There has been and continues to be considerable scientific interest in predicting bioremediation rates and endpoints. This requires the development of chemical techniques capable of reliably predicting the bioavailability of organic compounds to catabolically active soil microbes. A major issue in understanding the link between chemical extraction and bioavailability is the problem of definition; there are numerous definitions, of varying degrees of complexity and relevance, to the interaction between organic contaminants and microorganisms in soil. The aim of this review is to consider the bioavailability as a descriptor for the rate and extent of biodegradation and, in an applied sense, bioremediation of organic contaminants in soil. To address this, the review will (i) consider and clarify the numerous definitions of bioavailability and discuss the usefulness of the term 'bioaccessibility'; (ii) relate definition to the microbiological and chemical measurement of organic contaminants' bioavailability in soil, and (iii) explore the mechanisms employed by soil microorganisms to attack organic contaminants in soil. Understanding organic contaminant's behaviour in soil is key to chemically predicting biodegradation.

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.

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.

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.

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.

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.

Phytoremediation is potentially effective for managing excessive selenium (Se) in drainage sediment residing in the San Luis Drain in central California. This 2-year field study examined the feasibility of amending drainage sediment (containing 4.78 mg Se g 1) with methionine and casein to enhance volatilization without or with vegetation of Sporobolus airoides. Results show that without organic amendments, rates of Se volatilization were less than 25 mgm 2 d 1 in all plots. After amending the sediment with 71.4 mg methionine kg 1 soil, Se volatilization rates were 434 107 mgm 2 d 1 in vegetated plots and 289 117 mgm 2 d 1 in irrigated bare plots.With the amendment of 572 mg casein kg 1 soil, rates increased to 346 103 mgm 2 d 1 in irrigated bare plots and to 114 55 mgm 2 d 1 in vegetated plots. Both methionine and casein promoted biological remediation of Se via volatilization most effectively during the warmest months.

The soil compartment is an important interface between the atmosphere and the subsurface hydrosphere. In this paper a conceptual approach for regional hydrologic soil modelling (RHSM) is presented, which provides two important qualities for modelling. First, the soil compartment is directly coupled to the atmosphere via the land surface and to the aquifers. Second, extremely fine (5 cm vertical) resolutions of the soil system can be realized at regional scales (several hundreds of km2). This high-resolution modelling could be achieved by parallel computation techniques. The RHSM approach is applied to the Beerze-Reusel drainage basin, which belongs to the Meuse River basin. Moisture transport in the soil system was calculated with extremely high vertical resolution at a regional scale based on rainfall-evaporation data for the year 2000. As a result, highly resolved regional groundwater recharge pattern addressing the heterogeneity of soil systems could be determined. A real case application of concept of regional hydrologic soil modelling is presented.

Here we review mechanisms and factors influencing contaminant exposure among terrestrial vertebrate wildlife. There exists a complex mixture of biotic and abiotic factors that dictate potential for contaminant exposure among terrestrial and semi-terrestrial vertebrates. Chemical fate and transport in the environment determine contaminant bioaccessibility. Species-specific natural history characteristics and behavioral traits then play significant roles in the likelihood that exposure pathways, from source to receptor, are complete. Detailed knowledge of natural history traits of receptors considered in conjunction with the knowledge of contaminant behavior and distribution on a site are critical when assessing and quantifying exposure. We review limitations in our understanding of elements of exposure and the unique aspects of exposure associated with terrestrial and semi-terrestrial taxa. We provide insight on taxa-specific traits that contribute, or limit exposure to, transport phenomenon that influence exposure throughout terrestrial systems, novel contaminants, bioavailability, exposure data analysis, and uncertainty associated with exposure in wildlife risk assessments. Lastly, we identify areas related to exposure among terrestrial and semi-terrestrial organisms that warrant additional research. Both biotic and abiotic factors determine chemical exposure for terrestrial vertebrates.

The acid volatile sulphide (AVS) and simultaneously extracted metals (ΣSEM) method is increasingly used for risk assessment of toxic metals. In this study, we assessed spatial and temporal variations of AVS and ΣSEM in river sediments and floodplain soils, addressing influence of flow regime and flooding. Slow-flowing sites contained high organic matter and clay content, leading to anoxic conditions, and subsequent AVS formation and binding of metals. Seasonality affected these processes through temperature and oxygen concentration, leading to increased levels of AVS in summer at slow-flowing sites (max. 37 μmol g-1). In contrast, fast-flowing sites hardly contained AVS, so that seasonality had no influence on these sites. Floodplain soils showed an opposite AVS seasonality because of preferential inundation and concomitant AVS formation in winter (max. 3-30 μmol g-1). We conclude that in dynamic river systems, flow velocity is the key to understanding variability of AVS and ΣSEM. Flow velocity is the key to understanding variability of AVS and ΣSEM in river sediment.