Trace metal levels in Prochilodus lineatus collected from the La Plata River, Argentina

Most of the industrial, urban and sewage discharges are released into the La Plata River, Argentina without any previous treatment. However, few works have investigated the extent of metal contamination. The aim of this study was to assess the levels of cadmium, copper, lead and zinc in liver and gills of adults Prochilodus lineatus collected from three sampling stations along the coast of the La Plata River: Berazategui, Berisso and Atalaya (from north to south). Samplings were performed during 2002 and 2004. Berazategui and Berisso were located nearby the main ducts that discharge the urban and domestic waste disposal from the cities of Buenos Aires and La Plata, respectively. The third station, Atalaya, was free of sewage discharges. Levels of cadmium and copper in liver were always higher than those found in gills. Instead, for lead and zinc, high levels were observed either in liver or gills, depending on the sampling station and the sampling period. In both tissues, the concentrations of metals did not differ significantly between male and female fish. In liver samples, the concentrations of cadmium, copper and zinc tended to increase from north to south. Instead, the levels of lead followed an opposite pattern. No clear tendencies were observed in gill samples. The data may be useful as reference levels of metal contaminants in P. lineatus, the most important fish species in the La Plata River system.     

Vanadium recovery from oil fly ash by leaching, precipitation and solvent extraction processes

In order to reduce the environmental impact due to land disposal of oil fly ash from power plants and to valorize this waste material, the removal of vanadium was investigated using leaching processes (acidic and alkaline treatments), followed by a second step of metal recovery from leachates involving either solvent extraction or selective precipitation. Despite a lower leaching efficiency (compared to sulfuric acid), sodium hydroxide was selected for vanadium leaching since it is more selective for vanadium (versus other transition metals). Precipitation was preferred to solvent extraction for the second step in the treatment since: (a) it is more selective; enabling complete recovery of vanadate from the leachate in the form of pure ammonium vanadate; and (b) stripping of the loaded organic phase (in the solvent extraction process) was not efficient. Precipitation was performed in a two-step procedure: (a) aluminum was first precipitated at pH 8; (b) then ammonium chloride was added at pH 5 to bring about vanadium precipitation.     

Methane and carbon dioxide emission in a two-phase olive oil mill sludge windrow pile during composting

The aim of this work was to make some preliminary evaluations on CO(2) and CH(4) emissions during composting of two-phase olive oil mill sludge (OOMS). OOMS, olive tree leaves (OTL) and shredded olive tree branches (OTB) were used as feedstock for Pile I and Pile II with a 1:1:1 and 1:1:2v/v ratio, respectively. Each pile was originally 1.2m high, 2.0m wide and approximately 15.0m long. Four 500 ml volume glass funnels were inverted and introduced in each pile, two in the core (buried 50-60 cm from the surface) and two near the surface under a thin 10-15 cm layer of the mixture. Thin (0.5 cm diameter) plastic, 80 cm long tubes were connected to the funnels. A mobile gas analyser (GA2000) was used to measure the composition (by volume) of O2, CO2 and CH4 on a daily basis. The funnels were removed prior to each turning and reinserted afterwards. From each pair of funnels (core and surface) of both piles, one was kept closed between samplings. Two way ANOVA was used to test differences between piles and among the tubes. Post hoc Tukey tests were also used to further investigate these differences. There was a significant difference (at p<0.001) in the two piles for all three gases. The average concentrations of O2, CO2 and CH4 in Pile I, from all four funnels was 16.86%, 3.89% and 0.25%, respectively, where for Pile II the average values were 18.07%, 2.38% and 0.04%, respectively. The presence of OOMS in larger amounts in Pile I (resulting in more intense decomposing phenomena), and the larger particle size of OTB in Pile II (resulting in increasing porosity) are the probable causes of these significant differences. Samples from open funnels presented lower, but not significantly lower, O2 composition (higher for CO2 and CH4) in comparison with closed funnels in both depths and both piles. Not significant were also the different mean gas compositions between core and surface funnels in the same pile.     

Waste polyvinylchloride derived pitch as a precursor to develop carbon fibers and activated carbon fibers

Polyvinylchloride (PVC) was successfully recycled through the solvent extraction from waste pipe with an extraction yield of ca. 86%. The extracted PVC was pyrolyzed by a two-stage process (260 and 410 degrees C) to obtain free-chlorine PVC based pitch through an effective removal of chlorine from PVC during the heat-treatment. As-prepared pitch (softening point: 220 degrees C) was spun, stabilized, carbonized into carbon fibers (CFs), and further activated into activated carbon fibers (ACFs) in a flow of CO2. As-prepared CFs show comparable mechanical properties to commercial CFs, whose maximum tensile strength and modulus are 862 MPa and 62 GPa, respectively. The resultant ACFs exhibit a high surface area of 1200 m2/g, narrow pore size distribution and a low oxygen content of 3%. The study provides an effective insight to recycle PVC from waste PVC and develop a carbon precursor for high performance carbon materials such as CFs and ACFs.     

Effects of sewage sludge blending on the coal combustion: a thermogravimetric assessment

Combustion of urban sewage sludge together with coal in existing infrastructures may be a sustainable management option energetically interesting for these materials, usually considered wastes. Thermogravimetric analysis was used to study the combustion of a semianthracite coal and the modifications undergone when adding a small percentage (2%, 5%, 10%) of sewage sludge. Both Differential Scanning Calorimetric analysis and Differential Thermogravimetry burning profiles showed differences between coal and sewage sludge combustion. However, the effects of adding a percentage of sewage sludge equal or smaller than 10% was hardly noticeable in terms of heat release and weight loss during the coal combustion. This was further proved by non-isothermal kinetic analysis, which was used to evaluate the Arrhenius activation energy corresponding to the co-combustion of the blends. This work shows that thermogravimetric analysis may be used as an easy rapid tool to asses the co-combustion of sewage sludge together with coal.     

Androgenic and antiandrogenic activities in water and sediment samples from the river Lambro, Italy, detected by yeast androgen screen and chemical analyses

The river Lambro is the most polluted tributary of the river Po in North Italy and was chosen as a representative water course discharging industrialized areas. Water and sediment samples of the river Lambro were investigated regarding the presence of endocrine disrupting compounds. A combined procedure was used consisting of solid-phase extraction and HPLC based fractionation of samples, of screening for (anti)androgenic activity using the yeast androgen screen (YAS) and of chemical analysis using HPLC-MS/MS and GC-MS. Androgenic and antiandrogenic activities were found in specific fractions of the water and sediment while the total extracts showed antiandrogenic activity only. The chemical analysis of the fractions and total extracts with antiandrogenic activities revealed the presence of compounds with suspected antiandrogenic potency such as bisphenol A, iprodione, nonylphenol, p,p'-DDE and tert-octylphenol but other unknown compounds contributed mainly to the observed antiandrogenic activities. The antiandrogenic load of the river Lambro ranged between 1.34 and 17.1 microM flutamide-equivalents and may pose a risk to aquatic environments. Future screenings for EDC in the environment that have the potential to interfere with reproduction of aquatic organisms should be extended to different modes of actions including (anti)androgenic ones.     

Heavy metal resistance and genotypic analysis of metal resistance genes in gram-positive and gram-negative bacteria present in Ni-rich serpentine soil and in the rhizosphere of Alyssum murale

Forty-six bacterial cultures, including one culture collection strain, thirty from the rhizosphere of Alyssum murale and fifteen from Ni-rich soil, were tested for their ability to tolerate arsenate, cadmium, chromium, zinc, mercury, lead, cobalt, copper, and nickel in their growth medium. The resistance patterns, expressed as minimum inhibitory concentrations, for all cultures to the nine different metal ions were surveyed by using the agar dilution method. A large number of the cultures were resistant to Ni (100%), Pb (100%), Zn (100%), Cu (98%), and Co (93%). However, 82, 71, 58 and 47% were sensitive to As, Hg, Cd and Cr(VI), respectively. All cultures had multiple metal-resistant, with heptametal resistance as the major pattern (28.8%). Five of the cultures (about of 11.2% of the total), specifically Arthrobacter rhombi AY509239, Clavibacter xyli AY509235, Microbacterium arabinogalactanolyticum AY509226, Rhizobium mongolense AY509209 and Variovorax paradoxus AY512828 were tolerant to nine different metals. The polymerase chain reaction in combination with DNA sequence analysis was used to investigate the genetic mechanism responsible for the metal resistance in some of these gram-positive and gram-negative bacteria that were, highly resistant to Hg, Zn, Cr and Ni. The czc, chr, ncc and mer genes that are responsible for resistance to Zn, Cr, Ni and Hg, respectively, were shown to be present in these bacteria by using PCR. In the case of, M. arabinogalactanolyticum AY509226 these genes were shown to have high homology to the czcD, chrB, nccA, and mer genes of Ralstonia metallidurans CH34. Therefore, Hg, Zn, Cr and Ni resistance genes are widely distributed in both gram-positive and gram-negative isolates obtained from A. murale rhizosphere and Ni-rich soils.     

Electrochemical degradation applied to the metabolites of Acid Orange 7 anaerobic biotreatment

The electrochemical oxidation of the biotic degradation products of the textile dye C.I. Acid Orange 7 (AO7) was achieved using a boron doped diamond electrode (BDD). Tests were performed with model solutions of the biotic degradation products, sulphanilic acid (SA) and 1-amino-2-naphthol (AN), and also with real effluents obtained in experiments carried out in an up-flow anaerobic sludge blanket (UASB) reactor, fed with a simulated textile effluent containing AO7, working in mesophilic or thermophilic conditions. Bulk electrolysis was studied using two different supporting electrolytes - NaCl and Na(2)SO(4). The influence of initial metabolite concentration and current density on the electrodegradation rates of the biotic products was investigated. For the UASB effluents, oxidation tests were carried out for different electrolytes and at different current densities. Samples were collected at pre-selected intervals and absorbance measurements, chemical oxygen demand (COD) and total organic carbon (TOC) tests and high performance liquid chromatography (HPLC) analysis were performed. Results have shown an almost complete elimination of the persistent pollutants and a COD removal higher than 70% for both AN and SA. For the UASB effluents, COD removals between 45% and 90% and TOC removals varying from 19% to 41% were obtained.     

Structure of Mn-Zr mixed oxides catalysts and their catalytic performance in the gas-phase oxidation of chlorocarbons

The catalytic activity and selectivity of manganese zirconia mixed oxides were evaluated for the oxidation of two common chlorinated pollutants found in waste streams, namely 1,2-dichloroethane (DCE) and trichloroethylene (TCE). Mixed oxides with varying Mn-Zr content were prepared by coprecipitation via nitrates, and subsequent calcination at 600 degrees C for 4 h in air. These catalysts were characterised by means of several techniques such as atomic emission spectrometry, N2 adsorption-desorption, powder X-ray diffraction, temperature-programmed desorption of ammonia, pyridine adsorption followed by diffuse reflectance infrared spectroscopy and temperature-programmed reduction with hydrogen. The active catalytic behaviour of Mn-Zr mixed oxides was ascribed to a substantial surface acidity combined with readily accessible active oxygen species. Hence, the mixed oxide with 40 mol% manganese content was found to be an optimum catalyst for the combustion of both chlorocarbons with a T50 value around 305 and 315 degrees C for DCE and TCE oxidation, respectively. The major oxidation products were carbon dioxide, hydrogen chloride and chlorine. It was observed that the formation of both CO2 and Cl2 was promoted with Mn loading.     

Biodegradation of heavy crude oil Maya using spent compost and sugar cane bagasse wastes

Experiments were carried out to evaluate the use of some agroindustrial wastes as supports in solid state cultures for the biodegradation of crude oil Maya in static column reactors over 15-20 days periods. Spent compost and cane bagasse wastes showed superior qualities over peat moss waste as support candidates with the advantage that they contain appreciable densities of autochthonous microorganisms in the order of 10(2) cfu g(-1). Mercuric chloride (2%) was able to completely inhibit growth of these microfloras. Biodegradation was enhanced in the presence of the IMP consortium and highest when microflora from cane bagasse only was the bioaugmentation partner (180.7 mg kg(-1) day(-1)). Combination of these waste materials (3:1 ratio, respectively) was observed to significantly biodegrade the crude oil by approximately 40% in 15 days from an initial concentration of 10,000 mg kg(-1) with a four order of magnitude increase in microbial density during this period. Spent compost and cane bagasse wastes are veritable solid support candidates for use in the biodegradation of crude oil polluted systems.