2,4,6‐Trichlorophenol and phenol removal in methanogenic and partially‐aerated methanogenic conditions in a fluidized bed bioreactor

A fluidized bed bioreactor (FBBR) was operated for more than 575 days to remove 2,4,6‐trichlorophenol (TCP) and phenol (Phe) from a synthetic toxic wastewater containing 80 mg L^?1 of TCP and 20 mg L^?1 of Phe under two regimes: Methanogenic (M) and Partially‐Aerated Methanogenic (PAM). The mesophilic, laboratory‐scale FBBR consisted of a glass column (3 L capacity) loaded with 1 L of 1 mm diameter granular activated carbon colonized by an anaerobic consortium. Sucrose (1 g COD L^?1) was used as co‐substrate in the two conditions. The hydraulic residence time was kept constant at 1 day. Both conditions showed similar TCP and Phe removal (99.9 + %); nevertheless, in the Methanogenic regime, the accumulation of 4‐chlorophenol (4CP) up to 16 mg L^?1 and phenol up to 4 mg L^?1 was observed, whereas in PAM conditions 4CP and other intermediates were not detected. The specific methanogenic activity of biomass decreased from 1.01 ± 0.14 in M conditions to 0.19 ± 0.06 mmolCH₄ h^?1 gTKN^?1 in PAM conditions whereas the specific oxygen uptake rate increased from 0.039 ± 0.008 in M conditions to 0.054 ± 0.012 mmolO₂ h^?1 gTKN^?1, which suggested the co‐existence of both methanogenic archaea and aerobic bacteria in the undefined consortium. The advantage of the PAM condition over the M regime is that it provides for the thorough removal of less‐substituted chlorophenols produced by the reductive dehalogenation of TCP rather than the removal of the parent compound itself. Copyright © 2005 Society of Chemical Industry     

Preparation of glucose oxidase immobilized in different carriers using radiation polymerization

Glucose oxidase (EC 1.1.3.4) was immobilized on different polymeric materials using different immobilization techniques (entrapping by γ‐irradiation, and covalent binding using epichlorohydrin). Studies were carried out to increase the thermal stability of glucose oxidase (GOD) for different applications. The activity and stability of the resulting biopolymers have been compared with those of free GOD. The effect of different polyvinyl alcohol/polyacrylamide (PVA/PAAm) compositions of the copolymer carrier on the enzymatic activity of the immobilized GOD was studied. The maximum enzymatic activity was obtained with the composition ratio of PVA/PAAm of 60:40. The behaviour of the free and immobilized enzyme was analysed as a function of pH. A broadening in the pH profile (5.5–8) was observed for immobilized preparations. The activity and stability of the resulting biopolymers produced by immobilization of GOD onto different carriers have been compared, in both aqueous and organic media, with those of the free GOD. The enzyme's tolerance toward both heat and organic solvent was enhanced by immobilization onto polymers. The addition of different concentrations of organic solvents (10–50%, v/v) to the enzyme at higher temperature (60 °C) was found to stabilize the enzyme molecule. The strongest stabilizing effect on the enzymatic activity was achieved at a concentration of 10%. Copyright © 2005 Society of Chemical Industry     

An eight‐node hybrid‐stress solid‐shell element for geometric non‐linear analysis of elastic shells

This paper presents eight‐node solid‐shell elements for geometric non‐linear analysis of elastic shells. To subdue shear, trapezoidal and thickness locking, the assumed natural strain method and an ad hoc modified generalized laminate stiffness matrix are employed. A selectively reduced integrated element is formulated with its membrane and bending shear strain components taken to be constant and equal to the ones evaluated at the element centroid. With the generalized stresses arising from the modified generalized laminate stiffness matrix assumed to be independent from the ones obtained from the displacement, an extended Hellinger–Reissner functional can be derived. By choosing the assumed generalized stresses similar to the assumed stresses of a previous solid element, a hybrid‐stress solid‐shell element is formulated. Commonly employed geometric non‐linear homogeneous and laminated shell problems are attempted and our results are close to those of other state‐of‐the‐art elements. Moreover, the hybrid‐stress element converges more readily than the selectively reduced integrated element in all benchmark problems. Copyright © 2002 John Wiley & Sons, Ltd.     

Effects of a Nd—Fe—B magnetic filler on the crystallization of poly(phenylene sulfide)

The crystallization of poly(phenylene sulfide) (PPS) in a polymer–magnetic Nd—Fe—B powder suspension was studied. Isothermal crystallization behavior was analyzed by way of differential scanning calorimetry, and the kinetics were described via the Avrami equation. The Avrami parameters and the crystallization times were strongly affected by both the particle size and the presence of a coupling agent coated on the filler particles. The small Nd—Fe—B particles exhibited long induction and half‐times, whereas the large particles tended to have short crystallization times. Particles ranging from 38 to 150 μ appeared to have similar crystallization times and to have no significant change in the value of Avrami index with melt crystallization temperature. As a result of these analyses, the dynamic mechanical properties were determined to correlate the fundamental polymer crystallization characteristics and the physical properties of the PPS binder. The enhancement of the wetting of the filler to the binder was promoted through the coupling agent, as confirmed by dynamic mechanical testing performed on the samples. The storage modulus typically decreased because of the presence of the uncoated small particles. Conversely, the loss modulus was enhanced because of the presence of the coated small particles in the PPS binder. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1091–1102, 2002     

Screen‐printed biosensor for allergens

Allergen levels in indoor environments, leading to many diseases, eg asthma, rhinitis and conjunctivitis, affect a large and increasing fraction of the population. A quite effective and inexpensive method of a rough but very rapid overall assessment of total allergen level in the environment has been developed. The method involved estimation of protein in allergen extracts by screen‐printed electrodes using two different techniques. The biosensor comprised a rhodinised carbon working electrode, a silver/silver chloride reference electrode and a carbon counter electrode. In the first method the enzyme protease reacted with allergen protein to release amino acid, which produced hydrogen peroxide in the presence of amino acid oxidase. This was detected amperometrically. The second method used potassium bromide as electrolyte and the electrode was subjected to dual potential. Bromine, released due to electrolysis at higher potential, was consumed by the allergen protein at lower potential. In the first method, a unique technique was used to microencapsulate the enzyme protease and immobilise it on the surface of the electrode by in‐situ polymerisation to avoid contact with the amino acid oxidase. A total of seven allergens were tested and the results gave a good correlation with the standard protein measurement method. Environmental specimens from indoors, schools and workplaces can be evaluated for the aeroallergens produced by dust mites, animal hairs, cockroach debris, pollens, etc as a means of determining the exposure risk. Copyright © 2005 Society of Chemical Industry     

Development and simulation studies of an unsteady state biofilter model for the treatment of cyclic air emissions of an α‐pinene gas stream

This paper describes the development and simulation of an unsteady state biofilter model used to predict dynamic behaviour of cyclically‐operated biofilters and compares it with experimental results obtained from three, parallel, bench‐scale biofilters treating both periodically fluctuating concentrations and constant concentrations of an α‐pinene‐laden gas stream. The dynamic model, using kinetic parameters estimated from the constant concentration biofilter, was able to predict the performance of cyclic biofilters operating at short cycle periods (ie, in the order of minutes and hours). Steady state kinetic data from a constant concentration biofilter can be used to predict unsteady state biofilter operation. At a 24 h cycle period, the dynamic model compared well with experimental results. For long cycle periods (ie, hours and days), removal efficiency decreased after periods of non‐loading: the longer the period of non‐loading, the poorer the biofilter's performance at the re‐commencement of pollutant loading. At longer time scales the model did not effectively predict transient behaviour, as adsorption and changes in kinetic parameters were not accounted for. Modelling results showed that similar biofiltration performance for the cyclic and constant concentration biofiltration of α‐pinene is expected for biofilters operating solely in the first order kinetics regime. Poorer performance for cyclic biofilters following Monod kinetics spanning the entire kinetics range is expected as the cycle amplitude increases. The most important parameters affecting the performance of a cyclically‐operated biofilter with short cycle periods are: amplitude of cyclic fluctuations, C_{g, max}/C_g, relative value of the half‐saturation constant in the Monod expression, K_s, and effective diffusivity of α‐pinene in the biofilm, D_e. Copyright © 2005 Society of Chemical Industry     

Ultrasound‐activated Knoevenagel condensation of malononitrile with carbonylic compounds catalysed by alkaline‐doped saponites

α,β‐Unsaturated nitriles have been synthesized by Knoevenagel condensation of a carbonylic compound with malononitrile, assisted by sonochemical irradiation. Two alkaline‐promoted clays (Li⁺‐ and Cs⁺‐exchanged saponites) have been employed as catalysts. The influence of the carbonylic compound (benzaldehyde or cyclohexanone) and the use of a solvent on the catalytic activity have been studied. Remarkable increase in the conversion values has been found when the reaction is activated by ultrasound, as compared with the thermal activation. In this green, solvent‐free procedure, α,β‐unsaturated nitriles have been produced in very high yields (97%) when the Cs⁺‐saponite is used as catalyst. Copyright © 2004 Society of Chemical Industry     

Material state remapping in computational solid mechanics

A computational procedure for remapping material state information from one finite element mesh to another is described. The procedure is useful in connection with evolving meshes for inelastic problems, as for example occur in the context of fracture simulation and adaptive mesh refinement. The proposed method is based on weak enforcement of equality between corresponding fields on the two meshes, where piecewise‐constant fields on both meshes are generalized from the quadrature‐point values. The essential algorithmic problem is that of calculating the volume partition of an arbitrary convex region with respect to a covering set of disjoint convex regions. Instead of geometrically resolving the associated intersections, the problem is herein approximated by a constrained optimization problem, which may be readily and efficiently solved computationally. This formulation is a main contribution of the paper. Computational examples are given that illustrate the effectiveness of the proposed procedure. Copyright © 2002 John Wiley & Sons, Ltd.