movement of metals is more
acute in coarse textured soils due to less CEC and ground water may become
contaminated due to leaching. Fine-textured soil with high CEC retained more metals
16

than coarse-textured soil with lower CEC (Kuo et al., 1985), while McBride (1995) noted
that heavy metal retention was closely associated with metal organic complexation and
pH.
The reverse trend was observed in lateral or horizontal movement of DTPAextractable metals (Jeyabaskaran and Ramulu, 1996). Kuhad et al. (1989) observed that
irrigation with industrial effluent resulted in accumulation of Cd, Pb, Ni, Co, Zn, Mn and
Fe in the Ap horizon of a loamy sand soil, while no regular pattern of metal distribution
was observed in loamy sand and sandy loam soils at other sites investigated. Organic
matter contents and metal concentrations were generally higher in top layers of soils
receiving sewage irrigation (Khan et al., 1994; Bansal et al., 1992). Due to formation of
insoluble complexes with organic matter, mobility of Cd, Pb, Cu and Zn to lower
horizons was negligible (Singh and Singh, 1994). Most of the metals remained in the
topsoil, but a sampling at 5 cm intervals or sampling by horizons showed migration of Zn,
Pb, Cu and Cd into the subsoil (Lamy et al., 2006).
Salinity and sodicity indicators (ECe, SAR, and ESP) were relatively high in the
effluent-irrigated soils (Murtaza et al., 2008; Ahmad, 2007; Bashir et al, 2006; Chattha et
al., 2005; Ghafoor et al., 2004; Yadav et al., 2002; Qadir et al., 1997) compared with
canal or tubewell irrigated soils (Rattan et al., 2005). However, effect of high soluble salts
on crop growth in effluent irrigated soils need more attention due to changed soil
properties. The mean values of pHs, ECe and SAR of soil at Chak 217 RB and Marzipura,
Faisalabad were 7.85, 4.08 dS m-1 and 8.44, respectively while the same parameters in the
nearby canal irrigated soil were 7.8 (pHs), 1.78 dS m-1 (ECe) and 4.63 (SAR), respectively
(Ahmad, 2007).
A great concern of irrigating crops with raw effluent is of metal accumulation in
soils. Mean concentration of AB-DTPA extractable Cd in surface soil (0-0.2 m) at
Kernailwala and Judgewala effluent irrigated sites in Faisalabad was 0.080 and 0.101 mg
kg-1, respectively. Background levels of Cd were 0.006 mg kg-1 at Kernailwala and 0.008
mg kg-1 at Judgewala (Murtaza et al., 2008). Whereas mean soil metals were Pb (4.02 mg
kg-1), Cu (5.45 mg kg-1), Zn (2.05 mg kg-1) at same location of soils under vegetable
cultivation (Ghafoor et al., 2004). Here metal abundance followed the order of Fe > Cu >
Pb > Zn > Cd. Soil Cd: Cu: Zn ratios were 1, 68 and 25.

17

In long-term irrigation with effluent, mean concentration of DTPA-extractable Zn, Cu, Cd

and Pb was 7.31, 4.91, 0.20 and 1.91 and corresponding values for tubewell irrigated soil
were 0.99, 0.95, 0.14 and1.31 mg kg-1, respectively (Rattan et al., 2005). In this situation,
20 years effluent irrigation resulted into significant buildup of DTPA extractable Zn
(208%), Cu (170%) and Pb (29%) in soils over adjacent tubewell water irrigated soils.
Compared with canal irrigated soils, heavy metal concentration in effluent irrigated soils
was higher (Ghafoor et al., 1996; Midrar-ul-Haq et al., 2003).
It is clear from the forgoing paragraphs that buildup of metals in effluent irrigated
soils over adjacent tubewell or canal irrigated soils has been observed at many locations.
Soil is a sink for contaminants and higher concentration accumulates in surface soil due to
their restricted mobility. Heavy metals accumulate principally in the surface horizons and
their vertical and lateral movement may be very low except for poorly drained and light
textured soil. Soil clay contents, organic matter and CEC control movement of heavy
metals in soil. Long term effect of contaminants on soil, plants, environment and health
must be monitored to safeguard the produce quality and protect the agro-environment.
Therefore, it is desirable for safe crop production that builds up of heavy metals,
downward movement, their effects on social, environment and biological ecosystem
should be monitored.
2.9 Contamination limits for effluent irrigation water, soil and plants
Different regulation and critical limits of heavy metals, based on their effect on
human health, plants and environment exist. However, more authenticated permissible
limits are set by FAO and USEPA, 1992. Permissible upper limits of Cd, Zn and Cu of
0.005, 0-traces and 2.0 mg L-1 for drinking water; 0.01, 2.0 and 0.20, mg L-1 for irrigation
and effluent water; 20, 1500 and 775 mg kg-1 for soil, and 10, 1000 and 40 mg kg-1 for
animal feeds, respectively, are recommended by FAO (1998) and USEPA (1992). The
upper critical level of a metal is the lowest tissue concentration at which it has toxic
effects. Critical plant tissue concentration of 5 mg kg-1 for Cd; 10 mg kg-1 for Cu and Ni
and 100 mg kg-1 for Zn have been extracted by Macnicol and Beckett (1985) after
scrutiny of published work. However these critical levels differed widely in the test plants
due to variation in growth media, species and genotypes, tissue selection and their age.
Kent and Everes (1990) reported normal range of Cd, Zn and Cu in wheat as 0.1, 33.0 and
6.0 mg kg-1, respectively while Walker (1988) stated Cd permissible limit of 0.05 mg kg-1
in all foodstuffs including wheat grains.
18

2.10 Uptake of metals and their distribution in plant tissues

Several studies have shown that important soil factors affecting crop metal
concentration are soil texture, pH, specific metals concentration, organic matter, and
complexing ligands (McLaughlin et al., 1997; Jansson and Oborn, 2000). The metal
concentration in crops tends to be the highest in soils with low pH, low organic matter
content, high soil metal concentration and low or high soil opposing metal concentration.
Most research has been focused on soil factors in the plough layer. However, some plants
have deep roots growing into the sub-soil and thus soil factors in those layers are also
important. It has been shown that 15-37% of the Cd in wheat grains was taken up from
the sub-surface layers (Johnsson et al., 2002).
Modification of rhizosphere (Martino et al., 2000; Saleh Al-Garni, 2006) and
plant root architecture (Welch and Norvell, 1999) modify the solubility, mobility and
metal uptake by roots. Water and ion fluxes and their association to the kinetics of
membrane transport, ion interactions, and metabolic fate of absorbed ions, and the ability
of plants to adapt metabolically to changing metal stresses in the environment also
influence metal uptake by plants (Walter, 2005). The characteristics and behavior of a
plant species or variety are important in determining the amounts of heavy metals that are
taken up from soils. Such diversity may reflect different rates of absorption and transport
from root to shoot.
Large differences in accumulation of heavy metals by cereal and legume crops
have been reported (Kumar et al., 1995; Cieslinski et al., 1996) due to cereal and legume
crops difference in root architecture, orientation and metal uptake capacity (Marschner,
1995). On the other hand, plants also develop strategies to control metal mobility at their
interface with the soil. Selection of cereal varieties may add to safer crop production on
heavy metal contaminated sites (Chamon et al., 2005). Dicotyledonous crop plants tend to
accumulate more metals than monocotyledonous crops (Kabata-Pendias et al., 1993).
Monocots, which include most of the cereal crops, are known excluders of metal cations
(Baker, 1991). Metals transport to grain tissues is restricted (Kabata-Pendias et al., 1993;
Baker 1991) and most of the quantity is deposited in roots. Thus, cereal crops such as
wheat, barley, oat, rye and corn may be considered as excluders (Kabata-Pendias et al.,
1993). Wheat accumulated twice amounts of Cd in grains than rye, oat or barley
(Puschenreiter and Horak, 2000). Application of Cd (0-15 mg kg-1 soil) of Cd) reduced
dry matter production in the order of bread wheat > oat > maize > barley. While
19

application of 10 mg kg-1 of Zn increased dry matter production and decreased Cd

concentration in same crops (Adiloglu, 2002).
Various vegetable species (Murtaza et al., 2008), soybean and bean genotypes
(Bell et al., 1997; Belimov et al., 2003; Metwally et al., 2005), Mungbean (Wahid and
Ghani, 2008), rice varieties (Chamon et al., 2005; Abbas et al., 2006) and wheat cultivars
(Jalil et al., 1994; Li et al., 1996; Chamon et al., 2005) differed in metal uptake and
accumulation due to level in soil, metal characteristics, metal speciation, presence of
other counter species of ions (Hernandez et al., 1996); Obata and Umebayashi, 1997)
environmental growth condition and crop genetic factors. Cadmium accumulation
behavior varies not only on the species level or between cultivars but also in individual
plants. Plant species and even inbred lines of maize (Hinesly et al., 1982), maize and
beans (Guo and Marschner, 1996), wheat (Grant et al., 1998; McLaughlin et al., 1999)
and rice accumulated different level of Cd and Pb even at same metal concentration.
Among wheat cultivars, 2.5 times variation of Cd concentration in grain was observed
(Wenzel et al., 1996). With in plants variation in heavy metal accumulation exists and the
highest concentrations were found in roots followed by leaves and seeds (Machelett et al.,
1993).
Toxic metals accumulation in various plant tissues were reported in the order roots
> leaves > stems > inflorescences > seeds. However, this order on occasion varied with
plant species. Rattan et al. (2005) reported that effluent irrigated rice, wheat, maize and
oats accumulated 1.7, 1.4, 1.2, 1.3 times Zn, 2.2, 1.3, 1.1, 1.4 times Cu and 1.0, 1.0, 3.2,
0.5 times Ni over tubewell irrigated crops, respectively. Similar accumulation trends were
observed in oats with only exception of Mn (Datta et al., 2000; Yadav et al., 2002) for
some sewage-irrigated soils of India. Transfer factors for Zn and Fe in all the crops grown
in effluent-irrigated soils were lower than that for crops produced with tubewell water
irrigation.
The lowest transfer factors of Cd were found for grains of maize, peas, oat and
wheat where as the highest values were reported for leaves of spinach and lettuce. Low
transfer factors of Zn were reported in grains of maize and peas. The transfer factors of
Cd, Cu, and Zn were 0.30, 0.11 and 0.68 for maize grain and 0.08, 0.14 and 0.25 for bean
seed, respectively (Machelett et al. 1993; Puschenreiter et al., 2005). The Cd
accumulation by crop species decreases in the following order: leaf vegetable > root
vegetable grain crops (Page et al., 1987).
20

Adequate Cu concentrations in youngest mature leaves of chickpea and wheat reported in

the literature are 4-30 and 5-25 mg kg-1, respectively (Weir and Cresswell, 1982; Brennan
and Bolland, 2003). The highest proportions of Cu and Cd taken up by rice and wheat
varieties were retained in the root (Chamon et al., 2005). Spring wheat accumulated Cu
only between 2.12 to 6.84 mg kg-1 in soil ranging copper concentration of 26 to 199 mg
kg-1 (Nan and Cheng, 2001). Copper concentration in bean (Phaseoulus valgaris L.),
grown on a control (18 mg Cu kg-1) and contaminated soil (430 Cu mg kg-1) was 6.6 and
6.7 mg kg-1 (Bunzl et al., 2001).
Highest concentration of Cu were reported in root tissues compared with above
ground parts due to limited transport (Nan and Cheng, 2001) and Cu association with cell
wall due to its affinity for carboxylic, phenolic and sulfidryl groups as well as
coordination bonds with N, O and S atoms (Kopsell and Kopsell, 2006). When corn was
grown in solution culture at 5-10, 4-10 and 3-10 M Cu2+, Cu contents of roots was 1.5, 8,
and 10 fold greater respectively than control (Liu et al., 2001).
Barley (Hordeum vulgare) and pea (Pisum sativum) grown in Zn and Cu
contaminated soils showed reduced height and dry weight in pea (Hilber et al., 2007).
Marcelo et al. (2000) reported a mean grain concentration of Cd, Pb, Cu and Zn in wheat
as 0.040, 0.016, 3.4 and 33 mg kg-1, respectively. In the grains of effluent-irrigated wheat,
the concentration of Cd was found above the permissible levels recommended by WHO
for foodstuff sampled at Gandakhue, Mulkhanwala, Awanwala and Kanuwala along
Satiana road drain, Faisalabad (Farid, 2003).
Plant tissue analysis indicates the relative distribution of metals in various parts of
plant and that is important in relation to the transfer in the ecosystems. The transfer of Cd,
Zn and Cu to oat plant was found more from sandy soil than organic soil. Zinc and Cd
were observed more mobile in the plant than Cu. Addition of Cd resulted in higher Cd
concentrations in all plants while decreased Pb, Zn, Cu, Mn and Fe (Gerda and Schierup,
1985). Similar results were reported for wheat crop which accumulated a wide range of
heavy metals in different parts, in different concentrations under the application of
industrial sludge amendments. The value of transfer factor (TF) from root to shoot was
found larger than from shoot to grain (Sutapa and Bhattacharyya, 2008).
Agronomic and management factors had also been reported to affect metal
contents in the plant tissue (Puschenreiter et al., 2005). Results from long-term field
21

experiments indicated that Cd concentration in grain was the highest in wheat grown after
a legume such as lupins, the lowest in wheat grown after cereal. Cadmium in wheat grain
increased with increasing rates of N irrespective of the crop rotation. Cadmium in wheat
grain was influenced by Zn supply to the plant.
In cereal, accumulation is greatest in roots and decline towards the top of plant
(Cutler and Rains, 1974). The Cd concentration of crops grown in solution culture
increased in the order oat, wheat < bean, pea < corn, mustard < radish, Kale rape <
tomato, carrot < lettuce (Pettersson, 1977).
Gupta et al. (2006) observed that more quantities of Fe, Cu and Zn were
accumulated in seeds compared with the Cd and Cr by chickpea varieties when grown
under fly-ash having total metal concentration of Fe, Zn, Mn, Cu, Cr, Cd, Pb, Mo and Ni
of 4150.0, 82.0, 70.14, 58.6, 40.3, 42.3, 40.1, 33.4, and 204.0 mg kg-1, respectively.
Varietal difference was significant. Similarly a high genetic variability in 99 varieties of
pea was found in the presence of 5 mg Cd kg-1, where the concentration of Cd, Cu and Zn
in plant shoots varied between pea genotypes by a factor of 2.8, 2.7 and 4.0, respectively
(Belimov et al., 2003).
Rattan et al. (2005) found that mean content of metals in dry matter of effluent
irrigated rice, wheat, maize, oat and Egyptian clover were 49.6, 65.3, 78.8, 59, 91.9 mg
kg-1 for Zn and 51.6, 9.39, 14.9, 8.71, 18.3 mg kg-1 for Cu, respectively. Sewage irrigated
rice, wheat, maize, oats accumulated 1.7, 1.4, 1.2, 1.3 times Zn, 2.2, 1.3, 1.1, 1.4 times Cu
over tubewell irrigated crops, respectively. Pattern of metal accumulation in crops parts
was generally reported in the order of roots > leaves > stems > seeds. However, this order
sometimes varied with plant species. Chickpea seed accumulated Zn, Cu and Cd in the
range of 23.7-36.9, 62.8-90.2 and 1.03-1.75 mg kg-1, respectively when grown under
various fly-ashes amendments (Zn, 82 mg kg-1; Cu, 58.6 mg kg-1 and Cd, 42.3 mg kg-1)
(Gupta et al., 2006).
It is clear from above review that effluent irrigated plants tends to accumulate
high quantity of Cd, Zn and Cu which also varied with plant genetic make up, species and
varieties, condition of growth, soil properties and environmental factors. Legume crops
accumulated more Cd than cereal corps. Metal distribution in plant tissues were in the
order roots > shoot > seed. Large differences in accumulation of heavy metals are

22

reported in cereal and legume crops and selection of crop is prerequisite for safer crop
production on effluent contaminated soils.
2.11 Cadmium effect on plant growth
Effects of Cd on growth parameters are generally studied by using variable and
high concentrations of Cd in growth media, soil or irrigation water which may give
misleading results compared with field condition.
While investigating the effects of different levels of Cd concentration on rice
growth, Wu et al. (2006) found that the germination of rice was slightly stimulated under
low Cd concentration (0.01 to 1.50 mM Cd), while severely depressed under 2.0 mM Cd
concentration. Cadmium concentration in roots and shoots increased with increasing Cd
level. When rice genotypes were exposed to 0.5 and 1 mM Cd compared with control, Cd
concentration increased by 40.7 and 99.0 fold in shoots and 74.7 and 134.5 fold in roots,
respectively. Differences among genotypes with respect to the effects of Cd on rice crop
were remarkable in shoots rather than roots.
In mung bean, number of pods per plant and seeds per pods were reduced to 37%
and 26%, while 100 seed weight, seed yield and harvest index showed 61%, 79% and
54% reduction when subjected to Cd concentration of 6, 9 and 12 mg kg-1 in alkaline soil.
However, 2.5 mg kg-1 Cd had negligible effect (Wahid and Ghani, 2008). In wheat, Cd
uptake and accumulation was found maximum during the initial growth period that also
interfered with the uptake of Zn2+ and Mn2+ (Shukla et al., 2003) and K, Zn, Ca and Fe
(Vassilev, 2002) from growth medium.
Differential uptake of one metal in plant tissue is not well known while different
transporters are considered to be involved in the excretion of metal into the xylem and
finally into the leaves. Cadmium inhibited the transporters involved in the translocation
such as radial movement in the root, loading into the xylem vessels or absorption to the
leaf (Sandalio et al., 2001). A morphological change of the conducting xylem tissue is
also another reason that contributes to a limited translocation of nutrients from the roots
(Barcelo et al., 1988).
2.12 Interaction of Cd with Zn and Cu in soil and plants
Contaminated soils usually have high concentration of heavy metals like Cd, Cu
and Zn which show a wide range of interactions in soil crop system that are influenced by
management. Cadmium interaction with Zn, Mg, Cu, Fe, Se, Ca, Mn and P in soil and
23

plants has been reported in many studies (Page et al., 1981; Kabata-Pendias, 2001).
Cadmium interaction with both Cu and Zn at the root surface and Zn with Cu and Cd
within the plant has been reported. Zinc interaction with Cu and Cd are antagonistic while
Cd with Zn at the root surface is synergistic. On the other hand, Zn and Cu can effectively
substitute for each due to similar behavior (Luo and Rimmer, 1995). Kabata-Pendias
(2001) described the Zn-Cu interaction as an antagonistic. Luo and Rimmer, (1995)
observed 20% increase in Zn uptake by spring barley in pot experiment conducted in
sandy loam soil in the presence of 50 mg Cu kg-1 while the uptake of Cu was also affected
primarily by the interaction effects of Zn-Cu-Pb-Cd.
The presence of 0-50 M Cd as CdCI2 in the nutrient solution decreased the
uptake of Zn and to a lesser extent of Cu in the leaf (Sandalio et al., 2001). Changes in
H+, ATPase activity and transporter selectivity, or modifications of enzyme activity were
the subject that determines the transport of metals under Cd treatment (Chaoui et al.,
1997). Internal transport of metals from root towards shoot and grains was restricted. So
root and shoot exhibited significant differences in metal concentrations. Such metal
immobilization in root cell was related to an exclusion strategy (Baker, 1981).
Metals followed the accumulation trend of Fe > Zn > Mn > Pb > Ni > Cr > Cu >
Cd in wheat grown in soils amended with sludge @ 0, 10, 20 and 30% having DTPA
available Zn, Cu and Cd concentration of 25.02, 31.72 and 1.15 mg kg-1 dry weight.
Concentration of Cu and Cd except shoot Zn increased significantly with successive
stages of plant growth. Alkaline pH reduced the uptake of Cd in wheat plant shoots as
well as its translocation to grains (Sutapa and Bhattacharyya, 2008). Zinc > 34 mg kg-1 in
wheat grain was considered unfit for human consumption by Andersson and Pettersson
(1981).
2.13 Effect of Cd on metal concentrations in plants
Studies have been conducted to determine the effect of Cd on the uptake of
divalent cations such as Zn, Mn, Cu and Fe. Results from the studies conducted by
scientists indicated that Cd had antagonistic effect on the uptake of Zn in corn (Root et al.
1975) and barley (Akay and Koleli, 2007). Jalil et al. (1994) found decrease in Zn and
Mn concentration in roots and shoots of wheat and with no effect on Cu concentration by
Cd application. These conflicting results were due to different study condition, plant
varieties and species. Wu et al. (2006) observed that exposure of three genotypes of rice
24

seedlings to 1.124 to 224.0 mg L-1 Cd solution substantially affected uptake and

distribution of Zn, Cu, Fe, and Mn in plants. Zinc concentration increased up to 11.2 mg
L-1 for shoots and 56.2 mg L-1 for roots. However, further increase in Cd level caused a
marked decrease, in particular for shoots. Copper concentrations in roots and shoots were
also reduced especially in 56.2 and 112.4 mg L-1 Cd treatments.
2.14 Influence of commercial fertilizer on metal behavior in soil and plants
Nitrogen and P fertilizers besides providing plant nutrients may also modify some
soil properties like soil pH, type and content of organic matter, CEC, and complex
formation or directly react with heavy metal ions in soil that would result in the changes
in the form of metals and their bioavailability to plants (Tu et al., 2000). Zhao and Zhang
(1997) found that ammonium (NH4+) based fertilizers depressed pH while phosphate was
able to increase CEC of soil (the negative charge). Phosphate fertilization influenced
metal phytoavailabilty through cation exchange, adsorption, surface complexation and
precipitation. Phosphorus interactions with metals like Cd, Pb, Cu, Fe, Mn, Mo and Zn
have been reported in many studies.
2.14.1 Long term effect of fertilizer on soil
Phosphorus fertilizer is one of the major contaminant of Cd and Zn in agricultural
soil. Long term effect of P fertilizer due to its contamination is reviewed by Grant and
Sheppard (2008) in detail. Briefly a positive significant relationship between total P and
total Cd in soil was recorded in Saudi Arabia (Modaihsh et al. 2001; Saltali et al., 2004),
United States (Mulla et al., 1980), Europe (Baerug and Singh, 1990; Christensen and
Tjell, 1991; Nicholson et al., 1994; Loganathan et al., 2003) and Australia (Williams and
David, 1976) as a result of long term additions of P fertilizers.
About 22.4-44.0 kg ha-1 year-1 of P is applied in Pakistan which is imported from
Jordan, Marrakesh, USA or Russia. Information covering contamination level of these
fertilizers and their long term effect on environment is not available. Reports are available
where soil Cd increase was not observed due to application of low cadmium P fertilizer, <
5 mg kg-1 (Mortvedt, 1987; Richards et al., 1998) but monitoring of their long term
impact is necessary. Level of fertilizer contamination may lead to contrary results in
determining Cd or Zn accumulation in soil and plants. Therefore, further research is
needed in multi-cropping area where usually high rates of fertilizers are applied to crops.

25

2.14.2 Effect of P fertilization on metal accumulation in plants

Phyto-availability of Cd, Zn and Cu is affected by P application which is required
by plants particularly at early growth stage for root development and later for tillering,
flowering, fruiting and seed setting. Increased metals accumulation in crops is related to
high concentration in soil (Adams et al., 2004). Fertilizer application also causes increase
in soil and plant Cd (Eriksson, 1990b; Kashem and Singh, 2002). Brennan and Bolland
(2004) observed increased Cd concentration of canola and wheat from P fertilization in a
sandy soil.
A three year field study by Grant and Bailey (1998) indicated that yield and Cd
concentrations of durum wheat increased with banded and broadcast application of P and
N while remained unaffected by Zn fertilizers. Method of application was not consistently
influence either grain yield or Cd concentration. Yang et al. (1999) found in solution
culture that Cd concentrations in wheat and corn increased with added P at pH 5.0. A
complex interaction between P and Zn was observed by Grant and Bailey, 1993;
Bogdanovic et al., 1999; Zhu et al., 2001; Li and Zhu, 2002. The result confirmed that
application of P (0, 50, and 100 ppm) as KH2PO4 and Zn (0, 5, 100 ppm) as ZnSO4 in
alkaline clay loam soil (pH, 7.7-8.0) significantly increased shoot, grain and roots dry
matter yield and decreased the concentration of P, Cu and Fe while increased shoot and
root Mn in barley (Li and Zhu, 2002).
Applications of very high rates of P, above those normally used for crop production, can immobilize Cd by P-induced Cd2+ adsorption and/or precipitation of Cd (Bolan
and Duraisamy, 2003; McGowen et al., 2001). The increased adsorption was correlated to
increased surface charge, co-adsorption of P and Cd as an ion pair or surface complex
formation of Cd on the P compound. In laboratory studies, addition of mono-ammonium
phosphate decreased soil pH and the amount of Cd adsorbed by soil, while application of
DAP increased soil pH and led to Cd and Zn precipitation (Levi-Minzi and Petruzzelli,
1984). In silt loam soil (pH 6.4 and DTPA extractable Zn, 419 and Cd, 6 mg kg-1),
application of 100 mg kg-1 of P as DAP to soybean increased tissue concentration of Zn
and Cd from 923 to 1153 and 14.0 to 19.5 mg kg-1, respectively (Pierzynski and Schwab,
1993).
Mortvedt et al. (1981) reported that Cd concentrations in both grain and straw of
winter wheat was increased with the application of DAP (containing 760 mg Cd kg-1 of P)
26

to acid soil deficient in P while, Jaakola (1977) reported that Cd uptake by grain and
straw of spring wheat was not affected by the application of P fertilizers containing 10,
150, 285 and 405 mg Cd kg-1 P. Among the P sources, DAP was found more effective in
reducing the Cd uptake (Reuss et al., 1978). On the other hand, McLaughlin et al. (1995)
reported that type of P fertilizers had no effect on potato tuber Cd concentrations. Chien
and Menon (1994) found that Cd uptake by maize increased with the increasing rates of
Cd contained in P fertilizers and the Cd uptake depended upon the phosphate solubility;
the highest uptake being with P source of high solubility.
P fertilizers may also contain Zn contamination ranging from 50 to more than
1500 mg kg-1 (Alloway and Steinnes, 1999). Repeated applications of P fertilizers
increased soil solution concentrations of both Cd and Zn in field and laboratory
experiments (Lambert et al., 2007). Zinc and Cu are chemically similar and may compete
for binding sites in the soil system and for uptake and translocation within the plant
(Christensen and Huang, 1999). Addition of Zn can increase Cd desorption from soil and
may increase Cd concentration in the soil solution (Christensen, 1984). However,
competition between Zn and Cd for uptake and translocation by the plant may reduce
crop concentration of Zn in the above ground plant material (Grant et al., 2000; Jiao et
al., 2004; Zhao et al., 2005). Therefore, presence of Zn reduces the Cd accumulation in
crops.
2.14.3 Influence of P on uptake of Cd, Zn and Cu in plants
Addition of P fertilizer to soils also influenced availability of Cd and Zn through
its effects on soil pH, ionic strength, Zn concentration and plant growth. To explain
whether increase in the Cd concentration was due to contamination of fertilizer or due to
P effect on Cd, some researchers used reagent grade fertilizer. However, no significant
difference was observed between the Cd concentrations in durum wheat with commercial
compared with reagent grade P fertilizers (Choudhary et al., 1994; Jiao et al., 2004).
Under controlled conditions, Choudhary et al. (1994) applied reagent grade monoammonium phosphate to wheat which increased Cd and decreased Zn concentration.
Similarly, in a pot study, reagent grade triple superphosphate and mono-ammonium
phosphate both increased Cd concentration in flaxseed and durum wheat grain (Jiao et al.,
2004).

27

Fertilizer effects on Cd concentration in crops might be greater in pot studies than under
field conditions as high root density and the reduced soil volume in pot culture can
accentuate fertilizer effects (Guttormsen et al., 1995). Under field conditions, an annual
addition of fertilizer did not increase Cd concentration in cereals (Singh and Myhr, 1998).
Concentration of Cd in durum wheat at several locations across the Canada was increased
by application of P fertilizer. This increase was unrelated to the concentration of Cd
present in the fertilizer (Grant et al., 2002).
Phosphorus fertilization reduced Zn concentration in the plant tissues (Grant and
Bailey 1998; Jiao et al., 2004) due to interactions between Zn and P in the soil (Lambert
et al., 2007), interference of P with the Zn uptake process, or dilution of Zn concentration
in tissue from a yield response to applied P. Zinc and Cd competed for binding sites in the
soil system and for transport sites at the root cell plasma membrane (Hart et al., 2002;
Zhao et al., 2005). There may also be competition between Zn and Cd for sites related to
Cd transport out of xylem parenchyma cells into the xylem system, or Cd loading into and
out of phloem cells in the plant (Hart et al., 2002). Applications of Zn fertilizer up to 5.0
kg Zn ha-1 were found to decrease the Cd concentration in wheat grain grown in Zn
deficient soils in Australia and no further significant decreases in Cd concentration in
grain occurred at higher rates of Zn applied (Oliver et al., 1994; Choudhary et al., 1994;
Grant and Bailey, 1997).
The interactions between Zn, Cd and P had a significant effect on their
accumulation in both shoots and roots (Imtiaz et al., 2006). Zinc concentrations in 6
wheat cultivars increased when the P level in the soil was increased from 0 to 25 mg kg-1
except for one wheat cultivar. Zinc-P interactions showed that Zn concentrations in the
plant shoot decreased with each higher level of P (250 mg kg-1 soil). Phosphate and Zn
application also reduced Cu concentrations in the plant tissues significantly in most of the
cultivars
Panwar et al. (1999) studied the interactive effects of Cd (0, 2.5, 5, 10, and 20 mg
Cd kg-1 soil) and P (0, 20 and 40 mg P kg-1 soil) in cowpea and mungbean in alkaline
sandy soil. He found that Cd concentration in plants decreased with increasing levels of P
in soil. Application of Cd decreased dry matter yield significantly. In soil treated with 5
ppm Cd, mungbean Cd concentration was 3.8, 3.3 and 2.4 mg kg-1 at soil P level of 0, 20
and 40 mg kg-1 respectively. Cadmium and P concentration range in plant tissues was
0.20-0.27 and 0.15-0.21 mg kg-1, respectively. The decrease in tissue Cd concentration
28

with increasing soil P was mainly attributed to increased dry matter yield (Jalil et al.,
1994), reduced photosynthetic rate (Sandalio et al., 2001; Ekmekci et al., 2008), internal
water deficit in shoot system due to poor root development (Sanit di Toppi and Gabbrielli, 1999; Balestrasse et al., 2001).
In the sandy soil, the added Cd was readily available to plants due to the inability
of such soil to adsorb metal in large amounts (Christensen, 1984). However, addition of
DAP to a sandy soil reduced the Cd availability to plants and Cd precipitated due to the
poor buffering capacity of the soil (Levi-Minzi and Petruzzelli, 1984).
Zinc might inhibit Cd translocation from roots to shoots. Zhao et al. (2005)
reported the effect of Zn (0, 1, 5, 10 mg kg-1 soil) and P (0, 10, 50, 100 mg kg-1 soil)
application on growth and Cd accumulations in shoots and roots of winter wheat
seedlings. Phosphorus and Zn showed complex interactions in their uptake. Cadmium in
shoots decreased significantly with increasing Zn except at P addition of 10 mg kg-1. In
contrast, root Cd concentration increased significantly except at Zn addition of 5 mg kg-1.
Cadmium concentrations increased in shoots but decreased in roots with increasing P
supply.
Shukla and Singh (1979) observed decreased concentration of Cu in wheat grain
and straw when exposed to P (0, 25, 50, 100 and 250 ppm) and Cu (0, 2.5, 5, 10 and 50
ppm) in all possible combinations. The yield, P and Cu concentration were increased with
the application of Cu up to 5 ppm with P, and P up to 50 ppm with Cu compared with P
or Cu alone. In greenhouse study, Haldar and Mandal (1981) concluded that application
of P (0, 50 and 100 ppm) decreased Zn concentration in shoots and roots at all the levels
of Zn (0, 5 and 10 ppm) application. Copper concentration in shoots and roots decreased
with increasing levels of P or Zn application. Application of 100 ppm P decreased 13.6
and 15.4% Cu concentration in shoots and roots respectively. Application of P increased
the dry matter of shoots and roots however, the total uptake of Zn, Cu, Fe and Mn by
shoots and roots showed a declining trend.
2.15 Influence of N fertilizers on metal phyto-availability
Nitrogen fertilizers also influence movement of Cd, Cu, Zn and other metals to the roots,
rhizosphere composition and root growth. Cadmium in crops have also been reported to
increase with N fertilizers at agronomic rates of application (Mitchell et al., 2000;
Kashem and Singh, 2002) due to an increase in plant-available Cd caused by a fertilizer29

induced reduction in soil pH. Ammonium in fertilizer was responsible for higher Cd
concentration in crops on account of reduction in soil pH possibly due to nitrification or
plant uptake of NH4+ (Grant et al., 1999; Erikkson 1990). Conversely, concentration of
Cd, Cu, Zn, and Fe in rice shoot grown in contaminated soil (2 mg Cd, 10 mg Cu and 120
mg Zn) were not affected by the application of NH4NO3, NH4SO4, or NH4Cl source of N
whereas, NH4H2PO4 reduced Zn, and increased Cu (Ohtani et al., 2007). Landberg and
Greger (2003) in soil and nutrient solution studies observed a decrease in Cd
concentration in wheat grain with increasing N rates and N concentration in wheat grain
possibly due to dilution effect caused by an increase in biomass production. In long term
experiment Gavi et al. (1997) found no effect of N fertilization on grain Cd concentration.
Effects of N fertilization are not only due to pH changes. In pot studies, Cd and Zn
concentrations of oat increased with N fertilization, although pH was not decreased
(Kashem and Singh, 2002). Cadmium concentration of durum wheat increased with N
fertilization in the order Ca(NO3)2 = urea > (NH4)2SO4, with the increase unrelated to the
pH effects of the fertilizers (Brown et al., 1994). Cadmium was bound to cation exchange
in mucilage excretion of maize root tips (Morel et al., 1996) and to sites in root cell walls.
Pot studies using urea as N source increased Cd in durum wheat (Mitchell et al.,
2000). Fertilization effects may be greater in pot studies where root volume is restricted
but N fertilization has also been shown to increase crop Cd concentrations under field
conditions (Grant and Bailey 1998). Wangstrand et al. (2007) reported that each 10 kg of
applied N (in range of 100-235 kg N ha-1) as calcium ammonium nitrate increased wheat
grain HNO3 extractable Cd concentration by 0.001 to 0.003 mg kg-1 in field experiments
and Cd concentration was positively correlated with N concentration in grain.
2.16 Influence of P on sorption of Cd, Zn and Cu
The concentration of metals in soil solution depends upon many factors like pH
(Adriano, 2001), the nature and concentration of organic and inorganic ligands,
simultaneous presence of competing metals (Bolan et al., 1999; Naidu et al., 1994;
Kookana and Naidu, 1998; Harter and Naidu, 2001). The ability of soils to grasp metal
ions and interaction among them is of special interest and has consequences for metal
availability and environmental remediation of polluted soils. The sorption study of metals
is of supreme importance to understand how heavy metals are transferred from a liquid
mobile phase to the surface of a solid phase under the influence of applied P.
30

2.17 Sorption in soils

The term sorption describes the removal of metals in solution by the solid phases
(Chen et al., 1997) and includes all retention mechanisms controlling availability and
mobility (Serrano et al., 2005). Sorption includes adsorption, surface precipitation, and
fixation (Apak, 2002).
2.17.1 Factors influencing sorption of heavy metals
Soil type, metal concentration and their speciation, soil pH, solid to solution mass
ratio, and contact time, presence and concentration of other ligand ion pairs (Cavallaro
and McBride, 1980; Kent et al., 2000; Lal and Minhas, 2005) and metal properties such
as the radius number and electro-negativity of each element (Wahba and Zaghloul, 2007)
are the various parameters that influence heavy metal sorption and their distribution
between soil and water phases. During heavy metal sorption, the major interfaces in soils,
are organic and inorganic colloids (Bradl, 2002; Wong et al., 2007), metal oxides and
hydroxides (Apak, 2002), metal carbonates and phosphates (Bolan et al., 2003).
Relative selectivity is different for metals which depend on the factors given at
the beginning which may change the metal adsorption isotherms. The distribution
coefficient (Kd) is a useful parameter for comparing the sorption capacities of different
soils (Martin-Garin et al., 2002; Magesan et al., 2003; Voegelin and Kretzschmar, 2003).
In adsorption experiments CaCl2, NaCl and NaNO3 background electrolytes are
generally used in calcareous soils. For alkaline soils 0.01M CaCl2 is preferably used as
back ground electrolyte. Competition effect of monovalent metal in background
electrolytes is very little on adsorption of heavy metals; however, Ca ions do suppress
adsorption of Zn, Cu and Cd on Fe oxide (Cowan et al., 1991). The carbonate in
calcareous soils effectively immobilizes Cd and Cu by providing an adsorbing surface
and by buffering pH (McBride and Bouldin, 1984; Dudley et al. 1991).
2.17.2 Sorption behavior of Cd, Cu and Zn
Langmuir sorption equation is more popular among soil chemist for metal
adsorption (Sposito, 1982; Harter, 1983; Christensen, 1984; Wang and Dustin, 2005). It is
applied for adsorption of heavy metals ions onto soils and soil components in the form
qi=b(Kci) /1+Kci. If the Langmuir equation is fitted, the measured data should fall on a
straight line with slope of -K and x intercept of bK. Cadmium adsorption was found fast
process where more than 95% of the adsorption occurred within the first 10 minutes and
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equilibrium was attained within 1 hour (Santillan-Medrano and Jurinak, 1975). Cadmium
may be precipitated as CdCO3 form in sandy soils with low CEC and organic matter
while pH controlled Cd solubility at high Cd concentrations (McBride, 1980). The cations
like Ca2+ and Zn2+ competed with Cd2+ for sorption sites or favored desorption of Cd
from soils (Santillan-Medrano and Jurinak, 1975). In field soils, Cd2+ was preferably
adsorbed over Ca2+ (Cowan et al., 1991).
Soil minerals and PO4 are also most important sinks for Cu after Fe and Mn
oxides, soil OM, sulfides and CO3. Soil OM forms both soluble and insoluble Zn- humate
complexes. Zinc sorption increased with increase in soil pH (McBride, 1989). The Zn
also formed complexes with Cl-, PO43+, NO3-, and SO42- (Lindsay, 1979). Zinc sorption
was enhanced by H2PO4, compared with Cl- and NO3- in acid soil but generally decreased
in calcareous soils (Wang and Dustin, 2005).
2.17.3 Competitive adsorption of Cd, Zn and Cu
Sorption of Zn and Cu followed Freundlich equation in different soils and was
more affected by pH than CEC. The presence of Cu at low concentrations up to 15 g L-1
prevented Zn adsorption in one soil (Kurdi and Doner, 1983). In contrast, Cu was found
ineffective in competing for Zn adsorption sites over a pH range of 5-7 by McBride and
Blasiak (1979). Copper was unable to block adsorption of Zn proving that Zn and Cu
were preferentially adsorbed at different sites. In competitive sorption behavior of Cd,
Cu, Ni, Pb and Zn in concentration range from 10 to 200 M L-1, adsorption isotherms
showed that metal sorption was linearly related to its concentration in the equilibrium
solution. Selectivity between metals resulted in the following affinities based on their
distribution coefficient (Kd) values and amount sorbed, as Pb > Cu > Zn > Ni or Cd
(Veeresh et al., 2003; Usman, 2008).
2.17.4 Influence of P on sorption of Cd, Zn and Cu in soil
Main input of PO43- is phosphate fertilizer, especially DAP in Pakistan. Anioninduced metal adsorption due to increased negative charges has been reported for a
number of cations. It has been shown that Zn2+, Cd2+ or Cu2+ adsorption by variable
charge components in soils, such as Al and Fe oxides, can be enhanced by low or
moderate enrichment of oxides with P (Bolan et al., 1999).
Recently there has been increasing interest in the immobilization of Cd, Pb, Zn etc
in soils using soluble P compounds such as (NH4)2HPO4 or CaH2PO4 (Pierzynski and
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Schwab, 1993; Bolan et al., 1999; Rehman, 2008). Application of urea and DAP
fertilizers changed the distribution of Cu, Cr and Ni among fractions of soil. Diammonium phosphate at 10 g kg-1 was found the effective treatment by Basta and
McGowen (2004) for immobilizing of Cd, Pb and Zn with reductions of 94.6, 98.9 and
95.8%, respectively compared with respective total metal species. But this application
rate was much higher than agronomic application rate.
An enhanced adsorption of Cd, Pb and Zn by application of DAP, (NH4)2HPO4,
due to increase in pH is reported a possible mechanism for decreased metal activities
(Levi-Minzi and Petruzzelli, 1984) but McGowen et al. (2001) explained it as
precipitation of Cd and Zn as Cd3(PO4)2 and Zn3(PO4)2. Urea and K2HPO4 decreased the
mobility of the Cd, Pb and Zn in the soil (Liu et al., 2007).
It is not clear how P interacts with Zn in soils (Norvell et al., 1987). Treatment of
soils with K2HPO4 increased available and exchangeable Zn forms (Shuman, 1988). Zinc
sorption was decreased by H2PO4 in three out of four calcareous soils as predicted by
Langmuir maxima under various ionic backgrounds. In calcareous soils, the phosphate
retained 10-25% more of the sorbed Zn in the non labile pool. Zinc sorption could be
impacted by phosphate-Fe oxide interactions. Soil treated with P (0-2000 mg kg-1)
retained 42% more of the added Zn (0-200 mg kg-1) compared to that with the control
treatment in slightly acidic sandy loam soil (Agbenin, 1998). At neutral pH, Cd sorption
in the absence of P was related to net negative surface charge of soils.
Sorption of P increased negative charge on the soils but increase per unit amount
of P added decreased with increasing P sorption (Pardo, 2004). Soils negative charges
increased significantly with increasing phosphate sorption. Negative charges increased in
Andisols from 25.4 to 62.3 mmolc kg-1 for 0.0 and 140 mmolc kg-1 P added, respectively
(Pardo, 2004). Phosphate application time had a marked impact on Cu and Cd adsorption
and longer contact time resulted in more reduction of Cu and Cd adsorption and also
suppressed the maximum adsorption of Cu and Cd (Li et al., 2006).
It is clear from above review that application or pre-treatment of soil with P or its
level in soil plant system influence metal availability through P essential metal
imbalances in plant nutrition, metal sorption by phosphate compounds itself, phosphate
induced metal sorption and desorption, precipitation as metal phosphate with solution P.
Dissimilar results, i.e, mobilization and immobilization of metals in soil have been
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reported under P treatment. In city effluent contaminated soils, farmers generally applies
nil to half of the recommended dose of P to cereal crops than the normal soils. So
influence of agronomic levels of P on metal sorption and uptake by cereal and legume
crops in contaminated soil have environmental as well as health consequences.
Precipitation and P induced sorption is considered one of the primary mechanisms for the
immobilization of metals.
Our present understanding is that effluent is a huge source of irrigation water with
some to considerable plant nutrition. If not properly used, it is of environmental concern.
Heavy metal buildup in soils is another serious issue and needs action of industries
owners, policy makers and farmers to reduce the risk of contamination. More sitespecific
research is needed to overcom future crises of water shortage along with its monitoring
and safe use. The scientists should go to the technology package investigation for
reducing the metal contamination in food chain. Soil is an ultimate sink for contaminants
so the social attitude should be positive for effluent farming. Phosphorus fertilizers are
another source of heavy metals such as Cd, so its long term use needs the understanding
in addition to its effect on uptake of other metals.

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