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 effect of lead on the sorption of 2,4,6-trichlorophenol (2,4,6-TCP) on soil and peat was investigated using a batch equilibration method. Lead markedly diminished the sorption of 2,4,6-TCP, and 2,4,6-TCP had little effect on lead sorption. Peat was a more effective adsorbent for 2,4,6-TCP than soil. The desorption hysteresis of 2,4,6-TCP verified the presence of high-energy sorption sites. Mechanisms of lead suppression effect on the 2,4,6-TCP sorption included the following: Firstly, lead accelerated the aggregation of colloids, the aggregates covered the surface in part and shrunk the pore sizes of the adsorbents, hence decreased the sorption of 2,4,6-TCP. Secondly, X-ray absorption and Fourier transform infrared spectroscopy study suggested that lead competed with 2,4,6-TCP for carboxylic, phenolic and Si-OH groups of organic matter and clay minerals. Such competition was partly responsible for the overall suppression effect of lead on the sorption of 2,4,6-TCP. Lead diminished the sorption of 2,4,6-trichlorophenol onto soil and peat.

Recent studies have demonstrated that natural abundance 15N can be a useful tool for assessing nitrogen saturation, because as nitrification and nitrate loss increase, δ15N of foliage and soil also increases. We measured foliar δ15N at 11 high-elevation spruce-fir stands along an N deposition gradient in 1987-1988 and at seven paired northern hardwood and spruce-fir stands in 1999. In 1999, foliar δ15N increased from -5.2 to -0.7[per thousand] with increasing N deposition from Maine to NY. Foliar δ15N decreased between 1987-1988 and 1999, while foliar %N increased and foliar C:N decreased at most sites. Foliar δ15N was strongly correlated with N deposition, and was also positively correlated with net nitrification potential and negatively correlated with soil C:N ratio. Although the increase in foliar %N is consistent with a progression towards N saturation, other results of this study suggest that, in 1999, these stands were further from N saturation than in 1987-1988. Foliar δ15N increased with increasing N deposition from Maine to NY, but decreased between 1987-1988 and 1999

The use of a vegetation cover for the management of heavy metal contaminated soils needs prior investigations on the plant species the best sustainable. In this work, behaviors of Trifolium repens and Lolium perenne, growing in a metal-polluted field located near a closed lead smelter, were investigated through Cd, Pb and Zn-plant metal concentrations and their phytotoxicity. In these plant species, metals were preferentially accumulated in roots than in shoots, as follow: Cd > Zn > Pb. Plant exposure to such metals induced oxidative stress in the considered organs as revealed by the variations in malondialdehyde levels and superoxide dismutase activities. These oxidative changes were closely related to metal levels, plant species and organs. Accordingly, L. perenne seemed to be more affected by metal-induced oxidative stress than T. repens. Taken together, these findings allow us to conclude that both the plant species could be suitable for the phytomanagement of metal-polluted soils. Usefulness of Trifolium repens and Lolium perenne for the phytomanagement of heavy metal-contaminated soils.

Metal ions interact with biological materials and their decomposition products by ligation (coordination complex-formation with certain moieties containing O, N, S, etc.). The extent of this interaction depends on the identities of both ligand and metal ion and can be described by some equation derived from perturbation theory. Uptake of metal ions - including highly toxic ones - from soils is controlled by a competition between root exudate components and soil organic matter (SOM) for the ions. SOM consists of a variety of potential ligands which evolve during humification towards more efficient binding (retention) of metals such as Cu, Ni, Cr but also of toxicants like U, Cd. The actual way of interaction can be inferred from stoichiometry of the involved compounds and the C/N ratio in the soil, providing predictions as to which metals will be most efficiently shuttled into green plants or fungi, respectively. The latter, selective process is crucial for closing nutrient cycles and sensitively depends on C/N ratio and the extent of “forcing” by onfalling leaf or needle litter. Therefore, analytical data on the soil can be used to predict possible risks of exposition to toxic metals also for human consumption of plant parts. Degradation, amounts and evolution of N-free vs. nitrogenous SOM control transfer of essential and toxic metals from soil into plants, to be estimated from coordination (bio-)chemistry.

Berkheya coddii Roessler (Asteraceae) is a hyper-accumulator of nickel, which can be used in phytomining and phytoremediation. Chrysolina pardalina Fabricius (Chrysomelidae) is a phytophagous leaf beetle, which may be useful in controlling population levels of B. coddii after it has been introduced into a new habitat. The aim of this study was to investigate the response of C. pardalina to topical application of dimethoate. Data recorded included the activity of acetylcholinesterase (AChE), the concentration of glutathione (GSH), and the activity of selected enzymes connected with GSH metabolism. Assays were carried out several times during the first 24 h after exposure to dimethoate. At the dosages used in this study, dimethoate was not as toxic as expected. AChE activity was significantly decreased 14 and 24 h after application. GST activity was significantly decreased 24 h after application. GSTPx activity was significantly decreased 2, 14 and 24 h after application. GR activity was significantly increased 4 h after application. GSH concentration was significantly increased 24 h after application. Long-term exposure to high levels of nickel may have caused adaptive changes in the enzymes that enable C. pardalina to deal with other stressors, including organophosphate pesticides. Long-term exposure to high levels of nickel may have caused adaptive changes in the enzymes that enable Chrysolina pardalina to deal with other stressors, including organophosphate pesticides.

We conducted a field drought manipulation experiment in an evergreen oak Mediterranean forest from 1999 to 2005 to investigate the effects of the increased drought predicted for the next decades on the accumulation of trace elements that can be toxic for animals, in stand biomass, litter and soil. Drought increased concentrations of As, Cd, Ni, Pb and Cr in roots of the dominant tree species, Quercus ilex, and leaf Cd concentrations in Arbutus unedo and of Phillyrea latifolia codominant shrubs. The increased concentration of As and Cd can aggravate the toxic capacity of those two elements, which are already next or within the levels that have been shown to be toxic for herbivores. The study also showed a great reduction in Pb biomass content (100-135 g ha-1) during the studied period (1999-2005) showing the effectiveness of the law that prohibited leaded fuel after 2001. The results also indicate that drought increases the exportation of some trace elements to continental waters. Drought increased biomass concentrations of As and Cd and favors exportation of some trace elements to continental waters in a Mediterranean forest.

A Biotic Ligand Model was developed predicting the effect of cobalt on root growth of barley (Hordeum vulgare) in nutrient solutions. The extent to which Ca2+, Mg2+, Na+, K+ ions and pH independently affect cobalt toxicity to barley was studied. With increasing activities of Mg2+, and to a lesser extent also K+, the 4-d EC50Co2+ increased linearly, while Ca2+, Na+ and H+ activities did not affect Co2+ toxicity. Stability constants for the binding of Co2+, Mg2+ and K+ to the biotic ligand were obtained: log KCoBL = 5.14, log KMgBL = 3.86 and log KKBL = 2.50. Limited validation of the model with one standard artificial soil and one standard field soil showed that the 4-d EC50Co2+ could only be predicted within a factor of four from the observed values, indicating further refinement of the BLM is needed. Biotic Ligand Models are not only a useful tool to assess metal toxicity in aquatic systems but can also be used for terrestrial plants.

Residence time-dependent distribution patterns of hexachlorobenzene (HCB) and dichlorodiphenyltrichloroethane (DDT) among different soil organic matter fractions of three Chinese soils were investigated. Soil organic matter (SOM) was fractionated into fulvic acid (FA), humic acid (HA), bound-humic acid (BHA), lipid, and insoluble residue (IR) fractions using methyl isobutyl ketone (MIBK) method. Results revealed that as the residence time prolonged, the amounts of HCB and DDT in the FA, HA and BHA fractions decreased, while those in the lipid and IR fractions increased. One- and two-compartment first order, and one- and two-parameter pore-diffusion kinetic models were used to describe the mobility of HCB and DDT from the FA, HA and BHA fractions. The results suggest that excellent agreements were achieved between the experimental data and fits to the two-compartment first order kinetic model (R2 > 0.97). The transfer rates of HCB and DDT followed the order FA > HA > BHA. HCB and DDT tend to transfer from FA, HA and BHA fractions to lipid and IR fractions with increasing residence time.

Concern regarding the impacts of continued nitrogen and sulfur deposition on ecosystem health has prompted the development of critical acid load assessments for forest soils. A critical acid load is a quantitative estimate of exposure to one or more pollutants at or above which harmful acidification-related effects on sensitive elements of the environment occur. A pollutant load in excess of a critical acid load is termed exceedance. This study combined a simple mass balance equation with national-scale databases to estimate critical acid load and exceedance for forest soils at a 1-km2 spatial resolution across the conterminous US. This study estimated that about 15% of US forest soils are in exceedance of their critical acid load by more than 250 eq ha-1 yr-1, including much of New England and West Virginia. Very few areas of exceedance were predicted in the western US. This simple mass balance equation estimated that 17% of US forest soils exceed their critical acid load by more than 250 eq ha-1 yr-1, and these areas are predominantly located in the northeastern US.