Dissipation of a mix of priority PAHs in soils by using availability enhancers. Effect of aging and pollutant interactions.

A remediation strategy using three non-toxic availability enhancers (two cyclodextrins and a rhamnolipid biosurfactant) was applied to various soils artificially contaminated with a mix of Polycyclic Aromatic Hydrocarbons (PAHs) considered priority pollutants at two levels of contamination: only with 7 low molecular weight PAHs (LMW PAHs, 5 with 3-ring and 2 with 4-ring - fluoranthene and pyrene) or with 14 PAHs (from 3 to 6 rings). Natural attenuation of PAHs in all soils showed degradation capacity for the LMW PAHs, with a final content of LMW PAHs <5% of their initial concentration. Conversely, the rest of PAHs (high molecular weight PAHs, HMW) remained in the soils (61% - 83.5%), indicating abiotic dissipation of HMW PAHs due to formation of non-extractable residues in soils. The influence of the presence of HMW PAHs on the degradation of the 7 LMW PAHs was also tested, showing a general decrease in the time to obtain 50% dissipation (DT50), statistically significant for acenaphthene, acenaphthylene and fluorene. Availability enhancers showed different effects on PAHs dissipation. 2-hydroxypropyl-ß-cyclodextrin (HP) decreased DT50 of some of the lighter PAHs, whereas the rhamnolipid (RL) caused a slight DT50 increase due to its initial toxicity on native soil microorganisms, but showing later high degradation rate for LMW PAHs. On the contrary, randomly methylated-ß-cyclodextrin (RAMEB) slowed down PAHs degradation due to its high adsorption onto soil surface, blocking the desorption of PAHs from the soils. The high number of experimental factors not studied simultaneously before (soil type, co-contamination, availability enhancers and incubation time) allowed to conduct a statistical analysis which supported the conclusions reached. Principal Component Analysis separated the studied PAHs in 3 groups, in relation with their molecular weight and Kow. The first principal component was related with LMW PAHs, and separate the inefficient RAMEB from the other availability enhancers.

Effects of the presence of a composted biosolid on the metal immobilizing action of an urban soil.

The influence of a composted biosolid from urban wastewater treatment on the retention and solubility of Cu, Pb or Zn added to a soil was studied by batch adsorption/desorption experiments, equilibrating both materials and their mixtures with solutions containing various metal concentrations. The composted biosolid adsorbed less Cu or Pb and slightly more Zn than the soil, and thus caused a noticeable decrease in the retention of Cu or Pb and an increase in Zn adsorption by soil-biosolid mixtures, but these effects in the mixtures were not additive for any metal. The pH effects were studied by means of (log metal concentration)/pH diagrams. It was shown that Cu behaviour was different from that of the other metals: the relation between pH and Cu concentrations suggested similar solubilities in the presence of the biosolid and the mixtures, whereas the biosolid-free soil gave data located on a region of the diagram corresponding to slightly lower solubility. In the case of Pb or Zn, the data for the biosolid were located in a region of the diagram corresponding to clearly lower solubilities than those for the biosolid/soil mixtures. It was concluded that the biosolid has little effect on metal solubility when it is mixed with the soil in the proportions used here.

Estimating the extractability of potentially toxic metals in urban soils: a comparison of several extracting solutions.

Metals released by the extraction with aqua regia, EDTA, dilute HCl and sequential extraction (SE) by the BCR protocol were studied in urban soils of Sevilla, Torino, and Glasgow. By multivariate analysis, the amounts of Cu, Pb and Zn liberated by any method were statistically associated with one another, whereas other metals were not. The mean amounts of all metals extracted by HCl and by SE were well correlated, but SE was clearly underestimated by HCl. Individual data for Cu, Pb and Zn by both methods were correlated only if each city was considered separately. Other metals gave poorer relationships. Similar conclusions were reached comparing EDTA and HCl, with much lower values for EDTA. Dilute HCl extraction cannot thus be recommended for general use as alternative to BCR SE in urban soils.