Introduction Pakistan is an agricultural country.

Agriculture is the single largest sector of Pakistanis economy with 21 percent contribution to GDP and employing about 44 percent of the workforce. More than two-thirds of Pakistans population lives in rural areas and their livelihood continue to revolve around agriculture and allied activities (Economic Survey of Pakistan, 2007-2008). When agriculture is taken in to account, the use of chemicals and pesticides to enhance the quality of crop naturally comes to our mind. The primary role of agriculture is to produce a reliable supply of wholesome food to feed the burgeoning world population safely and without adverse effects on environment. The countries like Pakistan where agriculture is the backbone of economy, has dictated the increasing use of agrochemicals to meet the growing food demands. Among the commonly employed agrochemicals, shortly degradable group of compounds, i.e. organ phosphorous pesticides (OPPs) are generally preferred over their more environmental persistent counterparts, i.e. organochlorine pesticides (Cai et al., 2006). Ecologically and from the environmental prospective, it is important to understand the adsorption of soil-applied pesticides since it controls other processes such as leaching into groundwater, uptake by living organisms, transport into surface waters and the rate of volatilization of pesticides (Lesan and Bhandari, 2003). Understanding the behaviour of pesticides in the environment is of great importance for their application and regulation. It is important to use the sorption and desorption mechanisms of pesticides applied onto soil for understanding and predicting their fate in the environment (Hafeez et al ., 2005). Soils are classified according to the proportion of mineral particles of different sizes present. Pesticides become readily absorbed on to soil particles, in this way pesticide

persists much longer, and includes physical and chemical adsorption, hydrogen bonding, and forming metal complexes. Thus, knowledge of the pesticide adsorption desorption characteristics of soil is necessary for predicting their mobility and fate in soil environments. The application of pesticides has both benefits and risks in the environment. With the proper management, benefits can be maximized while minimizing other risks. Pesticides are one of the major organic contaminants in the environment because of its heavy use in agriculture and industry. Soils play an important role in the environment by controlling the fate and availability of organic compounds because of their sorption capability (Chiou et al ., 1998; Gunasekara, and Xing, 2003). Adsorption is a very complex process. It is affected by both soil properties, such as organic content of the soil (Lamber et.al., 1965), composition of soil (Pianke and Chester, 1973), soil water content (Grover and Hance, 1970), and bulk density as well as chemical properties such as chemical structure and water solubility. Adsorption is probably the most important mode of interaction between soil and pesticides and controls the concentration of the pesticide in the soil liquid phase. Adsorption processes may vary from complete reversibility to total irreversibility. The extent of adsorption depends on the properties of soil and the compound, which include size, shape, configuration, molecular structure, chemical functions, solubility, polarity, polarizability and charge distribution of interacting species, and the acidbase nature of the pesticide molecule (Bailey and White, 1970; Senesi, 1992; Pignatello and Xing, 1996). Adsorption processes cannot be predicted by simple universal rules. Experiments are required since different chemicals have different adsorption affinities to different soils. When a pesticide is applied to a crop or soil, it enters a dynamic ecosystem and immediately begins to be moved from one part of the system to another, degraded in situ or moved out of the system into other systems. It is important to determine the

relative importance of these processes, because, whereas pesticides that are completely degraded become harmless, those that move to other systems and persist may do some environmental damage. In order to achieve a good understanding about fate of pesticide in soil, study of adsorption process is essential. Adsorption was defined by Jury (1987) as, "the bonding of a solute to adsorption sites on the soil solids, either soil mineral surfaces or organic matter surfaces". Several studies in Pakistan (Bano and Siddique, 1991; Jabbar et al., 1993; Tehseen et al., 1994; Sanpera et al., 2002; Tariq et al., 2006) have reported the detection of pesticides in soils and their findings are similar to the researchers of developed world as have aforesaid (Abrahams, 2002; Burauel and Bassmann, 2005). In Pakistan, the province of the Punjab comprises of four distinct crop zones. In the north lies the rain fed area, next to it is the rice zone, in the centre is the mixed crop zone where sugarcane and maize dominate, while the southern part houses the cotton zone (Ahmad et al., 1994). Cotton occupies a unique position in the agrarian economy. As the country has the potential to be become a key player in the global cotton and textile market place, the Government has been giving priority to research and development programmers focusing on both the quantitative and qualitative improvements in cotton. Cotton crop was targeted to be sown in the area of 2.93 million hectare with a production target of 9.7 million bales against the last years achievement of 11.24 million bales. However, despite a notable increase in cotton production over the years, use of pesticides on the whole downgrade the quality of environment. It is recognized that the soil is also a potential pathway of pesticide transport to contaminate water, air, plants, food and ultimately in the human via, runoff and subsurface drainage; interflow and leaching; and the transfer of mineral nutrients and pesticides from soils into the plants and animals that constitute the human food chain (Abrahams, 2002).

Pesticides which are very persistent in soil, slowly break down and result in source of contamination (Stephenson and Solomon, 1993). Organophosphorus insecticides have been observed to be less persistent with a half-life ranging from 1 to 3 weeks. (Mehr and Sethi, 1992; Suri and Joja, 1996). In Punjab and Sindh Provinces, it is estimated that 5000 tons of obsolete pesticides and 3000 tons of contaminated materials are stored in 1900 warehouses located in a thickly populated area, and residents have complained of foul smell, strange taste in the water and recurring headaches for sometime (Environmental News Service, 1998; JICA, 1999). Generally, organophosphorus pesticides are much more unstable under alkaline conditions. The hydrolysis rate increases steeply at pHs greater than 8. There is a tendency for many of the O.P. pesticides to be strongly adsorbed to soil (Harris, 1964; Sharom et al., 1980). Thus, the mobility of O.P. pesticides is limited after application even though they are more water soluble than the O.C. pesticides (Graham- Bryce, 1969). Soil type may be the most important factor affecting the persistence of O.P. pesticides. Organophosphorus pesticide residue levels are generally low and are not accumulated in mineral soils (Carey et al., 1979). On the other hand, they may accumulate in soils with high organic matter. Currently, Organophosphorus pesticides (OPs) enjoy wide use in the world for the pest control with Organochlorine pesticides (Baker et al., 1996; and Wang et.al., 2006) which leads to increased world food production. These Organophosphorus pesticides are also widely used in Pakistan for controlling the agriculture pests. Although OPPs, as a whole, are not the most toxic pollutants, but their improper use may also result in the presence of residues of these substances in agricultural products, such as fruits, and vegetables (Driss et al., 1993).

The organophosphorous pesticides are among the most commonly detected pesticides in water streams around the world by watering or rinsing of rain and have potential pollution impact on the environment (Caro and Lorenzo, 2001). However, while the fate of organophosphate compounds is not clear (Gitahi et al., 2002), and FAO/WHO has not established maximum residue limits (MRL) for triazophos (Li et al., 2008), the most serious concern relating to the organophosphates is that they are still suspected to have serious toxicological impacts upon terrestrial wildlife and man (Gitahi et al., 2002). So it is necessary to decrease their concentration from water leading to a cleaner and safe ecosystem, if the complete removal is not possible. Triazophos belongs to the organophosphate class of pesticides. Triazophos is a common name for O,O-diethyl-O-1-phenyl-1H-1,2,4-triazol-3-yl phosphorothioate). Triazhphos is a moderately toxic chemical that is a broad spectrum and no systemic Organophosphorus pesticide that is used in large quantities throughout the world (Rani et al., 2001). Triazophos (TAP) is frequently used OPPs in agricultural field applications of cotton, wheat, rice and sugarcane crops in Pakistan due to their effectiveness pest, low price, and high toxicity besides low environmental persistence. (Rodrigues-Mozaz et al., 2004; Goncalves and Alpendurada, 2002).

It was introduced by Hoechst A.G. and its insecticidal properties were first described by M. Vulic, et al in 1970.

It is used to control aphids, bollworms, red spiders, fruit borers, leaf hoppers and cutworms on a variety of crops, such as fruits, cotton, maize, wheat, cereals and vegetables and is particularly effective in the control of plant nematodes (Li et al., 2008). They (Krawinkel, 1989; Ahmad et al., 2002b) have also documented nonoccupational pesticide exposure accidents due to pesticides left on commercial foods, home germicides, toilet cleaners, termicides and suicides. The same situation has already been recognized that people living in agricultural areas may have significant public health consequences by nonoccupational exposure (Scarborough et al., 1989; Simcox et al., 1995). The retention and mobility of a pesticide in soil is determined by the extent and strength of sorption reactions, which are governed by the chemical and physical properties of the soils and pesticides involved. The sorption interactions of pesticides in the soil environment may involve either the mineral or organic components, or both (Bailey and White, 1964; Hayes, 1970; Riise et.al., 1994; Arienzo and Buondonno, 1993; Jenks et al., 1998; Bekbolet et al., 1999) Cotton field workers in Southern countries are most vulnerable because of lack of awareness of pesticide impact, lack of strict implementation of safety measures, lack of readily available running water, exposure to pesticide-contaminated water for drinking or cleaning. Pesticides also affect wildlife, domestic animals, and biological diversity. Given the prevailing agronomic wisdom of the times, cotton farmers in the last half-century sought to transform the ecological system to eliminate insects altogether. Recently, the experiments at the Central Cotton Research Institute (CCRI), Multan, reveal that the two major cotton pests, the American bollworm and the whitefly have developed resistance against common pesticides (Ahmad et al., 2007). In countries like Pakistan another source of pesticide poisoning is the lack of information on pesticide handling. There are reported instances of obsolete and

banned pesticides, lack of information or safeguards for cotton pickers, and improper disposal of pesticide containers. The Agricultural Pesticides Act 1972, which regulates the use of pesticides in the country, does not address the issue of safety standards, and lack of information with farmers as well as chemical industry workers. Recently, it is also reported that approximately three million people are poisoned and 200,000 died each year around the world from pesticide poisoning whereas a majority of them belongs to the developing countries (WHO, 1990; FAO, 2000). The dilemma is due to those pesticides, which developing countries have banned due to their toxic effects, and are still being used in the developing countries (Wilson and Tisdell, 2001; Sankararamakrishnan et al., 2005). It is also believed that in developing countries like Pakistan, the incidence of pesticide poisoning may even be greater than reported due to under-reporting, lack of data and misdiagnosis (Forget, 1991; Tariq, 2005) Contamination of soils with toxic organic chemicals is one of the major environmental problems. Bioavailability of organic chemicals in soils is important for assessing the significance of soil contamination with these chemicals. It is essential to have a thorough understanding of their behaviour under different conditions to be aware of any possible adverse effects and to know how they can be minimised. The degree of toxicity of pesticides to humans and other organisms differs considerably between each type of pesticide: a small amount of one pesticide might cause severe illness or even death, while larger quantities of another pesticide might have little or no effect, even if ingested. A pesticide might also have selective toxicity, causing death of one type of organism, but having little or no effect on other types of organisms (Hassall 1987). Some pesticides degrade quickly on the crop and in the soil, whereas others may persist in one form or another for longer periods. These persistent pesticides, which are mostly lipophilic, accumulate in animal fat and in particular tissues such as liver and kidneys, and the pesticide levels become higher than those in crops. Continuous consumption of either animal fat, liver, or kidney might caused serious health problems (Oudejans, 1991).

Significance: This research focuses on the ability of natural soil to adsorb triazophos under different environmental parameters. It is significant in the cure of soil contaminated with organic compounds. It will help in developing a baseline data for adsorption of pesticide at variable pH and contact time.

Objectives: To detect the concentration of Triazophos in topsoil. To determine the effects of pH, organic matter, dose and time on the pesticide adsorption. To determine the adsorption time of the pesticide. To determine the concentration of metals and metal speciation. To assess the toxicity level of pesticide in soil.

Experimental The present study is aimed to investigate the adsorption behavior of pesticide Triazophos on the soil collected from Multan, Punjab. The soil was characterized for its physicochemical properties, total metal content, metal speciation nitrates, phosphates and sulfates etc. the synthetic batch experiments were conducted at variable pH and dosage of the pesticide to study the adsorption behavior under these variables. Reagents The stock solution (1N each) of Ni, Zn, Pb, Cd, Cr and Cu were prepared by dissolving 2.808g, 2.194 g, 2.24 g, 7.695 g, 2.664 g and 2.496 g of NiSO4.7H2O, Zn(CH3COO)2, Pb(CH3COO)2, CdSO4.8/3H2O, CrCl3.6H2O and CuSO4.5H2O respectively, up to 1 liter of the solution with the distilled water. All of the reagents used were of Analytical Reagent (AR) Grade. The standard stock solutions (1000 ppm) for the determination of sulfates, phosphates and nitrates were prepared by dissolving 7.102 g of Na2SO4, 4.394 g of KH2PO4 and 3.609 g of KNO3 up to 1 liter of the solution with distilled water. The working standards of different strengths for sulfates, phosphates and nitrates were made by dilution method. Calibration curves were obtained against the working standards. The standard and working solutions for the commercial and standard Triazophos were prepared accordingly for calibration curves. The commercial Triazophos was obtained from (Ali Akbar Group, Pakistan), whereas standard used was of (Dr. Ehrenstorfer GbmH).

Sampling Area The soil samples for this study were obtained from Multan, Punjab. The city of Multan is located in southern Punjab province at almost the exact centre of Pakistan. The area around the city is a flat plain and is ideal for agriculture. There are many canals that cut across the Multan District, providing water from nearby farms. This makes the land very fertile. The city also witnesses some of the most extreme weather in the country. During summer time, temperatures reach approximately 54 C (129 F), and in the winter 1 C (30.2 F) has been recorded. The average rainfall of the area is roughly estimated as 127mm. Wheat, cotton and sugarcane are the main crops grown in the district. Sampling Top soil samples (4-5") were collected from three different cotton fields of Multan. The sampling site is identified in the figure 1.
Figure 1 Sampling site

10

Three cotton fields from Kot Abbas Shaheed, Multan were selected for the purpose of sampling. They were coded as MCF-1, MCF-2 and MCF-3. The GPS data of the three sampling fields is 71.38426 latitude (E) and 30.17043 longitude (N), 71.38789 latitude (E) and 30.16882 longitude (N) and 71.38743 latitude (E) and 30.16926 longitude (N). A total of 30 sub-samples were collected in X pattern from each of the three cotton fields. The field temperature and pH of the samples were also noted. Composite soil samples representing each field were prepared by thorough mixing of airdried sub-soil samples. Three (3) composite soil samples (sieved through 2mm) were analyzed separately for its physicochemical properties. Potential for hydrogen ion (pH) and Electrical conductivity (EC) was measured using the pH (720, inolab, Germany) and EC meter (Cyber Scan Con 500, Singapore). Color was noted by comparing the Munsell color chart (See appendix). Bulk density and soil moisture content was determined by the standard procedures. The soil moisture content was calculated with the help of the following formula: Soil moisture content = Wet soil Dry soil x 100 Dry soil Soil organic matter was determined by Walkley Black method (Walkley, 1935). The percentage of organic matter was calculated by using the following formula: % Organic Matter = % Total C x1.72 0.58 The % total carbon was calculated from: %C = (B S) x M of Fe2+ x 12 x 100 g of soil x 4000 Where B is the ml of Fe2+ solution used to titrate blank, S is the ml of Fe 2+ solution used to titrate sample.12/4000 = milli equivalent weight of C in g.

11

Sulfates, nitrates and phosphates concentration was determined by using the UV visible Spectrophotometer (UV-1601, Shimadzu) at wavelengths 420nm, 430nm and 882nm respectively. The chlorides were calculated by multiplying the volume of the acid used (HCl) with 354.3. Metal Speciation Chemical species content for six selective trace-metals i.e. Zn, Pb, Ni, Cd, Cu and Cr was experimentally determined through sequential extraction into exchangeable, carbonate bound, Fe/Mn oxide bound and organic matter bound fractions (Tessier et al, 1979). The exchangeable fraction was extracted by shaking 8g of air-dried soil with 64 ml of 1M MgCl2 for 1 hour. The mixture was then centrifuged and filtered into filtrate A and residue A. the residue A was shaken with 64 ml of 1M CH 3COONa adjusted to pH 5 with CH3COOH for extraction of carbonate bound fraction. The mixture was centrifuged and filtered into filtrate B and residue B. The residue B was extracted for Fe-Mn oxide with 160 ml of 0.04 M NH 2OH.HCl in 25% CH3COOH (v/v) for 5 hours at 960C with occasional agitation, centrifuged and filtered into filtrate C and residue C. The residue C was extracted for organic bound fraction with 16 ml of 0.02 M HNO3 and stepwise addition of 72 ml of 30% H2O2 at pH 2 on water bath for 2 hours. After cooling, 40 ml of 3.2 M NH4OAc in 20% HNO3 was added to the mixture, diluted with distilled water to 160 ml, shaken for 30 minutes, centrifuged and filtered into filtrate D and residue D (residue was discarded). The extracted filtrates A, B, C and D were then analyzed for the determination of concentration of exchangeable, carbonate bound, Fe/Mn oxide bound and organic matter

12

bound chemical species, respectively in the soil samples for six elements with the help of the Flame Atomic Absorption spectrophotometer (SpectrAA220, Varian, Australia). Total metal concentration for six elements in the soil samples was also determined. For this, 2 g of each soil sample was digested in 50 ml of 0.1 M HCl. The mixture was stirred, diluted to 100 ml with distilled water and was then filtered. The filtrate was analyzed for the total metal concentration. Batch Experiments The batch experiments were designed to determine the adsorption capacity of the cotton field soil samples towards the selected pesticide. For experimental purposes, the commercial pesticide Triazophos was used, however pesticide standard was used for the calibration. The active ingredient (a.i) in commercial pesticide was determined experimentally from the calibration curve of the standard pesticide. It was found to be ranging from 0.020.056. Standard active ingredient was found to be 11.2%. Nine separate sets of batch experiments were conducted for the adsorption studies at variable pH of 4, 7 and 10; different masses of soil (1 g, 3 g and 5 g); and varying concentration of the induced pesticide (0.5 ppm, 1 ppm and 1.5 ppm). For each batch, sample was extracted at regular intervals of two minutes till the equilibrium is attained. Each extract was run on the pre-calibrated UV-Visible spectrophotometer (UV-1601, Shimadzu, Japan) at 247 nm (max for pesticide) and absorbance was noted. Concentration of each extract was determined from the standard calibration curve.

13

Results and Discussion Physicochemical analysis: This research was carried out to study the adsorption capacity of cotton field soil samples of Multan, Punjab for the pesticide Triazophos. The research has two parts. In the first part, the soil is characterized for its physicochemical properties to assess the physical and chemical nature of the soil. The other part is concerned with the actual adsorption properties. Batch experiments were conducted to study the adsorption behavior of the pesticide and different factors affecting it. The soil is characterized to determine the pH, Electrical Conductivity, Color, Bulk Density, content of moisture, organic matter, total metal, chemical species, phosphates, nitrates, sulfates, carbonates and chlorides in the soil. The results of physicochemical analysis of different soil samples are summarized in the table 1. It can be seen that pH falls in the alkaline range and does not vary widely. The pH ranges from 7.75 to 8.03 with an average value of 7.91. The alkaline pH is attributed to the calcium carbonate content which is up to 50% in most of the Pakistani soils (Memon et. al, 2001). The present study results of pH are supported by other studies by (Tirmizi et. al, 2005) reporting that the pH range of cotton growing areas of Punjab is 7.3-8.4 and 8.0-10.60 (Abid, et. al, 2003). The results indicate that the soil of MCF-1 has relatively more conductivity than the other two samples. Higher conductivity may be related to the lower pH and Bulk density of MCF1 as EC-pH and EC-Bulk density seem to be inversely related to each other. David (2001) established that the higher the EC, lower is the pH and bulk density of the soil (See Table 1). The density of soil samples is found close to each other in three different samples, showing an average value of 1.28g/cm3. The soil class of cotton field can be designated to be fine sandy loams and sand loams having the bulk density range of 1.28-1.44g/cm 3. It is

14

also reported in the literature that the bulk densities in excess of 1.6g/cm3 restrict the root penetration resulting in low conductivities (Memon, 2001).

Table 1. Physicochemical characteristics of different soil samples collected from Cotton fields of Multan

Physicochemical Characteristics Soil Parameter pH (at 250C) Electrical Conductivity (mS) Color/ Chrome value Bulk Density (g/cm3) Moisture Content (%) Organic Matter (%) Calcium Carbonate (%) Available Phosphorus (mg/kg) Nitrate Nitrogen (mg/kg) Sulfates as Barium sulfates (mg/kg) Chlorides (mg/kg) MCF1 7.75 11.75 Bright yellowish brown/ 7/6 1.26 0.13 0.08 48.4 0.5 18.45 0.75 460.59

Soil Sample Codes MCF2 8.02 5.79 bright yellowish brown / 7/6 1.31 0.10 0.06 50.3 0.45 9.35 0.5 425.16 MCF3 7.96 6.10 bright yellowish brown / 7/6 1.28 0.12 0.07 49.4 0.5 11.4 0.6 265.72 Average 7.91 7.88 1.283 0.12 0.07 49.4 0.48 13.05 0.61 383.82

15

Color of the soil samples, when compared to the Munsell Color Chart (See Appendix I) appears to be bright yellowish brown with the chrome value of 7/6. This color can be related to the reduced carbonates, phosphates and sulfide (Memon, 2001). The moisture content of MCF1 is almost 0.13% higher than the other two field soils. Higher moisture content facilitates more conduction of ions through soil resulting in more conductivity values and low density, also supported by Cherifi et al, (2009). The organic matter content is usually concentrated in the top soil (Stockfischa, 1999) and influences the bulk density through its low mass per unit volume. The present study results clearly show the closeness of organic matter content in three different top-soil samples of cotton field. It can be seen from table 1 that organic content is higher in soil where sulfates are higher in concentration, showing a direct relation to each other (Singh et al, 2004). The alkalinity of soil, which depends on the content of CaCO3 strongly influences the pH and vice versa. This is in conformity of the present study results (See Table 1). It is interesting to note the positive and negative correlation of pH with carbonates and phosphates, respectively. This relationship is clearly defined as the calcareous soils strongly retain P and consequently establish low P concentration in the soils (Sharif et al, 2000). The results indicate that the Nitrates concentration has a wide range (9.35-18.45mg/kg) in the soils. It shows an inverse relationship with the pH of the three domains ranging from 7.75 to 8.03 as nitrates are available over a wide range of pH 6.0 to 8.3 (Memon, 2001). It is interesting to note the positive correlation of nitrates and phosphates as both are the essential nutrients for plants. MCF1 showed remarkable higher nitrates concentration. It may be due to significantly higher electrical conductivity value in that particular domain.

16

The Sulfates did not show marked variation in three selected fields. It may be related to the insignificant difference in the organic matter content. Remarkably significant amount of chloride concentration is found in the soil and a direct relation with electrical conductivity is clearly visible, thus facilitating the movement of chloride ions through the soil media.

Metal speciation: Total metal content and chemical species of six metal i.e., Cd, Cr, Cu, Ni, Pb, Zn was determined experimentally following the sequential extraction procedure for the composite samples of three cotton field soils, separately. The results are summarized in Table 2. The average total metal content (mg kg-1) in soil samples of three different cotton fields showed the sequence as follow; Cr > Ni > > Zn 2.54 > Pb > Cu 0.18 > Cd 16.79 > 4.63 > 0.71 > > 0.091

The most abundant Cr is followed by Ni and Zn in all soil samples. This sequence is also supported in another study by Umoren 2009. The relative abundance of total metal content in three soil field samples is illustrated in Figure 2. It is interesting to note that the relative abundance of chromium and Nickel is correlated to their position in periodic table, the lower molecular weight elements shoed more retention in soil. It has been reported in literature that Chromium remains in soils as residual fraction for many years because of sewage sludge (Mcgrath et.al, 1992; Canet et.al, 1997; Walter and Cuevas, 1999; Chaudhuri et.al, 2003).The high distribution of Chromium in soil is also

17

attributed to its high sorption affinity to the solid phase (Gomez and Callao, 2006), thus
Trace Metal Metals chemical bound specie concentration (in mgkg-1) Bound to Bound to Exchangea Carbonate Total metal Fe-Mn organic ble bound oxide matter 0.3947 0.0240 0.3112 0.2727 0.1447 0.1021 0.2800 0.1178 0.5887 0.0243 0.0482 0.0095 0.3342 0.5896 0.1072 0.1816 0.1045 0.2544 0.4836 0.0920 Percentage (%) 11 27 52 10 0.1296 0.0289 0.4035 0.1517 0.1613 0.0871 0.2204 0.5236 0.2363 0.3783 0.0583 0.0044 0.3131 0.1855 0.1626 0.0916 0.0845 0.4134 0.1911 0.2340 Percentage (%) 9 45 21 25 17.1220 0.0486 0.1829 0.2189 0.0873 12.0356 0.3133 0.7328 0.3132 0.2086 21.2355 0.0129 0.3628 0.3089 0.1729 16.7977 0.1249 0.4261 0.2803 0.4688 Percentage (%) 10 33 21 36 3.5713 0.2084 0.2271 0.1734 0.2403 5.2479 5.0743 4.631 Percentage (%) 1.1244 0.2991 0.7210 0.7148 Percentage (%) 2.4589 2.3494 2.8362 2.5481 Percentage (%) 0.0311 0.0285 0.0893 10 0.638 0.1648 0.2489 0.3505 19 0.0122 0.1454 0.1609 0.1061 6 0.4982 0.1449 0.2900 32 0.2225 0.3806 0.2458 0.2829 16 0.2380 0.2824 0.2511 0.2571 13 0.6149 0.4124 0.4002 44 1.0437 0.9862 1.0776 1.0355 57 1.2531 1.3984 1.1409 1.2641 67 0.0978 0.0602 0.1327 14 0.1794 0.0571 0.2050 0.1471 8 0.2593 0.2554 0.2941 0.2696 14

Soil sample code MCF 1 MCF 2 MCF 3 Average MCF 1 MCF 2 MCF 3 Average MCF 1 MCF 2 MCF 3 Average MCF 1 MCF 2

Cu

Cd

Cr

Ni

MCF 3 Average MCF 1 MCF 2 MCF 3 Average MCF 1 MCF 2 MCF 3 Average

Pb

Zn

maintaining more Chromium in soil.

Table 2. Total metal content and Chemical fraction of trace metal in cotton fields of Multan

18

Figure 2. Relative abundance in percentage of total metal content in cotton fields of Multan

19

Table 3. Correlation matrix of total metal content of trace metal in cotton fields of Multan

Pb Cu Cr Ni Cd Zn

Pb 1 .777 .563 -.904 .582 .227

Cu 1 -.084 -.971 .964 -.437

Cr 1 -.155 -.345 .933

Ni

Cd

Zn

1 -.874 .212

1 -.660

20

However, chromium concentration showed variation in three different cotton fields. Soil sample MCF 2 has lowest chromium concentration as compared to other two fields. On comparison of total metal content in three different cotton fields soil samples, it is noted that MCF 3 showed relatively highest concentration of Chromium followed by Nikel which has a bit higher value in MCF-2. It may be attributed to the relatively higher organic matter content. The anomalous behavior seem to be dominated by other factors than organic matter, as factors like Phosphate and Sulfate, as reported in literature the negative correlation of Zn with Phosphorus compound (Norrish ,1975).

Positive correlation is depicted by Cd-Cu, Zn -Cr also reported by Umoren (2008), and Cu-Pb. However Cr-Pb show slight positive correlatoin. In addition positive correlation was also corresponding to the metal pairs of Zn-Pb, also supported by another study Dragovic et.al, 2008. On the other hand, results depict that other pairs i.e. Ni-Cu, Ni-Pb, Zn-Cu and Cd-Cr show relatively negative correlation. Although the total concentration of heavy metals in the soil is a useful parameter that indicates degree of contamination, it cannot predict the fate and the effects of any particular metal in the environment. The overall environmental consequences of the presence of heavy metals can be ascertained if the mobility and bioavailability of the metal could be estimated. The speciation of the metals into chemical fractions is shown in Figure 3. These fraction are obtained followed by of sequential extraction Tessier et.al (1979) are discussed below for each of the metals

21

Cadmium species: The present study indicates the presence of cadmium in carbonate bound, organic bound Fe-Mn oxide and exchangeable species average values (see Table 2) following the sequence of Carbonate > Organic bound > Fe-Mn oxide > Exchangeable 45% > 25% > 21% > 9% Relatively smaller value of organic complexes of Cd (Olajire et.al, 2003) is the contributing factor that Cd did not form stable complexes with organic matter (Sposito et.al, 1982). There is not significant variation in chemical species concentration in three different soil samples. Chromium species: It is interesting to note that chromium species exhibit almost the same sequence as for cadmium with a difference that Chromium is bound to organic matter in more concentration as compared to cadmium. However, the rest of the sequence is same. It may be related to the negative correlation of Cd-Cr pair (see table 3). However, Cd species shows significant variation of species concentration in three different soil samples that may be due variable contributing sources of Cr to soil (Fagliano and Savie et.al 1997). Relatively higher fraction of Fe-Mn oxide, chromium is reported due to its labile nature through water and other supporting systems (Jain et.al, 2007). Figure 4 (a) shows the percentage concentration of chemical species of chromium. A bit different percentage composition sequence is also reported by Mayur et.al, 2010 for Indian soil samples.

Lead species:

22

Lead Fe-Mn oxide fraction has second highest concentration comparing with other species. It has been investigated that Pb either co-precipitates with metal oxides or are adsorbed at metal oxide surface, thus retaining this chemical species into soil as long term source of contamination (Wasay et.al, 2001). The average percentage concentration of lead is found to be

Fe-Mn oxide > Exchangeable > Carbonate > Organic bound 57% > 19% > 16% > 8%

Copper species: Average percentage concentration of copper species is found to follow the pattern of Fe-Mn oxide > Carbonate > Exchangeable > Organic bound 52% > 27% > 11% > 10% It can be seen that most of the copper distribution is in Fe-Mn oxides followed by organic bound .In similar study by Alina (2001), greatest amount of Cu have been found for FeMn oxides fraction. On the other hand, copper is bound to organic matter in relatively low concentration. Nickel species: Results indicate that nickel species also follow the trend of

Fe-Mn oxide > Carbonate > Organic bound > 44% > 32% > 14% >

Exchangeable 10%

However, nickel species shows more concentration range 0.614 mg kg-1 comparing with copper from 0.095-0.58 mg kg-1(see Table 2). It is due to the fact that nickel can be easily 23

immobilized by changes in environment conditions such as pH, redox potential, salinity etc (Huang et. al, 2007; Jain et.al, 2007; Pais, 1997). The present study experimental results are comparable to another study conducted by Ab ollino et.al, 2006 and Alina, 2001).

Zinc species: The metal speciation analysis shows that zinc is strongly associated with reducible (FeMn oxide) fraction to the extent of 67%. Zinc Fe-Mn oxide fraction shows significantly higher concentration than any other species followed by lead as second highest. Zinc associated with organic bound (14%) and carbonates (13%) dont have much difference in percentage. Thus the fact that Zn-oxides in soil are easily transformed mainly to carbonates (Kabata et.al, 1993). This is agreement with Zn associated reported by Mayur et.al, 2010; Li and Thornton 2001; Hickey and Kittrick 1984. The present study results also show comparison of Zinc organic bound higher in sequence to exchangeable fraction with studies of Bulletin 1985; Huang et al. 2007; Ratuzny et al. 2009(see Figure 5). The cumulative response of all domains exhibits the optimum of organic species of Chromium (Finzgar et. al, 2007).

24

Figure 3. Speciation of trace metals in soils of cotton fields of Multan

25

60 Percentage (%) 50 40 30 20 10 0
Ca rb on at es Fe -M n ox id e O rg an ic bo un d Ex ch an g ab le

Cd Cr Pb

Chemical fraction

(a)

(b)
Figure 4 Percentage occurence of chemical fraction of (a) Cd ,Cr and Pb (b) Cu,Ni and Zn in cotton fields of Multan

26

Batch analysis Batch experiments were conducted to determine the adsorption capacity of soil of selected vegetable fields for Triazophos. 9 batch experiments were conducted in order to investigate the effect of varying pH, mass of soil and different dose of pesticide on adsorption. Effect of pH The effect of change in pH on pesticide adsorption was studied. The experiment was conducted for three different pH of 4, 7 and 10 in order to study the acidic, neutral and basic range. The results are summarized in Table in the Table 4. As it is clear from the data that pH has a significant role on adsorption. It is also observed that pH 7 is optimum for the adsorption of Triazophos for 1 g and 5 g mass of soil. However, for 3 g soil, the optimum pH is found to be 10. (see Figure 5) Another look into the analysis reveal that pH affect on adsorption is influenced by adsorbent mass and adsorbate dose as well. Figure 5 shows almost reversal of adsorption pattern indicating that pH is significantly affected by adsorbent mass and this point the pH 10 show decreasing pattern in contrast to the earlier results. On close investigation it appears that at relatively higher mass (5 g) adsorption for Ph 4, 7 and 10 becomes independent of competition for sites. Another peculiar and rather contrasting approach is evident for adsorption by 3 g of adsorbent. A competitive and to non-competitive behavior approach with increase in contact time. A noteworthy dimension of the affect of pH is on the equilibrium time. The data in Table 4 shows that generally both have a direct relation, equilibrium increases with increase in pH and this effect is manifested strongly at pH 10 (see Figure 5).

27

Figure 5.

Effect of pH on adsorption of triazophos on (a) 1g (b) 3g (c) 5g soil in cotton fields of Multan

28

Table 4

Concentration with time in cotton field of Multan

Ti me
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62 64 66

1g (0.5ppm) pH 4 pH 7
0.5 0.415 0.41 0.37 0.385 0.36 0.385 0.36 0.34 0.4 0.36 0.37 0.345 0.36 0.335 0.395 0.31 0.32 0.345 0.355 0.335 0.5 0.481 0.395 0.46 0.445 0.414 0.381 0.45 0.43 0.39 0.38 0.428 0.395 0.375 0.32 0.33 0.14 0.26 0.43 0.39 0.333 0.355 0.335 0.291 0.315 0.29 0.271 0.291 0.291

pH 10
0.5 0.417 0.409 0.39 0.39 0.274 0.317 0.34 0.307 0.334 0.319 0.376 0.277 0.227 0.272 0.17 0.154 0.272 0.284 0.256 0.249 0.225 0.214 0.081 0.349 0.384 0.374 0.349 0.251 0.324 0.277

3g (1ppm) pH 4 pH 7
1 0.8 0.79 0.74 0.75 0.84 0.79 0.81 0.775 0.775 0.75 0.775 0.79 0.795 0.775 0.82 0.775 0.79 0.8 0.73 0.77 0.795 0.74 0.79 0.79 1 0.85 0.86 0.685 0.845 0.76 0.825 0.701 0.825 0.75 0.65 0.58 0.725 0.52 0.64 0.615 0.635 0.605 0.585 0.473 0.591 0.445 0.601 0.52 0.5 0.42 0.591 0.55 0.54 0.49 0.52 0.52

pH 10
1 1.045 1.041 1.028 1.057 0.942 0.861 0.275 0.953 0.997 0.985 0.95 0.942 0.975 0.88 0.913 0.925 0.905 0.891 0.88 0.93 0.871 0.861 0.93 0.88 0.88 1.057 0.88 0.861 0.891 0.807 0.78 0.528

5g (1.5ppm) pH 4 pH 7
1.5 1.33 1.36 1.35 1.38 1.44 1.33 1.39 1.33 1.38 1.38 1.33 1.245 1.3 1.31 1.33 1.3 1.275 1.275 1.28 1.31 1.275 1.33 1.244 1.28 1.275 1.275 1.5 1.425 1.385 1.225 1.32 1.24 1.305 1.37 1.385 1.38 1.309 1.288 1.28 1.33 1.268 1.321 1.261 1.33 1.275 1.225 1.33 1.375 1.37 1.233 1.295 1.254 1.27 1.275 1.25 1.28 1.309 1.215 1.345

pH 10
1.5 1.073 1.653 1.135 1.295 0.955 0.885 1.135 1.135 1.135 0.885 0.699 1.185 0.885 0.885 0.955 0.955 1.135 1.073 1.073 1.325 0.885 0.699 0.699 1.26 1.073 1.185 1.26 0.645 1.073 1.185 1.135 0.885 0.645

Effect of Adsorbent mass 29

Adsorbent mass is another contributing component of adsorption. Three different masses of soil i.e.; 1 g, 3 g, and 5 g are investigated in the present study. Results are summarized in Table 4. The adsorbent mass influence the adsorption relates to an increase in surface area, which leads to an increase in binding sites thus facilitating the reaction between adsorbent and adsorbate (Gamal et al, 2009). It is generally observed that adsorption increases with increase in mass in going from 1g through 3g to 5g with an increase of 19.87 and 11.52% respectively. However, a significant jump of 31.39% is evident in moving from lowest to highest mass. Adsorbent mass seems to be independent of change in pH as similar trend of adsorption increase is seen in this study. Another significant aspect of adsorbent mass is on the equilibrium time. As it is clear from the data in Table 4 that equilibrium time increases with increase in mass however a significant increase of 20 minutes in moving from 1g to 3g at constant pH. Adsorption increases with increase of soil contents as reported by Bulut and Aydin, 2006 supports the present study while some other author (Gamal et al, 2009) report the inverse trend. Adsorbent to adsorbate ratio of 1:0.5, 3:1 and 5:1.5 investigated in the present study show subsequent increase in adsorption depicting that adsorbent mass is independent of adsorbate dose.

30

Table 5

Percentage adsorption of Triazophos in cotton fields of Multan at different pH

Time
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62 64 66 68

1g (0.5ppm) pH 4 pH 7
36.76 30.51 30.15 27.21 28.31 26.47 28.31 26.47 25.00 29.41 26.47 27.21 25.37 26.47 24.63 29.04 22.79 23.53 25.37 26.10 24.63 39.68 38.17 31.35 36.51 35.32 32.86 30.24 35.71 34.13 30.95 30.16 33.97 31.35 29.76 25.40 26.19 11.11 20.63 34.13 30.95 26.43 28.17 26.59 23.10 25.00 23.02 21.51 23.10 23.10

pH 10
39.09 32.60 31.98 30.49 30.49 21.42 24.78 26.58 24.00 26.11 24.94 29.40 21.66 17.75 21.27 13.29 12.04 21.27 22.20 20.02 19.47 16.73 6.33 27.28 30.02 29.24 27.28 19.62 25.33 21.65

3g (1ppm) pH 4 pH 7
55.87 44.69 44.13 41.34 41.90 46.93 44.13 45.25 43.30 43.30 41.90 43.30 44.13 44.41 43.30 45.81 43.30 44.13 44.69 40.78 43.02 44.41 41.34 44.13 44.13 52.63 44.74 45.26 36.05 44.47 40.00 43.42 36.89 43.42 39.47 34.21 30.53 38.16 27.37 33.68 32.37 33.42 31.84 30.79 24.89 31.11 23.42 31.63 27.37 26.32 22.11 31.11 28.95 28.42 25.79 27.37 27.37

pH 10
45.45 47.50 47.32 46.73 48.05 42.82 39.14 12.50 43.32 45.32 44.77 43.18 42.82 44.32 40.00 41.50 42.05 41.14 40.50 40.00 42.27 39.59 39.14 42.27 40.00 40.00 48.05 40.00 39.14 40.50 36.68 35.45 35.45

5g (1.5ppm) pH 4 pH 7
65.22 57.83 59.13 58.70 60.00 62.61 57.83 60.43 57.83 60.00 60.00 57.83 54.13 56.52 56.96 57.83 56.52 55.43 55.43 55.65 56.96 55.43 57.83 54.09 55.65 55.43 55.43 61.73 58.64 57.00 50.41 54.32 51.03 53.70 56.38 57.00 56.79 53.87 53.00 52.67 54.73 52.18 54.36 51.89 54.73 52.47 50.41 54.73 56.58 56.38 50.74 53.29 51.60 52.26 52.47 51.44 52.67 53.87 50.00 55.35 52.47

pH 10
49.92 35.71 55.01 37.77 43.09 31.78 29.45 37.77 37.77 37.77 29.45 23.26 39.43 29.45 29.45 31.78 31.78 37.77 35.71 35.71 44.09 29.45 23.26 23.26 41.93 35.71 39.43 41.93 21.46 35.71 39.43 37.77 29.45 39.43 29.45

31

60 50 % Adsorption 40 30 20 10 0 pH 4 pH 7 pH 10

Figure 6: % adsorption of Triazophos in at different pH

32

a)
70 Equilibrium time (min) 60 50 40 30 20 10 0
0. 5p pm 1p p 1. m 5p pm 4 pH 7 pH 10 1g 3g pH

b)

c)

Figure 7

Effect of

a) pesticide dose at constant pH b) mass of soil on

adsorption c) time on mass(g), dose(mg/kg) and pH

Effect of Dose 33

5g

In order to investigate the affect of dose on adsorption three different doses i.e. 0.5ppm, 1ppm and 1.5ppm were applied. Results are tabulated in table 4. It is clear that adsorption has a direct relation with dose as adsorption increases with increase in dose. The same behavior is reported in a number of studies (Spark and Swift, 2002), as rate of adsorption clearly depends on the induced concentration. A significant increase in adsorption is observed in moving from lower to higher dose, following the sequence as 1.5pp>1ppm>0.5ppm 55.65> 44.13> 24.26 Figure 7(a) shows the effect of dose on adsorption with time. It is clear that dose significantly affects the adsorption. It increases as the contact time increases for all the doses. The % increase in adsorption was 5.32 for 0.5-1 and 23.02 for 1-1.5ppm. The relation of dose with pH is also studied and it is clear from the Figure 7(b) that adsorption at different doses behave independently of pH and follow similar trends for pH 4, 7 and 10. Adsorbate dose is intrigued per dose to mass ratios of 0.5:1, 1:3 and 1.5:5 and results revealed that dose is not influenced by the mass. Effect of Time The purpose of studying the effect of time on adsorption is to establish the equilibrium reaction time between adsorbent and adsorbate. The adsorption batch experiments are investigated till the achievement of equilibrium. As it is dynamic equilibrium, in some instance more than one equilibrium times are established. Results are reported in Table 4.

34

The data show that time is a significant factor contributing largely to adsorption under different sets of conditions. In other words, adsorption is a time dependent parameter as time is required for adsorbate to diffuse into the adsorbent (Lafleur, 1979). Equilibrium time is investigated in the realm of adsorbent mass, dose and pH. A general increasing pattern of equilibrium time is noted with increase in dose, mass and pH. A number of studies relate to the fact that reaction increase with an increase in time, thus affecting the equilibrium achievement. In the present investigation, first equilibrium is attained within an average contact time of 38-40minutes. However this varies slightly depending on the nature of soil, its properties and other contributing factors. A cumulative response on contact time is depicted in Figure 8 it is very clear that equilibrium time is attained within 40 minutes contact time for 1g. Equilibrium time increases on increasing the adsorbent mass and dose.

35

Figure 8

Effect of Time on Mass(g), Dose (ppm) and pH.

36

Adsorption Trends Adsorption capacity of different field soil for Triazophos is assessed in relation to its adsorbed concentration till equilibrium (Figure.9). A sorption desorption pattern is very evident and it signifies that adsorbent adsorbate interaction in a solution either towards or away from the surface. It is generally observed that the rate of uptake of Triazophos is rapid in the beginning followed by a zigzag pattern. This behavior is reasonably approximated by an instantaneous equilibrium. It can be explained on the basis that initially, there is a rapid reversible sorption of the solute adhering to accessible sites of the soil surface. The adsorption trend is examined at variable pH, dose and mass of adsorbent. Due to the matter of fact that a variety of artifactual processes and effects take place when a batch equilibrium experiment is performed, followed by a subsequent desorption experiment. The results indicate that % adsorption increases with increase in pH, mass and dose. Adsorption kinetics Kinetic study of the adsorption gives an important insight to understand the mechanism. The present study is an attempt to understand the adsorption rate and sorption capacity in the presence of different contributing factors. Kinetics is investigated in relation to Kd, Koc and adsorption isotherm. Results are given in appendix and graphically presented on figure 9. The figure 9(a) shows that as the adsorbent mass increases the Kd value increases. This observation leads to the assumption that it is the soil organic matter acting as a non polar phase or surface that is the main sorbent of the soil, attracting the pesticide because typically it is a non polar organic molecule. High Kd values also suggests that pesticide is probably bioconcentrated, hydrophobic and highly insoluble as well, although there are exceptions. In general soil pH changes have minor effect on the adsorption of non ionic molecule (Kan and Tornson, 1990). Since the sorption of pesticide is a combination of sorption of ionized and non- ionized molecules and since the ratio of the

37

species in the solution changes ten folds with each unit increase in pH so the Kd is quite sensitive to the change in pH (Ukrainczky and Ajwa, 1996). (see figure 9 b) Partition coefficient for organic carbon (Koc) range from 50,000 to 4000,000, depending on the soil and method of determination. To conduct the isotherm studies, two models were used: Langmuir and Freundlich. The isotherm study indicate that the adsorption of triazophos in soil follow the Freundlich model giving a negative slope. The Freundlich model is a case for heterogeneous surface energies and it gives an exponential distribution of active sites. Figures 10 represents the value of slope -1.19795 and intercept value -0.64912.

38

a)

b) Figure 9 Kd values at a) different masses and b) varrying pH

39

Slope= -1.19795 Intercept= -0.64912

Figure 10

Freundlich Adsorption Isotherm

40

Conclusion From this study it is concluded that With increase in mass, adsorption increases. At higher pH adsorption is maximum. The more the time and initial concentration of pesticide the more is adsorption. As the organic matter increases, the rate of adsorption increases.

41

Bibliography

Abdur Rehim, 2009. Phosphate Fertilization Management to Improve Phosphorus use Efficiency and Wheat Yield on Calcareous Soils

Abid Niaz, S. A. Shahid and S. Javid, 2003. Effect of Chloride (Cl) and Sulphate (SO4) Ions on Solution Chemistry of Salt-Efflorescence from Desertic Soils of Punjab, Pakistan, Pakistan Journal of Water Resources,Vol.7(1)

Abollino O, Giacomino A, Malandrino M, Mentasti E, Aceto M, & Barberis R. 2006. Assessment o metal availability in a contaminated soil by sequencial extraction. Water, Air, and Soil Pollution, 137, 315 338.

Abrahams P W., 2002. Soils: Their implications to human health. Sci Total Environ;291:132.

Ahmad B., Chaudhry A, and Hassan, S, 1994. Cost of producing crops in the Punjab. Deptt. of Farm Management, University of Agriculture, Faisalabad.

Ahmad, Z., M.A. Gill, R.H. Qureshi, Hamud-ur-rehman and T. Mahmood. 2007. Phosphorus nutrition of cotton cultivars under deficient and adequate levels in solution culture. Commun. Soil Sci. Plant Analysis, 32: 171-187.

Ajayi I R., Gbadamosi A.E, Mohammed O.Z, 2009. Study on Effects of Soil Physico-Chemical Properties on Cocoa Production in Ondo State Ololade I.A, National Space Research and Development Agency (NASRDA)

42

Alina K B., 2001. Trace element in soil and plants,3rd edn,CRC press,Poland. Bailey G W., J.L. White, 1970. Residue Rev, pp. 32-29

Baker L W., Fitzell, D L., Seiber, J N., Parker, T R., Shibamoto, T, Poore, M W., Longley K E., Tomlin R P, Propper R and Duncan D W., 1996. Ambient Air Concentrations of Pesticides California. Environ. Sci. Technol., 30: 1365-1368.

Bal Ram Singh and Dale W. Johnson, 2004. Sulfate content and adsorption in soils of two forest watersheds in Southern Norway, Water, Air, & Soil Pollution. 31, issue 3-4, pp 847-856.

Baloch UK, 1985, Problems associated with the use of chemicals by agricultural workers. Basic Life Science.34, pp 6378.

Bano A, Siddique S A., 1991. Chlorinated hydrocarbons in the sediments from the coastal waters of Karachi (Pakistan). Pak J Sci Ind Res;34:704.

Bulletin 1. 1985. Advisory Soil Analysis and Interpretation, MISR/SAC, Aberdeen.

Burauel P, Bassmann F, 2005. Soils as filter and buffer for pesticides experimental concepts to understand soil functions. Environ Pollut;133:116.

Cai, L. Gong, S. Chen, M. Wu, C., Vinyl crown ether as a novel radical crosslinked solgel SPME fiber for determination of organophosphorus pesticides in food

43

Canet R, Pomares F and Tarazona F, 1997. Chemical extractability and availability of heavy metals after seven year application of organic wastes to a citrus soil, Soil Use and Management 13, pp. 117121.

Carey A. E., Douglas P.. Tai H., Mitchell W G., and Wiersma G B., 1979. Pesticide Residue Concentrations in Soils of Five United States Cities-Urban Soils Monitoring Program. Pest. Monit. J., 13:17-22.

Carro R A and Lorenzo, 2001. Simultaneous optimization of the solid-phase extraction of organochlorine and organophosphorus pesticides using the desirability function, Analyst 126; 10051010

Chaudhuri.D, Tripathy S, and Veeresh H, 2003, M.A. Powell and B.R. Hart, Mobility and bioavailability of selected heavy metals in coal ash- and sewage sludge-amended acid soil, Environmental Geology 44 (4), pp. 419432

Cherifi, M, S. Hazourlia and M. Ziatia, (2009), Initial Water Content and Temperature Effects on Electrokinetic Removal of Aluminium in Drinking Water Sludge, Physics Procedia. 2, Issue 3, pp 1021-1030.

Chiou C.T., S.E. McGroddy and D.E. Kile, 1998. Partition characteristics of polycyclic aromatic hydrocarbons on soils and sediments. Environ. Sci. Technol, 32: 264-269 concepts to understand soil functions. Environ Pollut 2005;133:116. crops and soil, Ecotoxicology and Environmental Safety 69 (2008) 312316.

Dr David G Rossiter, 2001. Soil Investigations on the Sulmac Farm, Naivasha, Kenya by the International Institute for Aerospace Survey & Earth Sciences (ITC), International Institute for Aerospace Survey and Earth Sciences.

Dragovic. S, Mihailovic. N and Gajic. B, (2008), Heavy metals in soils: Distribution, relationship with soil characteristics and radionuclides and

44

multivariate assessment of contamination sources, Chemosphere (72),pp. 491 495. Driss, M.R, M.-C. Hennion, M.L. Bouguerra, Determination of carbaryl and some organophosphorus pesticides in drinkingwater using on-line liquid chromatographic Economic Survey of Pakistan, 2007-08, Economic Affairs Advisors Wing, Finance Division, Government of Pakistan, Islamabad Environmental News Service. Pesticide dump sickens Pakistan residents. 1998. Fagliano J A., J Sarvin, 1997. Community exposure and medical screening near chromium waste site in New Jersey,Regulatory Toxicology and Pharmacy26,1-2 Foliar applications under tropical conditions. Pestic. Res. J. 1992 , 4(1), 37 41. function, Analyst 126 (2001) 10051010.

Gamal S, ElShafeia,, I.N. Nasrb, Ayman S.M. Hassanb, S.G.M. Mohammad, 2009, Kinetics and thermodynamics of adsorption of cadusafos on soils, Journal of Hazardous Materials. 172, pp 16081616.

Gamal S. ElShafeia,, I.N. Nasrb, Ayman S.M. Hassanb, S.G.M. Mohammad, (2009), Kinetics and thermodynamics of adsorption of cadusafos on soils, Journal of Hazardous Materials. 172, pp 16081616.

Gitahi, S.M, Harper, D.M, Muchiri, M.P. Tole, R.N. Ngng, Organochlorine and organophosphorus pesticide concentrations in water, sediment, and selected organisms in Lake Naivasha (Kenya), Hydrobiologia 488 (2002) 12312 samples, Analytica Chimica Acta 559 (2006) 8996.

45

Gomez V. and M.P. Callao, 2006. Chromium determination and speciation since 2000. TrAcTrends in Analytical Chemistry, 25: 1006-1015.

Goncalves C, Alpendurada M F., 2002. Multiresidue method for the simultaneous determination of four groups of pesticides in ground and drinking waters, using solid-phase microextractiongas chromatographywith electroncapture and thermionic specific detection, Journal of Chromatography A 968 177190.

Graham-Bryce, I. J. 1969 Diffusion of Organophosphorus Insecticides in Soils. J. Sci. Food Agric, 20:489-491.

Grover, R. and Hance, R. J. 1970 Effect of Ratio of SoiI to Water on Adsorption of Linuron and Atrazine. Sol I Sci., 109:136-138.

Gunasekara, A.S. and B. Xing, 2003. Sorption and desorption of naphthalene by soil organic matter: Importance of aromatic and aliphatic components. J. Environ. Qual., 32: 240-246.

Hafeez, H.F. and A.F. El-Aswad, 2005. Sorptiondesorption of atrazine in soil. Alex. Sci. Exch., 26(1): 41-53.

Hickey M G., and Kittrick M G., 1984. Chemical partitioning of cadmium, copper, nickel, and zinc in soils and sediments containing high levels of heavy metals. Journal of Environmental Quality, 13, 372376.

Huang J., Huang R., Jiao J. J., and Chen K, 2007. Speciation and mobility of heavy metals in mud in coastal reclamation areas in Shenzhen, China. Environmental Geology, 53, 221228. in south Pakistan. Bull Environ Contam Toxicol 2002;68:23744.

46

Jain, C. K., Malik, D. S., & Yadav, R., 2007. Metal fractionationstudy on bed sediments of lake nainital,Uttaranchal, India. Environmental Monitoring and Assessment, 130, 129139

Jury, W. A., 1987. Adsorption of Organic Chemicals onto Soil. In: Vadose Zone Modeling of Organic.

Kabata- Prndias,A., Behavioral properties of trace metals in soils Appl.Geochem.Suppl.,2,3,1993

Krogha K. A, T. Seborga,, B. Brodina and B. Halling-Srensena, (2008), Sorption and Mobility of Ivermectin in Different Soils, Journal of Environmental Quality.37, pp 2202-2211.

LaFleur KS, (1979)Sorption of metribuzin by model soil and agronomic soil : rates and equlibria, soil sci 127: 51-55.

Lambert, S. M., Porter, P. E., and Schieferstein, H. (1965) Movement and Sorption of Chemicals Applied to the Soil. Weeds, 13:185-190.

Lesan, H.M. and A. Bhandari, 2003. Atrazine sorption on surface soils: time-dependent phase distribution and apparent desorption hysteresis. Water Research, 37: 1644-1654.

Li W, Qiu S P., Wu Y J., Triazophos residues and dissipation rates in wheat. Li, X., & Thornton, L. (2001). Chemical partitioning of trace and major elements in soils contaminated by mining and smelting activities. Applied Geochemistry, 16, 16931706.

47

Malik D M., Khan M A., and Chaudhry T A 1984. Analysis method for soil, plant and water, Soil Fertility Survey and Soil Testing Institute, Punjab, Lahore, Pakistan.

McGrath, S. P., & Cegarra, J. (1992). Chemical extractabilityof heavy metals during and after long term applications of sewage-sludge to soil. Journal of Soil Science, 43, pp. 313321

Meher, H.C. and Sethi, C.L., Persistence of Fenamiphos in soil following soil and Mubeena Akhtara, Shahid Iqbalb, M.I. Bhangera, Muhammad Zia-Ul-Haqc, Muhammad Moazzam, (2009), Sorption of organophosphorous pesticides onto chickpea husk from aqueous solutions, Colloids and Surfaces B: Biointerfaces 69, pp 6370.

Memon K S., Rashid A., 2001. Soil Science, WordMate Islamabad, pp. 132

Munsell Color Company, (1967), Revised Standard soil color charts (Japanese). Revised Japanese addition based on Munsell Color Chart, Tokyo: Research Council for Agriculture, Forestry and Fisheries, Ministry of Agriculture and Forestry.

Norrish. K (1975),The geochemistry and mineralogy of trace metal elements, Trace elements in soil-plant animal system ,Nicholas, D.J.D and Egan, A. R., Eds., Academic press,new York, pp55

Obaid-Ur-Rehaman, A.M. Ranjha, S.M. Mehdi and A.A. Khan, (2005), Phosphorus Requirement of Wheat using Modified Freundlich Model in Sultanpur (Pakistan) Soil Series, International Journal of Agriculture and Biology,7.

48

Olajire, A. A., Ayodele, E. T., Oyedirdar, G. O., & Oluyemi, E. A. (2003). Levels and speciation of heavy metals in soils of industrial southern Nigeria. Environmental Monitoring and Assessment, 85, 135155.

Patricia A. Terry, (2007), Removal of Nitrates and Phosphates by Ion Exchange with Hydrotalcite, Environmental Engineering Science, 26(3), pp 691-696.

Pianke, H. B. and Chesters, G. (1973) Pesticide- Sediment-Water Interactions. J. Environ. Quality, 2:29-45

Pignatello, J.J. and B. Xing, (1996). Mechanisms of slow sorption of organic chemicals to natural particles. Environ. Sci. and Technol., 30: 1-11. preconcentration techniques, Journal of Chromatography A 639 (1993) 352358.

Radojevic M and V. N. Bashkin, (1999), Practical Environmental Analysis of organochlorine and organophosphorus pesticides using the desirability

Rani, S., V.K. Madan and T.S. Kathpal, 2001. Persistence and Dissipation Behavior of Triazophos in Canal Water under Indian Climatic Conditions. Ecotoxicol. Environ. Safety, 50: 82-84.

Rodriguez-Mozaz, M.J. Lpez De Alda, D. Barcel, Monitoring of estrogens, pesticides and bisphenol A in natural waters and drinking water treatment plants by solid-phase extractionliquid chromatographymass spectrometry, Journal of Chromatography A 1045 (2004) 8592.

Sanpera C, Ruiz X, Llorente GA, Jover L, Jabeen R. Persistent organochlorine compounds in sediment and biota from the Haleji Lake: a wildlife sanctuary Sharom, M. S., Miles, J. R. W., Harris, C. R., and McEwen, F. L. (1980) Behavior

49

of 12 Insecticides in Soil and Aqueous Suspensions of Soil and Sediment. Water Res., 14:1095-1100. Spark K.M, R.S. Swift, (2002), Effect of soil composition and dissolved organic matter on pesticide sorption, The Science of The Total Environment, 298, pp 147161.

Sposito, G., Lund, L. J., & Chang, A. C. (1982). Trace Metal Chemistry in Aridzone Field Soils Amended with Sewage Sludge: I. Fractionation of Ni, Cu, Zn, Cd, and Pb in Solid Phases. Soil Science Society of America Journal, 46, 260264

Stephenson GA, Solomon KR. 1993. Pesticides and the environment. Guelph, Ontario, Canada: Department of Environmental Biology, University of Guelph.

Stockfischa, N T. Forstreuterb and W. Ehlers, (1999), Ploughing effects on soil organic matter after twenty years of conservation tillage in Lower Saxony, Germany, Soil and Tillage Research. 52, Issues 1-2, pp 91-101.

Suri K.S., B.S. Joia. Persistence of Chlorpyriphos in soil and its terminal residues in wheat. Pestic. Res. J. 1996, 8(2) ,186 190.

Terry N, Zayed AM, de Souza MP, Tarun AS (2000) Selenium in higher plants. Annual Review of Plant Physiology and Plant Molecular Biology 51

Tessier, A., Campbell, P.G.C., and Bisson, M.: Sequential extraction procedure for the speciation of particulate trace metals. Analytical Chemistry, 51, 1979, p. 844-851.

50

Ukrainzyk L nad Ajwa HA(1996), primisnlfuron sorption on mineral and soils. Soil sci scam 60: 460-467.

Umoren I. U, Udousoro I. I. (2009) Fractionation of Cd, Cr, Pb and Ni in roadside soils of Uyo, Niger Delta Region: Nigeria using the optimized BCR sequential extraction technique, Springer Science Environmentalist (29) p.p280 286

Walkley, A. 1935. An examination of methods for determining organic carbon and nitrogen in soils. J. Agri. Sci. 25:598-601)

Walter and G. Cuevas (1999), Chemical fractionation of heay metals in a soil amended with repeated sewage sludge application, Science of the Total Environment , pp. 113119.

Wang, P., S. Jiang, D. Liu, H. Zhang and Z. Zhou, 2006. Enantiomeric Resolution of Chiral Pesticides by High-Performance Liquid Chromatography. J. Agric. Food Chem., 54: 1577-1583

51