In situ modification of activated carbons developed from a native invasive wood on removal of trace toxic metals from wastewater.

Activated carbons were developed by phosphoric acid activation of sawdust from Prosopis ruscifolia wood, an indigenous invasive species of degraded lands, at moderate conditions (acid/precursor ratio=2, 450 degrees C, 0.5h). For in situ modification of their characteristics, either a self-generated atmosphere or flowing air was used. The activated carbons developed in the self-generated atmosphere showed higher BET surface area (2281m2/g) and total pore volume (1.7cm3/g) than those obtained under flowing air (1638m2/g and 1.3cm3/g). Conversely, the latter possessed a higher total amount of surface acidic/polar oxygen groups (2.2meq/g) than the former (1.5meq/g). To evaluate their metal sorption capability, adsorption isotherms of Cu(II) ion from model solutions were determined and properly described by the Langmuir model. Maximum sorption capacity (Xm) for the air-derived carbons (Xm=0.44mmol/g) almost duplicated the value for those obtained in the self-generated atmosphere (Xm=0.24mmol/g), pointing to a predominant effect of the surface functionalities on metal sequestering behaviour. The air-derived carbons also demonstrated a superior effectiveness in removing Cd(II) ions as determined from additional assays in equilibrium conditions. Accordingly, effective phosphoric acid-activated carbons from Prosopis wood for toxic metals removal from wastewater may be developed by in situ modification of their characteristics operating under flowing air.

Basic butylated methacrylate copolymer/kappa-carrageenan interpolyelectrolyte complex: preparation, characterization and drug release behaviour.

The formation of a novel interpolyelectrolyte complex (IPEC) between basic butylated methacrylate copolymer and kappa-carrageenan was investigated and the product formed was characterized. Turbidity measurements and elemental analyses pointed to a 1:1 interaction of the repeating units. These results and FT-IR confirmed IPEC formation. Electronic microscopy images, particle size determination by image analysis and N(2) (77K) adsorption measurements were consistent with a porous material. This IPEC formed presented very good flowability and compactibility. Two maxima were observed in the swelling behaviour as a function of pH. The performance of the IPEC as a matrix for controlled release of drugs was evaluated, using ibuprofen as a model drug. Release profiles were properly represented by a mathematical model, which indicates that the system releases ibuprofen in a zero-order manner. These profiles could be controlled by conveniently modifying the proportion of the IPEC in the tablets.

Comparison of different types of biomasses for copper biosorption.

Three biomass, birch wood Betula sp., marine brown alga Fucus vesiculosus, and terrestrial moss Pleurozium schreberi, have been compared as raw materials for preparation of biosorbents for removal of copper ions from diluted water solutions. Small sample doses (0.5 g/100ml) of the biosorbents prepared from alga and moss enabled more than 90% removal of Cu(II) ions from diluted water solutions (5-20mg/l). The sample from sawdust was less effective. A pseudo-second-order rate model properly described the experimental kinetic data for the biosorbents. The maximum sorption capacities (Xm) determined from the experimental equilibrium isotherms by applying the Langmuir model showed that the alga had the best copper-binding ability (Xm=23.4 mg/g), followed by the moss (Xm=11.1mg/g), and the sawdust (Xm=4.9 mg/g). No visible damages or performance losses were detected for the alga and moss after five sorption-desorption cycles using diluted HCl as eluent.

Development and characterization of activated hydrochars from orange peels as potential adsorbents for emerging organic contaminants.

Activated hydrochars obtained from the hydrothermal carbonization of orange peels (Citrus sinensis) followed by various thermochemical processing were assessed as adsorbents for emerging contaminants in water. Thermal activation under flows of CO2 or air as well as chemical activation with phosphoric acid were applied to the hydrochars. Their characteristics were analyzed and related to their ability to uptake three pharmaceuticals (diclofenac sodium, salicylic acid and flurbiprofen) considered as emerging contaminants. The hydrothermal carbonization and subsequent activations promoted substantial chemical transformations which affected the surface properties of the activated hydrochars; they exhibited specific surface areas ranging from 300 to ∼620 m(2)/g. Morphological characterization showed the development of coral-like microspheres dominating the surface of most hydrochars. Their ability to adsorb the three pharmaceuticals selected was found largely dependent on whether the molecules were ionized or in their neutral form and on the porosity developed by the new adsorbents.

Nitrate uptake improvement by modified activated carbons developed from two species of pine cones.

Activated carbons from two species of pine cones (Pinus canariensis and Cupressus sempervirens) were prepared by phosphoric acid activation and tested for the removal of nitrate ions from aqueous solution. To investigate the feasibility of improving their nitrate adsorption capacity, two different post-treatments­a thermal treatment and a treatment with saturated urea solution­were also applied to the prepared activated carbons. Comparison of the treated and untreated activated carbons showed that both post-treatments improved the nitrate adsorption performance more than twice. The maximum adsorption capacity, as evaluated from determination of the adsorption isotherms for the P. canariensis based carbons, and their proper representation by the Langmuir model, demonstrated that the post-treatment with the urea solution led to activated carbons with increased nitrate removal effectiveness, even superior to other reported results. Enhancements in their adsorption capacity could be mainly ascribed to higher contents of nitrogen and basic functional groups, whereas porous structure of the activated carbons did not seem to play a key role in the nitrate uptake.

Arundo donax cane as a precursor for activated carbons preparation by phosphoric acid activation.

Canes from Arundo donax, a herbaceous rapid-growing plant, were used as precursor for activated carbon preparation by phosphoric acid activation under a self-generated atmosphere. The influence of the carbonization temperature in the range 400-550 degrees C and of the weight ratio phosphoric acid to precursor (R = 1.5-2.5) on the developed porous structure of the resulting carbons was studied for 1 h of carbonization time. Surface properties of the activated carbons were dependent on a combined effect of the conditions employed. Carbons developed either with R = 1.5 over the range 400-500 degrees C, or with R = 2 at 500 degrees C exhibited surface areas of around 1100 m2/g, the latter conditions promoting a larger pore volume and enhanced mesoporous character. For both ratios, temperature above 500 degrees C led to reduction in porosity development. A similar effect was found for the highest ratio (R = 2.5) and 500 degrees C. The influence of carrying out the carbonization either for times shorter than 1 h or under flowing N2 was also examined at selected conditions (R = 2, 500 degrees C). Shorter times induced increase in the surface area (approximately 1300 m2/g), yielding carbons with smaller mean pore radius. Activated carbons obtained under flowing N2 possessed predominant microporous structures and larger ash contents than the samples derived in the self-generated atmosphere.

Effect of pyrolysis temperature on composition, surface properties and thermal degradation rates of Brazil Nut shells.

Changes in chemical and surface characteristics of Brazil Nut shells (Bertholletia excelsa) due to pyrolysis at different temperatures (350 degrees C, 600 degrees C, 850 degrees C) were examined. For this purpose, proximate and ultimate analyses, physical adsorption measurements of N2 (-196 degrees C) and CO, (25 degrees C) as well as samples visualisation by scanning electronic microscopy (SEM) were performed. Appreciable differences in the residue characteristics, depending markedly on the pyrolysis temperature, were observed. Release of volatile matter led to the development of pores of different sizes. Progressive increases in micropore development with increasing pyrolysis temperature took place, whereas a maximum development of larger pores occurred at 600 degrees C. Furthermore, kinetics measurements of Brazil Nut shells pyrolysis from ambient temperature up to 900 degrees C were performed by non-isothermal thermogravimetric analysis. A model taking into account the significant changes in the residue during pyrolysis, through an increase in the activation energy with temperature and solid conversion, were found to properly fit the kinetics data over the wide range of degradation investigated.

Batch and dynamic biosorption of basic dyes from binary solutions by alkaline-treated cypress cone chips.

A simple alkaline pre-treatment of Cupressus sempervirens cone chips was performed to improve their biosorption capacity towards methylene blue and rhodamine B from aqueous solutions, in batch and continuous modes. Biosorption kinetics were determined from single and binary dyes solutions, and properly described by the pseudo-second-order rate model. Experimental single-dye equilibrium isotherms fitted the Langmuir-Freundlich model, with maximum biosorption capacities of 0.68mmol/g for methylene blue and 0.50mmol/g for rhodamine B. Single-dye dynamic biosorption showed that breakthrough time for methylene blue biosorption was almost four times longer than for rhodamine B and that the alkaline modification of the chips greatly improved the biosorption performance. Competitive dynamic biosorption demonstrated the preference of the modified cone chips for biosorbing methylene blue, confirmed by the exit concentration overshoots obtained in the breakthrough curves of rhodamine B.

Effectiveness of Cupressus sempervirens cones as biosorbent for the removal of basic dyes from aqueous solutions in batch and dynamic modes.

The feasibility of using cypress cone chips from Cupressus sempervirens as a low-cost biosorbent for the removal of two representative basic dyes, methylene blue (MB) and rhodamine B (RhB), from aqueous solutions was investigated in batch and continuous modes. Dyes biosorption was strongly dependent on the solution's pH. Sorption kinetics was determined and properly described by the pseudo-second-order rate model. Experimental equilibrium isotherms fitted the Langmuir model, showing maximum biosorption capacities of 0.62 mmol/g for MB and 0.24 mmol/g for RhB. Competitive experiments from a binary solution of the dyes demonstrated the preference of the cone chips for biosorbing MB. Very low desorption efficiencies were obtained for both dyes. Dynamic experiments showed that the breakthrough time was three times higher for MB biosorption than for RhB for the same conditions. Breakthrough curves were properly represented by a mathematical model.

Adsorption of volatile organic compounds onto activated carbon cloths derived from a novel regenerated cellulosic precursor.

Activated carbon cloths (ACC) were prepared from lyocell, a novel regenerated cellulose nanofibre fabric, by phosphoric acid activation in inert atmosphere at two different final thermal treatment temperatures (864 and 963 degrees C). Benzene, toluene and n-hexane isotherms at 298 and 273K were measured in order to gain insight into the porous structure of the ACC and to evaluate their performance for the removal of volatile organic compounds (VOCs). The Dubinin-Radushkevich equation was employed to evaluate textural parameters of the ACC. The textural characteristics of the ACC were compared with those previously determined from nitrogen (77K) and carbon dioxide (273K) adsorption data. The samples were essentially microporous. The textural parameters calculated from the hydrocarbon isotherms were in good agreement with those evaluated from nitrogen isotherms for the ACC with the wider microporosity. Additionally, the Freundlich model provided a good description of the experimental isotherms for the three volatile organic compounds. The ACC obtained at the higher temperature exhibited a larger adsorption capacity. The ACC were also electrically conductive and showed potential for regeneration by the Joule effect, as determined from macroscopic electrical measurements before and after n-hexane adsorption.

Potentiality of lignin from the Kraft pulping process for removal of trace nickel from wastewater: effect of demineralisation.

An industrial raw Kraft lignin was investigated to ascertain its potential use for removal of trace Ni(II) ion from wastewater by using dilute solutions (0.34-1.7 mM) as models. The effect of demineralisation on its metal sorption ability was examined by employing acid pre-treated samples. Under fixed pre-established equilibrium conditions, the raw lignin exhibited a lower effectiveness than the demineralised one, with the latter attaining an almost complete removal of Ni(II) ions. For both lignins, sorption kinetics was properly described by a pseudo-second order rate model. Equilibrium isotherms were also determined and adequately represented by conventional two-parameter models. The higher nickel sorption capacity for the demineralised lignin compared to the raw sample was consistent with enhancements in the negative magnitude of zeta potential, sodium sorption capacity, and content of phenolic hydroxyl groups occasioned by the acid pre-treatment. Accordingly, demineralisation appears as a readily convenient strategy to improve the behaviour of industrial Kraft lignin for potential use as a biosorbent of trace nickel from polluted water.