Fernando Pardo

Use of different kinds of persulfate activation with iron for the remediation of a PAH-contaminated soil

Contamination of soils by persistent pollutants is considered an important matter of increasing concern. In this work, activated persulfate (PS) was applied for the remediation of a soil contaminated with polycyclic aromatic hydrocarbons (PAHs), such as anthracene (ANT), phenanthrene (PHE), pyrene (PYR) and benzo[a]pyrene (BaP). PS activation was performed by different ways; where ferric, ferrous sulfate salts (1-5mmol·L(-1)) and nanoparticles of zerovalent iron (nZVI) were used as activators. Moreover, in order to improve the oxidation rate of contaminants in the aqueous phase, the addition of sodium dodecyl sulfate (SDS), as anionic surfactant, was tested. On the other hand, it was also studied the role of humic acids (HA), as reducing agent or surfactant, on PAHs conversion. Removal efficiencies near 100% were achieved for ANT and BaP in all the runs carried out. Nevertheless, remarkable differences on removal efficiencies were observed for the different techniques applied in case of PHE and PYR. In this sense, the highest conversions of PHE (80%) and PYR (near 100%) were achieved when nZVI was used as activator. Similar results were obtained when activation was carried out either with Fe(2+) or Fe(3+). This can be explained by the presence of quinone type compounds, as 9,10-anthraquinone (ATQ), that can promote the reduction of Fe(3+) into Fe(2+), permitting PS radicals to be generated. On the other hand, the addition of HA did not produce an improvement of the process while surfactant addition slightly increases the PAHs removal. Furthermore, a kinetic model was developed, describing the behavior of persulfate consumption, and contaminants removal under first order kinetics.

Use of Fenton reagent combined with humic acids for the removal of PFOA from contaminated water

Perfluorinated compounds (PFCs) are receiving significant attention due to its global distribution, high persistence, and bioaccumulation properties. Among them, perfluorooctanoic acid (PFOA) is one of the most commonly found in the environment. The strong bond C-F in PFOA is extremely difficult to degrade, therefore advanced oxidation processes (AOPs) at room temperature and pressure are not able to oxidize them, as was noticed here using Fenton like reagent (FR) or persulfate (PS) at 25°C. On the contrary, by using persulfate activated by heat (100mM and T=70°C) a complete defluorination of PFOA 0.1mM was noticed after 18h, with a sequential degradation mechanism of losing one CF2 unit from PFOA and its intermediates (perfluoroheptanoic acid (PFHpA), perfluorohexanoic acid (PFHxA), perfluoropentanoic acid (PFPA) and perfluorobutanoic acid (PFBA)). Since this thermal treatment is not usually desirable from an economical point of view, alternative process has been tested. For this scope, a hybrid process is proposed in this work, by adding humic acid, HA, (600mgL(-1)) and FR, (165mM in H2O2 and 3mM in Fe(3+)) to the 0.1mM PFOA solution. It was found that the HA was oxidized by FR. PFOA was entrapped quantitatively and irreversibly during HA oxidation, resulting PFOA non-available to the aqueous phase. Oxidized HA with PFOA entrapped precipitates. Both, the leftover Fe(III) acting as a coagulant and neutral pH enhance the separation of this solid phase. The precipitation noticed by adding HA to the PFOA solution in absence of FR was negligible.

Fate of iron and polycyclic aromatic hydrocarbons during the remediation of a contaminated soil using iron-activated persulfate: A column study

Remediation of contaminated soils under flow-through conditions is an issue of great interest since it provides a better approach to real case applications than batch experiments. In this work, a column filled with soil, artificially spiked and aged for three months with Phenanthrene (PHE), Anthracene (ANT), Pyrene (PYR) and Benzo(a)pyrene (BaP), was treated for 25days with persulfate (PS) activated by Fe(3+) and nanoparticles of zerovalent iron (nZVI). Effects of type of iron fed into the column (Fe(3+) or nZVI) and nZVI concentration were studied. PS inlet concentration was 0.2mmolcm(-3) and residence time in the column was close to 1.72days. Iron, PS and polycyclic aromatic hydrocarbons (PAHs) concentration, as well as pH, were monitored during treatment. Concentration profiles of iron and PAHs were observed along the column, with higher iron concentrations and higher PAHs removal efficiencies in the closest sections to the column entrance. BaP and ANT were completely depleted regardless the conditions used, but PHE and PYR showed higher resistance to oxidation, achieving near a 90% removal in the closest sections to the injection source in all runs, but decreasing significantly with column length. Besides, natural degradation of ANT resulted in the formation 9.10-anthraquinone (ATQ), an oxy-PAH which showed higher resistance than PHE and PYR. Although higher PAHs removal efficiencies were achieved when nZVI was used as activator, only a moderate improvement was noticed when the highest concentration of nZVI was used as a consequence of radical scavenging by an excess of Fe(2+). Finally, a kinetic model based on runs performed in batch, from a previous work, was able to predict the experimental average concentrations of PAHs in the column when Fe(3+) was used as activator.