Influence of injection conditions on EDDS-flushing of metal-contaminated soil.

This study evaluated the design of step-gradient, single-pulse, multi-pulse, and continuous injection of biodegradable EDDS ([S,S]-ethylene-diamine-disuccinic acid, under the same total dosage) and the significance of pore-water velocities during in situ soil flushing. In view of the metal breakthrough and extraction efficiency of each injection mode, single-pulse injection was found to be the least effective for all metals. Multi-pulse injection was consistently more effective than single-pulse injection, although the efficiency of second and third pulse injections significantly diminished. Continuous injection offered a simple operation and the greatest Ni and Cu extraction, whereas step-gradient injection was the best option for Zn and Pb extraction because it mitigated the influence of metal exchange. Moreover, a rinsing step with a background solution following the initial injection of the multi-pulse injection removed newly formed metal-EDDS complexes from soil pores effectively before further EDDS-flushing. A decrease in pore-water velocity provided a longer residence time for greater Ni and Cu extraction, but also enhanced the rate-limited metal exchange of Zn-EDDS and Pb-EDDS complexes and thus hindered Zn and Pb extraction. These results suggest a slower and continuous injection for the best Ni or Cu removal, but a faster and step-gradient injection for Zn or Pb removal.

Significance of metal exchange in EDDS-flushing column experiments.

Chelating agents have been widely studied for extracting heavy metals from contaminated soils, and the effectiveness of EDDS ([S,S]-ethylene-diamine-disuccinic acid) has aroused extensive attention because of its biodegradability in the natural environment. However, in the course of EDDS-flushing, metal exchange of newly extracted metal-EDDS complexes with other sorbed metals and mineral cations may result in metal re-adsorption on the soil surfaces. Therefore, this study investigated the relative significance of metal exchange under different travel distances of chelant complexes, characteristics of soil contamination, and solution pH in the column experiments. As a result of metal exchange, the elution of Zn and Pb was retarded and the cumulative extraction was lower than those of Ni and Cu, especially over a longer travel distance. Compared with the field-contaminated soils, the effects of metal exchange were even more substantial in the artificially contaminated soil because of a greater amount of extractable metals and a larger proportion of weakly bound fractions. By contrast, metal exchange was insignificant at pH 8, probably due to less adsorption of metal-EDDS complexes. These findings highlight the conditions under which metal exchange of metal-EDDS complexes and the resulting impacts are more significant during EDDS-flushing.

Interactions of chelating agents with Pb-goethite at the solid-liquid interface: Pb extraction and re-adsorption.

The use of ethylenediaminetetraacetic acid (EDTA) for soil remediation is under concern due to its non-biodegradability and toxicity; thus, its biodegradable structural isomer, [S,S]-ethylenediamine disuccinate ([S,S]-EDDS), has been proposed as an emerging substitute. In this study, batch experiments were performed to quantify the Pb extraction from goethite by EDTA and EDDS, respectively, and attenuated total reflectance-Fourier transform infrared (ATR/FT-IR) spectroscopy was used to investigate the corresponding mechanisms at the solid-liquid interface at different pH and reaction times. The Pb extraction was pH-dependent for both chelating agents; mildly alkaline condition was favorable for EDDS, while mildly acidic condition for EDTA. The discrepancy between two structural isomers might be caused by their pH-dependent zwitterionic structures. The ATR/FT-IR results revealed that under acidic conditions, hydrogen-bonded carboxyl groups were present in both zwitterionic EDDS and EDTA. However, ring structure of zwitterionic EDDS formed with stable intramolecular hydrogen bond might limit the availability for EDDS to extract Pb from goethite. On the other hand, each protonated amine of zwitterionic EDTA could form hydrogen bonds with two neighbouring carboxyl groups, intensifying the negative charge of carboxyl groups and enhancing the Pb extraction efficiency. However, there was a higher amount of re-adsorption of PbEDTA than PbEDDS, because zwitterionic EDTA resulted in a greater Pb extraction and facilitated iron dissolution which significantly altered the goethite morphology, particle size, and surface area. These results suggested that, despite being structural isomers, EDDS and EDTA resulted in varying extents of Pb extraction and re-adsorption due to their different zwitterionic properties.

Heavy metal extraction from an artificially contaminated sandy soil under EDDS deficiency: significance of humic acid and chelant mixture.

Biodegradable EDDS ([S,S]-ethylenediaminedisuccinic acid) has been suggested for enhancing heavy metal extraction from contaminated soils. Recent studies showed that Zn and Pb are less effectively extracted due to metal exchange and re-adsorption onto the soil surfaces, especially for EDDS-deficiency conditions. This study therefore investigated the influence of dissolved organic matter and the co-presence of EDTA (ethylene-diamine-tetraacetic acid) on metal extraction from an artificially contaminated sandy soil under deficient amount of chelants in batch kinetics experiments. The addition of 10 and 20mgL(-1) of humic acid as dissolved organic matter (DOC) suppressed metal extraction by EDDS, probably resulting from the competition of adsorbed humic acid for heavy metals and adsorption of metal-humate complexes onto the soil surfaces. The effects were most significant for Pb because of greater extent of metal exchange of PbEDDS and high affinity towards organic matter. Thus, one should be cautious when there is a high content of organic matter in soils or groundwater. On the other hand, compared to individual additions of EDDS or EDTA, the equimolar EDDS and EDTA mixture exhibited significantly higher Pb extraction without notable Pb re-adsorption. The synergistic performance of the EDDS and EDTA mixture probably resulted from the change of chemical speciation and thus less competition among Cu, Zn and Pb for each chelant. These findings suggest further investigation into an optimum chemistry of the chelant mixture taking into account the effectiveness and associated environmental impact.

Influence of EDDS-to-metal molar ratio, solution pH, and soil-to-solution ratio on metal extraction under EDDS deficiency.

In situ biodegradable EDDS ([S,S]-stereoisomer of ethylenediaminedisuccinic acid) applications at low concentration may present conditions where applied EDDS is insufficient relative to sorbed metals in soils. This study investigated the influence of EDDS-to-metal molar ratios (MR), solution pH and soil-to-solution ratio on metal extraction under EDDS deficiency (i.e., MR<1). Batch kinetics experiments showed that Pb and Zn extraction exhibited different kinetic behaviors at MR 0.35-0.75, while Cu extraction was comparable. At MR 0.75 or below, newly extracted Pb was re-adsorbed onto the soil surfaces. Similar re-adsorption phenomenon, to a lower extent, was observed for newly extracted Zn at MR 0.5 or below, whereas this appeared to be marginal at MR 0.75, reflecting Zn extraction was less affected by EDDS deficiency than Pb extraction. Moreover, Pb extraction at an alkaline condition was preferable under EDDS deficiency because at MR 0.5 it was 30% higher at pH 8 and 9 than pH 5.5 and 7. The influence of varying soil-to-solution ratios (1:50-1:5) at MR 0.5 was marginal compared with that of MR and solution pH. These findings indicated that Pb extraction by deficient EDDS would be more difficult to accomplish compared to Cu and Zn extraction.

Kinetic interactions of EDDS with soils. 1. Metal resorption and competition under EDDS deficiency.

Biodegradable EDDS ([S,S]-ethylenediaminedisuccinic acid) is an emerging chelant for enhancing heavy metal extraction. During soil remediation that involves continuous flushing, metal extraction is often limited by the amount of EDDS. Under EDDS deficiency, initial extraction of Zn and Pb followed by resorption was observed in batch kinetic experiments. Speciation calculations indicated that the percentages of ZnEDDS(2-) and PbEDDS(2-) in respective dissolved metal concentrations decreased with time, whereas the contribution of CuEDDS(2-) to total EDDS increased accordingly. This pointed to the metal exchange of newly formed ZnEDDS(2-) and PbEDDS(2-) with sorbed Cu on the soil surfaces, rather than with Fe oxides. A portion of displaced Zn and Pb was resorbed on the exchangeable and carbonate fractions, whereas the rest was mainly bound to dissolved organic matter (DOM) and remained in solution. On the other hand, although dissolved Al was the major mineral cation in solution under EDDS deficiency, the resulting competitive effect on metal extraction was marginal because Al readily dissociated from EDDS complexes and predominantly existed as colloidal precipitates, DOM-complexes, or hydrolyzed species. By contrast, under EDDS excess, metal resorption was indiscernible while more significant Al and Fe dissolution influenced the EDDS speciation.

Kinetic interactions of EDDS with soils. 2. Metal-EDDS complexes in uncontaminated and metal contaminated soils.

The effectiveness of biodegradable EDDS has aroused substantial interest over the past few years, yet there has been little information on the fate of metal-EDDS complexes that, prior to biodegradation, stay in contact with the soils. This study conducted 7-day batch experiments to investigate the kinetic interactions of CuEDDS(2-), ZnEDDS(2-), PbEDDS(2-), and AIEDDS(-), which are newly formed during EDDS application, with uncontaminated and metal-contaminated soils at pH 5.5 and 8. In uncontaminated soils, metal-EDDS complexes were adsorbed and induced mineral dissolution. In contaminated soils, on the contrary, significant metal exchange with sorbed metals on the soil surfaces (i.e., Cu, Zn, and Pb) resulted in a greater extent of metal resorption of the metal-EDDS complexes. The interactions of metal-EDDS complexes, moreover, are influenced by the characteristics of the metal center. Compared with ZnEDDS(2-) and PbEDDS(2-), CuEDDS(2-) was least adsorbed or exchanged, which may be attributed to higher ionic potential and the electron configuration of Cu. In addition, AIEDDS(-) was partially exchanged on the soil surfaces at low pH while entirely dissociated in solution at high pH. Therefore, the fate of individual metal-EDDS complexes in the subsurface depends on the metal center, other sorbed metals and mineral cations on soils, and solution pH.

Empirical modeling of heavy metal extraction by EDDS from single-metal and multi-metal contaminated soils.

The effectiveness of using biodegradable EDDS (S,S-ethylenediaminedisuccinic acid) for metal extraction has drawn increasing attention in recent years. In this study, an empirical model, which utilized the initial metal distribution in soils and a set of parameter values independently determined from sequential extraction, was developed for estimating the time-dependent heavy metal extraction by EDDS from single-metal and multi-metal contaminated soils. The model simulation provided a satisfactory description of the experimental results of the 7-d extraction kinetics of Cu, Zn, and Pb in both artificially contaminated and field-contaminated soils. Thus, independent and prior assessment of extraction efficiency would be available to facilitate the engineering applications of EDDS. Furthermore, a simple empirical equation using the initial metal distribution was also proposed to estimate the extraction efficiency at equilibrium. It was found that, for the same type of soils, higher extraction efficiency was achieved in multi-metal contaminated soils than in single-metal contaminated soils. The differences were 4-9%, 9-16%, and 21-31% for Cu, Zn, and Pb, respectively, probably due to the larger proportion of exchangeable and carbonate fractions of sorbed Zn and Pb in multi-metal contaminated soils. EDDS-promoted mineral dissolution, on the other hand, was more significant in multi-metal contaminated soils as a result of the higher EDDS concentration applied to the soils of higher total metal content.