A chronological sequence of urban soils 3–92 years old was studied to determine the effects of time on morphogenesis, artifact weathering, and the geochemical partitioning of Pb. Key chronofunctions determined are an increase in ˆA horizon Development Index (defined herein based on soil color) and water-soluble Pb, and a decrease in pH and C/N, with increasing soil age. Key artifact weathering reactions are: 1) portlandite in mortar altered to calcite, 2) ferrite in wrought-iron altered to ferrihydrite and goethite, and 3) carbonaceous materials altered to water-soluble organic substances. Mortar and wrought-iron were found to be Pb-bearing, but weather to produce immobilizing agents. Hence, they are both a source and a sink for Pb. The origin and mobilization of water-soluble Pb is complex and probably includes microbial extracellular polymeric substances, biodegraded soil organic matter, and solubilized organic substances derived from carbonaceous anthropogenic microparticles (soot, char and coal-related wastes).

Acid mine drainage (AMD) generated by some coal mines in New Zealand is currently treated by the addition of alkaline reagents which neutralize acidity, triggering the precipitation of dissolved metals as insoluble hydroxides. Some trace metals (Ni, Zn, Cu, Cd, and Pb) are discharged into receiving water bodies due to incomplete hydroxide precipitation at circum-neutral pH. This study investigated the incorporation of lignite-derived humic substances (HS) for metal complexation and removal during AMD treatment by Ca(OH)₂ and CaCO₃ neutralization. For Ca(OH)₂ neutralization, addition of HS (regardless of dosing sequence) enhanced the removal of Zn, Cu, and Cd, probably due to the incorporation of metal–humate complex into settling flocs (via aggregation, co-precipitation, and adsorption) that were subsequently removed by sedimentation. However, additional removal of Ni and Pb was statistically indeterminate, which was ascribed to the low complexation affinity of Ni and high removal of Pb by adsorption onto Fe/Al hydroxides. Conversely, for CaCO₃ neutralization, addition of HS only marginally enhanced Cd removal, with the removal of metals probably dominated by adsorption onto the abundant undissolved calcite. Equilibrium speciation modelling showed that about 25% and 38% of the remaining Cu and Pb in the treated AMD were complexed with HS, while only 5% of remaining Cd and less than 1 wt% of remaining Ni and Zn were organically complexed. In the AMD-receiving water bodies, about 20 mg l⁻¹ of HS would be required for complete complexation (>95%) of Cu and Pb and 50 mg l⁻¹ for Cd, whereas Zn and Ni complexation would not occur at natural stream HS concentrations.

A study was undertaken using urban soils in Detroit, MI and reference materials (cerussite, anglesite, pyromorphite, apatite, goethite, calcite, pyrolusite, and peat) to determine which geochemical forms of Pb measured by sequential extraction analysis are bioaccessible. The results suggest that the water soluble (Pb-fulvic acid complexes), exchangeable, and part of the carbonateoccluded fractions are bioaccessible. The Fe oxideoccluded, Mn oxide-occluded, and higher molecular weight component of the organically bound fraction are not bioaccessible. Sequential extraction predicts the presence of detectable levels of bioaccessible Pb in the rhizosphere when the summed total is ≥90 mg kg-1 and labile Pb is ≥30 mg kg-1. Cerussite (paint-Pb) and anglesite (auto-Pb), recovered mainly in the carbonateoccluded fraction, may cause an overestimation of calcite-Pb. Pyromorphite and apatite Pb (bone) may cause an overestimation of Fe oxide-occluded Pb. © Springer Science+Business Media Dordrecht 2013.

A soil column adsorption–desorption study was performed on an agricultural calcareous soil to determine the impact of sewage sludge spreading on nickel mobility. Ni adsorption experiments were followed by desorption tests involving the following liquid extractants: water, calcium (100 mg/L), oxalic acid (525 mg/L equivalent to 100 mg carbon/L), and sludge extracts (0.5 and 2.5 g/L). Desorption tests were also conducted after sewage sludge spreading at three application rates (30, 75, and 150 t/ha). According to the breakthrough curve, Ni adsorption was irreversible and occurred mainly through interactions with calcite surface sites. Nickel desorption from the soil column was promoted in presence of significant dissolved organic carbon (DOC) concentration as observed with oxalic acid elution and sludge extract at 2.5 g/L. In sludge-amended soil columns, the maximum Ni levels occurred in first pore volumes, and they were positively correlated to the sludge application rate. The presence of DOC in leaching waters was the main factor controlling Ni desorption from the sludge-amended soil columns. This finding implies that DOC generated by sludge applied on calcareous soils might facilitate the leaching of Ni due to the formation of soluble Ni–organic complexes. Thus, sludge application can have potential environmental impacts in calcareous soils, since it promotes nickel transport by decreasing Ni retention by soil components.

In this paper, particular attention was paid to the presence of aerosol solid particles, which occurred mainly as a result of exploitation and coal combustion in the thermal power plants of the Kolubara basin. Not all of the particles created by this type of anthropogenic pollution have an equal impact on human health, but it largely depends on their size and shape. The mineralogical composition and particle size distribution in the samples of aero sediments were defined. The samples were collected close to the power plant and open pit coal mine, in the winter and summer period during the year 2007. The sampling was performed by using precipitators placed in eight locations within the territory of the Lazarevac municipality. In order to characterize the sedimentary particles, several methods were applied: microscopy, SEM-EDX and X-ray powder diffraction. The concentration of aero sediments was also determined during the test period. Variety in the mineralogical composition and particle size depends on the position of the measuring sites, geology of the locations, the annual period of collecting as well as possible interactions. By applying the mentioned methods, the presence of inhalational and respiratory particles variously distributed in the winter and in the summer period was established. The most common minerals are quartz and feldspar. The presence of gypsum, clay minerals, calcite and dolomite as secondary minerals was determined, as well as the participation of organic and inorganic amorphic matter. The presence of quartz as a toxic mineral has a particular impact on human health.

A permeable reactive barrier (PRB) was installed in Aznalcóllar (Spain) in order to rehabilitate the Agrio aquifer groundwater severely contaminated with acid mine drainage after a serious mining accident. The filling material of the PRB consisted of a mixture of calcite, vegetal compost and, locally, Fe(0) and sewage sludge. Among the successes of the PRB are the continuous neutralisation of pH and the removal of metals from groundwater within the PRB (removals of >95 %). Among the shortcomings are the improper PRB design due to the complexity of the internal structure of the Agrio alluvial deposits (which resulted in an inefficient capture of the contaminated plume), the poor degradability of the compost used and the short residence time within the PRB (which hindered a complete sulphate reduction), the clogging of a section of the PRB and the heterogeneities of the filling material (which resulted in preferential flows within the PRB). Undoubtedly, it is only through accumulated experience at field-scale systems that the potentials and limits of the PRB technology can be determined.

Black crusts are recognized to have been, up to now, one of the major deterioration forms affecting the built heritage in urban areas. Their formation is demonstrated to occur mainly on carbonate building materials, whose interaction with an SO₂-loaded atmosphere leads to the transformation of calcium carbonate (calcite) into calcium sulfate dihydrate (gypsum) which, together with embedded carbonaceous particles, consequently forms the black crusts on the stone surface. An analytical study was carried out on black crust samples collected from limestone monumental buildings and churches belonging to the European built Heritage, i.e., the Corner Palace in Venice (Italy), the Cathedral of St. Rombouts in Mechelen (Belgium), and the Church of St. Eustache in Paris (France). For a complete characterization of the black crusts, an approach integrating different and complementary techniques was used, including laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), Fourier transform infrared spectroscopy, optical and scanning electron microscopy. In particular, the application of LA-ICP-MS permitted to obtain a complete geochemical characterization in terms of trace elements of the black crusts from the inner parts to the external layers contributing to the identification of the major combustion sources responsible for the deterioration over time of the monuments under study. In addition, the obtained results revealed a relation between the height of sampling and the concentration of heavy metals and proved that the crust composition can be a marker to evaluate the variation of the fuels used over time.

Different batches of valued mussel shell and waste mussel shell ash are characterised. Shell ash has pH > 12 and high electrical conductivities (between 16.01 and 27.27 dS m⁻¹), while calcined shell shows pH values up to 10.7 and electrical conductivities between 1.19 and 3.55 dS m⁻¹. X-ray fluorescence, nitric acid digestion and water extractions show higher concentrations in shell ash for most parameters. Calcite is the dominant crystalline compound in this ash (95.6 %), followed by aragonite. Adsorption/desorption trials were performed for mussel shell ash and for a waste mixture including shell ash, sewage sludge and wood ash, showing the following percentage adsorptions: Hg(II) >94 %, As(V) >96 % and Cr(VI) between 11 and 30 % for shell ash; Hg(II) >98 %, As(V) >88 % and Cr(VI) between 30 and 88 % for the waste mixture. Hg and As desorption was <5 % for both shell ash and the waste mixture, while Cr desorption was between 92 and 45 % for shell ash, and between 19 and 0 % for the mixture. In view of that, mussel shell ash and the mixture including shell ash, sewage sludge and wood ash could be useful for Hg(II) and As(V) removal.

Extracellular polymeric substances (EPS) were extracted from four anaerobic granular sludges with different procedures to study their involvement in biosorption of metallic elements. EPS extracts are composed of closely associated organic and mineral fractions. The EPS macromolecules (proteins, polysaccharides, humic-like substances, nucleic, and uronic acids) have functional groups potentially available for the binding of metallic elements. The acidic constants of these ionizable groups are: pK ₐ₁ (4–5) corresponding to the carboxyl groups; pK ₐ₂ (6–7) corresponding to the phosphoric groups; pK ₐ₃ (8–10) and pK ₐ₄ (≈10) corresponding to the phenolic, hydroxyl, and amino groups. The polarographic study confirms the higher affinity of the EPS to bind to lead than to cadmium. Moreover, the binding of these metallic compounds with the EPS is a mix of several sorption mechanisms including surface complexation, ion exchange, and flocculation. Inorganic elements were found as ions linked to organic molecules or as solid particles. The mineral fraction affects the binding properties of the EPS, as the presence of salts decreases the EPS binding ability. Calcite and apatite particles observed on SEM images of EPS extracts can also sorb metallic elements through ion exchange or surface complexation.

The adsorption of 12 pesticides of the phenylurea family was studied by batch experiments in order to determine the adsorption coefficient, K d. The study was conducted in two soils chosen for their differences in organic matter and calcite contents. K d pesticide adsorption coefficients were higher for soil S1 than for soil S2 due to the presence of a higher organic matter content and a lower calcite content in soil S1. To identify pesticide properties governing retention, 18 molecular descriptors were considered. Class-specific quantitative structure–property relationship (QSPR) soil sorption models using one, two, and three descriptors were developed from our experimental data using linear regressions. One of the aims of this work was to check whether QSPR models that did not include literature values of K ₒw were able to predict K d coefficients in satisfactory agreement with our experimental data. The influence of the level of theory in determining K ₒw and polarisability predictors on the predictive performance of the model was also examined by comparing quantum chemistry and empirical (QikProp) approaches. The one-descriptor model using “quantum” polarisability α was found to perform almost as well as or better than the other models.