Preparation and characterization of modified rice husks by biological delignification and acetylation for oil spill cleanup.

Cellulose is widely used as an effective sorbent to treat wastewater. Cellulosic sorbents have the advantage of biodegradability, as they are natural plant-based materials, compared with the synthetic materials such as polypropylene (PP) or polyurethane (PU). Among the raw biomass materials used for cellulose production, rice husk is one of the most cost competitive and widely available. In this work, biological treatments are compared to find the most effective treatment method for cellulose fibre production from rice husk. Using biological delignification, cellulose was extracted from raw rice husk and acetylated to acquire hydrophobicity. Delignification was performed using both bacteria and fungi and their results were compared. The white-rot fungi strain using 'Aspergillus flavus CICC 40258' was found to be the most effective treatment method, achieving a modified product with up to 55% w/w cellulose concentration. Acetylation further facilitated the sorption process and the maximum oil uptake capacity using delignification and acetylation treatment was found to be 20 g/g. The as-prepared sorbents exhibited high oil uptake rates and saturation capacity was reached after 5 min of contact with oil. The kinetic study presents a good correlation with the pseudo-second order model. The isothermal studies demonstrated that the oil sorption capacity of rice husk follows the Langmuir model as compared with the Freundlich model.

Multilayer Dye Adsorption in Activated Carbons-Facile Approach to Exploit Vacant Sites and Interlayer Charge Interaction.

Altering the textural properties of activated carbons (ACs) via physicochemical techniques to increase their specific surface area and/or to manipulate their pore size is a common practice to enhance their adsorption capacity. Instead, this study proposes the utilization of the vacant sites remaining unoccupied after dye uptake saturation by removing the steric hindrance and same-charge repulsion phenomena via multilayer adsorption. Herein, it has been shown that the adsorption capacity of the fresh AC is a direct function of the dye molecular size. As the cross-sectional area of the dye molecule increases, the steric hindrance effect exerted on the neighboring adsorbed molecules increases, and the geometrical packing efficiency is constrained. Thus, ACs saturated with larger dye molecules render higher concentrations of vacant adsorption sites which can accommodate an additional layer of dye molecules on the exhausted adsorbent through interlayer attractive forces. The second layer adsorption capacity (60-200 mg·g(-1)) has been demonstrated to have a linear relationship with the uncovered surface area of the exhausted AC, which is, in turn, inversely proportional to the adsorbate molecular size. Unlike the second layer adsorption, the third layer adsorption is a direct function of the charge density of the second layer.

Aluminosilicate-based adsorbent in equimolar and non-equimolar binary-component heavy metal removal systems.

Cadmium (Cd) and lead (Pb) are toxic heavy metals commonly used in various industries. The simultaneous presence of these metals in wastewater amplifies the toxicity of wastewater and the complexity of the treatment process. This study has investigated the selective behavior of an aluminosilicate-based mesoporous adsorbent. It has been demonstrated that when equimolar quantities of the metals are present in wastewater, the adsorbent uptakes the Pb²âº ions selectively. This has been attributed to the higher electronegativity value of Pb²âº compared to Cd²âº which can be more readily adsorbed on the adsorbent surface, displacing the Cd²âº ions. The selectivity can be advantageous when the objective is the separation and reuse of the metals besides wastewater treatment. In non-equimolar solutions, a complete selectivity can be observed up to a threshold Pb²âº molar ratio of 30%. Below this threshold value, the Cd²âº and Pb²âº ions are uptaken simultaneously due to the abundance of Cd²âº ions and the availability of adsorption sites at very low Pb²âº molar ratios. Moreover, the total adsorption capacities of the adsorbent for the multi-component system have been shown to be in the same range as the single-component system for each metal ion which can be of high value for industrial applications.

Combating oil spill problem using plastic waste.

Thermoplastic polymers (such as polypropylene, polyethylene, polyethylene terephthalate (PET) and high density polyethylene (HDPE)) constitute 5-15% of municipal solid waste produced across the world. A huge quantity of plastic waste is disposed of each year and is mostly either discarded in landfills or incinerated. On the other hand, the usage of synthetic polymers as oil sorbents, in particular, polyolefins, including polypropylene (PP), and polyethylene (PE) are the most commonly used oil sorbent materials mainly due to their low cost. However, they possess relatively low oil absorption capacities. In this work, we provide an innovative way to produce a value-added product such as oil-sorbent film with high practical oil uptake values in terms of g/g from waste HDPE bottles for rapid oil spill remedy.

Toxic heavy metal capture using a novel electronic waste-based material-mechanism, modeling and comparison.

In the modern communication era, the disposal of printed circuit boards is ecologically of dire concern on a global scale. The two prevalent methods applied for the disposal of this waste are either incineration or landfilling both of which are viewed with skepticism due to their negative environmental impact. Activation of the nonmetallic fraction of this waste leads to the development of a mesoporous material with highly functional groups which can potentially be applied for heavy metal uptake. The removal of copper, lead, and zinc was studied employing a cost-effective novel adsorbent based on waste printed circuit boards. The results indicate that the modification of the original e-waste material has a considerable effect on its surface area enhancement. Adsorption experiments revealed that the modified novel material had uptake capacities of 2.9 mmol Cu, 3.4 mmol Pb, and 2.0 mmol Zn per each gram of the adsorbent which are significantly higher values than its commercial counterparts used in industry.

Novel application of the nonmetallic fraction of the recycled printed circuit boards as a toxic heavy metal adsorbent.

Printed circuit boards (PCBs) constitute one of the major sources of toxicity in landfill areas throughout the world. Hence, PCB recycling and separation of its metallic and nonmetallic components has been considered a major ecological breakthrough. Many studies focus on the metallic fraction of the PCBs due to its economic benefits whereas the nonmetallic powder (NMP) has been left isolated. In this work, the feasibility of using NMP as an adsorbent to remove charged toxic heavy metal ions have been studied and its efficiency has been compared with two widely-used commercial adsorbents. The results indicated that the virgin NMP material has no adsorption capacity, while the application of an activation stage to modify the NMP process has a significant effect on its porosity and thus adsorption capacity. The Cu and Pb removal capacity of the activated sample (A-NMP) at a pH level of 4 was 3 mmol and 3.4 mmol per gram of the adsorbent, respectively, which was considerably higher than the commercial ones.

A comparative study on selective adsorption of metal ions using aminated adsorbents.

It is well-known that chitosan consists of amino groups for the chelation of metal ions while NH2-MCM-41 has excellent adsorption selectivities for metals. This work compares both adsorption capacities and selectivities of chitosan and NH2-MCM-41. It has been found that chitosan has adsorption capacities of 1.76 mmol/g, 1.03 mmol/g and 1.30 mmol/g for Cu2+, Ni2+ and Zn2+ respectively whereas NH-MCM-41 has adsorption capacity of 1.52mmol/g, 0.8mmol/g and 0.83mmol/g for Cu, Ni and Zn. The higher adsorption capacity in chitosan is attributed to its higher loading of amine groups. The single component adsorption isotherms were well-fitted using Freundlich model. The binary adsorptions of Cu2+-Zn2+ and Ni2+-Zn2+ systems showed similar adsorption selectivities for both adsorbents. However, chitosan has no preferential adsorption for Ni2+-Zn2+ system while NH2-MCM-41 has a good selectivity towards Zn2+. It is believed that the difference can be attributed to the heterogeneous surface of chitosan due to its organic nature. The multi-component adsorptions were best described by a multicomponent extended Freundlich model. Despite the surface functional group, this work indicates the importance of the adsorbent support on selective adsorption.

Alteration of xylose reductase coenzyme preference to improve ethanol production by Saccharomyces cerevisiae from high xylose concentrations.

A K270R mutation of xylose reductase (XR) was constructed by site-direct mutagenesis. Fermentation results of the F106X and F106KR strains, which carried wild type XR and K270R respectively, were compared using different substrate concentrations (from 55 to 220 g/L). After 72 h, F106X produced less ethanol than xylitol, while F106KR produced ethanol at a constant yield of 0.36 g/g for all xylose concentrations. The xylose consumption rate and ethanol productivity increased with increasing xylose concentrations in F106KR strain. In particular, F106KR produced 77.6g/L ethanol from 220 g/L xylose and converted 100 g/L glucose and 100g/L xylose into 89.0 g/L ethanol in 72h, but the corresponding values of F106X strain are 7.5 and 65.8 g/L. The ethanol yield of F106KR from glucose and xylose was 0.42 g/g, which was 82.3% of the theoretical yield. These results suggest that the F106KR strain is an excellent producer of ethanol from xylose.

Non-UV germicidal activity of fresh TiO2 and Ag/TiO2.

Fresh TiO2 was found to possess a strong germicidal activity even without UV irradiation. Live Yeast (Saccharomyces cerevisiae) cells in contact with fresh TiO2 were found deformed and dead after 15 min contact. The cause of germicidal activity was discussed from the observed cell deformation, lysis and increased absorption at 1680 cm(-1) in FT-IR spectra of the affected cells, which proved the oxidizing effect of fresh TiO2 to cells. The deformation caused by the stretching of cell wall and pressure built-up inside the cell, led to cell burst and release of intracellular materials. The degree of cell deformation was found positively related with the wetting property of TiO2. Cells are negatively charged, for Gram-negative cell (thinner cell wall), a higher germicidal effect was observed than Gram-positive cells. The germicidal effect of TiO2 gradually decreased after exposure to air at room temperature, as the wetting property decreased. This kind of germicidal activity was more effective compared to other germicidal process such as UVA/TiO2 or Ag+. This shed light on designing new germicidal material either maintained by visible light irradiation, or by oxidation effect generated by reactive oxygen species.

Non-UV based germicidal activity of metal-doped TiO2 coating on solid surfaces.

A stain-based screening method was developed to screen different catalyst coatings for their germicidal activity. A Baclight dead/live bacteria viability kit (invitrogen, molecular probes) was used for staining the cell. The screening was carried out following a standard procedure. This included loading cell suspension to solid surface and maintaining contact for 30 min, then staining with a mixture containing dyes. The stained cells were observed using an epifluorescent microscope and photographed with a CCD camera under UV. Metal-doped TiO2 coatings on Al plates were prepared and tested for non-UV germicidal activity without using UV. It was tested using model microorganisms such as Bakers Yeast (Saccharomyces cerevisiae), Bacillus subtilis, Pseudomonas putida, and Escherichia coli. On the basis of the germicidal activity of catalyst and the degree of damage caused to the cells, the stained cells may appear green (viable), green with red or yellow nuclei and yellow (compromised) or red (nonviable). According to their stained color, cells were counted to calculate the percentage of dead, live, and compromised cells. Compromised cells are cells that grow very slowly after reculturing indicating a degree of reversible cell damage. Screening the germicidal activity using this staining method is accurate and efficient, and requires less time than the culture-based method. A modification to the procedure for measuring germicidal activity of rough surfaces or fibrous coatings was developed. Both TiO2 and metal-doped TiO2 (Ag, Pt, Au, Cu) possess non-UV based germicidal activity. The germicidal activity of TiO2 was found to be related with its wetting property and can be improved by UV irradiation before testing. It is not greatly affected by contact time, indicating a fast acting germicidal activity.

Development of a glucose-6-phosphate biosensor based on coimmobilized p-hydroxybenzoate hydroxylase and glucose-6-phosphate dehydrogenase.

This work reports the development of an amperometric glucose-6-phosphate biosensor by coimmobilizing p-hydroxybenzoate hydroxylase (HBH) and glucose-6-phosphate dehydrogenase (G6PDH) on a screen-printed electrode. The principle of the determination scheme is as follows: G6PDH catalyzes the specific dehydrogenation of glucose-6-phosphate by consuming NADP(+). The product, NADPH, initiates the irreversible the hydroxylation of p-hydroxybenzoate by HBH in the presence of oxygen to produce 3,4-dihydroxybenzoate, which results in a detectable signal due to its oxidation at the working electrode. The sensor shows a broad linear detection range between 2 microM and 1000 microM with a low detection limit of 1.2 microM. Also, it has a fast measuring time which can achieve 95% of the maximum current response in 20s after the addition of a given concentration of glucose-6-phosphate with a short recovery time (2 min).

Development of an oxygen-rich biosensor using enzymatic reaction.

This work reports a novel strategy for the development of an O2-rich biosensor. The principle is based on an enzymatic reaction between catalase and H2O2 to release O2, thus to increase the O2 amount in the enzyme matrix. This method improves the determination reliability by alleviating the O2 dependence.

A disposable, screen-printed electrode for the amperometric determination of azide based on the immobilization with catalase or tyrosinase.

A disposable, screen-printed electrode based on the immobilization of catalase or tyrosinase was developed to construct biosensors for the amperometric determination of azide. The determination principles for azide by these two methods are based on inhibiting the enzymatic consumption of an electrode-detectable substance (hydrogen peroxide or catechol) on an enzyme-immobilized electrode. Both of these methods show a sensitive detection range and a short measuring time.

Determination of poly(3-hydroxybutyrate) using a combination of enzyme-based biosensor and alkaline hydrolysis.

The combination of an enzyme-based biosensor and alkaline hydrolysis was developed for the measurement of poly(3-hydroxybutyrate) (PHB). The principle of the determination is based on that the alkaline condition converts PHB to produce its monomer, 3-hydroxybutyrate (3-HB), which generates a detectable current signal by an amperometric biosensor through coupled two-enzyme reactions on an electrode. This method takes less than 40 min, and results in a linear detection range of 0.5-110 mg L-1 PHB with a detection limit of 0.3 mg L-1 by the saturated production of 3-HB; it can also take less than 15 min and result in a linear detection range of 1.0-160 mg L-1 PHB with a detection limit of 0.5 mg L-1 by a part production of 3-HB. The method also shows simple operation and high reproducibility.

Development of a bienzyme system for the electrochemical determination of nitrate in ambient air.

This work reports the development of a bienzyme system consisting of salicylate hydroxylase (SHL) and nitrate reductase (NaR) for the electrochemical determination of nitrate. This method measures the concentration of nitrate directly under ambient air without suffering from oxygen interferences. The determination is based on the detection of NADH consumption, and the principle is as follows: NADH initiates the irreversible decarboxylation and hydroxylation of salicylate by SHL in the presence of oxygen to produce catechol, which results in a detectable signal due to its oxidation at the working electrode; the second enzyme, NaR, in the presence of nitrate, reduced the availability of NADH, and consequently, the current difference after the injection of nitrate is proportional to its concentration. This method shows high performance characteristics for nitrate determination with a broad detection range between 10 microM and 1,000 microM, a short measuring time of around 5 min, and a simple operation without sample pretreatment by inert gas purge or oxygen scavenger.

Biosensor for rapid phosphate monitoring in a sequencing batch reactor (SBR) system.

A thick-film phosphate biosensor based on hydrogel immobilized pyruvate oxidase (POD) has been developed for rapid phosphate process control monitoring in an experimental sequencing batch reactor (SBR) system. We have employed a phosphate biosensor in an off-line monitoring of phosphate concentrations in a bench scale SBR. Measurements with biosensor show a good correlation (r2=0.98) with those of commercial colorimetric phosphate testing kits. The signal response time was 1 min with a detection limit of 5 microM. The biosensor method showed a good operational stability, needed less experimental procedures and a small sample size (approximately 20 microl). This allows its practical application for rapid phosphate measurements to obtain real time process data in a SBR system.

Solar photocatalytic thin film cascade reactor for treatment of benzoic acid containing wastewater.

A solar photocatalytic cascade reactor was constructed to study the photocatalytic oxidation of benzoic acid in water under various experimental and weather conditions at HKUST. Nine stainless steel plates coated with TiO(2) catalyst were arranged in a cascade configuration in the reactor. Photolytic degradation and adsorption were confirmed to be insignificant total organic carbon (TOC) removal mechanisms. A turbulent flow pattern and, hence, improved mixing in the liquid film were achieved due to the unique cascade design of the reactor. The photoinduced consumption of oxygen during reactions was demonstrated in a sample experiment. The proposed rate equations provided good fits to 90 data points from 17 experiments. The regression results showed that the TOC removal rates averaged over 30 min intervals did not illustrate significant dependence on TOC(0) and that I(mean) was more important in affecting the photocatalytic process within the ranges of the data examined. The percentage removal of TOC in 7 l of 100 mg/l (or 100 ppm) benzoic acid solutions increased from 30% to 83% by adding 10 ml of hydrogen peroxide solution (30 wt%). Hydrogen peroxide was also shown to enhance the efficiency of the degradation process at elevated temperatures. Ortho-, meta- and para-hydroxybenzoic acids were identified by HPLC analysis as the intermediates of benzoic acid during reactions without the addition of hydrogen peroxide solutions.