Removal of heavy metals from landfill leachate using zero valent iron and granular activated carbon.

The possibility of a landfill leachate pre-treatment, aiming at heavy metals removal, by means of either zero valent iron (ZVI), or granular activated carbon (GAC) or by a mixture of the two materials, was investigated in this paper through batch and column tests. For this purpose, a synthetic landfill leachate containing heavy metals (i.e. Cu, Ni, Zn), chloride, sulphates, ammonium and organic matter was prepared. Batch tests results demonstrated the efficiency of ZVI, GAC and ZVI/GAC mixture in heavy metals removal (efficiency > 90%) and their negligible effect on the other contaminants. Column tests showed as pure ZVI is by far more efficient than pure GAC in the long term. The influence of humic acids (HA) on the reactive and hydraulic behaviour of ZVI was also studied through column tests. The presence of HA in the leachate caused a reduction of ZVI removal efficiency and a considerable decrease in its hydraulic conductivity. Results of a column test carried out using the ZVI/GAC granular mixture showed as the removal efficiency over time ranges from 100% to 89% for Cu, from 93% to 80% for Ni and from 98% to 95% for Zn. The use of a filter filled with the ZVI/GAC mixture could find application for leachate pre-treatment having the objective of removing heavy metals prior the final co-treatment with municipal wastewater minimizing adverse side effect on the process (e.g. transfer of heavy metals in the excess sludge to be used in agriculture).

The removal efficiency and long-term hydraulic behaviour of zero valent iron/lapillus mixtures for the simultaneous removal of Cu2+, Ni2+ and Zn2.

Granular mixtures composed of zero valent iron (ZVI) and lapillus at two different weight ratios (i.e. 30:70 and 50:50) were tested through column experiments for the simultaneous removal of Cu2+, Ni2+ and Zn2+ present in aqueous solutions at high concentrations. The results were used to evaluate the feasibility of the above-mentioned granular mixtures as reactive media in permeable reactive barriers (PRB) for the remediation of groundwater polluted by metals. Test results showed that the two granular reactive media efficiently removed the three heavy metals under study according to the following removal sequence Cu > Zn > Ni. The granular mixture with the higher iron content showed a proportionally higher removal rate but also a higher reduction of hydraulic conductivity over time. Different removal mechanisms occurred for the three contaminants in question. Considering that for Ni and Zn the main removal mechanism was probably adsorption, we used different mathematical models, in order to predict the breakthrough curves for the adsorption mechanisms. The Adams-Bohart model showed the best fit with the experimental data and it was thus used to predict the zinc removal front within the barrier thickness. Finally, we showed that the mathematical approach may be used for the design of PRBs for the reactive media and contaminants used in this research.

Selective removal of heavy metals from landfill leachate by reactive granular filters.

The pre-treatment of landfill leachate prior to its co-treatment in the municipal plants of waste water processing could represent an appropriate and cost-effective solution for its management. Pre-treatment is necessary especially to remove heavy metals, which may be transferred to the excess sludge preventing its valorisation. In the present paper, we propose a chemical-physical pre-treatment of leachate using four different granular reactive media able to selectively remove the contaminants present in the leachate. The efficiency of these materials was investigated using synthetic leachate through batch tests and a column test. In the latter case the four materials were placed in two columns connected in series and fed an under constant upward flow (0.5 mL/min). The first column was filled half (50 cm) with a granular mixture of zero valent iron (ZVI) and pumice and half (50 cm) with a granular mixture of ZVI and granular activated carbon (GAC). The second column, which was fed with the effluent of the first column, was filled half with zeolite (chabazite) and half with GAC. Heavy metals were mainly removed by the ZVI/pumice and ZVI/GAC steps with a removal efficiency that was higher than 98, 94 and 90% for copper, nickel and zinc, respectively, after 70 days of operation. Ammonium was removed by zeolite with a removal efficiency of 99% up to 23 days. The average reduction of the chemical oxygen demand (COD) was of 40% for 85 days, whereas chloride and sulphate removal was negligible.

Improving the sustainability of granular iron/pumice systems for water treatment.

Metallic iron (Fe(0)) is currently used in subsurface and above-ground water filtration systems on a pragmatic basis. Recent theoretical studies have indicated that, to be sustainable, such systems should not contain more than 60% Fe(0) (vol/vol). The prediction was already validated in a Fe(0)/sand system using methylene blue as an operational tracer. The present work is the first attempt to experimentally verify the new concept using pumice particles. A well-characterized pumice sample is used as operational supporting material and is mixed with 200 g of a granular Fe(0), in volumetric proportions, varying from 0 to 100%. The resulting column systems are characterized (i) by the time dependent evolution of their hydraulic conductivity and (ii) for their efficiency for the removal of Cu(II), Ni(II), and Zn(II) from a three-contaminants-solution (about 0.3 mM of each metal). Test results showed a clear sustainability of the long term hydraulic conductivity with decreasing Fe(0)/pumice ratio. In fact, the pure Fe(0) system clogged after 17 days, while the 25% Fe(0) system could operate for 36 days. The experimental data confirmed the view that well-designed Fe(0) PRBs may be successful at removing both reducible and non-reducible metal species.

Heavy metals removal and hydraulic performance in zero-valent iron/pumice permeable reactive barriers.

Long-term behaviour is a major issue related to the use of zero-valent iron (ZVI) in permeable reactive barriers for groundwater remediation; in fact, in several published cases the hydraulic conductivity and removal efficiency were progressively reduced during operation, potentially compromising the functionality of the barrier. To solve this problem, the use of granular mixtures of ZVI and natural pumice has recently been proposed. This paper reports the results of column tests using aqueous nickel and copper solutions of various concentrations. Three configurations of reactive material (ZVI only, granular mixture of ZVI and pumice, and pumice and ZVI in series) are discussed. The results clearly demonstrate that iron-pumice granular mixtures perform well both in terms of contaminant removal and in maintaining the long-term hydraulic conductivity. Comparison with previous reports concerning copper removal by ZVI/sand mixtures reveals higher performance in the case of ZVI/pumice.