A conceptual model of solute transport with bioremediation processes using sawdust as a matrix to improve the efficiency of bioremediation in porous media is presented. The transport part of the model solves the advection dispersion differential equations and the reaction part describes the heterotrophic metabolisms of several groups of bacteria. The bacterial growth is formulated using the double Monod kinetic equation. The model depicts the utilization of oxygen, nitrate, manganese, iron oxides and sulfate as electron acceptors for oxidation of organic carbon in porous media. Exchange between the different phases (mobile pore water phase, bio phase and matrix phase) is also considered in this model. Model parameters were adopted from literature on bioremediation processes. Feasibility and applicability of parameters were assessed by conducting a laboratory soil-sawdust columns experiments and comparing the simulated results with the experimental data. The results indicate that sawdust could be employed as low-cost materials to enhance the bioremediation processes in porous media. While the availability of organic carbon is one of the most important factors that affect bacterial activity in porous media, this study demonstrates that using sawdust as a carbon source can improve the bacterial activity and increase the column permeability.

This is a study of trace metal competition in the complexation of Pb(II) by well-characterized humic substances, namely Suwannee River Fulvic Acid (SRFA) in model solutions. It was found that Cu(II) seems to compete with Pb(II) for strong binding sites of SRFA when present at the same concentration as Pb(II). However, Cd(II) and Zn(II) did not seem to compete with Pb(II) for strong binding sites of SRFA. These two metals did compete with Pb(II) for the weaker binding sites of SRFA. Heterogeneity of SRFA was found to play a crucial role in metal-SRFA interactions. The environmental significance of this research for freshwater is that even at relatively low Pb(II) loadings, the metals associated with lead in minerals, e.g. Cu(II), may successfully compete with Pb(II) for the same binding sites of the naturally occurring organic complexants, with the result that some of the Pb(II) may exist as free Pb²⁺ ions, which has been reported to be one of the toxic forms of Pb in aquatic environment.

This work describes recent research carried out in an extremely acidic (pH 0.61–0.82) and hypersaline (e.g., 134 g/L SO₄ ²⁻, 74 g/L Fe, 7.5 g/L Al, 3 g/L Mg, 2 g/L Cu, 1 g/L Zn) leachate which seeps from a pyrite pile in San Telmo mine (Huelva, SW Spain) and forms evaporative pools of ultra-concentrated water in which attractive crystals of Zn-rich melanterite (FeᴵᴵSO₄ 7H₂O) are formed. Geochemical modeling with the Pitzer method indicates that the acidic brine was near saturation with respect to melanterite (SIMₑₗ = 0 ± 0.2). The microbiological investigation has revealed a surprisingly high biomass (1.4 × 10⁶ cells mL⁻¹) and an exotic ecosystem composed of acidophilic, Fe-oxidizing archaea (mainly Ferroplasma spp., representing 52% of the microbial population), and minor numbers of acidophilic bacteria (including Leptospirillum spp. (3.2%), Acidithiobacillus spp. (1.6%), and Alphaproteobacteria (2.8%)). The microbial production of Feᴵᴵᴵ allows the oxidative dissolution of pyrite and other sulphides, which results in additional inputs of Feᴵᴵ, SO₄ ²⁻ and acidity to the system. The surfaces of the pyrite crystals show a typical etch-pitted texture, as well as blobs of elemental sulphur, which are both compatible with this indirect, microbially mediated oxidation mechanism. The composition of the acidic leachate seems to result from the combination of several processes which include: (1) formation of melanterite within the pile during relatively dry seasons, (2) subsequent dissolution of melanterite during rainy episodes, (3) microbial oxidation of Feᴵᴵ, (4) sulphide oxidation mediated by Feᴵᴵᴵ, (5) dissolution of chlorite and other aluminosilicates present in the pile, and (6) cooling and/or evaporation of seepage from the pile and consequent melanterite precipitation.

A critical load data base was developed for Europe and Northern Asia using the latest data bases on soils, vegetation, climate and forest growth. Critical loads for acidity and nutrient nitrogen for terrestrial ecosystems were computed with the Simple Mass Balance model. The resulting critical loads are in accordance with critical loads from previous global empirical studies, but have a much higher spatial resolution. Critical loads of acidity are sensitive to both the chemical criterion and the critical limit chosen. Therefore a sensitivity analysis of critical loads was performed by employing different chemical criteria. A critical limit based on an acid neutralizing capacity (ANC) of zero resulted in critical loads that protect ecosystems against toxic concentrations of aluminium and unfavourable Al/Bc ratios, suggesting that ANC could be an alternative to the commonly used Al/Bc ratio. Critical loads of nutrient nitrogen are sensitive to the specified critical nitrate concentration, especially in areas with a high precipitation surplus. If limits of 3-6 mg N l⁻¹ are used for Western Europe instead of the widely used 0.2 mg N l⁻¹, critical loads double on average. In low precipitation areas, the increase is less than 50%. The strong dependence on precipitation surplus is a consequence of the simple modelling approach. Future models should explore other nitrogen parameters (such as nitrogen availability) instead of leaching as the factor influencing vegetation changes in terrestrial ecosystems.

Many industrialized regions in the world are faced with local overproductions of animal manure requiring processing in an economic sound manner. Intensive animal production in Flanders and the Netherlands has resulted in a considerable overproduction of animal manure. Spreading the excess manure over arable land has resulted in contamination and eutrophication of groundwater and surface waters. Over the last 4 years, research was conducted towards the potential of more economic constructed wetlands for the final treatment step. Although, initial results with laboratory flow field experiments were insufficient to reach stringent discharge criteria (Meers et al., Water Air Soil Pollut 160:15-26, 2005a), progressive optimisation of the tertiary treatment as well as of the preceding conditioning has resulted in a consistently performing pilot scale system (1,000 m³ year⁻¹ capacity) with effluent concentrations below the discharge criteria of 15 mg l⁻¹ N, 2 mg l⁻¹ P and 125 mg l⁻¹ COD (chemical oxygen demand), at a cumulated cost (operational plus investment) of 3-4 [Euro Sign] m⁻³ of pre-treated pig manure. Construction of full-scale installations with annual capacity of 10,000-25,000 m³ based on this pilot model are scheduled, with the first installation currently under way. The concept has the potential to provide a low cost, in situ treatment system allowing animal farmers to process excess animal manure themselves without the requirement of expensive ex situ treatment based on industrial scale membrane technology facilities. This paper presents the research findings of the first year of the pilot scale installation.

The competing ligand exchange method was used to investigate the competitive binding of Ni(II) by Al(III) and Fe(III) in model aqueous solutions and freshwaters. Graphite furnace atomic absorption spectrometry and adsorptive cathodic stripping voltammetry were used to monitor the rate of uptake of the Ni by Chelex 100 chelating resin and dimethylglyoxime as the competing ligands, respectively. The results have revealed that Ni(II)-humate complexes were more labile in presence of the mixture of Al(III) and Fe(III), compared to the lability of the Ni(II)-humate complexes when only one of the two, Al(III) or Fe(III), was present. The environmental significance of this work is that in model solutions simulating freshwater containing humic substances and the target trace metal Ni(II) and cations, Al(III) and Fe(III), the competitive binding of Ni(II), Al(III) and Fe(III) by humic substances makes Ni(II)-humate complexes labile, releasing free Ni²⁺-aqua complex, which reported to be toxic.

We investigated the coupling of abundance of bacteria, phytoplankton and ciliates with hydrocarbons in the surface water and sediments of five interconnected ponds in the arid Sfax solar salterns. This study aimed at determining the potential sources of hydrocarbons and the effects of salinity gradients on microorganism metabolism. Hydrocarbon analysis was performed by gas chromatography (GC-FID) and gas chromatography coupled with mass spectrometry (GC-MS). The GC-FID allowed the detection of aliphatic hydrocarbons and n-alkanes ranging from n-C₁₃ to n-C₃₀. Total aliphatic hydrocarbon concentrations varied from 92.5 mg. l-¹ in the first pond (having marine characteristics) to 661.1 mg. l-¹ in the last pond (crystallizer) (316.8 ± 120.1 mg. l-¹) for water samples and from 26.7 to 127.8 μg. g-¹ dry weight for sediment samples. The GC-MS enabled us to detect halogenated hydrocarbons (bromoalkanes and chloroalkanes) and n-alkenes. The distribution of n-alkanes indices coupled to several environmental factors suggests that a major fraction of hydrocarbons resulted from both prokaryotic (bacteria) and eukaryotic (protists) developments. A low hydrocarbon fraction might be petrogenic.

In 1997, total petroleum hydrocarbon (TPH) remediation started at a former Air Force Base, which operated from 1940 to 1991. TPH had been released to soil and groundwater at the site by military activities. The TPH was 70% jet fuel and the affected area covered 28 ha. Remediation involved a combination of technologies, including removal of volatile organic compounds using soil vapor extraction and air sparging, free product vacuum recovery and aerobic biodegradation of organics with oxygen supplied by the air sparging system, along with nutrient addition. The primary remedial method was found to be biodegradation, which has removed 93% of the contaminants from the site to date. A significant aspect of the remedial action was performance monitoring, including documentation of remediation efficiency. The goal of the research was to assess the relative accuracy of methods commonly used for monitoring in situ TPH remediation. Two such methods were selected for the research: monitoring change in soil TPH concentration (specified as non-polar extractable substances) and monitoring respiration activity in soil with a subsequent stoichiometric mass balance to estimate the mass of TPH destroyed. The study demonstrated that both of the methods provided comparable results regarding the effectiveness of in situ TPH remediation, despite the fact that their methodologies are very different.

To increase the phytoextraction efficiency of heavy metals and to reduce the potential negative effects of mobilized metals on the surrounding environment are the two major objectives in a chemically enhanced phytoextraction process. In the present study, a biodegradable chelating agent, NTA, was added in a hot solution at 90°C to soil in which beans (Phaseolus vulgaris L., white bean) were growing. The concentrations of Cu, Zn and Cd, and the total phytoextraction of metals by the shoots of the plant from a 1 mmol kg-¹ hot NTA application exceeded those in the shoots of plants treated with 5 mmol kg-¹ normal NTA and EDTA solutions (without heating treatment). A significant correlation was found between the concentrations of metals in the shoots of beans and the relative electrolyte leakage rate of root cells, indicating that the root damage resulting from the application of a hot solution might play an important role in the process of chelate-enhanced metal uptake in plants. The application of hot NTA solutions did not significantly increase metal solubilization in soil in comparison with a normal application of solution of the same dosage. Therefore, the application of a hot NTA solution may provide a more efficient alternative in chemical-enhanced phytoextraction, although further studies of techniques of application in fields are sill required.

The major objective of this paper is to provide insights to sources and sinks of nitrous acid in urban areas, and their seasonal dependency on meteorology, photochemistry and long range transport. With this aim, nitrous acid (HONO) mixing ratios and other compounds were measured in Ashdod (south of Tel Aviv, Israel), a typical Mediterranean urban area. Statistical data analysis revealed the expected correlation between HONO and nitrogen oxides during the autumn campaign when HONO sources appeared to be traffic-, harbor-, and industry-related. Conversely, during summer HONO and NO₂ were no longer correlated: NO₂ at nighttime was probably deposited onto surfaces, soil and plants, whereas HONO at daytime was likely destroyed photolytically contributing to the OH concentration. Photolysis was expected to be the dominant HONO sink at daytime, especially during the summer period. Using modeled photolytical HONO lifetimes we estimate the magnitude of heterogeneous and/or organic electron transfer source reactions of HONO as 6-8 ppbv/h.