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4 ANIONIC AND NONIONIC SURFACTANT ASSISTED ELECTROKINETIC REMEDIATION FOR DIESEL REMOVAL IN SOIL

4.3. Results and Discussion

4.3.1 Moisture content, pH and electric conductivity

Initially, the soil moisture for all experiments was 20%. At the end of the electrokinetic remediation process, the moisture content reduced to contents of up to 16.4% (Fig. 2b, 2c and 2d), with higher contents in the lower fractions than in the upper fractions. This decrease can be observed in a more accentuated way in Exp Blank, with fractions presenting contents with half of the initial moisture (Fig. 2a). This reduction in moisture can be attributed to water evaporation (Saini et al., 2021).

Umidade solo - exp branco

Fig. 2. Moisture at different sampling points. Soil bottom (♦), soil intermediate (■) and soil upper (●). Experimental conditions: (a) Exp Blank, (b) Exp Tap water/Tap water, (c) Exp Tap water/SDS solution and (d) Exp Tap water/Tween 80 solution.

The pH in anode and cathode reservoirs over the 14 days of electrokinetic remediation is shown in Fig. 3 (a, b, c). The initial pH value of tap water used as electrolyte was 7.2 and 8 for the SDS and Tween 80 solutions. After 24 hours from the beginning of the treatment, in all experiments, it was observed that the pH in the anode compartments decreased to values close to 2 while the pH in the cathode compartments increased to values between 10.6 and 12.5.

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 compartments by applying 1 V cm-1 for 14 days. Experimental conditions: (a) Exp Tap water/Tap water, (b) Exp Tap water/SDS solution and (c) Exp Tap water/Tween 80 solution.

This behavior is explained by the electrolysis reactions that occur due to the application of the electric field, resulting in the oxidation reaction (anode), generating oxygen gas and H+ ions, and in the reduction reaction (cathode), which produces hydrogen gas and OH- ions , as shown in Eqs. (2) and (3), respectively (Acar and Alshawabkeh, 1993; Paixão et al., 2020;

Reddy and Cameselle, 2009; Rocha et al., 2019b; Santos et al., 2020; Virkutyte et al., 2002).

Ânodo (oxidação): 2 H2O (l) → O2(g) + 4 H+(aq) + 4 e- E0 = - 1,229 V (2) Cátodo (redução): 4 H2O (l) + 4 e- → 2 H2(g) + 4 OH-(aq) E0 = - 0,828 V (3)

Fig. 4 (a, b, c, d) shows the pH values in the soil fractions after treatment. The formation of H+ ions during the oxidation reactions did not cause a significant decrease in the pH values of the soil fractions close to the anode and, consequently, the acid front was not so evident.

However, a basic front was generated in the soil samples in the cathodic zones in the Exp Tap water/Tap water, Exp Tap water/SDS solution and Exp Tap water/Tween 80 solution, with pH values between 8.5 – 10 in most fractions in this region. This front occurs due to the formation of OH- ions during the reduction reaction (Hassan et al., 2017; Santos et al., 2015; Yeung and Gu, 2011).

Furthermore, it is possible to observe that in the Exp Tap water/Tap water and Exp Tap water/SDS solution

experiments higher pH values in the cathode fractions were obtained when compared with the pH values of the Exp Tap water/Tween 80 solution for the fractions of same region. This suggesting that the use of Tween 80 is able to better stabilize soil pH in relation to the use of SDS and tap water as electrolytes during the electrokinetic remediation process. Previous works reported that the removal of non-ionic pollutants can be increased with the maintenance of a basic environment within the soil (Alcántara et al., 2012).

6

Fig. 4. Changes in pH measured after post mortem analysis in soil bottom (♦), soil intermediate (■) and soil upper (●). Experimental conditions: (a) Exp Blank, (b) Exp Tap water/Tap water, (c) Exp Tap water/SDS solution and (d) Exp Tap water/Tween 80 solution.

The electrical conductivity (EC) in anode and cathode reservoirs over the 14 days of electrokinetic remediation is shown in Fig. 5. It is clear that the conductivity of anode reservoirs is superior to the conductivity obtained in cathode reservoirs. It is observed that the highest conductivity values were obtained when the electroosmotic flux reached its maximum (Fig 7).

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

Fig. 5. Conductivity changes, during the EK tests, measured in the electrolyte wells in (●) anodic and (▲) cathodic compartments by applying 1 V cm-1 for 14 days. Experimental conditions: (a) Exp Tap water/Tap water, (b) Exp Tap water/SDS solution and (c) Exp Tap water/Tween 80 solution.

Fig. 6 shows the electrical conductivity values in the soil portions after treatment.

Clearly, higher conductivity values are observed in the lower portions of the soil and lower values in the upper portions in all experiments. This behavior is compatible with the behavior of soil moisture after electrokinetic treatment, where higher water contents were obtained in the lower portions and lower values in the upper portions. Therefore, the conductivity of the soil

after the remediation process is directly related to the concentration of water in the soil portions.

However, the contribution of the movement of other ions available in the soil cannot be ignored (Ramírez et al., 2015).

When relating the conductivity behavior of Exp Tap water/Tap water (Fig. 6b) with the Exp

Tap water/SDS solution and Exp Tap water/Tween 80 solution (Fig.6c and 6d), it is observed that in the experiments with use of the surfactants, the electrical conductivity of the soil fractions did not show significant differences in relation to the proximity of the fractions with the anode and cathode. Meanwhile, in the experiment using only tap water as electrolyte, higher soil conductivity values were obtained in the vicinity of the cathode and lower values were observed in the vicinity of the anode. This suggests that the use of SDS and Tween 80 surfactants influenced the soil conductivity during and after electrokinetic treatment. While in the experiment using only tap water as electrolyte, higher values of soil conductivity were obtained near the cathode and lower values were observed in the vicinity of the anode. This suggests that the use of SDS and Tween 80 surfactants influenced the soil conductivity during and after intermediate (■) and soil upper (●). Experimental conditions: (a) Exp Blank, (b) Exp Tap water/Tap water, (c) Exp Tap water/SDS solution and (d) Exp Tap water/Tween 80 solution.

4.3.2. Electroosmotic flow

The application of an electric field to the soil results in the transport of water from the anode to the cathode, a process known as electro-osmosis. This generated flow contributes to improve the pollutants removal efficiency, as it provides an increase in soil interactions with the contaminant (López Vizcaíno et al., 2018; Paixão et al., 2020; Reddy et al., 2006; Rocha et al., 2019b). For soil contaminated with organic compounds, this is the mechanism that acts most significantly (Ng et al., 2014), and is the main mechanism that determines the kinetics of electrokinetic remediation (Lim et al., 2016b). Fig. 7 shows the electroosmotic flux (EOF) during soil remediation experiments. During the course of treatment, in all experiments the level of the volume of the cathode reservoir increased, while the level of the volume of the anodic reservoir decreased, indicating that the direction of EOF occurred from the anode to the cathode (López-Vizcaíno et al., 2012; Ren et al., 2019).

As shown in Fig. 7, Exp Tap water/Tap water and Exp Tap water/SDS solution exhibited higher EOF compared to Exp Tap water/Tween 80 solution. The highest values for Exp Tap water/Tap water and Exp Tap water/SDS solution were reached on the third day of electrokinetic treatment, while for Exp Tap water/Tween 80 solution the EOF was higher between days 5 and 9. This behavior can be justified by the Helmholz-Smoluchowski theory, which states that the electroosmotic flow velocity is directly proportional to the fluid's dielectric constant and inversely proportional to the fluid's viscosity (Reddy and Cameselle, 2009; Sandu et al., 2017), which it is in accordance with the properties of the fluids used.

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

0 2 4 6 8 10

ExpTap water/tap water ExpTap water/SDS s olution ExpTap water/Tween 80 s olution

Time / days

EOF / mL h-1

Fig. 7. Electroosmotic flow. Experimental conditions:

Exp Tap water/Tap water (●), Exp Tap water/SDS solution (♦) and Exp

Tap water/Tween 80 solution (▲).

4.3.3. Distribution and removal of TPH in the soil after treatment

The concentrations of total petroleum hydrocarbons (TPH) distributed in the soil fractions after electrokinetic treatment are shown in Fig. 8. The Exp Blank (Fig. 8a) shows the loss of the contaminant by evaporation (17.4 - 48%) or even in the sample contaminant extraction step. Concentrations between 6043.12 – 8261.59 mg kg-1 of TPH were quantified in the soil after 14 days for Exp Blank. In Exp Tap water/Tap water (Fig. 8b) it is possible to observe higher concentrations of TPH in fractions P3 and P4 than in fractions close to the anode, evidencing the occurrence of electroosmosis as the main transport mechanism acting in the removal of the pollutant in this experimental condition (Fdez-Sanromán et al., 2021; Reddy and Cameselle, 2009; Virkutyte et al., 2002).

The distribution of TPH in the soil after treatments using the surfactants SDS (Fig. 8c) and Tween 80 (Fig. 8d) presented a different behavior than Exp Tap water/Tap water. In these last experiments, the distribution of the concentration of the contaminant in the soil fractions, indicate the occurrence of transport of the contaminant also by electrophoresis, since high concentrations of TPH were also obtained in the soil fractions close to the anode. In this transport mechanism, charged colloids, such as surfactant micelles, help transport contaminants, which are attached to the surface of these colloids (Lim et al., 2016b; Reddy et al., 2006; Virkutyte et al., 2002).

TPH solo exp tween 80 - corrigido

0

Fig. 8. Spatial distribution of TPH concentration in the soil after the remediation process for 14 days. Experimental conditions: (♦) soil bottom, (■) soil intermediate and (●) soil upper. (a) Exp Blank, (b) Exp Tap water/Tap water, (c) Exp Tap water/SDS solution and (d) Exp Tap water/Tween 80 solution.

Studies involving the treatment of polluted soil with persistent organic compounds often use the total organic carbon content (TOC) as evidence of removal efficiency (Carvalho de Almeida et al., 2019a, 2019b; Dos Santos et al., 2014; Vieira dos Santos et al., 2017). In this study, TOC was determined in the fluids of anode and cathode reservoirs after 14 days of electrokinetic treatment. The TOC contents obtained in the anode reservoirs were 16.50, 79.01 and 57.60 mg L-1 and 71.70, 193.75 and 26.80 mg L-1 in the cathode reservoirs for Exp Tap water/Tap water, Exp Tap water/SDS solution and Exp Tap water/ Tween 80 solution, respectively. These values corroborate the transport mechanisms (electrophoresis and electroosmosis) observed through the distribution of TPH in the soil fractions already discussed.

The residual concentration of TPH in the soil was 6986.97, 4981.84, 3754.83 and 4240.29 mg kg-1 for the Exp Blank, Exp Tap water/tap water, Exp Tap water/SDS solution and Exp Tap water/Tween 80 solution, respectively. The highest TPH removal efficiencies were obtained using electrokinetic remediation combined with the use of surfactants, showing a removal of 46.25% using SDS and 39.31% using Tween 80. Removal without the use of surfactants was 28.70%. SDS more effectively removed the HTPs from the soil as it is an anionic surfactant and has lower soil adsorption, which substantially increases the availability of micelle formation (de Melo Henrique et al., 2019). These removals were higher than those presented in studies of electrokinetic treatment of soil contaminated with 10000 mg kg-1 of diesel after 14 days of remediation (Mena et al., 2016; Ramírez et al., 2015; Song et al., 2018), as shown in Table 3.

Table 3.

Removal efficiency in polluted soil with 10000 mg kg-1 of diesel after 14 days of electrokinetic remediation.

Treatment Diesel removal (%) Reference

EK 28.7 This work

EK + Solubilizing agent (SDS) 46.3 This work

EK + Solubilizing agent (Tween 80) 39.3 This work

EK + Bio-PRB 29 Ramírez et al., 2015

EK + Bio-PRB 36 Mena et al., 2016

EK + ISCO 33 and 44 Song et al., 2018

These results suggest that surfactant-assisted electrokinetic remediation can be used as a soil pre-treatment in cases of large diesel leaks, and that a complementary treatment should then be applied.

4.4. Conclusions

In this study, the performance of electrokinetic remediation using solar energy and enhanced treatment using surfactants was investigated in diesel contaminated soil. The main conclusions were:

 Considerable diesel content can be lost through evaporation during electrokinetic treatment.

 The combination of EK-surfactants showed TPH removals higher than those shown in electrokinetic treatment studies of soil contaminated with 10000 mg kg-1 of diesel after 14 days of remediation.

 The addition of surfactants increased the efficiency of TPH removal, promoting the transport of hydrocarbons by electrophoresis and electroosmosis.

 The use of the nonionic surfactant Tween 80 increased the diesel removal by the electrokinetic process by 10.61%, while the anionic surfactant SDS increased the efficiency of this same process by 17.55%.

 This type of treatment has potential applicability as a pre-treatment for cases of polluted soils with high concentrations of diesel, resulting from large leaks.

4.5. Acknowledgements

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