Assessment of chemical, biochemical and ecotoxicological aspects in a mine soil amended with sludge of either urban or industrial origin

A greenhouse pot experiment was conducted to evaluate the effect of sewage sludge (SS), of sugar beet sludge (SBS), or of a combination of both, in the remediation of a highly acidic (pH 3.6) metal-contaminated soil, affected by mining activities. The SS was applied at 100 and 200 Mg ha(-1) (dry weight basis), and the SBS at 7 Mg ha(-1). All pots were sown with Italian ryegrass (Lolium multiflorum Lam.). After 60 d of growth, shoot biomass was quantified and analysed for Cu, Pb and Zn. The pseudo-total and bioavailable contents of Cu, Pb and Zn and the enzymatic activities of beta-glucosidase, acid phosphatase, cellulase, protease and urease were determined in the soil mixtures. Two indirect acute bioassays with leachates from the soil (luminescent inhibition of Vibrio fischeri and Daphnia magna immobilization) were also used. The SS, in particular when in combination with SBS, corrected soil acidity, while increasing the total organic matter content and the cation exchange capacity. The application of SS led to a decrease in the level of effective bioavailable metals (extracted by 0.01 M CaCl(2), pH 5.7, without buffer), but caused an increase in their potential bioavailability (extracted by a solution of 0.5M NH(4)CH(3)COO, 0.5 M CH(3)COOH and 0.01 M EDTA, pH 4.7). Plant biomass increased more than 10 times in the presence of 100 Mg SS ha(-1), and more than five times with the combined use of 100 Mg SS ha(-1) and SBS, but a considerable phytotoxic effect was observed for the application rate of 200 Mg SS ha(-1). Copper, Pb and Zn concentrations in the shoots of L. multiflorum decreased significantly when using 100 Mg SS ha(-1) or SBS. The activities of beta-glucosidase, urease and protease increased with increasing SS applications rates, but cellulase had a reduced activity when using 200 Mg ha(-1)SS. Both amendments were able to suppress soil toxicity to levels that did not affect D. magna, but increased the soil leachate toxicity towards V. fischeri, especially with the application of 200 Mg SS ha(-1). This study showed that for this type of mine soils, and when using SS of similar composition, the maximum SS application rate should be 100 Mg ha(-1), and that liming the SS amended soil with SBS did not contribute to a further improvement in soil quality.     

Significance of urinary arsenic speciation in assessment of seafood ingestion as the main source of organic and inorganic arsenic in a population resident near a coastal area

In order to characterize the different sources of exposure to arsenic (As), urinary excretion of total As, the sum of inorganic As+MMA+DMA determined by the hydride generation-atomic absorption spectrophotometry technique, and the species As(3), As(5), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and arsenobetaine were determined in 49 workers at a steel foundry, with presumed occupational exposure to As, and 50 subjects from the general population, all males. No evidence of occupational exposure to As resulted from environmental monitoring performed in the foundry, although the analysis of minerals used as raw materials showed the presence of As, particularly in fossils and fine ores. The urinary concentrations of As(3), MMA, DMA, the sum of inorganic As+MMA+DMA and total As were not different in the two groups, while arsenobetaine appeared significantly higher in the controls than in the workers. The different species of urinary As were all significantly correlated. Urinary excretion of As(3) was associated with the consumption of mineral water and with residence in an industrial zone, while MMA, DMA, arsenobetaine, the sum of inorganic As+MMA+DMA and total As urinary excretion were associated with the consumption of crustaceans and/or shellfish 3 days or less before urine collection. Multiple regression analysis confirmed these results. In conclusion, in populations with a high consumption of seafood, living in areas characterized by coastal/marine As pollution, only speciation of As can identify a prevalent role of environmental sources, like the consumption of seafood contaminated by As, in determining urinary As excretion, and exclude an occupational origin of the exposure.     

Effect of modified Fenton treatment on the thermal behavior of contaminated harbor sediments

This study presents the results of experimental Fenton-like treatments conducted on marine sediment slurries (2g sediment vs. 20 ml liquid). The sediment was collected in a harbor situated in a high density industrial area, characterized by a great hydrocarbon C>12 and PAHs contamination. The investigated parameters were: the H(2)O(2) dose, the reagent's pH and the effect of a phosphate salt and ferrous iron addition. To evaluate sediment's characteristics COD, particle size, thermogravimetric and differential thermal analyses were performed under N(2) and O(2) atmosphere while dissolved organic carbon and COD analyses were performed on the filtrate. Results indicate that the treatment was able to change the organic matter to a less hydrophobic state, to destroy part of the organic carbon (up to 78% decrease of the 200-400 degrees C labile organic matter), to lower the COD of the sediment (60% COD removal maximum) and to increase the cumulated distribution undersize. In addition as the treated sediment showed easier-to-handle characteristics, reduced caking and lower aggregation capacity, the modified Fenton treatment could also be considered a pre-treatment of a successive thermal treatment.     

Preparation of a porous clay heterostructure and study of its adsorption capacity of phenol and chlorinated phenols from aqueous solutions.

A porous clay heterostructure (PCH) from a Mexican clay was prepared and characterized, and its aqueous phenol and dichlorophenols (DCPs) adsorption capacities were studied using a batch equilibrium technique. The PCH displayed a surface area of 305.5 m2/g, 37.2 A average porous diameter, and a basal space of 23.2 A. The adsorption capacity shown by the PCH for both phenol and DCPs from water (14.5 mg/g for phenol; 48.7 mg/g for 3,4-DCP; and 45.5 mg/g for 2,5-DCP) suggests that the PCH has both hydrophobic and hydrophilic characteristics, as a result of the presence of silanol and siloxane groups formed during the pillaring and calcination of the PCH. The values of maximal adsorption capacity for dichlorophenols were higher than those reported for aluminum pillared clays and some inorgano-organo clays and comparable with some ionic exchange resins.     

Heavy metals extraction from contaminated soil: recovery of the flushing solution

The optimum conditions for the recovery of copper from a contaminated soil by using the soil flushing technique are evaluated. Tests on a soil artificially contaminated with copper chloride were carried out in order to evaluate the influence of the speed of percolation and of the chelating agent concentration (aqueous solution of an ethylendiaminotetraacetic acid di-sodium salt Na2-EDTA). At pH=7.3 an efficiency up to 93.9% for copper extraction was achieved by flushing 500 ml of Na2-EDTA 0.05 M solution and 100 ml of pure water at 0.792 cm/h. At these operating conditions the formation of EDTA complexes with other competitive cations (calcium and iron) was negligible. The experimental results were in agreement with the ones obtained using a model describing the chemistry of metal extraction. This model assessed that above pH=6 the formation of calcium and iron EDTA complexes was excluded and only the chelation of copper was allowed. The recovery of 91.6% of EDTA was also achieved by evaporating and acidifying the extracted solution: after filtration, solid EDTA was obtained, through the addition of sodium hydroxide Na2-EDTA. About 99.5% of the extracted copper was finally precipitated under alkaline conditions from the liquid phase.     

Performances and application of a passive sampling method for the simultaneous determination of nitrogen dioxide and sulfur dioxide in ambient air

The performances and applicability of a diffusion tubesampler for the simultaneous measurements of NO₂ andSO₂ in ambient air were evaluated. SO₂ andNO₂are collected by the passive sampler using triethanolamine astrapping agent and are determined as sulphate and nitrite withion chromatography. The detection limit (2.3 g m^-3 ofNO₂ and 4.2 g m^-3 of SO₂ for two weekssampling) is adequate for the determination of concentrationsin urban and industrial areas. Precision of the method as RSDis in mean 5% for NO₂ and 12% for SO₂ at theconcentration levels in urban areas. Calibration of the methodwas performed in the field conditions by comparison between theresponses of sampler and the concentrations measured by thecontinuous monitors. High degree of linearity (correlationcoefficients > 0.8) is found between the passive sampler tubeand the continuous monitor data for both NO₂ and SO₂.To reduce the wind velocity influence on passive sampling ofdiffusion tubes, a protective shelter was tested in this study.The overall uncertainty of one measure for the optimised methodis estimated at 5 g m^-3 for NO₂ and 6g m^-3 for SO₂. Suitability of this passivesampling method for air pollution monitoring in urban areas wasdemonstrated by the results shown in this paper on a campaigncarried out in the French agglomeration.     

Monitoring the quality of the marine environment

As part of the monitoring program from Instituto Hidrográfico, since 1981 sediment and water samples have been collected from four different estuarine areas located along the continental coast of Portugal. The concentrations of different parameters were measured in the water and sediment samples. After normalization, the concentrations of chromium, mercury, lead and zinc in the sediments from the different areas were compared.