Bentonite as a Functional Material Enhancing Phytostabilization of Post-Industrial Contaminated Soils with Heavy Metals.

Growing awareness of the risks posed by pollution of the soil environment is leading to the development of new remediation strategies. The technique of aided phytostabilization, which involves the evaluation of new heavy-metal (HM)-immobilizing amendments, together with appropriately selected plant species, is a challenge for environmental protection and remediation of the soil environment, and seems to be promising. In this study, the suitability of bentonite for the technique of aided phytostabilization of soils contaminated with high HM concentrations was determined, using a mixture of two grass species. The HM contents in the tested plants and in the soil were determined by flame atomic absorption spectrometry. The application of bentonite had a positive effect on the biomass of the tested plants, and resulted in an increase in soil pH. The concentrations of copper, nickel, cadmium, lead and chromium were higher in the roots than in the above-ground parts of the plants, especially when bentonite was applied to the soil. The addition of the analyzed soil additive contributed significantly to a decrease in the levels of zinc, copper, cadmium and nickel in the soil at the end of the experiment. In view of the above, it can be concluded that the use of bentonite in the aided phytostabilization of soils polluted with HMs, is appropriate.

Quality of heavy metal-contaminated soil before and after column flushing with washing agents derived from municipal sewage sludge.

Removal of heavy metals (HMs) from soil is a priority in soil washing/soil flushing. However, for further management of remediated soil, it should be characterized in detail. This study presents, for the first time, an evaluation of soil quality after column flushing with new-generation washing agents (WAs) recovered from municipal sewage sludge (dissolved organic matter, DOM; soluble humic-like substances, HLS; soluble humic substances, SHS) and Na2EDTA as a standard benchmark. Sandy loam soil was spiked with industrial levels of Cu, Pb and Zn, then flushed in a column reactor at two WA flow rates (0.5 and 1.0 ml/min). Soil quality was assessed by determining both physico-chemical (pH, total HMs and their mobility, soil organic matter, OM, humic substances, HS and their fractions, macroelements) and biological indicators (dehydrogenase activity, DHA; germination rate, GR; and inhibition factors for roots and shoots of Triticum aestivum). Total residual HMs contents and HMs contents in the mobile fraction were significantly lower in soil flushed at 1.0 ml/min than in soil flushed at 0.5 ml/min. With all WAs, the decrease in Cu content was larger than that of the other HMs, however this HM most effectively was removed with DOM. In contrast, Pb most effectively was removed by HLS and Na2EDTA, and DOM should not be used to remediate Pb-contaminated soil, due to its very low effectiveness. Flow rate did not appear to affect the fertilizing properties of the soil, DHA activity or soil toxicity indicators. Soil flushing with all SS_WAs increased OM, HS, and exchangeable P, K and Na content in remediated soils, but decreased exchangeable Ca content, and in most cases, exchangeable Mg content. Soil flushing substantially improved DHA activity and GR, but only slightly improved the shoot and root inhibition factors.

Kinetics of Cu, Pb and Zn removal during soil flushing with washing agents derived from sewage sludge.

This paper presents the first tests of Cu (7875 mg/kg), Pb (1414 mg/kg) and Zn (566 mg/kg) removal from contaminated soil with sewage-sludge-derived washing agents (SS_WAs) (dissolved organic matter, DOM; soluble humic-like substances, HLS; soluble humic substances, SHS) and Na2EDTA (as a standard benchmark) in column experiments. Flow rates of 0.5 ml/min and 1 ml/min were used. Using a 1. order kinetic model, the kinetic constant (k), the maximum concentrations of each metal removed (Cmax), and the initial rates of metal removal (r) were established. At both flow rates, stable flow velocity was maintained for approximately eight pore volumes, for flushing times of 8 h (1.0 ml/min) and 16 h (0.5 ml/min). Although the flow rate did not influence k, it influenced Cmax: at 1 ml/min, Cmax values were higher than at 0.5 ml/min. For Cu and Zn, but not Pb, k was about twofold higher with Na2EDTA than with SS_WAs. Although Na2EDTA gave the highest kCu, Cmax,Cu was highest with DOM (Na2EDTA, 66%; DOM 73%). For Pb removal, HLS was the most effective SS_WA (77%; Na2EDTA was 80% effective). kZn was about twofold higher with Na2EDTA than with SS_WAs. Cmax,Zn was highest with HLS. The quick mobilization of Cu, Pb and Zn with most of the WAs corresponded to efficient metal removal from the exchangeable (F1) fraction.

Suitability of environmental indices in assessment of soil remediation with conventional and next generation washing agents.

Remediation of soils contaminated with metal must ensure high efficiency of metals removal, reduce bioavailability of residual metals and decrease ecological risk. Thus, for comprehensive environmental soil quality assessment, different indices must be used. In this study, suitability of 8 indices was used for soil highly contaminated with Cu (7874.5 mg kg-1), moderately with Pb (1414.3 mg kg-1) and low with Zn (566.1 mg kg-1), washed in batch and dynamic conditions with both conventional and next-generation washing agents. The following indices were used: modified contamination factor (mCf), modified contamination factor degree (mCdeg), mobility factor (MF), reduced partition index (IR), potential ecological risk factor (Er,Z), modified potential ecological risk factor (Er,m), potential ecological risk index (RIZ) and modified ecological risk index (RIm). For mCf, mCdeg and IR own classification scale was proposed. It was proven that most useful indices for assessment of soil pollution with metals were mCf and mCdeg. The mCf together with the IR allow to simultaneous assessment of soil pollution and stability for individual metals. These indices were appropriate for soil contaminated with different concentrations of metals, washed under both hydrodynamic conditions using various washing agents and different effectiveness of metals removal. Thus, they may be considered as most useful for evaluation of remediation method, feasibility of washing agent and assessing soil quality after washing.

New-Generation Washing Agents in Remediation of Metal-Polluted Soils and Methods for Washing Effluent Treatment: A Review.

Soil quality is seriously reduced due to chemical pollution, including heavy metal (HM) pollution. To meet quality standards, polluted soils must be remediated. Soil washing/soil flushing offers efficient removal of heavy metals and decreases environmental risk in polluted areas. These goals can be obtained by using proper washing agents to remove HMs from soil. These washing agents should not pose unacceptable threats to humans and ecosystems, including soil composition. Currently, it is desirable to use more environmentally and economically attractive washing agents instead of synthetic, environmentally problematic chemicals (e.g., ethylenediaminetetraacetic acid (EDTA)). The usefulness of novel washing agents for treatment of heavy metal-contaminated soils is being intensively developed, in terms of the efficiency of HM removal and properties of washed soils. Despite the unquestionable effectiveness of soil washing/flushing, it should be remembered that both methods generate secondary fluid waste (spent washing solution), and the final stage of the process should be treatment of the contaminated spent washing solution. This paper reviews information on soil contamination with heavy metals. This review examines the principles and status of soil washing and soil flushing. The novel contribution of this review is a presentation of the sources and characteristics of novel washing agents and chemical substitutes for EDTA, with their potential for heavy metal removal. Methods for treating spent washing solution are discussed separately.

Tannic acid for remediation of historically arsenic-contaminated soils.

Soil washing effectively and permanently decreases soil pollution. Thus, it can be considered for the removal of the most toxic elements, for example arsenic (As). In this study, historically As-contaminated soils (2041-4294 mg/kg) were remediated with tannic acid (TA) as the washing agent. The scope of this study included optimization of the operational conditions of As removal, determination of As distribution in soil before and after double soil washing, and measurement of TA loss during washing. The optimum conditions for As removal were 4% TA, pH 4 and 24 h washing time. The average As removal after single and double washings was 38% and 63%, respectively. TA decreased As content in amorphous and poorly crystalline oxides by >90%. Although TA increased the amount of As in the easily mobilizable As fraction, the stability of As in washed soils increased, with reduced partition indexes of 0.52-0.66 after washing. The maximum capacity of the soils to adsorb TA (qmax) was 50.2-70.4 g C/kg. TA sorption was higher at alkaline than at acidic conditions. Only TA removes As from soils effectively if the proportion of As in amorphous and poorly crystalline oxides is high. Thus, it can be considered for remediation of historically contaminated soils.

Ecological risk assessment of sewage sludge from municipal wastewater treatment plants: a case study.

The aim of this study was to characterize sewage sludge from mechanical-biological wastewater treatment plants (WWTPs) in terms of total concentrations of heavy metals (HMs) and their distribution. Moreover, HM mobility, stability and ecological risk were assessed by calculating the mobility factor (MF), the reduced partition index (Ir) and the ecological risk index (ERI). Hierarchical cluster analysis (CA) was used to group the HMs in the sludges on the basis of their MF, Ir and ERI. The concentration of HMs decreased in the following order: Zn > Cu > Ni > Pb > Cd. HM mobility, as indicated by the MF values, was as follows: 18.7%-30.6% (Zn), 8.1%-36.4% (Ni), 6.8%-11.1% (Cu), 3.2%-32.2% (Pb) and 0% (Cd). Based on the average Ir values, the stability of the metals in the sludge increased in this order: Zn (0.23)=Pb (0.23)

Suitability of humic substances recovered from sewage sludge to remedy soils from a former As mining area - a novel approach.

Batch washing experiments were performed to evaluate the feasibility of using a solution of humic substances (HS) extracted from municipal sewage sludge as a washing agent to remove As from soils at a former As mining area. Soils (S1, S2, S3) differed in organic matter content, pH and As concentration. At pH 4 and a HS concentration of 4000mgTOCL-1, As removal efficiency ranged from 18% (S2) to 27% (S3). In all cases, As removal proceeded according to pseudo-second-order kinetics (equilibrium As concentrations ranged from 625mgkg-1 (S3) to 1250mgkg-1 (S3); rate constants, from 1.02×10-5kgmg-1min-1 (S1) to 2.05×10-5kgmg-1min-1 (S3). The time needed to reach equilibrium was 12h. With double washing, the efficiency of As removal was 1.5-times higher (on average) than with single washing. Double washing increased As stability, as indicated by the reduced partition index, especially in soils S1 and S3. Moreover, HS effectively decreased the content of the most toxic As(III) (by 95-97%).

Feasibility of using humic substances from compost to remove heavy metals (Cd, Cu, Ni, Pb, Zn) from contaminated soil aged for different periods of time.

There is a need for inexpensive, readily-available and environmentally-friendly soil washing agents to remediate polluted soils. Thus, batch washing experiments were performed to evaluate the feasibility of using a solution of humic substances (HS) extracted from compost as a washing agent for simultaneous removal of Cu, Cd, Zn, Pb and Ni from artificially contaminated soils aged for 1 month, 12 months and 24 months. The efficiency of metal removal in single and multiple washings and kinetic constants (equilibrium metal concentration qe and rate constant k from the second-order kinetic equation) were determined. On average, triple washing removed twice as much metal as that removed with a single washing. At pH 7 and a HS concentration of 2.2 g C L(-1), metal removal from all soils decreased in this order: Cd (79.1-82.6%) > Cu (51.5-71.8%) > Pb (44.8-47.6%) > Ni (35.4-46.1%) > Zn (27.9-35.8%). However, based on qe (mg kg(-1)), metal removal was in this order: Pb > Zn ≈ Cu > Ni > Cd. This difference was due to different concentrations of metals, which is typical for multi-metal contaminated soils. Regardless of washing mode, removal of Cd and Pb was not affected by soil age, whereas removal of Cu, Ni and Zn was higher in soils that had been aged for a shorter time. These results indicate that HS are suitable for remediating soil contaminated with multiple heavy metals in extremely high concentrations.