Assessment of the effects of soil PAH accumulation by a battery of ecotoxicological tests

Surface soils were collected at remote, urban and industrial sites in the Southern of Italy in order to evaluate PAH concentrations and assess the toxic effects by a battery of ecotoxicological tests. The tests were performed on whole soils and on both organic and aqueous extracts. Further goal of this study was to integrate the results coming from each test and matrix in a synthetic toxicity index. The highest summation sigmaPAH concentrations were measured at the industrial soil, although this one did not show an high ecotoxicological risk. Among the performed tests, the phytotoxicity tests showed the highest sensitivity. For whole soil, the worst case always has been represented by test through bacteria. Our results could represent the first step toward the selection of a proper battery to characterize the soil ecotoxicological risk.     

Adsorption of a dye on clay and sand. Use of cyclodextrins as solubility-enhancement agents

Laboratory-scale studies were aimed at elucidating the physico-chemical aspects on the removal process of crystal violet (CV) from waters and solid substrates. The laponite clay (RD) and sand were chosen for the double aim at investigating them as CV adsorbents for water treatment and as substrates which mime the soil components. Sand is very effective in removing CV from waters. The cyclodextrins (CDs) were exploited as solubility-enhancement agents to remove CV from the solid substrates. They are powerful solvent media because they extract the CV from sand forming water-soluble CV/CD inclusion complexes and do not show affinity for sand. Optimum performance was shown by the modified CDs (i.e. hydroxypropyl-β-cyclodextrin and methyl-β-cyclodextrin). A linear correlation between the logarithm of the equilibrium constant for the CV/CD inclusion complexes formation (K_cpx) and the maximum amount of CV extracted from sand in the columns experiments at a flow rate of 1.5 ml min⁻¹ was drawn. This relationship predicts that CDs with K_cpx < 180 M⁻¹ are not suitable for CV removal from sand. CDs failed to displace CV from RD because they generate the formation of RD clusters where CV remains entrapped.     

Acid-base properties of humic substances from composted and thermally-dried sewage sludges and amended soils as determined by potentiometric titration and the NICA-Donnan model

The acid-base properties of humic acids (HAs) and fulvic acids (FAs) isolated from composted sewage sludge (CS), thermally-dried sewage sludge (TS), soils amended with either CS or TS at a rate of 80 t ha(-1)y(-1) for 3y and the corresponding unamended soil were investigated by use of potentiometric titrations. The non-ideal competitive adsorption (NICA)-Donnan model for a bimodal distribution of proton binding sites was fitted to titration data by use of a least-squares minimization method. The main fitting parameters of the NICA-Donnan model obtained for each HA and FA sample included site densities, median affinity constants and widths of affinity distributions for proton binding to low and high affinity sites, which were assumed to be, respectively, carboxylic- and phenolic-type groups. With respect to unamended soil HA and FA, the HAs and FAs from CS, and especially TS, were characterized by smaller acidic functional group contents, larger proton binding affinities of both carboxylic- and phenolic-type groups, and smaller heterogeneity of carboxylic and phenolic-type groups. Amendment with CS or TS led to a decrease of acidic functional group contents and a slight increase of proton binding affinities of carboxylic- and phenolic-type groups of soil HAs and FAs. These effects were more evident in the HA and FA fractions from CS-amended soil than in those from TS-amended soil.     

Vegetable and synthetic tannins induce hormesis/toxicity in sea urchin early development and in algal growth

Mimosa tannin and phenol-based synthetic tannin (syntan) were tested for toxicity to sea urchin (Paracentrotus lividus and Sphaerechinus granularis) early development and to marine algal growth (Dunaliella tertiolecta). Sea urchin embryogenesis was affected by vegetable tannin and syntan water extracts (VTWE and STWE) at levels >or=1mg/L. Developmental defects were significantly decreased at VTWE and STWE levels of 0.1 and 0.3mg/L when control cultures displayed suboptimal quality, i.e. <70% "viable" (normal or retarded) larvae. Fertilization success of sea urchin sperm was increased up to 0.3 mg/L STWE or VTWE, then was inhibited by increasing tannin levels (1-30 mg/L). Offspring abnormalities, following sperm exposure to VTWE or STWE, showed the same shift from hormesis to toxicity. Cell growth bioassays in D. tertiolecta exposed to VTWE or STWE (0.1-30 mg/L) showed non-linear concentration-related toxicity. Novel criteria are suggested in defining control quality that should reveal hormetic effects.     

Leaf accumulation of trace elements and polycyclic aromatic hydrocarbons (PAHs) in Quercus ilex L

Quercus ilex L. leaves were collected four times in one year at six urban sites and one remote area in order to determine trace element and PAH accumulation through concomitant analyses of unwashed and water-washed leaves. Both unwashed and washed leaves showed the highest amounts of trace elements and PAHs in the urban area. Unwashed leaves showed greater differences between urban and remote areas and among the urban sites than washed leaves for trace element and PAH concentrations. Water-washing resulted in a significant (P<0.001) decrease in leaf concentrations of Cr, Cu, Fe, Pb, V and Zn. By contrast, Cd and total PAH concentrations showed no differences between unwashed and washed leaves.