Zerovalent iron (Fe0, ZVI) has drawn great interest as an inexpensive and effective material to promote the degradation of environmental contaminants. A focus of ZVI research is to increase degradation kinetics and overcome passivation for long-term remediation. Halide ions promote corrosion, which can increase and sustain ZVI reactivity. Adding chloride or bromide salts with Fe0 (1% w/v) greatly enhanced TNT, RDX, and HMX degradation rates in aqueous solution. Adding Cl or Br salts after 24 h also restored ZVI reactivity, resulting in complete degradation within 8 h. These observations may be attributed to removal of the passivating oxide layer and pitting corrosion of the iron. While the relative increase in degradation rate by Cl- and Br- was similar, TNT degraded faster than RDX and HMX. HMX was most difficult to remove using ZVI alone but ZVI remained effective after five HMX reseeding cycles when Br- was present in solution. The addition of halide ions promotes the degradation of high explosives by zerovalent iron.

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.

The experiment was carried out on a short rotation coppice culture of poplars (POP-EUROFACE, Central Italy), growing in a free air carbon dioxide enriched atmosphere (FACE). The specific objective of this work was to study whether elevated CO2 and fertilization (two CO2 treatments, elevated CO2 and control, two N fertilization treatments, fertilized and unfertilized), as well as the interaction between treatments caused an unbalanced nutritional status of leaves in three poplar species (P. x euramericana, P. nigra and P. alba). Finally, we discuss the ecological implications of a possible change in foliar nutrients concentration. CO2 enrichment reduced foliar nitrogen and increased the concentration of magnesium; whereas nitrogen fertilization had opposite effects on leaf nitrogen and magnesium concentrations. Moreover, the interaction between elevated CO2 and N fertilization amplified some element unbalances such as the K/N-ratio. CO2 enrichment reduced foliar nitrogen and increased the magnesium concentration in poplar.

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 hydrolysis of 4-Nitrophenylphosphate (NPP) in the presence of Ferrous and Ferric ions in Oil in water microemulsion media was investigated. The reaction was monitored by measuring the absorbance of the nitrophenolate ion produced in the reaction aliquots with time. The order of effectiveness of the microemulsion system towards the hydrolysis of NPP was found to be cationic > anionic> aqueous in the presence of Ferrous, Ferric and Turnbull's blue at neutral pH. The result of the present investigation enriches our understanding of the possible roles polymetallic ions play in hydrolysis reactions. The reactions mimic the roles of purple acid phosphatases in the hydrolysis of phosphate esters. The application of the above systems for environmental decontamination of organophosphates is also envisoned.

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.

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.

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.

For the routine determination of metals in environmental samples, we require microwave-assisted digestion methods that yield 'total' or 'near-total' recoveries while avoiding the use of HF acid. As inductively coupled plasma mass spectrometry (ICP-MS) is the method of detection, it is desirable to minimize the use of HCl to avoid spectral interferences caused by high Cl- concentrations. Using certified reference materials, we performed a series of modifications to the US EPA method 3051 which included: increasing the temperature and durations of microwave digestion, varying the ratio of sample mass to acid volume, and alterations to the compositions of the acid digestion mixture. The experiments were conducted using urban particulate matter (NIST-1648), coal fly ash (NBS-1633) and six CANMET certified reference materials (Till-2, Till-3, Till-4, LKSD-1, LKSD-2 and LKSD-4), in two laboratories (Health Canada and Environment Canada) using different microwave digestion systems and different ICP-MS instruments. Our modified microwave-assisted nitric acid digestion method improved recoveries for Pb, Zn, V, Fe and Cu approaching 'total' recoveries in the same matrices determined using X-ray fluorescence (XRF) and instrumental neutron activation analysis (INAA) as reported in the certificates of analysis. Recoveries for other elements such as Cr and Ni compared well with 'near-total' recoveries yielded by traditional (non-assisted) acid digestion methods.