Lead in Egyptian soils: Origin, reactivity and bioavailability measured by stable isotope dilution.

The current availability of Pb in Egyptian soils and associated plants were studied in 15 locations (n=159) that had been historically subjected to industrial and automobile Pb emissions. Isotopic dilution with enriched 204Pb was used to estimate the soil Pb labile pool (PbE); results showed that %PbE values were mostly <25% which is likely due to the alkaline nature of the soils. Nonetheless, lability of Pb was significantly higher in urban and industrial locations indicating greater reactivity of anthropogenic Pb in comparison to geogenic-Pb. A plot of 206Pb/207Pb vs 208Pb/207Pb showed that all soils were aligned close to a virtual binary line between two apparent end member signatures (petrol and geogenic-Pb) suggesting that they are the major sources of Pb in the Egyptian environment. Soils with greater Pb concentrations (urban and industrial locations) displayed a significantly greater ratio of labile petrol-Pb to labile geogenic-Pb in comparison to less-contaminated soils. However, this difference was marginal (±5%) suggesting that historically emitted petrol-Pb has substantially mixed with geogenic-Pb into a common pool as a result of prolonged contact with soil. The proportion of petrol-Pb in fruits and leaf vegetables was significantly (P<0.005) greater than that of the associated soils suggesting preferential uptake of the more labile petrol-Pb as opposed to the relatively immobile geogenic-Pb. However, it is also possible that the major source of Pb intake by Egyptian consumers is extraneous Pb dust enriched with petrol Pb rather than systematic Pb via roots uptake.

Evaluating the mobility of polymer-stabilised zero-valent iron nanoparticles and their potential to co-transport contaminants in intact soil cores.

The use of zero-valent iron nanoparticles (nZVI) has been advocated for the remediation of both soils and groundwater. A key parameter affecting nZVI remediation efficacy is the mobility of the particles as this influences the reaction zone where remediation can occur. However, by engineering nZVI particles with increased stability and mobility we may also inadvertently facilitate nZVI-mediated contaminant transport away from the zone of treatment. Previous nZVI mobility studies have often been limited to model systems as the presence of background Fe makes detection and tracking of nZVI in real systems difficult. We overcame this problem by synthesising Fe-59 radiolabelled nZVI. This enabled us to detect and quantify the leaching of nZVI-derived Fe-59 in intact soil cores, including a soil contaminated by Chromated-Copper-Arsenate. Mobility of a commercially available nZVI was also tested. The results showed limited mobility of both nanomaterials; <1% of the injected mass was eluted from the columns and most of the radiolabelled nZVI remained in the surface soil layers (the primary treatment zone in this contaminated soil). Nevertheless, the observed breakthrough of contaminants and nZVI occurred simultaneously, indicating that although the quantity transported was low in this case, nZVI does have the potential to co-transport contaminants. These results show that direct injection of nZVI into the surface layers of contaminated soils may be a viable remediation option for soils such as this one, in which the mobility of nZVI below the injection/remediation zone was very limited. This Fe-59 experimental approach can be further extended to test nZVI transport in a wider range of contaminated soil types and textures and using different application methods and rates. The resulting database could then be used to develop and validate modelling of nZVI-facilitated contaminant transport on an individual soil basis suitable for site specific risk assessment prior to nZVI remediation.

Zinc solubility and fractionation in cultivated calcareous soils irrigated with wastewater.

The solubility, lability and fractionation of zinc in a range of calcareous soils from Peshawar, Pakistan were studied (18 topsoils and 18 subsoils). The lability (E-value) of Zn was assessed as the fraction isotopically exchangeable with (70)Zn(2+); comparative extractions included 0.005 M DTPA, 0.43 M HNO3 and a Tessier-style sequential extraction procedure (SEP). Because of the extremely low concentration of labile Zn the E-value was determined in soils suspended in 0.0001 M Na2-EDTA which provided reliable analytical conditions in which approximately 20% of the labile Zn was dissolved. On average, only 2.4% of soil Zn was isotopically exchangeable. This corresponded closely to Zn solubilised by extraction with 0.005 DTPA and by the carbonate extraction step (F1+F2) of the Tessier-style SEP. Crucially, although the majority of the soil CaCO3 was dissolved in F2 of the SEP, the DTPA dissolved only a very small proportion of the soil CaCO3. This suggests a superficial carbonate-bound form of labile Zn, accessible to extraction with DTPA and to isotopic exchange. Zinc solubility from soil suspended in 0.01 M Ca(NO3)2 (PCO2 controlled at 0.03) was measured over three days. Following solution speciation using WHAM(VII) two simple solubility models were parameterised: a pH dependent 'adsorption' model based on the labile (isotopically exchangeable) Zn distribution coefficient (Kd) and an apparent solubility product (Ks) for ZnCO3. The distribution coefficient showed no pH-dependence and the solubility model provided the best fit to the free ion activity (Zn(2+)) data, although the apparent value of log10 Ks (5.1) was 2.8 log units lower than that of the mineral smithsonite (ZnCO3).