Remediation of Smelter Contaminated Soil by Sequential Washing Using Biosurfactants.

This paper presents experimental results from the use of biosurfactants in the remediation of a soil from a smelter in Poland. In the soil, concentrations of Cu (1659.1 mg/kg) and Pb (290.8 mg/kg) exceeded the limit values. Triple batch washing was tested as a soil treatment. Three main variants were used, each starting with a different plant-derived (saponin, S; tannic acid, T) or microbial (rhamnolipids, R) biosurfactant solution in the first washing, followed by 9 different sequences using combinations of the tested biosurfactants (27 in total). The efficiency of the washing was determined based on the concentration of metal removed after each washing (CR), the cumulative removal efficiency (Ecumulative) and metal stability (calculated as the reduced partition index, Ir, based on the metal fractions from BCR sequential extraction). The type of biosurfactant sequence influenced the CR values. The variants that began with S and R had the highest average Ecumulative for Cu and Pb, respectively. The Ecumulative value correlated very strongly (r > 0.8) with the stability of the residual metals in the soil. The average Ecumulative and stability of Cu were the highest, 87.4% and 0.40, respectively, with the S-S-S, S-S-T, S-S-R and S-R-T sequences. Lead removal and stability were the highest, 64-73% and 0.36-0.41, respectively, with the R-R-R, R-R-S, R-S-R and R-S-S sequences. Although the loss of biosurfactants was below 10% after each washing, sequential washing with biosurfactants enriched the soil with external organic carbon by an average of 27-fold (S-first variant), 24-fold (R first) or 19-fold (T first). With regard to environmental limit values, metal stability and organic carbon resources, sequential washing with different biosurfactants is a beneficial strategy for the remediation of smelter-contaminated soil with given properties.

Short-Term Soil Flushing with Tannic Acid and Its Effect on Metal Mobilization and Selected Properties of Calcareous Soil.

Cadmium, Cu, Ni, Pb, and Zn removal via soil flushing with tannic acid (TA) as a plant biosurfactant was studied. The soil was treated for 30 h in a column reactor at a constant TA concentration and pH (3%, pH 4) and at variable TA flow rates (0.5 mL/min or 1 mL/min). In the soil leachates, pH, electrical conductivity (EC), total dissolved organic carbon, and metal concentrations were monitored. Before and after flushing, soil pH, EC, organic matter content, and cation exchange capacity (CEC) were determined. To analyze the organic matter composition, pyrolysis as well as thermally assisted hydrolysis and methylation coupled with gas chromatography-mass spectrometry were used. Metal fractionation in unflushed and flushed soil was analyzed using a modified sequential extraction method. The data on cumulative metal removal were analyzed using OriginPro 8.0 software (OriginLab Corporation, Northampton, MA, USA) and were fitted to 4-parameter logistic sigmoidal model. It was found that flushing time had a stronger influence on metal removal than flow rate. The overall efficiency of metal removal (expressed as the ratio between flushed metal concentration and total metal concentration in soil) at the higher flow rate decreased in this order: Cd (86%) > Ni (44%) > Cu (29%) ≈ Zn (26%) > Pb (15%). Metals were removed from the exchangeable fraction and redistributed into the reducible fraction. After flushing, the soil had a lower pH, EC, and CEC; a higher organic matter content; the composition of the organic matter had changed (incorporation of TA structures). Our results prove that soil flushing with TA is a promising approach to decrease metal concentration in soil and to facilitate carbon sequestration in soil.

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.

Properties of biochars from conventional and alternative feedstocks and their suitability for metal immobilization in industrial soil.

In contaminated soils, excessive concentrations of metals and their high mobility pose a serious environmental risk. A suitable soil amendment can minimize the negative effect of metals in soil. This study investigated the effect of different biochars on metal (Cu, Pb, Zn) immobilization in industrial soil. Biochars produced at 300 and 600 °C from conventional (MS, maize silage; WP, wooden pellets) and alternative (SC, sewage sludge compost; DR, digestate residue) feedstocks were used as soil amendments at a dosage of 10 % (w/w). The type of feedstock and pyrolysis temperature affected the properties of the biochars and their ability to immobilize metal in soil. Compared to production at 300 °C, all biochars produced at 600 °C had higher pH (6.2-10.7), content of ash (7.2-69.0 %) and fixed carbon (21.1-56.7 %), but lower content of volatile matter (9.7-37.2 %). All biochars except DR biochar had lower dissolved organic carbon (DOC) content (1.4-2.3 g C/L) when made at 600 °C. Only MS and SC biochars had higher cation exchange capacity (25.2 and 44.7 cmol/kg, respectively) after charring at 600 °C. All biochars contained low concentrations of Cd, Cu, Ni, Pb and Zn; Cd was volatilized to the greatest extent during pyrolysis. Based on FTIR analysis and molar ratios of H/C and O/C, biochars had a greater degree of carbonization and aromaticity after charring at 600 °C. The efficiency of the biochars in metal immobilization depended mainly on their pH, ash content, and concentration of DOC. SC and DR biochars were more effective for Cu and Zn immobilization than MS and WP biochars, which makes them attractive options for large-scale soil amendment.

Behaviors of heavy metals (Cd, Cu, Ni, Pb and Zn) in soil amended with composts.

This study investigated how amendment with sewage sludge compost of different maturation times (3, 6, 12 months) affected metal (Cd, Cu, Ni, Pb, Zn) bioavailability, fractionation and redistribution in highly contaminated sandy clay soil. Metal transformations during long-term soil stabilization (35 months) were determined. In the contaminated soil, Cd, Ni and Zn were predominately in the exchangeable and reducible fractions, Pb in the reducible fraction and Cu in the reducible, exchangeable and oxidizable fractions. All composts decreased the bioavailability of Cd, Ni and Zn for up to 24 months, which indicates that cyclic amendment with compost is necessary. The bioavailability of Pb and Cu was not affected by compost amendment. Based on the reduced partition index (IR), metal stability in amended soil after 35 months of stabilization was in the following order: Cu > Ni = Pb > Zn > Cd. All composts were more effective in decreasing Cd, Ni and Zn bioavailability than in redistributing the metals, and increasing Cu redistribution more than that of Pb. Thus, sewage sludge compost of as little as 3 months maturation can be used for cyclic amendment of multi-metal-contaminated soil.

Phytoextraction of Cd and Zn as single or mixed pollutants from soil by rape (Brassica napus).

This paper analyses the capacity of the rape (Brassica napus) to extract Cd and Zn from the soil and the effect of these metals on the morphometric parameters of the plant (length, weight, surface area, fractal dimension of leaves). Rape plants were mostly affected by the combined toxicity of the Cd and Zn mixture that caused a significant reduction in the rate of seed germination, the plant biomass quantity and the fractal dimension. In the case of Cd soil pollution, the bioaccumulation factor (BAF), bioaccumulation coefficient (BAC) as well as the heavy metal root-to-stalk translocation factor (TF) were determined. The results showed that B. napus had a great potential as a cadmium hyperaccumulator but not as an accumulator of Zn or Cd + Zn mixture. The efficiency of phytoextraction rape was 0.8-1.22 % for a soil heavily polluted with cadmium.

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.

Humic substances from sewage sludge compost as washing agent effectively remove Cu and Cd from soil.

Although commercially available biosurfactants are environmentally friendly and effectively remove heavy metals from soil, they are costly. Therefore, this study investigated whether inexpensive humic substances (HS) from sewage sludge compost could effectively remove copper (Cu) and cadmium (Cd) from highly contaminated sandy clay loam (S1) and clay (S2). The optimum HS concentration and pH were determined, as well process kinetics. Under optimum conditions, a single washing removed 80.7% of Cu and 69.1% of Cd from S1, and 53.2% and 36.5%, respectively, from S2. Triple washing increased removal from S1 to almost 100% for both metals, and to 83.2% of Cu and 88.9% of Cd from S2. Triple washing lowered the potential ecological risk (Er(i)) of the soils, especially the risk from Cd. HS substances show potential for treating soils highly contaminated with heavy metals, and HS from other sources should be tested with these and other contaminants.

Tannic acid and saponin for removing arsenic from brownfield soils: Mobilization, distribution and speciation.

Plant biosurfactants were used for the first time to remove As and co-existing metals from brownfield soils. Tannic acid (TA), a polyphenol, and saponin (SAP), a glycoside were tested. The soil washing experiments were performed in batch conditions at constant biosurfactant concentration (3%). Both biosurfactants differed in natural pH, surface tension, critical micelle concentration and content of functional groups. After a single washing, TA (pH 3.44) more efficiently mobilized As than SAP (pH 5.44). When both biosurfactants were used at the same pH (SAP adjusted to 3.44), arsenic mobilization was improved by triple washing. The process efficiency for TA and SAP was similar, and depending on the soil sample, ranged between 50%-64%. Arsenic mobilization by TA and SAP resulted mainly from decomposition of Fe arsenates, followed by Fe(3+) complexation with biosurfactants. Arsenic was efficiently released from reducible and partially from residual fractions. In all soils, As(V) was almost completely removed, whereas content of As(III) was decreased by 37%-73%. SAP and TA might be used potentially to remove As from contaminated soils.

The usability of the IR, RAC and MRI indices of heavy metal distribution to assess the environmental quality of sewage sludge composts.

To assess the environmental quality of compost, it is insufficient to use only total metal concentration. Therefore in this study, the stability of metals in compost and the environmental risk they pose were assessed by three indices that have been proposed for soils or sediments: the IR, the RAC and the MRI. In mature composts, the highest bonding intensity was for Ni (0.79

Metal (Cu, Cd and Zn) removal and stabilization during multiple soil washing by saponin.

The influence of multiple saponin washing on copper, cadmium and zinc removal and stability in three types of soils (loamy sand, loam, silty clay) was investigated. Distribution of metals and their mobility measured as the ratio of exchangeable form to the sum of all fractions in soils was differential. After single washing the highest efficiency of metal removal was obtained in loamy sand (82-90%) and loam (67-88%), whereas the lowest in silty clay (39-62%). In loamy sand and loam metals had higher mobility factors (44-61% Cu, 60-76% Cd, and 68-84% Zn) compared to silty clay (9% Cu, 28% Cd and 36% Zn). Triplicate washing led to increase both efficiency of metal removal and percentage content of their stable forms. In consequence, fractional patterns for metals before and after treatment changed visibly as a result of their redistribution. Based on the redistribution index, the most stable metal (mainly in residual and organic fractions) after triplicate washing was Cu in loamy sand and loam. For silty clay contaminated with Cd, effective metal removal and its stabilization required a higher number of washings.