EXPERIMENTAL STUDIES ON REMEDIATION OF ARSENIC CONTAMINATED SOILS USING A NOVEL SOLVENT EXTRACTANT MIXTURE

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ABSTRACT
Remediation of arsenic contaminated soil was studied in this work, experiments were carried out using simulated soil contaminated arsenic is treated with an extractant solution comprising of Citric acid, Oxalic acid, Sodium Hydroxide and Sodium Carbonate. Experiments were carried out by treating the soil with the extractant solution and vibrating in a shaker for one hour at 150 rpm. The experiments were done to determine the optimal conditions of the extractant solution that effect maximum efficiency in removal of arsenic from the soil. The optimized conditions for the extractant solution were found to be at .05 M and 8 pH.

Keywords: Remediation, arsenic, Citric acid, Oxalic acid, Sodium Hydroxide, Sodium Carbonate.

INTRODUCTION Soil contamination is caused by the presence of man-made chemicals or other alteration in the natural soil environment. This type of contamination typically arises from the rupture of underground storage tanks, application of pesticides, and percolation of contaminated surface water to subsurface strata, oil and fuel dumping, leaching of wastes or direct discharge of

industrial wastes to the soil. The most common chemicals involved are petroleum hydrocarbons, solvents, pesticides, lead and other heavy metals. The concern over soil contamination stems primarily from health risks, both of direct contact and from secondary contamination of water supplies. In recent years, attention has focused on the development of in situ (in place) immobilization methods that are generally less expensive and disruptive to the natural landscape, hydrology and ecosystems than are conventional excavation, treatment, and disposal methods. In-situ immobilization of metals using inexpensive

amendments such as minerals (apatite, zeolite, or clay minerals) is a promising alternative to current remediation methods. In polluted soils, metals (arsenic) which is held on inorganic soil particles and complexed with organic components can be dissolved or extracted by passing a solution through it. Soluble contaminants are subject to migration with soil water, uptake by plants or aquatic organisms. Metals in soil may be associated with various phases that are reactive, semi-reactive or non-reactive. Arsenic compounds have been used for many years in the paint industry, dyes and pigments, insecticides/herbicides, wood preservatives. Such compounds and their residues are known toxins and, for this reason, arsenic is one of several commonly occurring elements designated as a priority pollutant. Arsenic trioxide (As2 O3) has been applied as a herbicide at a number of utility sites, resulting in contaminated soils and groundwaters from applications of this weed killer. Arsenic trioxide is a suspected carcinogen and is highly toxic by ingestion or dust inhalation. The Maximum Contaminant Level (MCL) allowable in drinking water supplies in 0.050 mg/L. In a recent study, arsenic was described as being "at the forefront" of liver, lung, kidney and bladder cancer risks. The arsenic drinking water standard is anticipated to be set at a near-zero level. Generally, arsenic concentrations range up to 3500 ppm in the soil, with one value of 8300 ppm(in central India) observed. Therefore there is a dire need for the removal of arsenic from the soil. For these reasons, the removal of arsenic contaminants has been an ongoing concern. Common methods of treatment typically involve excavating the contaminated soil/material and treating it with a solidifying agent such as cement. However, such treatment is costly and results in a large net-volume increase of disposable material. In any event, there is evidence to suggest that such treatments are not entirely effective in preventing leaching. Other methods include washing the effected soil or waste with a solution, then collecting the leachate for removal and disposal. However, such methods typically result in a collection of concentrated heavy metals which may themselves be hazardous. The other existing methods of arsenic removal involving coagulation/precipitation with lime, alum or ferric sulfate are costly, produce a wet bulky sludge and often require final filters for polishing. Other technologies which have been investigated include ion exchange, foam flotation and adsorption (onto activated carbon and activated alumina). These technologies, while advantageous in some respects, are disadvantaged by requiring, inter alia, soil excavation. This invention is an improved method for removal of arseniccontaminants in soil. It overcomes certain well-known problems and deficiencies, including those outlined above, while providing an effective, cost-efficient solution to a wide-spread environmental concern. In part, the present invention is a method for remediating an arsenic-contaminated soil medium without excavating the soil, including (1) contacting the soil medium with an aqueous extractant solution wherein the extractant is citric acid, Oxalic acid , sodium Hydroxide and Sodium

Carbonate (2) directing the extractant solution through the soil and into a groundwater source below the soil, (3) transferring the groundwater to the soil surface whereby the groundwater contains arsenic compounds and the extractant solution, (4) consolidating the arsenic compounds contained within the transferred groundwater, and (5) stabilizing the consolidated arsenic compounds to minimize leaching during storage EXPERIMENTAL PROCEDURE Clayey soil was collected from the agricultural land in St Peters Engineering College, Chennai. Arsenic Trioxide, As2O3 LR Grade (Mercks) was added to the soil in different proportions and left for a week. The extractant solution comprising of Citric acid, Oxalic acid, Sodium Hydroxide and Sodium Carbonate (equal moles) was added to the soil and the amount of arsenic removed was analyzed. Batch studies were performed with different concentrations and pH of the extractant solution to determine the optimum conditions that effect maximum arsenic removal. Concentration Studies 100 grams of the arsenic contaminated soil (10,000 ppm of arsenic) was treated with 100 ml of the extractant solution prepared at different concentrations ranging from .01M to .10M are placed in a shaker at 150 rpm for 1 hour. The arsenic removal was then analyzed in all the soil samples.

Figure 1 Effect of Concentration of the extractant solution on the arsenic removal efficiency. From the figure 1, it is seen that the efficiency of arsenic removal is maximum at a concentration of .05M and the efficiency remains relatively constant for the other increasing solutions concentrations. Since a solution of .05M is optimal when compared with the higher concentrated solutions (namely . 06M, .07M, .08M, .09M and .10M) and it gives the same percentage removal, the above said concentration is the optimum concentration for arsenic removal from the contaminated soil. pH Studies 100 grams of the same soil (containing 10,000 ppm of arsenic) was treated with 100 ml of .05M extractant solution prepared at different pH namely 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12 and the arsenic removal efficiency was analyzed.

The solution prepared with optimum concentration, pH and volume was then used to treat contaminated soil (100 gram) with different concentrations of arsenic in it, such as 2000, 4000, 6000, 8000, 10000, 12000, 14000, 16000, 18000 and 20000 (in ppm). The soil samples were then analyzed for the percentage of arsenic removal.

Figure 2 Effect of pH of the extractant solution on the arsenic removal efficiency. From the figure 2, it is seen that the removal is maximum at 8pH. At other pH below 8, the efficiency was found to increase culminating at a value of 8. At the pH above 8, the efficiency is found to decrease and so the extractant solution has to be prepared at a concentration of .05M and at 8pH. Volume Recognition Studies 100 grams of the same soil (containing 10,000 ppm of arsenic) was treated with the extractant solution of .05M at a pH of 8 with different volumes of the solution namely 25 ml, 50 ml, 75 ml, 100 ml, 125 ml, 150 ml, 175 ml, 200 ml, 225 ml and 250 ml to find the optimum volume of the solution required to treat the given contaminated soil. From the figure 3, it is observed that the optimum volume of the extractant solution to treat 100 gram of the soil is 125 ml. The percentagr of arsenic removal is found to be maximum at 125 ml and the efficiency stays relatively constant with increasing volumes (upto 250 ml). As a lower volume is economical, it represents the optimum volume to be employed. Therefore the said extractant solution is to be prepared at a concentration of . 05M, 8pH and a volume of 125 to treat 100 gram of the soil.

Figure 4 Effect of Concentration of arsenic in soil on its removal efficiency. From the figure 4, it is seen that the efficiency of arsenic removal is found to be appreciable with decrease in concentrations. The extractant solution developed is thus capable of treating soils with higher degree of contamination as well as those with a lower degree of contamination. Scope for In-Situ Implementation The present investigation can be used as a in-situ method for extracting arsenic contaminants from a soil matrix. The method comprises immobilizing the arsenic contaminant through interaction with a solution containing citric acid, oxalic acid, sodium hydroxide and sodium carbonate. Likewise, the solution has an extractant concentration of about 0.05 and 8pH. The steps involved in the in-situ implementation are (1) contacting the soil with an extractant solution to mobilize the arsenic compounds (2) directing the extractant solution through the soil and into a groundwater source below the soil, (3) transferring the groundwater to the soil surface whereby the groundwater contains arsenic compounds and the extractant solution, (4) consolidating the arsenic compounds contained within the transferred groundwater, and (5) stabilizing the consolidated arsenic compounds to minimize leaching during storage.

Figure 3 Effect of Volume of the extractant solution on the arsenic removal efficiency.

arsenic contaminants that are stabilized to minimize leaching during storage. 1: Extractant Solution 2: Soil Layers 3: Groundwater Table 4: Production Well 5: Iron or Aluminum Salts 6: pH Modifier 7: Clarifier Figure 5 shows the steps involved in In-situ Remediation of arsenic contaminated soil. The extractant solution 1 consisting of citric acid, oxalic acid, Sodium Hydroxide and Sodium carbonate is applied over the soil surface by spraying injection lines or pipes or other such methods. The solution passes down the soil layers 2 and mobilizes the arsenic contaminants, which are carried away as a result to the groundwater table 3. Production well 4 is established, connecting the water table to the soil surface which is laden with one or more arsenic compounds. At the surface, groundwater is deposited in a reactor, as shown by arrow. The extraction/removal aspects can be repeated as necessary until the groundwater pumped to the surface is free of arsenic contamination. On-site treatment reactor includes the addition of iron or aluminum salts 5, such as aluminum sulfate, ferrous sulfate, ferric sulfate and ferric chloride at concentrations sufficient to bring the arsenic contaminants out of solution. Iron or aluminum oxyhydroxides can form in the reactor along with ferric or aluminum arsenate. Remaining unbound arsenate can sorbs to the surface of an oxymetal hydroxide. Where at least a portion of the arsenic contaminant is present as an arsenite, hydrogen peroxide, potassium permanganate, or similar oxidizing agent can be added in an amount sufficient to convert arsenite to arsenate. Addition of a pH modifier 6 such as any suitable acid or base may be necessary to achieve a pH7 for removal of the arsenic, present mainly as arsenate. From reactor, the reaction mixture is transferred to clarifier 7 where the sludge is allowed to settle and clarified effluent is removed. The groundwater portion of effluent 8 may be subsequently treated or purified and returned to the water table. The Sludge may undergo further solid/liquid separation, as shown in filter press 9. Following removal of additional effluent, as shown by arrow 10, the remaining contaminant solids may be solidified/stabilized, onsite or elsewhere, with cement- or lime-based composites, thermoplastic, or organic polymers, or other stabilizing materials. Final disposal form 11 so produced represents the 8: Water sent back to the groundwater table 9: Filter Press 10: Effluent removed from the solids. 11: Stabilized contaminated solids Table 1 shows the notations that represent various terms in figure 5. CONCLUSION The novel extractant solution developed has been found to be efficient in removing the arsenic contaminants in soil. The InSitu method stated can be satisfactorily employed without excavating the soil. The chemical compounds involved in the extractant solution are relatively and hence the process is economical.

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