Beatriz Cerqueira

Time of flight secondary ion mass spectrometry and high-resolution transmission electron microscopy/energy dispersive spectroscopy: a preliminary study of the distribution of Cu2+ and Cu2+/Pb2+ on a Bt horizon surfaces.

Relatively new techniques can help in determining the occurrence of mineral species and the distribution of contaminants on soil surfaces such as natural minerals and organic matter. The Bt horizon from an Endoleptic Luvisol was chosen because of its well-known sorption capability. The samples were contaminated with Cu(2+) and/or Pb(2+) and both sorption and desorption experiments were performed. The preferential distribution of the contaminant species ((63)Cu and (208)Pb) to the main soil components and their associations were studied together with the effectiveness of the surface sorption and desorption processes. The results obtained were compared with non-contaminated samples as well as with previous results obtained by different analytical techniques and advanced statistical analysis. Pb(2+) competes favorably for the sorption sites in this soil, mainly in oxides and the clay fraction. Cu(2+) and Pb(2+) were mainly associated with hematite, gibbsite, vermiculite and chlorite. This study will serve as a basis for further scientific research on the soil retention of heavy metals. New techniques such as spectroscopic imaging and transmission electron microscopy make it possible to check which soil components retain heavy metals, thereby contributing to propose effective measures for the remediation of contaminated soil.

Enrichment of marsh soils with heavy metals by effect of anthropic pollution

The impact of waste disposal on marsh soils was assessed in topsoil samples collected at eight randomly selected points in the salt marsh in Ramallosa (Pontevedra, Spain) at 4-month intervals for 2 years. Polluted soil samples were characterized in physico-chemical terms and their heavy metal contents determined by comparison with control, unpolluted samples. The results revealed a marked effect of waste discharges on the soils in the area, which have low contents in heavy metals under normal environmental conditions. In fact, the studied soils were found to contain substantial amounts of total and DTPA-extractable Cd, Cu, Pb and Zn. Based on the relationship of the redox potential with the DTPA-extractable Cd, Cu, Pb, and Zn contents of the soils, strongly reductive conditions raised the total contents in these elements by effect of their remaining in the soils as precipitated sulphides. Such contents, however, decreased as oxidative conditions gradually prevailed. The contents in DTPA-extractable metals increased with increasing Eh through the release of the metals in ionic form to the soil solution under oxidative conditions. The contents in heavy metals concentrating in the polluted soils were several times higher than those in the control soils (viz. 2 vs. 6 for Cd, 4 vs. 6 for Cu, 4 vs. 20 for Pb, and 2 vs. 15 for Zn, all in mgkg(-1)). This can be expected to influence the amounts of available heavy metals present in the soils, and hence the environmental quality of the area, in the near future. Based on its geoaccumulation index (Class >/=3 for Cd and Cu, and 1-4 for Pb and Zn), the Ramallosa marsh is highly polluted with Cd and moderately to highly polluted with Cu, Pb and Zn. The enrichment factors obtained confirm that the salt marsh is highly polluted (especially with Cd) as the primary result of anthropic activity.

Retention and Mobility of Copper and Lead in Soils as Influenced by Soil Horizon Properties

Abstract The mobility and bioavailability of heavy metals in soils is largely governed by sorption and desorption phenomena. Cu2+ and Pb2+ are among the most potentially toxic heavy metals and they are present, often concomitantly, in many polluting spills and in agrochemicals. The objective was to assess and compare the competitive sorption and desorption capacities and sorption hysteresis of Cu2+ and Pb2+, as well as their migration through the profiles of four natural soils: a Humic Umbrisol, an Umbric Cambisol, an Endoleptic Luvisol and a Humic Cambisol. In all horizons Pb2+ was invariably sorbed and retained to a greater extent than Cu2+. The sorption and retention of Cu2+ were most influenced by pH, effective cation exchange capacity (CECe) and Mn oxide content. On the other hand, the fixation capacity of Pb2+ was most influenced by pH, CECe, and Mn oxide and organic matter contents. pH and CECe were the individual soil properties most markedly influencing Cu2+ and Pb2+ sorption and retention. In all the horizons Pb2+ exhibited greater hysteresis than Cu2+. In each soil the hysteresis in the A horizon was greater than that in the B horizon, except in the Bt horizon of the Endoleptic Luvisol, due to its high pH and vermiculite content. Based on migration indices, Pb2+ was less mobile than Cu2+ in the studied soils.

Validation of TOF-SIMS and FE-SEM/EDS Techniques Combined with Sorption and Desorption Experiments to Check Competitive and Individual Pb2+ and Cd2+ Association with Components of B Soil Horizons

Sorption and desorption experiments were performed by the batch method on the B horizons of five natural soils: Umbric Cambisol, Endoleptic Luvisol, Mollic Umbrisol, Dystric Umbrisol, and Dystric Fluvisol. Individual and competitive sorption and desorption capacity and hysteresis were determined. The results showed that Pb2+ was sorbed and retained in a greater quantity than Cd2+ and that the hysteresis of the first was greater than that of the second. The most influential characteristics of the sorption and retention of Pb2+ were pH, ECEC, Fe and Mn oxides and clay contents. For Cd2+ they were mainly pH and, to a lesser extent, Mn oxides and clay content. The combined use of TOF-SIMS, FE-SEM/EDS and sorption and desorption analyses was suitable for achieving a better understanding of the interaction between soil components and the two heavy metals. They show the preferential association of Pb2+ with vermiculite, chlorite, Fe and Mn oxides, and of Cd2+ with the same components, although to a much lesser extent and intensity. This was due to the latter’s higher mobility as it competed unfavourably with the Pb2+ sorption sites. TOF-SIMS and FE-SEM/EDS techniques confirmed the results of the sorption experiments, and also provided valuable information on whether the soil components (individually or in association) retain Cd2+ and / or Pb2+; this could help to propose effective measures for the remediation of contaminated soils.