María Teresa Barral

Enhancement of copper and cadmium adsorption on kaolin by the presence of humic acids.

The competitive adsorption equilibrium isotherms of Cu2+ and Cd2+ on kaolin have been measured at 298 K, in the presence and the absence of humic acids (HAs). HAs were found to enhance the metal adsorption capacity of mineral surfaces, in particular kaolin. This enhancement was also observed in the competitive adsorption of copper and cadmium on kaolin and kaolin-HA complex. This competitive adsorption shows that the presence of Cd2+ has not an important effect on Cu2+ adsorption, whereas a dramatic decrease is observed on the adsorption of Cd2+ in the presence of Cu2+. The Freundlich isotherm equation was found to provide an excellent fit to the experimental data. These results were compared with the independent adsorption of both heavy metals.

Valorization of winery waste vs. the costs of not recycling.

Wine production generates huge amounts of waste. Before the 1990s, the most economical option for waste removal was the payment of a disposal fee usually being of around 3000 Euros. However, in recent years the disposal fee and fines for unauthorized discharges have increased considerably, often reaching 30,000-40,000 Euros, and a prison sentence is sometimes also imposed. Some environmental friendly technologies have been proposed for the valorization of winery waste products. Fermentation of grape marc, trimming vine shoot or vinification lees has been reported to produce lactic acid, biosurfactants, xylitol, ethanol and other compounds. Furthermore, grape marc and seeds are rich in phenolic compounds, which have antioxidants properties, and vinasse contains tartaric acid that can be extracted and commercialized. Companies must therefore invest in new technologies to decrease the impact of agro-industrial residues on the environment and to establish new processes that will provide additional sources of income.

Effects of iron and organic matter on the porosity and structural stability of soil aggregates

Knowledge of the soil components controlling aggregate formation and stability is fundamental to the conservation of soil structure. In this work, the effects of Fe and organic matter (OM) on the porosity and structural stability of aggregates <4 mm of two cropped soils from Galicia (NW Spain) were determined. Porosity was estimated directly, by mercury intrusion porosimetry, and indirectly, from moisture characteristic and shrinkage curves. The three porosities obtained were similar and indicated that Soil 1, with the highest Fe and OM contents, had lower total porosity and a wider pore-size distribution than Soil 2. As regards structural stability, Henin and Monniers test, simulated rainfall and dispersion experiments, and determination of textural tensile strength all indicated Soil 1 to be the more stable soil. Oxidation of OM and selective extraction of Fe, which were most concentrated in the clay and silt fractions, indicated both these components to be important soil aggregants. It is suggested that the higher content of Soil 1 in Fe and OM is responsible for its greater stability.

Trace metals in river bed sediments: an assessment of their partitioning and bioavailability by using multivariate exploratory analysis.

In this study, river bed sediments were submitted to a BCR sequential extraction, together with three bioavailability tests: a weak acid elutriate (HCl), a physiologically based extraction test (PBET) and a toxicity characteristic leaching procedure (TCLP). The most remarkable features of the BCR procedure were: i) Mn and Zn showed the highest proportion of the F1 exchangeable fraction; ii) in addition to Fe, Pb and Zn were the metals with the higher percentages in the F2 reducible fraction; iii) Fe and Cu were the elements with the highest proportion of the F3 oxidizable fraction; iv) the application of Principal Component Analysis to the metals in each of the three fractions did not show clear associations between metals and sediment components considered as metal scavengers, v) considering the sum of the three BCR fractions, the elements showed a decreasing availability of: Fe > Pb > Zn > Cu > Mn > Ni > Cr. The single extractions followed a decreasing extractability order of: HCl > PBET > TCLP and they were far from the extractability deduced from the sum of fractions in the BCR extraction.

Evaluation of the potential capacity as biosorbents of two MSW composts with different Cu, Pb and Zn concentrations

The Cu, Pb and Zn adsorption capacity of two municipal solid waste composts was studied in batch experiments where the equilibrium isotherms were determined. Both composts, despite having very different metal concentrations, showed high sorption capacities for the three elements, with the following affinity sequence: Pb>Cu>Zn. The maximum sorption capacities of the composts, on the basis of the Langmuir isotherm, were roughly equivalent to 1 mmol g(-1) for Pb, 1/2 mmol g(-1) for Cu, and 1/3 mmol g(-1) for Zn, which makes of both composts good biosorbents. Although a slightly higher adsorption capacity was seen for the compost with the lowest previous metal content, this fact alone could not explain the difference in the performance of the composts, and other factors such as its higher organic matter concentration and higher cation exchange capacity could have been more determinant.

Reduction of the short-term availability of copper, lead and zinc in a contaminated soil amended with municipal solid waste compost

The effect of two municipal solid waste composts on the availability of Cu, Pb and Zn in a soil contaminated in the laboratory was evaluated. An agricultural acid soil developed on granite was amended with the composts at two rates (3% and 6% dry weight), contaminated with 1000 mg kg(-1) of Cu, Pb and Zn, and incubated in the laboratory for three months. Determinations of soil pH, CaCl(2)-extractable and EDTA-extractable Cu, Pb, and Zn were run monthly during the incubation. At the end, a leaching test (TCLP) and selective extractions were performed for these elements. The analysis of the CaCl(2)-extractable elements demonstrated a strong capacity of both composts to decrease the solubility of the metals added to the soil, specially for Cu and Pb. The percentage of reduction of the soluble forms with respect to the initial addition was higher at the highest rate of compost, and reached 99% for Cu and Pb, and 80% for Zn in the compost-amended soil, whereas the soil without amendment was able to reduce Cu availability by a 94%, but not Zn or Pb availability. The TCLP test showed that compost also reduced the leachability of the three elements. Nevertheless, EDTA extracted a major amount (around 90%) of the elements added in all the treatments. Given that EDTA has a strong ability to extract elements bound to organic matter, it can be hypothesized that the main mechanism of the observed insolubilization was the formation of low-solubility organo-metallic complexes with both soil and compost organic matter. The selective extractions confirmed that compost reduced the exchangeable fraction of the elements, and that the organically bound fraction (pyrophosphate-extractable) was the main one for the three elements.

Ex Situ Treatment of Hydrocarbon-Contaminated Soil Using Biosurfactants from Lactobacillus pentosus

The utilization of biosurfactants for the bioremediation of contaminated soil is not yet well established, because of the high production cost of biosurfactants. Consequently, it is interesting to look for new biosurfactants that can be produced at a large scale, and it can be employed for the bioremediation of contaminated sites. In this work, biosurfactants from Lactobacillus pentosus growing in hemicellulosic sugars solutions, with a similar composition of sugars found in trimming vine shoot hydrolysates, were employed in the bioremediation of soil contaminated with octane. It was observed that the presence of biosurfactant from L. pentosus accelerated the biodegradation of octane in soil. After 15 days of treatment, biosurfactants from L. pentosus reduced the concentration of octane in the soil to 58.6 and 62.8%, for soil charged with 700 and 70,000 mg/kg of hydrocarbon, respectively, whereas after 30 days of treatment, 76% of octane in soil was biodegraded in both cases. In the absence of biosurfactant and after 15 days of incubation, only 1.2 and 24% of octane was biodegraded in soil charged with 700 and 70,000 mg/kg of octane, respectively. Thus, the use of biosurfactants from L. pentosus, as part of a well-designed bioremediation process, can provide mechanisms to mobilize the target contaminants from the soil surface to make them more available to the microbial population.

Partial Characterization of Biosurfactant from Lactobacillus pentosus and Comparison with Sodium Dodecyl Sulphate for the Bioremediation of Hydrocarbon Contaminated Soil

The capability of a cell bound biosurfactant produced by Lactobacillus pentosus, to accelerate the bioremediation of a hydrocarbon-contaminated soil, was compared with a synthetic anionic surfactant (sodium dodecyl sulphate SDS-). The biosurfactant produced by the bacteria was analyzed by Fourier transform infrared spectroscopy (FTIR) that clearly indicates the presence of OH and NH groups, C=O stretching of carbonyl groups and NH nebding (peptide linkage), as well as CH2–CH3 and C–O stretching, with similar FTIR spectra than other biosurfactants obtained from lactic acid bacteria. After the characterization of biosurfactant by FTIR, soil contaminated with 7,000 mg Kg−1 of octane was treated with biosurfactant from L. pentosus or SDS. Treatment of soil for 15 days with the biosurfactant produced by L. pentosus led to a 65.1% reduction in the hydrocarbon concentration, whereas SDS reduced the octane concentration to 37.2% compared with a 2.2% reduction in the soil contaminated with octane in absence of biosurfactant used as control. Besides, after 30 days of incubation soil with SDS or biosurfactant gave percentages of bioremediation around 90% in both cases. Thus, it can be concluded that biosurfactant produced by L. pentosus accelerates the bioremediation of octane-contaminated soil by improving the solubilisation of octane in the water phase of soil, achieving even better results than those reached with SDS after 15-day treatment.

Interaction of Hg(II) with kaolin-humic acid complexes

Abstract The adsorption and desorption of Hg(II) by humic acid (HA) previously adsorbed on kaolin was studied. In the range of HA concentration investigated (0.0 -26.9 mg g-1), the Hg(II) adsorption capacity of kaolin at pH 4 is enhanced by the presence of HA. For the complexes with the highest HA concentration and for low Hg(II) initial concentrations, adsorption was lower, i.e. as HA concentration on the complexes increases, Hg(II) equilibrium concentration also increases. This behaviour is due to the increasing presence of dissolved organic matter as the HA concentration on the complexes increases. The dissolved organic matter is able to form a soluble complex with Hg, thus decreasing adsorption. Hg(II) adsorption from a 2.5 × 10-5MHg(II) solution was influenced by pH. For kaolin, a pHmax (pH where maximum adsorption occurs) of 4.5 was observed. At pH values >pHmax retention decreased with increasing pH. This same behaviour was observed for the kaolin-HA complex containing the lowest HA concentration (6.6 mg g-1). For the other kaolin-HA complexes there was little effect of pH on Hg(II) adsorption between pH 2.5 and pH 6.5. The presence of HA increased the adsorption of Hg(II) on kaolin all along the pH range studied. Desorption experiments showed that the amount of Hg(II) desorbed was quite low (<1%) for all the HA and Hg(II) concentration range studied, except for the kaolin at acid pH (pH 2.5) where the Hg(II) released was >50% of Hg(II) previously adsorbed. The presence of HA dramatically reduced this percentage of desorption to values of <3%, indicating reduced risk of toxicity problems in surface and subsurface waters. The addition of Cu(II) did not favour any Hg(II) desorption, even though Cu exhibits a strong affinity for organic matter.

Extraction study of algal pigments in river bed sediments by applying factorial designs

Phytopigment content of river bed sediments changes in response to different concentrations of available nutrients and results in a useful descriptor of their trophic state and environmental quality. In this work three incomplete factorial designs of experiments were carried out for extracting algal pigments from river sediments using dimethylsulphoxide (DMSO), methanol or acetone. The independent variables used in this study and their variation limits were: extractant:sediment ratio (1-5mL/g), temperature (40-80 degrees C) and duration of treatments (30-90min). The experimental data obtained (chlorophyll-a, chlorophyll-b and total carotenoids content) allowed the development of empirical models for each phytopigment, describing the interrelationship between operational and experimental variables by equations, including linear, interaction and quadratic terms. The experimental results obtained showed that methanol and acetone were less effective extractants for phytopigments from river sediments when compared to DMSO. The model predicted that in a single extraction using 3.6mL of DMSO/g of sediment at 38 degrees C during 40min, DMSO releases the 89% of chlorophyll-a in the range tested, whereas the best conditions for extracting chlorophyll-b and total carotenoids are achieved using 3.6-3.7mL of DMSO/g of sediment, at 64-67 degrees C for 50-51min, respectively, releasing the 76% of the chlorophyll-b and the 100% of the total carotenoids in a single extraction.