Daniel C.W. Tsang

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.

Soil stabilisation using AMD sludge, compost and lignite: TCLP leachability and continuous acid leaching

Utilising locally available industrial by-products for in situ metal stabilisation presents a low-cost remediation approach for contaminated soil. This study explored the potential use of inorganic (acid mine drainage (AMD) sludge and zero-valent iron) and carbonaceous materials (green waste compost, manure compost, and lignite) for minimising the environmental risks of As and Cu at a timber treatment site. After 9-month soil incubation, significant sequestration of As and Cu in soil solution was accomplished by AMD sludge, on which adsorption and co-precipitation could take place. The efficacy of AMD sludge was comparable to that of zero-valent iron. There was marginal benefit of adding carbonaceous materials. However, in a moderately aggressive environment (Toxicity Characteristic Leaching Procedure), AMD sludge only suppressed the leachability of As but not Cu. Therefore, the provision of compost and lignite augmented the simultaneous reduction of Cu leachability, probably via surface complexation with oxygen-containing functional groups. Under continuous acid leaching in column experiments, combined application of AMD sludge with compost proved more effective than AMD sludge with lignite. This was possibly attributed to the larger amount of dissolved organic matter with aromatic moieties from lignite, which may enhance Cu and As mobility. Nevertheless, care should be taken to mitigate ecological impact associated with short-term substantial Ca release and continuous release of Al at a moderate level under acid leaching. This study also articulated the engineering implications and provided recommendations for field deployment, material processing, and assessment framework to ensure an environmentally sound application of reactive materials.

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.

Enhancement of phenanthrene adsorption on a clayey soil and clay minerals by coexisting lead or cadmium.

Phenanthrene is commonly present together with heavy metals at many contaminated sites. This study investigated the influence of coexisting lead (Pb(2+)) or cadmium (Cd(2+)) on phenanthrene adsorption on soils. Batch experiments were conducted under different geochemical conditions including pH, mineral structure, organic matter content, and varying amounts of heavy metals. The results showed that the presence of heavy metals in solution at a fixed pH of 5.8±0.1 enhanced phenanthrene adsorption, the extent of which was closely related to the concentrations and the electro-negativity of the metals. The enhancement on phenanthrene adsorption was positively correlated to the amount of adsorbed metals. Although Cd(2+) is a softer Lewis acid, Pb(2+) displayed a more significant effect as it was adsorbed to a greater extent on the soil surfaces. Thus, density of cation accumulation appears to be more influential than metal softness in enhancing phenanthrene adsorption. Moreover, with a portion of organic matter removed by heating at 550°C, there was a stronger enhancement of phenanthrene adsorption by coexisting Pb(2+), indicating an increasingly dominant mechanisms associated with Pb(2+) at a lower organic matter content. Similar enhancement phenomenon was observed on bentonite and kaolinite, probably resulting from the cation-π bonding between the adsorbed soft metal cations and the aromatic ring of phenanthrene in solution. The desorption experiments further suggested that the bonding of phenanthrene adsorption was strengthened in the presence of Pb(2+) and that a larger proportion of adsorbed phenanthrene remained on the soils (residual fraction) even after sequential methanol extractions. Further spectroscopic analyses and surface characterization are required to provide direct evidence of the formation and relative significance of cation-π bond for phenanthrene adsorption.

Removal of Pb by EDTA-washing in the presence of hydrophobic organic contaminants or anionic surfactant

Heavy metals and organic contaminants often coexist in contaminated soils, of which the remediation requires a combined or sequential use of surfactant and chelant in chemical-enhanced soil washing. This study investigated the Pb removal by EDTA-washing in the presence of the coexisting hydrophobic organic contaminants (marine diesel fuel, MDF) or anionic surfactant (sodium dodecyl sulfate, SDS). The results of batch experiments indicated a negative impact of MDF on Pb removal, whereas a positive or negative influence of SDS depending on the molar ratio of [EDTA]:[Pb]. The surface of MDF-contaminated soil was partially covered by free-phase MDF limiting the interaction between EDTA and sorbed Pb, especially at [EDTA]:[Pb]=1:1. Despite the ability of SDS itself for extracting Pb to some extent, probably through electrostatic interaction and dissolution of soil organic matter (SOM), the addition of SDS into EDTA solution only slightly enhanced Pb removal at [EDTA]:[Pb]=1:1 but inhibited at [EDTA]:[Pb]=2:1. This may be attributed to the SOM dissolution and the potential formation of ternary surface complexes, respectively. Along the same line of reasoning, it was not surprising that the optimal sequence for Pb removal was EDTA- followed by SDS-washing rather than the reverse sequence or simultaneous EDTA- and SDS-washing.

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.

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.

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.

Soil washing enhanced by humic substances and biodegradable chelating agents

Industrial timber treatment sites have resulted in widespread soil contamination by Cu, Cr, and As, presenting potential long-term liability and associated risks to human health and the environment. This study evaluated the roles of natural humic substances (lignite-derived humic substances, standard and commercially available humic acids) and biodegradable chelating agents (ethylenediamine-N,N-disuccinic acid (EDDS) and glutamic-N,N-diacetic acid (GLDA)) for soil washing. Batch kinetic experiments revealed that humic substances promoted Cu extraction at pH 8, but they were significantly adsorbed on the soil at pH 4, possibly posing impediment to soil remediation. The metal extraction by EDDS and GLDA was comparable to that of EDTA (ethylenediamine-tetraacetic acid), and it was more effective at pH 4 than pH 8, probably due to acidic dissolution of metal precipitates and oxides. Metal distribution analysis indicated that the carbonate fraction of Cu and the oxide fraction of As and Cr were mainly extracted, while the exchangeable fraction of Cu increased. The residual leachability tests showed that humic substances reduced the Cu and As leachability but the reduction was insufficient. In contrast, EDDS was able to reduce the leachate concentrations of Cu and As to below 5 mg L−1, meeting the waste acceptance criteria for landfill disposal. Nevertheless, soil washing methods and remediation strategy may need further modifications to facilitate site restoration and promote soil recycling.