Environmental Monitoring and Assessment (2005) 109: 147160 DOI: 10.

1007/s10661-005-5845-5

c Springer 2005

A NOVEL TECHNIQUE FOR MONITORING CONTAMINANT TRANSPORT THROUGH SOILS

P. R. KUMAR1, and D. N. SINGH2
1

Department of Civil Engineering, Faculty of Technology, Alemaya University, DireDawa, Ethiopia; 2 Department of Civil Engineering, Indian Institute of Technology Bombay, Powai, Mumbai, India ( author for correspondence, e-mail: rajeev p14@yahoo.com)

(Received 30 March 2004; accepted 1 November 2004)

Abstract. An experimental setup which is capable of simulation as well as monitoring contaminant transport through soil mass has been developed. Efciency of the experimental setup has been demonstrated by comparing the results obtained from the argentometric method. Reynolds number ( Re ) and the Peclet number ( Pe ) have been found to be less than unity. This indicates that ow of the solute through soil mass is laminar and the dominant contaminant transport mechanism is diffusion. Keywords: clays, contaminant transport, diffusion, monitoring, Peclet number, Reynolds number, silty soil

1. Introduction Due to excessive usage of pesticides and fertilizers in various agricultural activities, and the indiscriminate disposal of hazardous wastes, such as radionuclide wastes, contamination of the soil is becoming a matter of great concern to mankind. These chemicals interact with water and contaminate the ground water regime as well as the subsurface soil layers. Such a situation calls for continuous monitoring of the chemicals present in the soils, and their migration through it, subsequently. This necessitates development of a technique that can be used to study and monitor the interaction and migration of various chemicals in the soilwater system. Various geo-chemical processes control the interaction and migration of these chemicals when they come in contact with the soilwater system (Folkes, 1982; Mackay et al., 1985; Rowe, 1988). Many researchers have employed mathematical models or numerical methods (Freeze and Cherry, 1979; Pinder, 1984; Rowe and Booker, 1985; Shackelford, 1995) to study migration of contaminants through the soil mass. Input parameters for these models are obtained by conducting laboratory column tests (Crooks and Quigley, 1984; De Smedt and Wierenga, 1984; Gillham et al., 1984; Rowe et al., 1985; Shackelford and Daniel, 1991; Badv and Rowe, 1996) wherein the soil and pore water samples are collected from different locations along the length of the soil sample (column) to determine the concentration of the contaminant present. Using these data, the concentration proles for a contaminant can be developed as a function of time for a given soil (Crooks and Quigley, 1984;

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Acar et al., 1985; Shackelford, 1988; Acar and Haider, 1990). However, this is a cumbersome method and suffers from several disadvantages such as changes in the pore structure of the soil column due to sampling and chemical analysis of the collected samples is quite tedious. This calls for development of a technique that is efcient in detecting the presence of contaminants in the soil mass, without sampling the soil and the pore water. Efforts were made to develop a soil contaminant detector (SCD) for determining concentration of contaminants in the soil mass. NaCl solution, which is a non-reactive contaminant, has been used to demonstrate efciency of the SCD in detecting presence and migration of Cl through locally available silt and clay samples. Validity of the technique has been demonstrated with the help of argentometric method (APHA, 1989). As several factors such as the effect of compaction energy, degree of saturation and effect of clay content play important roles, their inuence on the migration of contaminants through the soil mass has been studied in detail.

2. Details of the Technique The technique developed for the purpose is a non-destructive testing methodology and deals with development of an instrument, the soil contaminant detector (SCD), and is depicted in Figure 1. This consists of an electrode array, a signal conditioning circuit, a data acquisition module and a computer for processing the obtained data. The presence of contaminant(s) in the soil mass can be detected by sending a low frequency sinusoidal signal into it and recording the differential output voltage, OV, in mV, across each pair of the electrodes. To avoid changes in the water content, soil structure, and pore-uid chemistry i.e., polarization of the pore-uid, an alternating

Figure 1. Basic schematic diagram for the soil contaminant detector, SCD.

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current has been used as suggested by earlier researchers (Yong and Hoppe, 1989; Abu-Hassanein et al., 1996).

3. Experimental Investigations 3.1. M ATERIAL

PROPERTIES

Locally available silty soil, denoted as S, and commercially available white clay, denoted as C, were used in the present study. By mixing 60% white clay and 40% silty soil, a soil mix CS, was created. Minerals present in soils S and C were identied with the help of XRD (X-ray diffraction) analysis, using an XRD-spectrometer (RIGAKU, Japan). The presence of anorthite, albite, illite, montmorillonite, and microcline in soils S, and halloysite, muscovite, and illite in soil C has been conrmed (JCPDS, 1994). The specic gravity of the soil samples has been determined as per ASTM D854-92. The specic surface area of the soil samples has been determined as per ASTM C-204-84, using a Blaines apparatus and Portland cement as the standard material. For obtaining the gradational characteristics of the soil samples, dry sieving along with the hydrometer analysis has been conducted (ASTM D-422-63). The standard Proctor compaction characteristics of the three soil samples were obtained in accordance with the guidelines provided by ASTM D-698-91. Table I presents details of the soil characteristics. 3.2. C ALIBRATION
OF THE SOIL CONTAMINANT DETECTOR ( SCD )

Calibration of the SCD has been done with the help of these soils corresponding to their virgin (mixed with distilled water) and contaminated (mixed with NaCl solution of different concentrations) states. For calibration of the SCD, six soil samples (S1, S2, S3, C1, C2, C3, CS1, CS2 and CS3), as depicted in Table II have been selected. These soil samples correspond to different compaction states (i.e., degree of saturation, Sr , dry density, dry , molding moisture content, w and saturated permeability, ksat ). A 1 N NaCl solution was prepared by dissolving 58.44 g NaCl in 1 L of distilled water. Similarly, solutions with different concentration of NaCl were prepared. However, solutions of higher concentration (>1 N) were not prepared for the present study due to the fact that at higher concentration the effect of van Der Waal forces (electrostatic attraction based upon closeness of atoms) on the electrical conductivity of the NaCl solution cannot be measured accurately (Worthington et al., 1990; USEPA, 1990; Butler and Knight, 1995). An appropriate amount of oven-dried soil is mixed with different weight percentages of NaCl solutions, of different concentrations (=0.0000011 N), and is

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TABLE I Properties of soils Soil Property Physical characteristics Specic gravity Specic surface area (cm2 /g) Particle size distribution Clay (%) (<0.002 mm) Silt (%) (0.0020.075 mm) Sand (%) (0.0754.75 mm) Compaction characteristics Maximum dry density (g/cc) Optimum moisture content (%) Atterberg limits Liquid limit (%) Plastic limit (%) Plasticity index (%) Soil classication (USCS) Chemical characteristics pH Cation exchange capacity (meq/100 g)

CS

2.65 14 374 61 39 0 1.39 20.8 46 25 21 CH 8.93 35.25

2.73 2945 19 34 47 1.59 21.4 38 28 10 ML 6.50 54.25

2.68 11 438 40 40 20 1.61 20.3 39 27 12 ML 7.80 45.00

Corresponding to a liquid-to-solid ratio of 10. TABLE II Soil samples used for calibration of the soil contaminant detector Soil S1 S2 S3 C1 C2 C3 CS1 CS2 CS3 Sr (%) 50.2 70.2 90.9 49.5 70.2 89.9 49.8 69.9 90.1 dry (g/cc) 1.49 1.57 1.51 1.38 1.39 1.33 1.52 1.59 1.55 w (%) 15.3 19.0 26.9 17.2 24.0 33.7 14.2 17.9 24.5 ksat (109 m/s) 16.18 1.40 4.09 1.48 0.19 0.20 1.43 1.40 1.42

allowed to precondition for a period of 24 h in airtight polythene bags. Later, this preconditioned soil is compacted to the states of soils as depicted in Table II, in a Perspex cylindrical mold of 60 mm diameter and 35 mm height as depicted in Figure 2. For achieving the desired dry , the preconditioned soil is compacted in

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Figure 2. Experimental setup used for calibrating the soil contaminant detector, SCD.

three layers, by imparting 39 blows to each layer using a 445 g hand rammer (Kumar, 2002). After compaction is completed, the brass electrodes (1/8 diameter) are inserted 10 mm deep into the soil sample. SCD is connected to a pair of electrodes and the output differential voltage (in mV), OV, is data logged and is later converted to the concentration of the Cl in the soil mass, as discussed in the following. For the nine soil samples, the measured OV values are plotted as a function of Cl concentration in the soil mass, as depicted in Figure 3. For soil samples mixed with distilled water, the Cl concentration is assumed to be 1 107 N. For the sake of simplicity it is assumed that the variation of Cl concentration in the soil, Cl , which is measured in terms of N (1 N 35 440 ppm) with OV is linear. With this assumption, a linear relationship between log (Cl ) and OV, represented by Equation (1), is tted to the trends depicted in Figure 3, for each of the nine soil samples considered in the present study. log(Cl ) = k1 + k2 (OV) (1)

where k1 and k2 are constants. Detailed methodology for developing a linearized relationship between log(Cl ) and OV, for the soil sample C2, is depicted in Figure 4. From the gure, it can be noticed that corresponding to 0 to 1675 mV the linear t AB yields a coefcient of regression ( R 2 ) of 0.9822 along with k1 and k2 equal to 0.25 and 0.002, respectively. However, for 1675 to 2500 mV output voltage range these parameters are equal to 33.86 and 0.02, respectively, and R 2 is equal to 0.8944, corresponding to the linear t CD. Similarly, the linear relationships between the log(Cl ) and OV, for other soil samples are tted, as depicted in Figure 5. Details of the parameters k1 and k2 along with the R 2 values are presented in Table III. However, it can be noted

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Figure 3. Variation of the differential output voltage with Cl concentration for different soils.

from the trends depicted in Figure 6 that for the silty soil samples (S1, S2 and S3) the log (Cl ) versus OV relationship is a straight line for all ranges of the differential output voltage. 3.3. VALIDATION
OF THE RESULTS OBTAINED FROM THE SOIL CONTAMINANT DETECTOR ( SCD )

To validate Equation (1), the argentometric method (APHA, 1989) has been employed. About 1 g oven-dried soil is mixed with 50 mL of distilled water and the solution is ltered with Whatman No. 42 lter paper. The ltrate is titrated against 0.01 N AgNO3 with K2 CrO4 as indicator. Using Equation (2) the concentration of Cl can be determined. Concentration of Cl = (a b) N 35 440 V (2)

where a is the volume of the AgNO3 used for the ltrate (in mL), b is the volume of the AgNO3 used for the blank solution (distilled water) (in mL), N is the normality of the AgNO3 and V is the volume of the ltrate.

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Figure 4. Proposed bi-linear variation of the pore uid concentration with the output voltage for soil sample C2.

To demonstrate validity of the results obtained from the SCD, soils S, C and CS are mixed with 0.005 N NaCl and are compacted to the compaction states depicted in Table II, as described earlier, to form a soil sample which is 60 mm in diameter and 35 mm high. As discussed earlier, one pair of the brass electrodes, placed diametrically opposite, is inserted into the soil sample and the OV values are recorded using the SCD and a data logger. The observations are presented in Table IV. Using Equation (1), the measured OV values are converted to the Cl concentration and the same is compared with the values obtained from Equation (2), as depicted in Table IV. It can be observed from the data presented in Table IV that the results obtained from Equations (1) and (2) are very close to each other and for all practical purposes they may be assumed to be identical. This demonstrates efciency and utility of soil contaminant detector for measuring the concentration of contaminants in the soil mass. A marginal deection in the results may be attributable to the difculty associated with the preparation of exactly identical soil samples that are homogeneous in terms of their compaction characteristics.

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Figure 5. Calibration relationships for different soil samples.

3.4. C OLUMN

TESTS

The experimental setup used for column tests is depicted in Figure 6. The required amounts of the dry soil and the distilled water were mixed and were stored in an airtight polyethylene bag for preconditioning. Later this preconditioned soil sample

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TABLE III Parameters used in the linear relationship for different soil samples Parameter Sample S1 S2 S3 C1 C2 C3 CS1 CS2 Range of OV (mV) For all ranges A (103 ) 4572.93 2782.15 1021.25 393.36 52796.19 246.92 33856.93 10776.61 8547.47 509.14 18064.96 307.61 5386.51 206.0 11358.69 B (103 ) 10.70 9.77 7.72 1.39 24.09 1.85 21.82 9.82 8.27 1.67 12.51 2.23 6.97 2.08 11.11 R2 0.9757 0.9970 0.9796 0.9787 0.8902 0.9822 0.8944 0.8290 0.8799 0.9860 0.9922 0.9857 0.9911 0.9925 0.8298

0 to 2250 2250 to 2500 0 to 1675 1675 to 2500 0 to 1345 1345 to 2500 0 to 1600 1600 to 2500 0 to 1160 1160 to 2500 0 to 1200 1200 to 2500

CS3

TABLE IV Validation of calibration relationships of estimation of Cl concentration in various soils Cl concentration (104 N) Sample S1 S2 S3 C1 C2 C3 CS1 CS2 CS3 OV (mV) 640 518 427 1935 1372 1331 1626 1158 1196 Using Eq. (1) 53.10 52.21 53.02 50.39 50.92 50.37 52.38 53.12 52.19 Using Eq. (2)

53.70

50.90

52.00

was compacted to the compaction states presented in Table II in the inner cylinder of the test setup depicted in Figure 6 to achieve the desired density. Soon after preparation of the soil sample, ten pairs of brass electrodes (1/8 diameter) were inserted into the soil sample, as depicted in Figure 6 and with the help of SCD, the value of OV corresponding to each electrode pair is recorded. These OV values

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Figure 6. Experimental setup for the column tests.

were adjusted to the OV values corresponding to the concentration of the Cl equal to 1 107 N, as depicted in Figure 3. After this, 1 N NaCl is poured on the top of the soil sample. The height of the source solution (1 N NaCl) is xed as 65 mm and this quantity of the NaCl solution is sufcient enough to ll the air voids in the soil sample completely. The OV values are recorded over a period of 150 days. The height of the contaminant solution is readjusted to 65 mm by adding the adequate amount of the source solution before taking the next set of observations whenever drop in the head is noticed to be more than 2 mm. 4. Results and Discussions Using the data obtained from the column tests, the variation of Cl concentration along the length of the nine soil samples corresponding to different durations (=7,

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Figure 7. Variation of Cl concentration along the sample length for different soil samples obtained from the column tests.

14, 35, 90 and 150 days) has been plotted, as depicted in Figure 7. It can be observed from the gure that the entire soil column attains a Cl concentration which is equal to the concentration of source solution (=1 N) within 35 days for samples S1, S3, C1, C2, C3 and CS1. However, for samples S2, CS2 and CS3 the upper half of the soil column achieves a Cl concentration of 1 N within 35 days and the full soil column within 150 days. One of the reasons for this phenomenon can be attributed

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TABLE V Values of Re and Pe for various soil samples in the column tests d10 Sample S1 S2 S3 C1 C2 C3 CS1 CS2 CS3 e 0.832 0.739 0.808 0.921 0.906 0.993 0.764 0.686 0.729 vs (m/s) 4.72E08 4.37E09 1.21E08 4.09E09 5.30E10 5.32E10 4.37E09 4.56E09 4.46E09 Re 6.08E09 5.62E10 1.56E09 4.45E10 5.77E11 5.79E11 5.20E10 5.42E10 5.30E10 Pe 3.02E05 2.80E06 7.77E06 2.22E06 2.87E07 2.88E07 2.59E06 2.70E06 2.64E06 Re 2.80E07 2.59E08 7.20E08 5.26E10 6.82E11 6.85E11 2.17E09 2.26E09 2.21E09 D50 Pe 1.40E03 1.29E04 3.58E04 2.62E06 3.39E07 3.41E07 1.08E05 1.12E05 1.10E05

to the higher e values, as depicted in Table V, for samples S1, S3, C1, C2, C3 and CS1 (range being 0.760.99) as compared to samples S2, CS2 and CS3 for which the same varies from 0.68 to 0.74. As NaCl solution is a non-reactive (conservative) contaminant, the possibility of its sorption on to the soil can be ignored (Crooks and Quigley, 1984). To identify contaminant migration mechanism prevailing in these soil samples, Reynolds number, Re , and Peclet number, Pe , have been computed using Equations (3) and (4) (Bear 1972), and the obtained values are presented in Table V. Re = l vs f vs l Pe = D (3) (4)

where f and are the density and viscosity of the NaCl solution, respectively, vs is the seepage velocity, l is the characteristic microscopic length (such as particle size) and is equal to either d10 or d50 (Bear, 1972). d10 and d50 correspond to the grain sizes, which are ner than 10% and 50% of the material by weight, respectively, and D is the diffusion coefcient of the Cl . Values of , f , and D for the NaCl solution are taken as 1.01 103 N s/m2 , 1000 kg/m3 and 20.3 1010 m2 /s, respectively. It must be noticed that for the column tests, the hydraulic gradient, i, is equal to 1.325. For the sake of completeness the seepage velocity, vs , for different soil samples are presented in Table V. It can be observed from the data presented in Table V that both Re and Pe are several orders less than unity for all soil samples considered in the present study. This ensures the hydrodynamic dispersion remains independent of velocity of ow and hence diffusion dominates the migration mechanism in these samples (Bear, 1972).

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The study also brings out the fact that although soils S, C and CS are quite different in their physical, chemical, mineralogical, and geotechnical properties, the migration mechanism for a contaminant remains the same. This indicates that for soils with d10 < 2 m and d50 < 100 m, the governing contaminant migration mechanism would be diffusion. However, to generalize these guidelines extensive studies must be conducted, with different soils and using different (non-reactive as well as reactive) contaminants.

5. Conclusions The present work is an attempt to model migration of contaminants through the soil mass. A simple, cost effective and nondestructive testing methodology has been proposed which is found to be quite efcient for monitoring Cl migration through different soils. Based on the present study, the following conclusions can be drawn: 1. The test setup developed for simulating contaminant migration mechanisms through the soil mass is found to be quite efcient. 2. The soil contaminant detector, SCD, fabricated for monitoring the presence and migration of contaminants in the soil mass works efciently. 3. The differential output voltage from the soil conductivity meter is inversely proportional to the Cl concentration in the soil mass. 4. The proposed calibration equation relating differential output voltage, OV, from the SCD to Cl concentration in the soil mass, works efciently when results are compared to the argentometric method. 5. Re and Pe are several orders of magnitude less than unity. This indicates that ow is laminar and the dominant contaminant transport mechanism is diffusion.

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