Enhancing methane yield from crude glycerol anaerobic digestion by coupling with ultrasound or A. niger/E. coli biodegradation.

Anaerobic digestion of crude glycerol from biodiesel production is a feasible way for methane production. However, crude glycerol (CG) contains impurities, such as long-chain fatty acids (LCFA) that can inhibit methanogenic microorganisms. Ultrasound promotes the hydrolysis of LCFA and deagglomerates the microorganisms in biological flocs. Furthermore, Aspergillus niger and Escherichia coli produce lipases capable of degrading LCFA. This study aims at improving the methane yield from anaerobic digestion by coupling with ultrasound or E. coli/A. niger biodegradation. The effect of the different treatments was first assessed in a perfectly mixed batch reactor (PMBR), using diluted CG at concentrations of 0.2%, 1.7%, and 3.2% (v/v). Later, the best conditions were replicated in an upflow anaerobic sludge blanket (UASB) reactor to simulate full-scale practical applications. Experiments in the PMBR showed that ultrasound or A. niger biodegradation steps improved methane yield up to 11% for 0.2% CG and 99% for 1.7% CG, respectively. CG biodegradation by E. coli inhibited the subsequent anaerobic digestion for all concentrations tested. Using a UASB digester, ultrasonic treatment of CG led to an average increase of 29% in methane production. The application of ultrasound led to a lower accumulation of propionic acid in the digested material and increased biogas production. On the other hand, an average 77% increase in methane production was achieved using a preliminary CG biodegradation step by A. niger, when operated at a loading rate of 2.9 kg COD m-3 day-1. Under these conditions, an energy gain of 0.48 kWh day-1, with the production of the 0.434 m3 CH4 kg-1 CODremoval and 0.573 m3 CH4 kg-1 VS, and a biogas quality of 73% in methane were obtained. The digested material was analyzed for the detection and quantification of added-value by-products in order to obtain a broad assessment of the CG valorization through anaerobic digestion. In some experiments, propionic and oxalic acid were detected. However, the accumulation of propionic caused the inhibition of the acetogenic and methanogenic microorganisms.

Removal of Cd(II), Zn(II) and Pb(II) from aqueous solutions by brown marine macro algae: kinetic modelling.

Specific marine macro algae species abundant at the Portuguese coast (Laminaria hyperborea, Bifurcaria bifurcata, Sargassum muticum and Fucus spiralis) were shown to be effective for removing toxic metals (Cd(II), Zn(II) and Pb(II)) from aqueous solutions. The initial metal concentrations in solution were about 75-100 mg L(-1). The observed biosorption capacities for cadmium, zinc and lead ions were in the ranges of 23.9-39.5, 18.6-32.0 and 32.3-50.4 mg g(-1), respectively. Kinetic studies revealed that the metal uptake rate was rather fast, with 75% of the total amount occurring in the first 10 min for all algal species. Experimental data were well fitted by a pseudo-second order rate equation. The contribution of internal diffusion mechanism was significant only to the initial biosorption stage. Results indicate that all the studied macro algae species can provide an efficient and cost-effective technology for eliminating heavy metals from industrial effluents.

Cadmium(II) and zinc(II) adsorption by the aquatic moss Fontinalis antipyretica: effect of temperature, pH and water hardness.

The biosorption of cadmium(II) and zinc(II) ions onto dried Fontinalis antipyretica, a widely spread aquatic moss, was studied under different values of temperature, initial pH and water hardness. The equilibrium was well described by Langmuir adsorption isotherms. Maximum biosorption capacity of cadmium was independent on temperature and averaged 28.0 mg g(-1) moss, whereas for zinc, capacity increased with temperature, from 11.5 mg g(-1) moss at 5 degrees C to 14.7 mg g(-1) moss at 30 degrees C. Optimum adsorption pH value was determined as 5.0 for both metal ions. Cadmium uptake was unaffected by the presence of calcium ions, but zinc sorption was improved when water hardness increased from 101.1 to 116.3 mg CaCO(3)l(-1). Inversely, as hardness increases, the competition with calcium ions strongly reduces the affinity of the biosorbent for zinc.

Uptake and release of zinc by aquatic bryophytes (Fontinalis antipyretica L. ex. Hedw.).

The zinc uptake and posterior release by an aquatic bryophyte-Fontinalis antipyretica L. Ex Hedw.--was experimentally studied in laboratory exposing the plants to different zinc concentrations in the range, 1.0-5.0 mg 1(-1), for a 144 h contamination period, and then exposed to metal-free water for a 120 h decontamination period. The experiments were carried out in perfectly mixed contactors at controlled illumination, using mosses picked out in February 1997, with a background initial zinc concentration of 263 mg g(-1) (dry wt.). A first-order mass transfer kinetic model was fitted to the experimental data to determine the uptake and release constants, k1 and k2, the zinc concentration in mosses at the end of the uptake period, C(mu), and at the equilibrium, for the contamination and decontamination stages, C(me) and C(mr), respectively. A bioconcentration factor, BCF = k1 /k2 (zinc concentration in the plant, dry wt./zinc concentration in the water) was determined. A biological elimination factor defined as BEF = 1 - C(mr)/C(mu) was also calculated. BCF decreases from about 4500 to 2950 as Zn concentration in water increases from 1.05 to 3.80mg 1(-1). BEF is approximately constant and equal to 0.80. Comparing Zn and Cu accumulation by Fontinalis antipyretica, it was concluded that the uptake rate for Zn (145 h(-1)) is much lower than for Cu (628 h(-1)) and the amount retained by the plant decreased by a factor of about seven.