Journal of Hazardous Materials 235236 (2012) 384387

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Short communication

Washing of metal contaminated soil with EDTA and process water recycling
Maja Pociecha, Domen Lestan
Agronomy Department, Biotechnical Faculty, University of Ljubljana, Jamnikarjeva 101, 1000 Ljubljana, Slovenia

h i g h l i g h t s
EDTA and process water recycling in pH gradient. The salinity and toxicity of recycled process waters. The efciency of the recycled EDTA to extract metals.

a r t i c l e

i n f o

a b s t r a c t
We demonstrate here, in a laboratory scale experiment, the feasibility of using the base/acid pair Ca(OH)2 /H2 SO4 to impose a pH gradient for EDTA recycling and, coupled with an electrochemical advanced oxidation process using a graphite anode, of recycling process water as part of a novel remediation technology for multi-metal contaminated soils. In the rst batch, 60 mmol EDTA kg1 of soil removed 72, 27, and 71% of Pb, Zn, and Cd, respectively, from soil contaminated with 5329 685, 3401 193, and 35 6 mg kg1 of Pb, Zn, and Cd, respectively. In the subsequent four batches, we demonstrated that up to 88% of EDTA was recycled from each batch, with the potential to extract up to 98, 94, and 109% of Pb, Zn, and Cd, respectively, that the fresh EDTA extracted. Accumulation of salts in the process water through multiple remediation batches/recycles was prevented by CaSO4 precipitation. Recycled process water toxicity testing indicated no signicant effect on plant seed germination but some inhibition of root elongation. 2012 Elsevier B.V. All rights reserved.

Article history: Received 14 May 2012 Received in revised form 31 July 2012 Accepted 1 August 2012 Available online 7 August 2012 Keywords: Metal contamination Soil remediation Reagent recycling Water toxicity

1. Introduction Contamination of soils with toxic metals (TMs) is a widespread problem across the globe. One of the most promising remediation options is soil washing, whereby TMs are separated from soil solid phases by solubilizing in a washing solution with a chelating agent. EDTA is most frequently used, due to its efciency, availability, and relatively low cost [1,2]. The main problem with soil washing technologies is the generation of vast amounts of toxic waste solution [3]. In relation to this, we recently reported on a novel EDTA and process water recycling method after remediation of multi-metal contaminated soil [4]. We recovered EDTA from used soil washing solution by using acid precipitation with HCl and H2 SO4 , coupled to initial alkaline (NaOH) removal of Fe. An electrochemical advanced oxidation process was then used to degrade the remaining EDTA and remove the TMs. The cleansed process water was used to prepare recycled washing solution by re-dissolving the recycled EDTA.

However, a build-up of salts of Na+ and Cl or SO4 2 and deterioration of the process water quality remained a problem. In this study, we improved the proposed remediation method by using Ca(OH)2 and H2 SO4 as the base/acid pair for imposing a pH gradient for EDTA recovery, while accumulation of salts in the recycled process water was prevented by precipitation and removal of poorly soluble CaSO4 . The effect of variables (temperature and pH) on process efciency was examined and recycling efciency evaluated through four soil remediation batches. Finally, the toxicity of the process water after the last recycle was examined. 2. Experimental 2.1. Soil remediation process Soil was collected from a vegetable garden in the Mezica Valley (Slovenia), which has been exposed to more than three hundred years of active lead mining and smelting. The soil contained 5329 685 mg kg1 Pb, 3401 193 mg kg1 Zn, and 35 6 mg kg1 Cd. The novel soil remediation is a batch-mode process (Fig. S1, supplementary material), comprising soil extraction (Fig. S1, Step 1), substitution of metals complexed on EDTA with Ca in alkaline pH

Corresponding author at: Centre for Soil and Environmental Science, Biotechnical Faculty, University of Ljubljana, Jamnikarjeva 101, 1000 Ljubljana, Slovenia. Tel.: +386 01 423 1161; fax: +386 01 423 1088. E-mail address: domen.lestan@bf.uni-lj.si (D. Lestan). 0304-3894/$ see front matter 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.jhazmat.2012.08.001

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(Step 2), protonation and precipitation of recycled EDTA in acidic pH (Step 3), electrolytic degradation of EDTA remaining in the washing solution, removal of released metals and cleansing and recycling of process water (Step 4), and dissolution of the recycled EDTA in the recycled process solution to obtain recycled washing solution (Step 5). In this study, four consecutive soil remediation batches were performed. After initial soil washing, all consecutive batches were done in triplicate. The initial soil washing solution was obtained after extraction of 75 kg of soil with 75 L of Na2 -EDTA solution (60 mM EDTA kg1 soil) in a concrete mixer for 2 h. After extraction, the soil suspension was rst ltered through a 2 mm sieve and the soil solid phase was separated from the spent soil washing solution in a chamber lter press (lter cloth thickness 0.6 g cm2 , air permeability 22 dm3 dm2 min1 , Ecotip, Slovenia). Consecutive soil extractions with recycled 30 mmol kg1 EDTA washing solution were performed on a rotating shaker for 2 h, in parallel with extractions with fresh 30 mmol kg1 Na2 EDTA in deionized water (pH 5). Since some water and EDTA were lost during the process, the consecutive batches/recycles were conducted in increasingly smaller volumes. In the rst batch (after initial soil washing) we used 12 L of EDTA solution and 6 kg of soil and in the fourth batch we used 300 mL of EDTA solution and 150 mg of soil. The operating solid:liquid ratio, however, was kept at 1:2 in all batches performed on a rotating shaker. The soil solid phase was separated by centrifugation at 2880 g for 10 min. In the substitution step, used soil washing solution was alkalinized using different weights of Ca(OH)2 , from 1.1 to 7.0 g L1 , to optimize Ca substitution and precipitation of Fe and TMs, which were removed from the solution by centrifugation at 3760 g for 10 min. In the protonation step, the pH of the solution was adjusted to values between 1.0 and 2.2 using 96% H2 SO4 to precipitate the EDTA, which was removed from the solution by ltration (lter pores 2 m) after incubation at two different temperatures (3 C and 24 C) for 24 h. Recycled EDTA was dried at 60 C to a constant weight and stored. In the electrolytic degradation step, the residual solution was owed-through electrolytic cells equipped with a graphite anode and stainless cathode (electrode surface 68 cm2 , distance between electrodes 13 mm). The washing solution (500 mL) was circulated from a magnetically stirred jar through the electrolytic cells using a peristaltic pump (ow rate 14 mL s1 ). A DC power supply (Elektronik Invent, Ljubljana, Slovenia) provided a constant electrical current density of 88 mA cm2 . The initial pH of the solution was adjusted to different pH values (2, 7, and 10) by drop-wise addition of 5 M KOH. The contact time of the solution in the electrolytic cell was calculated as the ratio of cell volume and the volume of washing solution, multiplied by the operating time (initially 19 min of operating time equaled 4 min of contact time). Ten mL samples were periodically collected and stored in the cold for TMs and EDTA analysis. The cathode was etched at the end with 30 mL of 65% HNO3 to dissolve the electro-deposited TMs. In the dissolution step, the recycled EDTA from the protonation step was dissolved in the electrochemically cleansed process solution to obtain recycled washing solution. The pH of recycled washing solutions was adjusted to 5 using 5 M KOH. 2.2. Germination and root elongation test A germination and root elongation test was performed with three plant species: Lepidium sativum L. (garden cress), Lactuca sativa L. (lettuce), and Cichorium intybus L. (chicory). We tested recycled process water after the third consecutive electrolysis according to the US EPA procedure [5]. We assessed the % of seed germination (SG), root elongation (RE), and relative root elongation

Pb (mg L-1) Zn (mg L-1) Cd (mg L-1) Fe (mg L-1)

1500 1000 500 0 300 200 100 0 8 6 4 2 0 800 600 400 200 0 8 9 10 11 12 13

pH
Fig. 1. Concentrations of dissolved TM chemical species in the used soil washing solution along the increasing pH gradient of solution achieved by Ca(OH)2 addition.

ratio (rRE). Root length was dened as the length from the tip of the root to the transition point between the hypocotyl and root, and germination was dened as a root length of at least 5 mm. 2.3. Metals and EDTA determination Air-dried soil samples were prepared, digested in aqua regia and analyzed for metals in AAS as previously described [4]. The metal concentration in the solutions was determined by AAS directly. The limit of quantication for Pb, Zn, Cd, and Fe were 0.1, 0.01, 0.02, 0.09, and 0.06 mg L1 , respectively. The concentration of EDTA was determined spectrophotometrically according to the procedure of Hamano as previously reported [4]. The limit of EDTA quantication was 20 mg L1 . The Duncan multiple range test was used to determine the statistical signicance (p < 0.05) between data measured in different treatments, using the computer program Statgraphics 4.0 for Windows. 3. Results and discussion The rst batch extraction (60 mmol EDTA kg1 soil) removed 72, 27, 71, and 6.6% of Pb, Zn, Cd, and Fe, respectively, from the contaminated soil. The concentration of EDTA, Pb, Zn, Cd, and Fe in the used washing solution was 11,578, 1109, 267, 7.1, and 805 mg L1 , respectively; the solution pH was 7.3. Fe was found to interfere with acidic EDTA precipitation [4] from used washing solution, presumably due to the high stability of FeEDTA complexes at low pH, compared to other metals [2]. Using NaOH to increase the pH above 11 made the formation of Fe-EDTA complexes less favorable, leading to Fe hydrolysis and Fe(OH)3 precipitation [4]. However, using NaOH did not remove Pb, Zn, and Cd from the solution. As shown in Fig. 1, using Ca(OH)2 efciently removed not only Fe but also TMs (applying inexpensive lime or milk of lime was equally effective, data not shown). Apparently Ca forms complexes with EDTA at high pH, which are more stable than Pb, Zn, and Cd-EDTA complexes. Similarly, Jiang et al. [6] developed a simple Ca(OH)2 -based replacementprecipitation process, and applied it to the removal of EDTA-chelated Cu in wastewater.

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Another similar process was adopted by Zeng et al. [7], in which Pb, Zn, Cd, and Cu-EDTA complex solution was treated with Ca(OH)2 . The pH of the solution was elevated up to 10.5 to precipitate the metals. Ca(OH)2 is poorly water-soluble (1.65 g L1 at 20 C [8]) and its solubility decreases with pH. Nevertheless, our results indicate a pH increase up to 12.4 due to Ca(OH)2 dissolution (at this point 4.7 g L1 of Ca(OH)2 was applied). Ca(OH)2 dissolution was presumably enhanced due to Ca consumption for substitution of Fe and TMs in EDTA complexes. Protonated EDTA (H4 EDTA) is poorly soluble in acidic media [9] and, after H2 SO4 addition, precipitated from the solution (Fig. S2A, supplementary material). EDTA precipitation was studied at two different T. Precipitation at 3 C was not statistically significantly different from precipitation at 24 C. As also observed in our previous study [4] Pb-EDTA complexes are unstable at pH < 1.8, leading to PbSO4 precipitation and removal from used washing solution (Fig. S2B). Again, T was not a signicant parameter. To avoid contamination of recycled EDTA with Pb, the used washing solution was acidied to pH 2 in subsequent batches. In addition to EDTA, excess Ca in the washing solution was removed as poorly soluble CaSO4 (CaSO4 , solubility is 2.98 g L1 at 20 C [8]). This prevented accumulation of added reagents after multiple recycles. Six percent more EDTA was recycled from the washing solution compared to our previous study, in which NaOH was used [4], presumably due to complete removal of Fe and the majority of TMs in the Ca(OH)2 alkaline phase (Fig. 1). After Fe, TMs, EDTA, and CaSO4 removal along a pH 12.2 gradient, the used washing solution still contained some residual TMs (Fig. S3, supplementary material) and EDTA, although Pb, Zn, and Cd concentrations were 4.4, 17, and 1.4-times lower than in our previous study [4]. The washing solution was therefore further treated using an electrochemical advanced oxidation method with a hydroxyl-radical producing graphite anode. The mechanisms of electro-oxidation processes are given elsewhere [4]. The initial pH of the solution (2, 7, 10) did not have a signicant effect on TMs removal. As also indicated in Fig. S3, the pH varied in a narrow pH interval during the electrolysis. EDTA was totally removed from the solution at all pH values. TMs were partly electro-deposited on the stainless-steel cathode and partly precipitated (data not shown). The removal of TMs was more complete than in the previous study [4], particularly of Zn, for which the average nal concentration (0.53 0.91 mg L1 ) was 68-times lower. The treatment time (and thus electricity consumption) was also somewhat shorter. Electrolysis at initial pH 2 was used in subsequent batches. The electrochemically cleansed solution was used to dissolve recycled EDTA to obtain recycled washing solution. Recycled EDTA retained TMs extraction efciency through all four recycles (soil remediation batches), Fig. 2, and had the potential to extract up to 98, 94, and 109% of Pb, Zn, and Cd, respectively, compared to equimolar fresh EDTA. It has been similarly reported that Na2 CaEDTA was less effective for Pb and Zn extraction from soil compared to Na2 -EDTA [10]. We may also have underestimated the extent of hydration of recycled EDTA during drying and therefore weighed less EDTA. Current EDTA-based soil remediation methods are problematic because of the generation of EDTA-containing wastewaters, which need to be treated separately before discharge. Although in our novel remediation method, the process water is recycled (and not discharged), its purity and safety are important, particularly if used for soil rinsing (removal of residual EDTA-mobilized metallic species). The toxicity of the electrochemically cleansed process water was evaluated using a seed germination and root elongation test. The germination rate was quite high, above 79% relative to the control (deionized water) with all plant species (Table 1). A higher germination rate of a test species in control water means

Fig. 2. Relative efciency of recycled EDTA compared to original EDTA of the same molarity, during 4 consecutive batches of soil extraction/EDTA recycles. Error bars represent standard deviation from the mean value (n = 3).

Table 1 Seed germination (SG) in the recycled soil washing solution after the third consecutive electrolysis and in deionized water (control). Average root elongation (RE) and relative root elongation factor (rRE) of three plant species are presented (n = 5, SD). SG (%) Lepidium sativum L. Recycled solution Control solution Lactuca sativa L. Recycled solution Control solution Cichorium intybus L. Recycled solution Control solution
a

RE (mm) 9.2a 1.0 11.0a 6.5 0.35a 0.57 5.9a 1.3 6.0a 1.5 12.7a 4.6

rRE 0.16

81a 8 84a 10 19a 19 83a 10 83a 7 79a 6

0.94

0.53

Statistically signicant difference (Duncan test, p < 0.05).

lower uncertainty of test results [11]. There were also no statistically signicant differences in the germination of garden cress and chicory seeds in recycled washing solution compared to the control, only lettuce seeds show a statistically signicant seed germination decrease in recycled washing solution. Root elongation proved to be more sensitive, which is consistent with previous studies [12], and showed a statistically signicant inhibition effect of recycled process solution, especially on lettuce (Table 1). This can presumably be attributed to reported formaldehyde and ethylenediamine as a by-product of anodic EDTA oxidation [13]. Nevertheless, the recycled process water did not exhibit acute toxicity or a lethal effect on plants. 4. Conclusions Using Ca(OH)2 and H2 SO4 as a base/acid pair to impose a pH gradient for EDTA and process water recycling is feasible and represents improvement over published novel soil remediation method [4]. Using Ca(OH)2 instead of NaOH in the alkaline process phase efciently removed not only Fe but also Pb, Zn, and Cd from the used washing solution. Yield of recycled EDTA was higher and time of electrolytic process water recycling was shorter (lower electricity consumption). The electrolytic removal of toxic metals from recycled process water was more complete and the accumulation of salts was prevented by precipitation of scarcely soluble CaSO4 . The novel technology was tested over several soil remediation batches/reagent and water recycles. The following conclusions can be drawn: Up to 88% of EDTA was recycled from each batch.

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The efciency of the recycled EDTA to extract metals remained unchanged through the batches. The metal extraction efciency of the recycled EDTA was slightly lower than that of fresh EDTA. Recycled process water was not toxic for seed germination but showed some inhibition effect on seed root elongation. The amended remediation technology is currently being tested in a pilot-scale study. Acknowledgment This work was supported by the Slovenian Research Agency, Grant J4-3609. Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/ j.jhazmat.2012.08.001. References
[1] D. Lestan, C. Luo, X. Li, The use of chelating agents in the remediation of metal-contaminated soils: a review, Environ. Pollut. 153 (2008) 313.

[2] C. Kim, Y. Lee, S.-K. Ong, Factors effecting EDTA extraction of lead from lead-contaminated soils, Chemosphere 51 (2003) 845853. [3] F.I. Khan, T. Husain, R. Hejazi, An overview and analysis of site remediation technologies, J. Environ. Manage. 71 (2004) 95122. [4] M. Pociecha, D. Lestan, Novel EDTA and process water recycling method after soil washing of multi-metal contaminated soil, J. Hazard. Mater. 201202 (2012) 273279. [5] US EPA, Ecological Effects Test Guidelines. OPPTS 850.4200, Seed Germination/Root Elongation Toxicity Test, 1996. [6] S.X. Jiang, F.L. Fu, J.X. Qu, Y. Xiong, A simple method for removing chelated copper from wastewaters: Ca(OH)2 -based replacementprecipitation, Chemosphere 73 (2008) 785790. [7] Q.R. Zeng, S. Sauve, H.E. Allen, W.H. Hendershot, Recycling EDTA solutions used to remediate metal-polluted soils, Environ. Pollut. 133 (2005) 225231. [8] B.E. Poling, G.H. Thomson, D.G. Friend, R.L. Rowley, W.V. Wilding, Physical and chemical data, in: D.W. Green, R.H. Perry (Eds.), Perrys Chemical Engineers Handbook, eighth ed., McGraw-Hill, New York, 2007. [9] L. Di Palma, P. Ferrantelli, C. Merli, F. Bianciori, Recovery of EDTA and metal precipitation from soil washing solutions, J. Hazard. Mater. 103 (2003) 153168. [10] P. Theodoratos, N. Papassiopi, T. Georgoudis, A. Kontopoulos, Selective removal of lead from calcareous polluted soils using the Ca-EDTA salt, Water Air Soil Pollut. 122 (2000) 351368. [11] W. Wang, P.H. Keturi, Comparative seed germination tests using ten plant species for toxicity assessment of a metal engraving efuent sample, Water Air Soil Pollut. 52 (1990) 369376. [12] M. Di Salvatore, A.M. Carafa, G. Carratu, Assessment of heavy metals phytotoxicity using seed germination and root elongation tests: a comparison of two growth substrates, Chemosphere 73 (2008) 14611464. [13] J.W. Johnson, H.W. Jiang, S.B. Hanna, W.J. James, Anodic oxidation of ethylenediaminetetraacetic acid on Pt in acid sulphate solution, J. Electrochem. Soc. 119 (1972) 574580.