Antoni Sánchez

Evaluation of the ecotoxicity of model nanoparticles

Since society at large became aware of the use of nanomaterials in ever growing quantities in consumer products and their presence in the environment, critical interest in the impact of this emerging technology has grown. The main concern is whether the unknown risks of engineered nanoparticles (NPs), in particular their impact on health and environment, outweighs their established benefits for society. Therefore, a key issue in this field is to evaluate their potential toxicity. In this context we evaluated the effects on plants and microorganisms of model nanoparticles, in particular of a stable metal (Au, 10nm mean diameter), a well-known bactericide (Ag, 2 nm mean diameter) and the broadly used Fe(3)O(4) (7 nm mean diameter). The toxicity of these nanoparticles was assayed using standard toxicity tests. Specifically, germination (cucumber and lettuce), bioluminescent (Photobacterium phosphoreum) and anaerobic toxicity tests were performed. Germination tests were conducted at a NP dose of 62, 100 and 116 microg mL(-1) for Au, Ag, and Fe(3)O(4), respectively. The bioluminscent testing (P. phosphoreum) was conducted at a dose of 28, 45 and 52 microg mL(-1) for Au, Ag, and Fe(3)O(4), respectively. Finally, anaerobic tests were conducted at a NP dose of 10, 16 and 18 microg mL(-1) for Au, Ag, and Fe(3)O(4), respectively. In all cases low or zero toxicity was observed. However, some perturbation of the normal functions with respect to controls in germinating tests was observed, suggesting the necessity for further research in this field. At the same time, the effect of NP-solvents was sometimes more significant than that of the NPs themselves, a point that is of special interest for future nanotoxicological studies.

The use of life cycle assessment for the comparison of biowaste composting at home and full scale.

Environmental impacts and gaseous emissions associated to home and industrial composting of the source-separated organic fraction of municipal solid waste have been evaluated using the environmental tool of life cycle assessment (LCA). Experimental data of both scenarios were experimentally collected. The functional unit used was one ton of organic waste. Ammonia, methane and nitrous oxide released from home composting (HC) were more than five times higher than those of industrial composting (IC) but the latter involved within 2 and 53 times more consumption or generation of transport, energy, water, infrastructures, waste and Volatile Organic Compounds (VOCs) emissions than HC. Therefore, results indicated that IC was more impacting than HC for four of the impact categories considered (abiotic depletion, ozone layer depletion, photochemical oxidation and cumulative energy demand) and less impacting for the other three (acidification, eutrophication and global warming). Production of composting bin and gaseous emissions are the main responsible for the HC impacts, whereas for IC the main contributions come from collection and transportation of organic waste, electricity consumption, dumped waste and VOCs emission. These results suggest that HC may be an interesting alternative or complement to IC in low density areas of population.

In search of a reliable technique for the determination of the biological stability of the organic matter in the mechanical-biological treated waste

The biological stability determines the extent to which readily biodegradable organic matter has decomposed. In this work, a massive estimation of indices suitable for the measurement of biological stability of the organic matter content in solid waste samples has been carried out. Samples from different stages in a mechanical-biological treatment (MBT) plant treating municipal solid wastes (MSW) were selected as examples of different stages of organic matter stability in waste biological treatment. Aerobic indices based on respiration techniques properly reflected the process of organic matter biodegradation. Static and dynamic respirometry showed similar values in terms of aerobic biological activity (expressed as oxygen uptake rate, OUR), whereas cumulative oxygen consumption was a reliable method to express the biological stability of organic matter in solid samples. Methods based on OUR and cumulative oxygen consumption were positively correlated. Anaerobic methods based on biogas production (BP) tests also reflected well the degree of biological stability, although significant differences were found in solid and liquid BP assays. A significant correlation was found between cumulative oxygen consumption and ultimate biogas production. The results obtained in this study can be a basis for the quantitative measurement of the efficiency in the stabilization of organic matter in waste treatment plants, including MBT plants, anaerobic digestion of MSW and composting plants.

Effect of cerium dioxide, titanium dioxide, silver, and gold nanoparticles on the activity of microbial communities intended in wastewater treatment

Growth in production and use of nanoparticles (NPs) will result increased concentrations of these in industrial and urban wastewaters and, consequently, in wastewater-treatment facilities. The effect of this increase on the performance of the wastewater-treatment process has not been studied systematically and including all the microbial communities involved in wastewater treatment. The present work investigates, by using respiration tests and biogas-production analysis, the inhibitory effect of four different commonly used metal oxide (CeO(2) and TiO(2)) and zero-valent metal (Ag and Au) nanoparticles on the activity of the most important microbial communities present in a modern wastewater-treatment plant. Specifically, the actions of ordinary heterotrophic organisms, ammonia oxidizing bacteria, and thermophilic and mesophilic anaerobic bacteria were tested in the presence and absence of the nanoparticles. In general, CeO(2) nanoparticles caused the greatest inhibition in biogas production (nearly 100%) and a strong inhibitory action of other biomasses; Ag nanoparticles caused an intermediate inhibition in biogas production (within 33-50%) and a slight inhibition in the action of other biomasses, and Au and TiO(2) nanoparticles caused only slight or no inhibition for all tested biomasses.

Comparison of aerobic and anaerobic stability indices through a MSW biological treatment process

A complex mechanical-biological waste treatment plant designed for the processing of mixed municipal solid wastes (MSW) and source-selected organic fraction of municipal solid wastes (OFMSW) has been studied by using stability indices related to aerobic (respiration index, RI) and anaerobic conditions (biochemical methane potential, BMP). Several selected stages of the plant have been characterized: waste inputs, mechanically treated wastes, anaerobically digested materials and composted wastes, according to the treatment sequence used in the plant. Results obtained showed that the main stages responsible for waste stabilization were the two first stages: mechanical separation and anaerobic digestion with a diminution of both RI and BMP around 40% and 60%, respectively, whereas the third stage, composting of digested materials, produced lesser biological degradation (20-30%). The results related to waste stabilization were similar in both lines (MSW and OFMSW), although the indices obtained for MSW were significantly lower than those obtained for OFMSW, which demonstrated a high biodegradability of OFMSW. The methodology proposed can be used for the characterization of organic wastes and the determination of the efficiency of operation units used in mechanical-biological waste treatment plants.

Odours and volatile organic compounds emitted from municipal solid waste at different stage of decomposition and relationship with biological stability

Odours (OU(E)) and volatile organic compounds (VOC) emission during biological process used to treat MSW were studied under standardized conditions in order to detect potential risk for workers and population. Results obtained indicated that odours and VOCs emitted depend on the biological stability of waste measured by the dynamic respiration index (DRI) and a very good correlation were found between these parameters (OU(E) vs. DRI, r=0.96, p<0.001, n=6; VOC vs. DRI, r=0.97, p<0.001, n=6). GC-MS study of the VOCs indicated the presence of a group of molecules that were degraded during the process. On the other hand, a second group of molecules, i.e. aromatic and halogenated compounds, and furan persisted in the waste sample, although molecule concentrations were always lower than Threshold Limit Value-Time Weighted Average (TLV-TWA).

Chromium VI adsorption on cerium oxide nanoparticles and morphology changes during the process.

In this study, suspended cerium oxide nanoparticles stabilized with hexamethylenetetramine were used for the removal of dissolved chromium VI in pure water. Several concentrations of adsorbent and adsorbate were tested, trying to cover a large range of possible real conditions. Results showed that the Freundlich isotherm represented well the adsorption equilibrium reached between nanoparticles and chromium, whereas adsorption kinetics could be modeled by a pseudo-second-order expression. The separation of chromium-cerium nanoparticles from the medium and the desorption of chromium using sodium hydroxide without cerium losses was obtained. Nanoparticles agglomeration and morphological changes during the adsorption-desorption process were observed by TEM. Another remarkable result obtained in this study is the low toxicity in the water treated by nanoparticles measured by the Microtox(®) commercial method. These results can be used to propose this treatment sequence for a clean and simple removal of drinking water or wastewater re-use when a high toxicity heavy metal such as chromium VI is the responsible for water pollution.

Air filled porosity measurements by air pycnometry in the composting process: a review and a correlation analysis.

Air filled porosity (AFP) appears as the best measure to determine the available porosity in a composting material or, in general, in an organic matrix. Several methodologies, including theoretical and empirical approaches have been developed to estimate AFP. Among them, air pycnometry has been considered the most suitable and accurate technique to obtain reliable measures of AFP. In this review, the published methodologies to determine AFP by air pycnometry are explained in detail, and the main advantages and disadvantages of such methodologies are discussed. Also, a massive sampling of several organic wastes and mixtures intended for composting has been characterized by air pycnometry, and the theoretical and empirical correlations proposed in literature are compared in terms of accuracy in AFP measurement. Results obtained show that some theoretical correlations are suitable for estimating AFP in the majority of organic wastes studied. However, some waste samples need an experimental determination to obtain a realistic value of AFP.

Different indices to express biodegradability in organic solid wastes.

Respiration indices are suggested in literature as the most suitable stability determination and are proposed as a biodegradability measure in this work. An improved dynamic respiration index methodology is described in this work. This methodology was applied to 58 samples of different types of waste including municipal solid wastes and wastewater sludge, both raw materials and samples collected in a mechanical-biological treatment plant at different stages of biodegradation. The information obtained allowed to establish a qualitative classification of wastes in three categories: highly biodegradable, moderately biodegradable, and wastes of low biodegradability. Results were analyzed in terms of long and short-term indices and index expression: dynamic respiration indices expressed as average oxygen uptake rate (mg O(2) g(-1) dry matter [DM] h(-1)) at 1 and 24 h of maximum activity (DRI(1h), DRI(24h)); and cumulative oxygen consumption in 24 h of maximum activity and 4 d (AT(24h), AT(4)). The statistical comparison of indices and wastes is also presented. Raw sludge presented the highest biodegradability followed by the organic fraction of municipal solid waste and anaerobically digested sludge. All indices correlated well but different correlations were found for the different wastes analyzed. The information in the dynamic respiration profile allows for the calculation of different indices that provide complementary information. The combined analysis of DRI(24h) and AT(4) is presented here as the best tool for biodegradable organic matter content characterization and process requirements estimation.

Highly enantioselective esterification of racemic ibuprofen in a packed bed reactor using immobilised Rhizomucor miehei lipase.

A systematic study of the enantioselective resolution of ibuprofen by commercial Rhizomucor miehei lipase (Lipozyme(R) IM20) has been carried out using isooctane as solvent and butanol as esterificating agent. The main variables controlling the process (temperature, ibuprofen concentration, ratio butanol:ibuprofen) have been studied using an orthogonal full factorial experimental design, in which the selected objective function was enantioselectivity. This strategy has resulted in a polynomial function that describes the process. By optimizing this function, optimal conditions for carrying out the esterification of racemic ibuprofen have been determined. Under these conditions, enantiomeric excess and total conversion values were 93.8% and 49.9%, respectively, and the enantioselectivity was 113 after 112 h of reaction. These conditions have been considered in the design of a continuous reactor to scale up the process. The esterification of ibuprofen was properly described by pseudo first-order kinetics. Thus, a packed bed reactor operating as a plug-flow reactor (PFR) is the most appropriate in terms of minimizing the residence time compared with a continuous stirred tank reactor (CSTR) to achieve the same final conversion. This reactor shows a similar behavior in terms of enantioselectivity, enantiomeric excess, and conversion when compared with batch reactors. A residence-time distribution (RTD) shows that the flow model is essentially a plug flow with a slight nonsymmetrical axial dispersion (Peclet number = 43), which was also corroborated by the model of CSTR in series. The stability of the system (up to 100 h) and the possibility of reutilization of the enzyme (up to four times) lead to consider this reactor as a suitable configuration for scale up of the process.