Three experiments were conducted to optimize the use of ethylenediaminetetraacetic acid (EDTA) for reclaiming urban soils contaminated with trace metals. As compared to Na2EDTA, (NH4)2EDTA extracted 60% more Zn and equivalent amounts of Cd, Cu and Pb from a sandy loam. When successively saturating and draining loamy sand columns during a washing cycle, which submerged it once with a (NH4)2EDTA wash and four times with deionised water, the post-wash rinses largely contributed to the total cumulative extraction of Cd, Co, Cr, Cu, Mn, Ni, Pb and Zn. Both the washing solution and the deionised water rinses were added in a 2:5 liquid to soil (L:S) weight ratio. For equal amounts of EDTA, concentrating the washing solution and applying it and the ensuing rinses in a smaller 1:5 L:S weight ratio, instead of a 2:5 L:S weight ratio, increased the extraction of targeted Cr, Cu, Ni, Pb and Zn. A single EDTA addition is best utilised in a highly concentrated washing solution given in a small liquid to soil weight ratio.

Options for wetland creation or restoration might be limited because of the presence of contaminants in the soil. The influence of hydrological management on the pore water concentrations of Cd, Cr, Cu, Fe, Mn, Ni and Zn in the upper soil layer of a contaminated overbank sedimentation zone was investigated in a greenhouse experiment. Flooding conditions led to increased Fe, Mn, Ni and Cr concentrations and decreased Cd, Cu and Zn concentrations in the pore water of the upper soil layer. Keeping the soil at field capacity resulted in a low pore water concentration of Fe, Mn and Ni while the Cd, Cu, Cr and Zn concentrations increased. Alternating hydrological conditions caused metal concentrations in the pore water to fluctuate. Formation and re-oxidation of small amounts of sulphides appeared dominant in determining the mobility of Cd, Cu, and to a lesser extent Zn, while Ni behaviour was consistent with Fe/Mn oxidation and reduction. These effects were strongly dependent on the duration of the flooded periods. The shorter the flooded periods, the better the metal concentrations could be linked to the mobility of Ca in the pore water, which is attributed to a fluctuating CO2 pressure. The hydrological regime is a key factor in determining the metal concentration in the pore water of a contaminated sediment-derived soil.

Previously recommended rhizosphere-based method (RHIZO) applied to moist rhizosphere soils was integrated with moist bulk soils, and termed adjusted-RHIZO method (A-RHIZO). The A-RHIZO and RHIZO methods were systematically compared with EDTA, DTPA, CaCl2 and the first step of the Community Bureau of Reference (BCR1) methods for assessing metal phytoavailability under field conditions. Results suggested that moist bulk soils are equally suited or even better than rhizosphere soils to estimate metal phytoavailability. The A-RHIZO method was preferred to other methods for predicting the phytoavailability of Ni, Cu, Zn, Cd, Pb and Mn to wheat roots with correlation coefficients of 0.730 (P < 0.001), 0.854 (P < 0.001), 0.887 (P < 0.001), 0.739 (P < 0.001), 0.725 (P < 0.001) and 0.469 (P < 0.05), respectively. When including soil properties, other extraction methods were also able to predict phytoavailability reasonably well for some metals. Soil pH, organic matter and Fe-Mn oxide contents, and cation-exchange capacity mostly influenced the extraction and phytoavailability of metals. An adjusted-RHIZO method was the most promising approach for predicting metal phytoavailability to wheat under field conditions.

This study vividly presents results from a seasonal particulate matter measurement campaign conducted at world's largest ship-breaking yard i.e., Alang-Sosiya (Gujarat, India) at six locations and a reference station at Gopnath which is 30 km south of this ship-breaking yard. The collected suspended particulate matter (SPM) 24-h samples were critically analyzed for heavy metals (Pb, Cd, Co, Ni, Cr, Mn, Fe, Cu, Zn). The average concentration of SPM within the ship-breaking yard during the investigation was 287.5 ± 20.4 μg m-³ and at reference station it was 111.13 ± 5.81 μg m-³. These values are found to be in excess of the permitted national standards. The levels of heavy metals at Alang-Sosiya are very high as compared to US EPA and WHO guidelines. The mean concentrations of all metals are in the order: Fe >>Zn >Cu > Mn > Cd >Pb > Co >Ni >Cr. The results on enrichment factors (EF) suggest that most of the metals in the ship-breaking yard exhibit EF values of near or above 100 which must have been comprehensively affected by ship-breaking activities. Metal data was used to evaluate the role of spatial factors on their distribution characteristics. Thereafter, factor analysis was carried out to identify the main components liable for the variance of the data set.

The bursting of the mining dam of Aznalcollar (Seville, Spain) triggered an increase in the concentration of heavy metals in the soils of the river Guadiamar valley as a result of the leaching of the pyritic sludge deposited on them. After the cleaning operations which included, as well as mechanical clearing, the addition of different amendments, some areas with residual sludge remained, from which some heavy metals are being mobilized by the cyclical recharge and discharge processes of water in the profiles. This paper analyzes the effect of the soil recovery operations and the climatology on the concentration of metals and their distribution in the soil profile in an area affected by the toxic spill. Fourteen points have been selected in a plot in which acidity persists, there is no vegetation, and residual sludge stains can be seen at a glance. The temporal and spatial evolution of the extractable metals: Fe, Cu, Mn and Zn, the pH and the oxidable fraction has been measured in-depth. The results obtained up to now indicate a leaching of the pollutant towards deeper horizons, finding, at a depth of 757 cm, pH values of 3.5 and very high Fe and Mn concentrations available, especially in the profiles with large sized pores, with a big fraction of sand. On the surface, seasonally, there are low pH values of around 2.5 and extractable Fe contents of over 4000 ppm, which might have an influence on the quality of surface runoff or underground water.

Mn biogeochemistry was studied from 1994 to 2003 in a small forested catchment in the central Czech Republic using the watershed mass balance approach together with measurements of internal stores and fluxes. Mn inputs in bulk deposition were relatively constant during a period of sharply decreasing acidic deposition, suggesting that the Mn source was terrestrial, and not from fossil fuel combustion. Mn inputs in bulk deposition and Mn supplied by weathering each averaged 13 mg m-² year-¹ (26 mg m-² year-¹ total input), whereas Mn export in streamwater and groundwater averaged 43 mg m-² year-¹. Thus an additional Mn source is needed to account for 17 mg m-² year-¹. Internal fluxes and pools of Mn were significantly greater than annual inputs and outputs. Throughfall Mn flux was 70 mg m-² year-¹, litterfall Mn flux was 103 mg m-² year-¹, and Mn net uptake by vegetation was 62 mg m-² year-¹. Large pools of labile or potentially labile Mn were present in biomass and surficial soil horizons. Small leakages from these large pools likely supply the additional Mn needed to close the watershed mass balance. This leakage may reflect an adjustment of the ecosystem to recent changes in atmospheric acidity.

An important component of monitoring pollution of urban road-deposited sediment (RDS) is an understanding of the temporal variability in its composition and physical characteristics. This study set out to determine what the monthly variability in metal concentrations, organic matter content, grain-size and grain-size fraction metal-loadings are in inner city sites in Manchester, northwest England. The results show that there is significant temporal variability in metal (Pb, Zn, Fe, Mn) concentration in RDS from inner city Manchester. There was no significant temporal variability in grain-size characteristics or organic matter content, indicting that these metal variations were the result of variation in sources and accumulation processes. Pb and Zn displayed local variability, suggesting local controls on variability, whereas Fe and Mn displayed consistent variability across all sites, suggesting a common, larger-scale control on variability. The finest grain-size fraction (<63 μm) contained the highest Pb, Cu and Zn concentrations, but for the case of Fe and Mn, the coarser fractions (>300 μm) commonly contained the highest concentrations, again suggesting differing controls. For all metals, due to the weight percent dominance of the coarser fractions, the dominant loading of metals is in the coarser fractions. This has implications on management strategies, via street sweeping and the subsequent waste disposal, and on the modelling of the input of RDS and associated metals into surface waterways. The recognition of significant temporal variability of metal concentrations in RDS, independent of grain-size changes, implies that the monitoring of urban road sediment pollution will require not just consideration of spatial variability, but the design of schemes that will capture temporal variability also.

Former mining activities lasting 140 years in the Ducktown Mining District, Tennessee, USA, has contaminated the streams draining the district with acid-mine drainage (AMD). North Potato Creek and its major tributary, Burra Burra Creek, are two of the most heavily AMD-impacted streams in the district. The removal of dissolved metals from the water in these creeks is largely attributable to the sorption of Cu, Zn, Co, Al, and Mn on suspended hydroxide precipitates of Fe. The fraction of trace metals remaining in solution decreases with increasing pH in the sequence Pb < Cu < Zn < Co. The concentration of Fe in solution also decreases with increasing pH due to the formation of ferric hydroxide precipitates which accounted for up to 81.4% by weight of the total suspended sediment. The concentration of suspended sediment substantially decreases as the water of North Potato Creek flows through a large settling basin, where 1.3 (±0.3) x 10⁶ kg/year of trace-metal-laden suspended sediment would be annually deposited. In spite of this attempt to purify it, the water discharged into the river is acidic (pH 3.6) and still contains high concentrations of dissolved trace metals, which would resorb on to suspended sediment and be ultimately transported to a downstream reservoir, Ocoee No. 3 Lake.

Industrial soils near Zn-Pb mines and metallurgical plants in the vicinity of Olkusz (southern Poland) are exposed to high environmental stress related to heavy metal pollution (Zn, Pb, Cd, Mn, Fe, Tl and As) from waste disposal sites and primary ores. X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive spectrometry analyses (EDS) and Atomic Absorption Spectroscopy (AAS) were used to analyse rhizosphere soil samples from the area. The mineral composition of the rhizosphere soils was determined. Carbonates of lead, cadmium and zinc, arsenic-lead sulphosalts and other minerals occurring on the root epiderm are described. Mineral aggregates of secondary origin include polymineralic spherules containing high concentrations of Zn (up to 2.3%), Pb (up to 0.7%), Fe (up to 23%), Cd (up to 427 mg kg-¹) and Tl (up to 139 mg kg-¹). Processes on the rhizoplane, and in the zone where plant-root exudation solutions are active, promote the crystallization of metalliferous minerals. ESEM is recommended as an efficient method for examining alteration occurring in the rhizosphere environment.

A multi-media monitoring field investigation, which included atmospheric, road sediment and soil samples, was carried out at two highway study sites to identify past and present Pb sources. Past Pb anthropogenic sources such as paint and leaded gasoline were linked to significant Pb accumulation in roadside soils at both sites through Pb isotopic analyses. This was achieved by identifying the distinct Pb isotopic composition in older versus newer Pb accumulation at different depths across the soil profile. Older Pb accumulations exhibited lower ²⁰⁶Pb/²⁰⁷Pb isotopic ratios, consistent with Canadian Pb-bearing ores, whereas newer Pb accumulations reflected a mixture of the ²⁰⁶Pb/²⁰⁷Pb ratios of road sediment samples, with the Pb isotopic signature of uncontaminated soil. Isotopic analyses were also helpful in identifying road sediment as an important current source of Pb in roadside soils, by comparing the isotopic signatures derived from road sediment and atmospheric dustfall. The known association of Pb with anthropogenic sources was used to indirectly relate other metals (Cu, Mn, Zn) to the same source by the Enrichment Ratio method. Significant positive correlations at the 90-95% confidence level were found between Cu, Zn and Pb Enrichment Ratios in roadside and dust deposition samples. Weaker correlations were found between Mn and Pb, at the highway study site with the least amount of traffic. However, correlations between these two metals were significant at the 90% confidence level for the busier highway site highlighting Mn potential anthropogenic source. An isotopic tracer study is suggested to further investigate the process of Mn redistribution in the environment due to exhaust fuel emissions. More research is needed regarding the potential impact from using a Mn-based fuel additive.