Electrokinetic Remediation of Cadmium-Contaminated Soil Using Zero-Valent Iron Particles

Mahesh Rawat
[email protected]

ABSTRACT
Electrokinetic remediation technique (Ek) has shown impressive results in soil remediation. Several research and experimental work have been carried out recently to enhance the Electrokinetic remediation process. There are certain enhancing techniques which have been developed like pH control, desorbing agent concentration, washings solution and use of zero valent iron particle as a permeable reactive barrier. Due to their minute size and higher surface area zero valent iron particle become highly reactive in EkR process. The use of iron particle as a permeable reactive barrier as shown remarkable result in enhancing the Electrokinetic remediation process. The present paper deals with the use of zero-valent iron (ZVI) particle as a permeable reactive barrier and its effect on Ek process for cadmium contaminated soil. Three experiments have been conducted: first the soil is washed with distilled water with distilled water used as a purging solution; second the soil is washed with distilled water with ammonium citrate used as purging solution; third the soil is washed with distilled water with ammonium citrate used as purging solution and a permeable reactive barrier of zero valent iron particle has been created. The results show that without the use of zero valent iron powder 62% removal efficiency has been recorded and with use ZVI as permeable reactive barrier 83% removal efficiency has been recorded. The present work is a progressive research work at MNNIT Allahabad India, on the subject of Electrokinetic remediation of fine grained soil now that the Electrokinetic process has been enhanced by using ZVI.

KEYWORDS: Ammonium citrate, cadmium, Electrokinetic remediation, ZVI.

INTRODUCTION
Due to intensive industrialization every year, millions of tons of hazardous waste are generated in the world. Due to inefficient waste handling techniques and hazardous waste leakage in the past, thousands of sites have been contaminated by heavy metals like cadmium, copper chromium and lead, among others. Cadmium is a naturally occurring rare element, one of the metallic components in the earths crust and oceans, and present everywhere in our environment. It was first discovered in Germany

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in 1817 as a by-product of the zinc refining process. Basic pigments were used as early as 1850 and appeared prominently in the paintings of Vincent Van Gogh in the late 1800s. Thomas Edison in the United States and Waldemar Junger in Sweden developed the first nickel-cadmium batteries early in the 20th Century. However, the most significant early use of cadmium was as a corrosion-protection coating Releases of cadmium to the environment from the manufacture of cadmium products are well controlled and, today, are insignificant contributors to human exposure to cadmium. Similarly, consumer use and disposal of cadmium-containing products, such as batteries, pigments and coatings, have been shown not to contribute significantly to increased human exposure to cadmium. In the human body, cadmium accumulates mainly in the kidneys. At high levels, it can reach a critical threshold and can lead to serious kidney failure. Recent studies (Buchet & Bernard 1998) have shown that kidney effects may be reversible at low exposures once cadmium exposure is reduced or removed. The first Electrokinetic phenomenon was observed at the beginning of the 19th Century, when Reuss applied a direct current to a clay water mixture (Acar and Alshawabkeh, 1993). However, Helmholtz and Smoluchowski were the first scientists to propose a theory dealing with the electro-osmotic velocity of a fluid and the zeta potential under an imposed electric gradient (Acar and Alshawabkeh, 1993). Electrokinetic remediation, variably named as electrochemical soil processing, Electro-migration, Electrokinetic decontamination or electro reclamation uses electric currents to extract radionuchdes, heavy metals, certain organic compounds, or mixed inorganic species and some organic wastes from soils and slurries. The application of electric current has several effects: (1) It produces an acid in the anode compartment that is transported across the soil and desorbs contaminants from the surface of soil particles; (2) It initiates Electromigration of species available in the pore fluid and those introduced at the electrodes; and (3) It establishes an electric potential difference which may lead to Electroosmosis generated flushing of different species (Acar et al., 1995). The dielectric constant and viscosity are properties of the pore fluid. The zeta potential depends on several factors, including the charge on the particle surface and the conductivity of the pore solution. The zero point of charge (ZPC) refers to the pH at which the net charge on the particle surface is zero. Generally, when the pH is below its ZPC, a soil has a positive zeta potential and the electro-osmotic flow occurs towards the anode. Conversely, when the pH is above the ZPC, the soil has a negative zeta potential and the electroosmotic flow occurs towards the cathode. Electro-osmotic flow can be determined by Eq. (1.1) q = ke ie A Where q is electro-osmotic flow rate, ke is electro-osmotic permeability, ie is electrical potential gradient and A is the area normal to the flow. in contrast to hydraulic conductivity of soil which varies over an extremely wide range that depends upon the size of void of the soil and consequently grain size. The coefficient of electro-osmotic permeability is almost independent of grain size. Generally for saturated soil it lies in range of 0.4 to 0.6104m/s Great efforts have been made on the studies for removal of contaminants from soil in recent past. There were few remedial technologies like soil flushing, phytoremediation, bioremediation etc. but all these technologies are not satisfactory in low permeable soils where electrokinetics has proved its own ability in such soils (Stichnothe et al., 1996).

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OBJECTIVE OF THE STUDY

The main objectives of this study are: 1. To determine feasibility of Electrokinetic remediation process 2. To determine the removal efficiency of the soil for different amount of sorption and for the different concentrated ammonium citrate. 3. To evaluate the migration behavior of cadmium. 4. To determine the overall effect of the purging chemicals on the removal of cadmium from soil. 5. To standardize the analysis procedure. This mainly includes the effect of variation in the voltage, current, pH across the cell and at anode and cathode end, on the removal efficiency of the process. 6. Concentrations of cadmium in the soil compartment are also compared for different cases.

MATERIALS AND METHODS

In the present method soil sample has been collected from unpollted site meja village of Allahabad district Uttar Pradesh India at shallow depth of 1-2 meter. After collection, the soil sample was air first Dried and washed through 0.425mm sieve to obtain fine grained soil. Particle size distribution analysis indicated that the soil contained approximately 15% clay-size particles. Quartz, feldspar, calcite, dolomite, hematite and the predominant clay minerals Illite and Kaolinite constituted the bulk mineralogy. The virgin soil physico-chemical properties were taken from previous study (P. Balaramudu, 2007). Cadmium nitrate (Cd (NO3)24H2O), tri-ammonium citrate (NH4)3C6H5O7), HNO3 and other required reagents have been used in the present study. The soil digestion procedure followed is to take 3 g soil samples in BOD bottles and add 30 mL of 1.6 M HNO3. Resulting slurries were shaken continuously for 24 h at room temperature in a shaker. Subsequently, the slurries and filtrates were tested in atomic absorption spectrophotometer (AAS) for analysis at the specific wave length of 228.8nm, for cadmium. Composition and properties of soil Sr. No. 1. Property Particle Size Distribution Gravel (%) Sand (%) Silt (%) Clay (%) Atterberg Limits Liquid Limit (%) Value 6.60 18.4 60.0 15.0 52

2.

Vol. 15 [2010], Bund. B Plastic Limit (%) Shrinkage Limit (%) Plasticity Index (%) Activity Specific gravity Maximum Dry Unit Weight (kN/m3) Optimum Moisture Content (%) Hydraulic Conductivity (m/sec) Specific Surface Area (m2/g) Cation exchange capacity (USEPA) (meq/100 g) pH Organic Content (%) Loss on Ignition (LOI) (%) CaCO3 (%) Soil classification (USCS) Cd Silica-Sesquioxide ratio (SSR)

4 21 13 31 1.87 2.62 18.68 14.4 4 x 10-9 0.18 22 8.52 6.25 9.93 2.5 CL Not traceable 5.74

3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16.

EXPERIMENTAL SET UP
A schematic test setup used in this experiment is shown in Fig. The test set up consists of cylindrical cell made up of Perspex material containing a sample compartment of 6.9 cm inner diameter and 35 cm in length having two electrode compartments) with an anode reservoir and cathode reservoir. At each end of the soil cell, a cork with nylon net is used as reinforcement. It is immediately provided next to filter paper to prevent spreading of fine soil particles from entering into the reservoir. Gas vents were provided in both the electrode compartments to pass gases generated from the electrolysis process. Graphite anode and cathode were fitted at the end of reservoir were connected with a direct-current power supply. Along the longitudinal axis of the cylindrical cell, five auxiliary electrodes were arranged for the purpose of electric field distribution along the sample. The unit was powered by 12 V batteries 40 AH of 4 nos. and current of 40 A outputs. The voltage, current and various incremental voltages of the unit were monitored and logged manually using digital millimeters at regular intervals.

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Dummy electrode

Purging solution

Cathode

Anode Contaminated Soil

Experimental Design
To evaluate the Electrokinetic Remediation, with iron powder, a series of tests were performed in three phases. A total 3 Electrokinetic experiment were conducted on clayey soil. First Electrokinetic Remediation was conducted with distilled water as a desorbing agent to study the basic EK Principles and theories for 5 days till the current stablise. Second Electrokinetic Remediation was conducted with Tri ammonium citrate as a desorbing agent with 2 M molarity without iron powder day till the current stablise. Third Electrokinetic Remediation was conducted with Tri ammonium citrate as a desorbing agent with 2 M molarity for 6 day till the current stablise and with iron powder with specification 300 mesh , finer than 75 micron . In all investigations, an applied electric field induced electro-osmotic flow moved the pore fluid through the clay from anode towards cathode. At the anode end a purging solution of chosen chemical was introduced at atmospheric pressure and drawn into the clay also by electro-osmosis For each Electrokinetic test, approximately 2 kg of dry soil were saturated (washed) with 4 liter of water and then mixed with 18.2 4 =72.8 gm cadmium solution and mixed thoroughly by hand for several minutes in order to achieve homogeneity.. Afterwards, the soil sample was tamped into the cell using a hand compactor so that the amount of void space was minimized and desired density was achieved. Then soil sample was left for 7 days for proper mixing of cadmium with soil with maximum sorption capacity of soil.

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After 7 days contaminated soil is mixed with 40 % of water i.e. 800 ml water and filled into EK cell. A constant DC electric potential was then applied across the specimen in all the experiments for a treatment time of 5 days Current and voltage at each 1 hour interval was measured at every section of cell like A-1, A2, A-3, A-4, A-5, A-C At the end of the experiments the soil was segmented into slices from anode towards cathode. The number of slices was 6, and the length of slices at anode to section 1 and cathode to section 5 was 15 mm thick. The middle slices lengths were 80 mm thick. For each of these slices the cadmium concentration measured by AAS(Atomic adsorption spectrophotometer). Zero valent iron particle as a barrier. 10 gm of sand and 10 gm of iron particle are used as barrier material. ZVI powder as a following type of specification Minimum assay Arsenic Copper Sulphate Lead Mesh size 98.5 % 0.0005 % 0.01% 0.02 % 0.002 % 300 mesh

Thickness of barrier was calculated by following formulae (/4) d2 h = weight of barrier / (density of iron and sand) Where d = internal diameter of cell H = thickness of barrier

(/4) 6.52 h = 20 /9.402 Iron density = 7.8 gm /cc Sand density = 1.602 gm /cc After calculating H = 6 mm thick barrier was used

RESULTS
Cadmium Remaining after Removal across the Cell

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Variation of parameters for deionised water as a purging solution

Cadmium concentration
Cd concentration(gm/kg) 13 12.8 12.6 12.4 12.2 12 11.8 11.6 0 1 2 3 4 5 6 7 compartements

Cadmium removal efficiency = (13.20 12.53)/13.2 X 100 = 5.075 %

Electro-osmotic flow (k x I xA)

0.2400 Electro-osmotic flow cc/sec 0.2350 0.2300 0.2250 0.2200 0.2150 0 20 40 60 80 100 120 140 Time(hour)

70 60 Current(mA) 50 40 30 20 10 0 0 50 Time (hours) 100 150

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Variations of parameters using 2 M ammonium Citrate as a purging solution without iron powder
Cadmium concentration
Cd concentration(gm/kg) 5.2 5 4.8 4.6 4.4 4.2 0 1 2 3 4 5 6 7 compartements

Cadmium removal efficiency = (13.20 4.91)/13.2 X 100 = 62 %

Electro-osmotic flow (k x I xA)
0.2400 0.2380 0.2360 0.2340 0.2320 0.2300 0.2280 0.2260 0.2240 0 20 40 60 80 100 120 140 Time(hour)

Current (mA)

Electro-osmotic flow(cc/sec)

250 200 150 100 50 0 0 20 40 60 80 100 Time (hour)

Variations parameters using 2 M ammonium Citrate as a purging solution with iron powder as permeable reactive barrier

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Cadmium concentration
Cd concentration(gm/kg) 3 2.5 2 1.5 1 0.5 0 0 1 2 3 4 5 6 7 compartements

Cadmium removal efficiency = (13.20 2.24)/13.2 X 100 = 83.03 % The maximal adsorption capacity of cadmium contaminated soil was calculated as 13.2 g /kg and the adsorption coefficient (b) was obtained as 0.13. (Yauvz et al. 2003)
Electro-osmotic flow (k x I xA)
0.2380 0.2360 0.2340 0.2320 0.2300 0.2280 0.2260 0.2240 0.2220 0.2200 0 20 40 60 80 100 120 140 Time(hours)

Electro-osmotic flow(cc/sec)

current 300 250 Current(mA) 200 150 100 50 0 0 50 Time (hours) 100 150

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DISCUSSION
Concentration of remaining cadmium at different compartment shows that Cd have a lesser value at A-1, A-2 which increases toward A-4, A-5 and A-6. Maximum removal amount of cadmium was found at A-6. But after use of zero Valent iron powder as a barrier the maximum removal of 83.03 % was recorded at compartment 3 onwards which may be due to adsorption of cadmium at the surface of iron particles are there may be some possibility of chemical interaction between ferrous and cadmium ion. For the first case when distilled water was used as purging solution average electro-osmotic flow recorded was 0.2266 cm3/sec and with ammonium citrate average electro-osmotic flow recoded was 0.2330 cm3/sec. When Electrokinetic process was started with ammonium citrate as purging solution and zero valent iron powder as permeable reactive barrier initially the Electroosmotic flow show same pattern observed in previous two cases. Electro-osmotic flow started with 0.2280 cm3/sec and attained lowermost value 0.222 cm3/sec at the 17 hour .Then it started increasing this might be due to standard half reaction of zero valent iron yielding a ferrous cation and two electrons as shown below . Fe0 Fe2+ + 2eFe2+ ions try to migrate towards cathode ,therefore a higher removal of Cd is observed after 60 hours electro-osmotic flow again tends to increase which might happen due to reaction of zero valent iron particle with water to yield ferrous cation ,hydroxyl anion and hydrogen gas. Fe0 + 2H2O Fe2+ + 2H2 + 2OH. Which try to accelerate the reaction and due to this reason the current recorded was 133 mA at the end of experiment. For the first case when distilled water was used as purging solution maximum value was recorded 60 mA, and the minimum value of current recorded was 4 mA. When ammonium citrate was used as a purging solution a maximum value was recoded 204 mA and minimum value of current recorded was 12 mA. For the third case when ammonium citrate was used as a purging solution and iron particle as permeable reactive barriers the maximum value of current was recorded 275 mA and minimum value of current recorded in Ek experiment was 35 mA. The higher value of current shows the influence of zero valent iron particles used as a permeable reactive barrier.

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