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.

The purpose of this study is to develop a mechanistic model to describe a conceptually new “flux-biological response” approach based on biotic ligand model (BLM) and Michaelis-Menten (M-M) kinetics to allow the linkage between valve closure behavior and sodium (Na) transport mechanism in freshwater clam Corbicula fluminea in response to waterborne copper (Cu). We test the proposed model against published data regarding Na uptake kinetics in rainbow trout and Na uptake profile in C. fluminea, confirming that the predictive model is robust. Here, we show that the predicted M-M maximum Cu internalization flux in C. fluminea is 0.369 μmol g-1 h-1 with a half-saturation affinity constant of 7.87 x 10-3 μM. Dynamics of Na uptake and valve closure daily rhythm driven by external Cu can also be predicted simultaneously. We suggest that this “Na transport-valve closure behavior” approach might provide the basis of a future design of biomonitoring tool. A new flux-biological response model can link valve closure and sodium transport mechanisms in freshwater clam in response to copper.

Metals released by the extraction with aqua regia, EDTA, dilute HCl and sequential extraction (SE) by the BCR protocol were studied in urban soils of Sevilla, Torino, and Glasgow. By multivariate analysis, the amounts of Cu, Pb and Zn liberated by any method were statistically associated with one another, whereas other metals were not. The mean amounts of all metals extracted by HCl and by SE were well correlated, but SE was clearly underestimated by HCl. Individual data for Cu, Pb and Zn by both methods were correlated only if each city was considered separately. Other metals gave poorer relationships. Similar conclusions were reached comparing EDTA and HCl, with much lower values for EDTA. Dilute HCl extraction cannot thus be recommended for general use as alternative to BCR SE in urban soils. Dilute HCl extraction is tested as an alternative to the BCR sequential extraction in urban soils.

There have been growing concerns about the environmental impact of Cu applied in the catfish pond aquaculture. In this paper, sediments taken from three commercial catfish ponds were studied for content, leachability, bioaccessibility, and speciation of sediment-bound Cu. Results showed that the Cu was concentrated in the top 10 cm of the sediments and the peak Cu concentrations ranged from the background level to about 200 mg/kg. Toxicity characteristic leaching procedure showed only 1-8% of sediment Cu was leachable while bioaccessible Cu, evaluated by physiological based extraction test, accounted for up to 40-85% of total Cu. Due to the high redox potential in the surface sediments, acid-volatile sulfide was not a significant binding phase. The sequential extraction results showed that the residual phase (forms in lattices of primary and secondary minerals) was the major Cu fraction in the first two pond sediments but carbonate-bound, Fe/Mn oxide-bound and organically bound Cu, as well as the residual fraction, seemed equally important in the third pond. Careful disposal of the Cu-laden pond sediment is necessary.

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.

In industrial barrens adjacent to a nickel-copper smelter at Monchegorsk, the Kola Peninsula, root colonisation in Deschampsia flexuosa by arbuscular mycorrhizal (AM)-type of hyphae was lower than in unpolluted forests (60.9 vs. 80.4%), while Olpidium-colonisation showed a marginally significant decline, and dark septate endophytic (DSE) hyphal colonisation was not affected. We detected an interactive effect of pollution and a neighbouring tree on DSE hyphal colonisation: at the highly polluted sites, colonisation was lower in D. flexuosa growing near trees, whereas at sites with low pollution the presence of the neighbouring tree had no effect on colonisation. High numbers of intracellular DSE sclerotia in the industrial barrens (13.3 vs. 3.4%) may indicate a survial strategy in an unfavourable environment and a dispersal strategy into a more favourable environment. While lower root colonisation by AM fungi has been also earlier reported in graminoids for heavy metal contamination, the results on other ubiquitous fungi colonising D. flexuosa roots are more novel. Severe pollution decreased root colonisation by some fungal groups; neighbouring trees decreased root colonisation by dark septate endophytic fungi in highly polluted sites.

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.

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.

The sorption of hydrophobic organic pollutants on soils or sediments has been widely studied. However, more attention in the previous studies has been paid to sorption mechanism and effects of relevant environmental factors, few studies were reported on effects of heavy metals on the sorption of hydrophobic organic pollutants. In this paper, sorption of phthalate esters (diethyl phthalate, DEP, and di-n-butyl phthalate, DnBP) and copper on the Yellow River sediment was investigated with particular attention to the effects of copper on the phthalate sorption. The experimental results show that the sorption isotherms of phthalates could be reasonably described by the Freundlich equation. Higher sorption equilibrium constant was obtained for DnBP due to its greater hydrophobicity. The existence of copper would enhance the sorption of DnBP. Moreover, strong sorption of copper to sediment were found and attributed to abundant carbonates in the Yellow River sediment. After carbonates were removed, notable effects of copper on the phthalate sorption were observed due to the decrease of copper sorption and the increase of aqueous copper concentration. With 153 mg l-¹ copper added, the partition coefficient decreases by 52% for DEP and increases by 79% for DnBP. Primary factors that may influence interaction between the sorption of copper and DEP and DnBP were also investigated, such as complexation between copper and phthalate, and phthalate hydrophobicity. The complexation between phthalate esters and copper was substantiated by polarogram and fluorescence spectrograph, and the calculated mol ratio of complexation (copper : phthalate) was found to be 2:1.