The Gorka pit lake was formed in an inactive Jurassic limestone quarry after cessation of open-pit dewatering. The main problem of the water quality in this area is linked to a large volume of extremely alkaline leachate disposed in the flooded quarry. The lake is meromictic due to a large density contrast between shallow and deep water layers. Water in the lake is of the Na-CO₃-OH type, pH is in the range from 11.5 to 13.3, and there are high concentrations of sulfate and several toxic elements (Al, As, Cr, Mo, P, and V). The chemical composition of the extremely alkaline leachate was formed as a result of the groundwater interaction with the industrial red mud wastes containing 5-10 wt.% of sodium carbonate. There is a trend of increasing concentrations and pH values with depth, mainly due to the in-gassing of atmospheric CO₂ into the surface layer and due to density stratification in the water column. Similar stratification is observed in groundwater wells around the lake. High dissolved concentrations of oxyanionic contaminants such as As, Cr, and V are caused by their high mobility and desorption under extremely alkaline conditions. In spite of reducing conditions at the bottom of the lake, caused by high concentrations of dumped organic matter, sulfate behaves conservatively because sulfate reducing bacteria do not survive in this pH range.

The main goals of this study were (1) to standardize a simple and reliable embryotoxicity test for environmental contaminants and (2) to evaluate the presence and possible protective role of the multidrug resistance-associated (MRP) protein-mediated multixenobiotic defense in two Mediterranean sea urchin species, Paracentrotus lividus and Arbacia lixula. Toxic end-point used was the success of the first cell division in sea urchin embryos. Embryotoxicities of three environmentally relevant contaminants: mercuric chloride (HgCl2, 0.05–6 μM), trybutiltin (TBT, 2.5–500 nM), and oxybenzone (OXI, 0.1–100 μM); as well as seawater samples collected from the polluted and unpolluted locations, were determined and compared. A. lixula embryos were more sensitive to all three toxic compounds, and both P. lividus and A. lixula embryos were highly sensitive to TBT at nanomolar concentrations (EC50 49 ± 5 and 36.8 ± 3 nM, respectively). Inhibition of MRP protein by specific inhibitor MK571 caused significant increase in embryotoxic potency of HgCl2 (EC50 0.697 ± 0.03 and 0.245 ± 0.04 μM, respectively), TBT (EC50 24 ± 3 and 7.4 ± 1 nM, respectively) and polluted seawater sample, but not of OXI or unpolluted, natural seawater. Therefore, our results demonstrated for the first time the protective relevance of MRP proteins in early development of these two Mediterranean sea urchin species. Finally, the embryotoxicity protocol described in this study represents a simple and rapid bioassay for determination of environmentally relevant seawater contamination.

The sequential elution technique (SET) is used to determine the distribution of elements in the different cell fractions of mosses. The extracellular extractants most commonly used in this technique are NiCl2 and EDTA, although there are certain disadvantages associated with their use. In order to avoid such problems, we searched for new extractants that displace extracellularly bound metals, either because they are present at high concentrations (Ca) or because they have a high affinity for cation exchange sites (Hg and Au). The compounds HCl, NaCl, and CaCl2 were tested as extractants of the former type, as possible alternatives for the determination of extracellular metals in the moss Pseudoscleropodium purum. Calcium chloride was finally chosen as is it potentially the most successful in terms of binding to the cation exchange sites without altering the membrane permeability. The concentration chosen was 160 mM, as this yielded maximum displacement of Zn without membrane alterations. An experiment was then carried out to test the efficiency of Ca in extracting extracellular Zn, under laboratory and field conditions. In addition, Hg and Au were tested, at different concentrations, as extractants with high affinity for cation exchange sites, as neither of these elements has previously been used in the SET, and both display electronic characteristics that suggest their potential usefulness in displacing other cations from cation exchange sites. The results obtained show that extraction of extracellularly bound metal by high concentrations of Ca should be ruled out, as total extraction of Zn was not achieved. Both Hg and Au produced membrane alterations at low concentrations and moreover, neither was more efficient at extracting Zn than the reference extractant (20 mM NiCl2).

The degradation of diesel and phenanthrene in waste water was studied in a column combining a submerged trickling-flow with a fixed-film at a determined biofilm thickness with recirculation. Degradation efficiencies were found to be high with the production of a biofilm thickness of 789 μm structured in a package material with proper adsorption and physicochemical properties necessary to reach a stable state condition for the degradation of recalcitrant components in 78% at a retention time of 3 h. Improved degradation rates were reached with a biofilm built from an adapted inoculum that showed the presence of Pseudomonas sp., Klebsiella sp. Enterobacter in a concentration of 6.45 × 109 CFU mL−1. Moreover, the biodegradation rate of the inoculumn was quantified. The diesel kinetic experimental data were well described by Gompertz model which provides a specific grow rate (Kb) of 0.76 ±â€‰0.36 h−1 and a correlation of R 2 = 0.93. The integral approach study of the variables of a complex degradation process lead to improve the complete operation of the reactor in comparison with other more specific component-based approaches.

Mechanism of zinc iron removal by zero-valent iron was discussed through zinc removal responses to several operational conditions of a packed column reactor with zero-valent iron powder. The adsorption isotherm observed implied that a kind of chemisorption was responsible for zinc removal. Zinc removal by zero-valent iron was enhanced by dissolved oxygen and ferric ion addition. However, it was deteriorated under acidic pH. In addition, zinc adsorbed on zero-valent iron was eluted by a reducing agent such as citric acid, whereas the zinc was not eluted by diluted sulfuric acid. Consequently, the zinc removal mechanism by zero-valent iron was inferred to be as follows: Zero-valent iron was firstly corroded and oxidized into ferric ion by dissolved oxygen. The ferric ion was precipitated as iron hydroxide onto the surface of the zero-valent iron powder. Zinc ion was adsorbed on and/or coprecipitated with the iron hydroxide. The iron hydroxide was finally oxidized and transformed into iron oxides.

Assessment of native plants and laboratory-scale phytoextraction tests are fundamental and preliminary steps in checking the feasibility and practice of low-cost and low-impact phytoremediation. In this study, we investigated the absorption of B by plants as a tool to remove boron in sediments from different areas of the Cecina River basin in Tuscany, Italy. The investigation was performed analyzing total and available B fraction in sediment samples as well as the B content in different tissues of native plants colonizing the contaminated areas. In laboratory scale, a phytoextraction screening test was performed. Selected high biomass crops (Brassica juncea, Zea mays, and Helianthus annuus) were evaluated in the most contaminated sample in two consecutive growing cycles. Results from field survey showed no hyperaccumulator native plant was present in the investigated areas although, high accumulation levels were found in native species from Bulera dump (Rumex crispus—259 mg kg−1 and Poa spp—203 mg kg−1). Results from laboratory phytoextraction tests showed a higher ability of B. juncea which removed about 18.5 mg B kg−1 sediment in after the two consecutive growing cycles, representing on the whole 45% of the initial available B fraction. The sediment characteristics affected by the phytoextraction processes were also discussed.

Diffused petroleum and chlorinated hydrocarbon contamination was detected in a sandy aquifer below a chemical plant in Southern Italy. The contamination was due to underground leaking tanks and pipes. The site is located near the shore line and is bordered by canals which, in combination with pumping wells, control the groundwater flow direction toward the sea. In this study, a comprehensive three-dimensional flow model was developed and calibrated to simulate the general groundwater flow system and to individuate a flow line. On this latter, a detailed field investigation was performed in order to determine the fate of dissolved hydrocarbons. Depth profiles obtained from multi-level samplers located along the modelled flow line, including measurements of hydrocarbons, all major ions and dissolved gasses, were used to constrain the conceptual model. These data were then included into a two-dimensional transport model in order to verify the efficacy of the hydraulic barrier (HB) in preventing the hydrocarbon plume to reach the shore line. Two different approaches were used in the transport simulation, one accounting for density-dependent flow and the other not. The calibrated models show that the plume length and consequently, the submarine groundwater discharge of contaminants is slightly different for the two approaches. For the simulation not accounting for the density contrast between freshwater and saltwater, the mass of contaminant discharged downstream to the HB was underestimated and also the reconstructed plume geometry was different than the observed. Moreover, the reconstruction of the saltwater intrusion interface (SWII) with the two different approaches was substantially different. This study demonstrates that at field site, variable density processes should be carefully taken into account not only when the modelling is devoted to the reconstruction of the SWII but also when the modelling is targeting the fate of hydrocarbons at sites affected by SWII, in order to provide accurate data on which soundly environmental management of the coastal zone can be based.

Humic substances are characterized by a strong binding capacity for both metals and organic pollutants, affecting their mobility and bioavailability. The understanding of the mechanisms of proton and metal binding to humic substances is of fundamental importance in geochemical modelling and prediction of cation speciation in the environment. This work reports results on copper binding on humic acids obtained through a thorough experimental and modelling approach. Two humic acids, a reference purified peat humic acid isolated by the International Humic Substances Society (IHSS) and a humic acid from a Greek soil, were experimentally studied at various pH values (4, 6 and 8), humic acid concentrations (ranging from 20 to 200 mg L−1) and ionic strength (0.1 and 0.01 M NaNO3). The binding of copper to humic acids was determined over wide ranges of copper ion concentrations using a copper ion selective electrode. The copper binding isotherms obtained at different conditions have shown that copper binding is dependent on the pH and ionic strength of the solution and on the concentration of both humic acids. Copper binding experimental data were fitted to non-ideal competitive adsorption NICA-Donnan model and the model parameter values were calculated. Both Cu2+ and CuOH+ species binding to humic acid with different binding affinities were considered. Two sets of the NICA-Donnan parameters have been calculated: one for humic acid concentrations of ≥100 mg L−1and one for humic acid concentration of 20 mg L−1. The meaning of the parameters values for each concentration level is also discussed.

Fungicides are used to prevent foliar diseases on a wide range of vegetable, field, fruit, and ornamental crops. They are generally more effective as protective rather than curative treatments, and hence tend to be applied before infections take place. Less than 1% of US soybeans were treated with a fungicide in 2002 but by 2006, 4% were treated. Like other pesticides, fungicides can move-off of fields after application and subsequently contaminate surface water, groundwater, and associated sediments. Due to the constant pressure from fungal diseases such as the recent Asian soybean rust outbreak, and the always-present desire to increase crop yields, there is the potential for a significant increase in the amount of fungicides used on US farms. Increased fungicide use could lead to increased environmental concentrations of these compounds. This study documents the occurrence of fungicides in select US streams soon after the first documentation of soybean rust in the US and prior to the corresponding increase in fungicide use to treat this problem. Water samples were collected from 29 streams in 13 states in 2005 and/or 2006, and analyzed for 12 target fungicides. Nine of the 12 fungicides were detected in at least one stream sample and at least one fungicide was detected in 20 of 29 streams. At least one fungicide was detected in 56% of the 103 samples, as many as five fungicides were detected in an individual sample, and mixtures of fungicides were common. Azoxystrobin was detected most frequently (45% of 103 samples) followed by metalaxyl (27%), propiconazole (17%), myclobutanil (9%), and tebuconazole (6%). Fungicide detections ranged from 0.002 to 1.15 μg/L. There was indication of a seasonal pattern to fungicide occurrence, with detections more common and concentrations higher in late summer and early fall than in spring. At a few sites, fungicides were detected in all samples collected suggesting the potential for season-long occurrence in some streams. Fungicide occurrence appears to be related to fungicide use in the associated drainage basins; however, current use information is generally lacking and more detailed occurrence data are needed to accurately quantify such a relation. Maximum concentrations of fungicides were typically one or more orders of magnitude less than current toxicity estimates for freshwater aquatic organisms or humans; however, gaps in current toxicological understandings of the effects of fungicides in the environment limit these interpretations.

In this study, the photocatalytic degradation of commercial azo dye (Remazol Red 133) in the presence of titanium dioxide (TiO2) suspensions as photocatalyst was investigated. The effect of various operational parameters, such as pH of dye solution and catalyst concentration on the photocatalytic degradation process, was examined. The mineralization of dye was also evaluated by measuring the chemical oxygen demand of the dye solutions. The extent of photocatalytic degradation was found to increase with increasing TiO2 concentration. For the Remazol Red dye solutions, a 120-min treatment resulted in 97.9% decolorization and 87.6% degradation at catalyst loading of 3 g/L. Experiments using real textile wastewater were also carried out. Textile wastewater degradation was enhanced at acidic conditions. The decolorization and degradation efficiencies for textile wastewater were 97.8% and 84.9% at pH 3.0, catalyst loading of 3 g/L, and treatment time of 120 min.