Degradation mechanisms of benzo[a]pyrene and its accumulated metabolites by biodegradation combined with chemical oxidation

A high degradation extent of benzo[a]pyrene (BaP) should not be considered as the sole desirable criterion for the bioremediation of BaP-contaminated soils because some of its accumulated metabolites still have severe health risks to human. Two main metabolites of BaP, benzo[a]pyrene-1,6-quinone (BP1,6-quinone) and 3-hydroxybenzo[a]pyrene (3-OHBP) were identified by high performance liquid chromatography (HPLC) with standards. This study was the first time that degradation of both BaP and the two metabolites was carried out by chemical oxidation and biodegradation. Three main phases during the whole degradation process were proposed.

Hydrogen peroxide–zinc (H₂O₂–Zn), the fungus – Aspergillus niger and the bacteria – Zoogloea sp. played an important role in the different phases. The degradation parameters of the system were also optimized, and the results showed that the effect of degradation was the best when fungus–bacteria combined with H₂O₂–Zn, the concentration range of BaP in the cultures was 30–120 mg/l, the initial pH of the cultures was 6.0. However, as co-metabolites, phenanthrene significant inhibited the degradation of BaP. This combined degradation system compared with the conventional method of degradation by domestic fungus only, enhanced the degradation extent of BaP by more than 20% on the 12 d. The highest accumulation of BP1,6-quinone and 3-OHBP were reduced by nearly 10% in the degradation experiments, which further proved that the combined degradation system was more effective as far as joint toxicity of BaP and its metabolites are concerned.

Biodegradation of benzo[a]pyrene in soil by Mucor sp. SF06 and Bacillus sp. SB02 co-immobilized on vermiculite

Two indigenous microorganisms, Bacillus sp. SB02 and Mucor sp. SF06, capable of degrading polycyclic aromatic hydrocarbons (PAHs) were co-immobilized on vermiculite by physical adsorption and used to degrade benzo[a] pyrene (BaP). The characteristics of BaP degradation by both free and co-immobilized microorganism were then investigated and compared. The removal rate using the immobilized bacterial-fungal mixed consortium was higher than that of the freely mobile mixed consortium. 95.3% of BaP was degraded using the co-immobilized system within 42 d, which was remarkably higher than the removal rate of that by the free strains. The optimal amount of inoculated co-immobilized system for BaP degradation was 2%. The immobilized bacterial-fungal mixed consortium also showed better water stability than the free strains. Kinetics of BaP biodegradation by co-immobilized SF06 and SB02 were also studied. The results demonstrated that BaP degradation could be well described by a zero-order reaction rate equation when the initial BaP concentration was in the range of 10—200 mg/kg. The scanning electronic microscope (SEM) analysis showed that the co-immobilized microstructure was suitable for the growth of SF06 and SB02. The mass transmission process of co-immobilized system in soil is discussed. The results demonstrate the potential for employing the bacterial-fungal mixed consortium, co-immobilized on vermiculite, for in situ bioremediation of BaP.

Surfactant-mediated biodegradation of polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons (PAHs) are toxic environmental pollutants that are known or suspected carcinogens or mutagens. Bioremediation has been used as a general way to eliminate them from the contaminated sites or aquifers, but their biodegradation is rather limited due to their low bioavailability because of their sparingly soluble nature. Surfactant-mediated biodegradation is a promising alternative. The presence of surfactants can increase the solubility of PAHs and hence potentially increase their bioavailability. However, inconclusive results have been reported on the effects of surfactant on the biodegradation of PAHs. In this work, surfactant-mediated biodegradation of PAHs is reviewed.

Effect of a commercial alcohol ethoxylate surfactant (C11–15E7) on biodegradation of phenanthrene in a saline water medium by Neptunomonas naphthovorans

Biodegradation of poorly soluble polycyclic aromatic hydrocarbons (PAHs) has been a challenge in bioremediation. In recent years, surfactant-enhanced bioremediation of PAH contaminants has attracted great attention in research. In this study, biodegradation of phenanthrene as a model PAHs solubilized in saline micellar solutions of a biodegradable commercial alcohol ethoxylate nonionic surfactant was investigated. The critical micelle concentration (CMC) of the surfactant and its solubilization capacity for phenanthrene were examined in an artificial saline water medium, and a type of marine bacteria, Neptunomonas naphthovorans, was studied for the biodegradation of phenanthrene solubilized in the surfactant micellar solutions of the saline medium. It is found that the solubility of phenanthrene in the surfactant micellar solutions increased linearly with the surfactant concentrations, but, at a fixed phenanthrene concentration, the biodegradability of phenanthrene in the micellar solutions decreased with the increase of the surfactant concentrations. This was attributed to the reduced bioavailability of phenanthrene, due to its increased solubilization extent in the micellar phase and possibly lowered mass transfer rate from the micellar phase into the aqueous phase or into the bacterial cells. In addition, an inhibitory effect of the surfactant on the bacterial growth at high surfactant concentrations may also play a role. It is concluded that the surfactant largely enhanced the solubilization of phenanthrene in the saline water medium, but excess existence of the surfactant in the medium should be minimized or avoided for the biodegradation of phenanthrene by Neptunomonas naphthovorans.

Biodegradation of pentachlorophenol in a membrane bioreactor

Pentachlorophenol (PCP) is a toxic chemical, often used in the formulation of pesticide, herbicide, anti fungal agent, bactericide and wood preservative. This study is aimed at evaluating the potential of membrane bioreactor (MBR) to treat PCP contaminated wastewater. Synthetic wastewater with COD of 600 mg/L was fed into the MBR at varied PCP loading rate of 12–40 mg/m3/d. A PCP removal rate of 99% and a COD removal rate of 95% were achieved at a hydraulic retention time of 12 hs and a mixed liquor suspended solids (MLSS) concentration of 10,000 mg/L. When sodium pentachlorophenol (NaPCP), which has higher solubility in water, was used in the second phase of the study, at loading rates varying from 20 to 200 mg/m3·d, the removal rate of NaPCP was higher than 99% and the removal rate of COD was more than 96%. It was also found that at higher biomass concentrations, biosorption played an important role besides the biodegradation process. Batch experiments conducted in this study revealed that the sorption capacity to be 0.63 (mg PCP/g biomass) and occurred rapidly within 60 min. This phenomenon could enhance the PCP degradation through increased contact between microorganism and PCP. Further, the membrane resistance was low (trans-membrane pressure of 14 kPa) even after more than 100 ds of operation. In addition, the toxic level of PCP in the influent could have induced the microorganisms to secrete more extra-cellular polymeric substances (EPS) for their protection, which in turn must have increased the viscosity of the mixed liquor.

Control of biodegradation of a Mg alloy in simulated body fluid

Mg alloy AZ31 is an attractive candidate for coronary artery stents, as it possesses excellent biocompatibility in human body and good mechanical properties. However, AZ31 magnesium alloys generally have poor corrosion resistance in the body environment. This paper reports on the early stages of an investigation into the corrosion mechanism and the morphology of corrosion of AZ31 in simulated body fluid (SBF). The investigation will also consider ways of improving corrosion resistance of this alloy in SBF through the use of ionic liquids. The results to date have shown that AZ31 suffers severe localized pitting corrosion in SBF. The pits mainly develop adjacent to the Al-Mn intermetallic second phase in the α matrix. Energy Dispersive X-Ray Spectroscopy results revealed the presence of Mg, O, Ca, and P in the layer of corrosion product. Treatment of the AZ31 alloy prior to corrosion testing in SBF with the ionic liquid trimethyl (butyl) phosphonium diphenyl phosphate (P1444DPP) produced some increase in the corrosion resistance of the alloy.

Structure and biodegradation mechanism of milled Bombyx mori silk particles

The aim of this study was to understand the structure and biodegradation relationships of silk particles intended for targeted biomedical applications. Such a study is also useful in understanding structural remodelling of silk debris that may be generated from silk-based implants. Ultrafine silk particles were prepared using a combination of efficient wet-milling and spray-drying processes with no addition of chemicals other than those used in degumming. Milling reduced the intermolecular stacking forces within the β-sheet crystallites without changing the intramolecular binding energy. Because of the rough morphology and the ultrafine size of the particles, degradation of silk particles by protease XIV was increased by about 3-fold compared to silk fibers. Upon biodegradation, the thermal degradation temperature of silk increased, which was attributed to the formation of tight aggregates by the hydrolyzed residual macromolecules. A model of the biodegradation mechanism of silk particles was developed based on the experimental data. The model explains the process of disintegration of β-sheets, supported by quantitative secondary structural analysis and microscopic images. © 2012 American Chemical Society.

Graphene/tri-block copolymer composites prepared via RAFT polymerizations for dual controlled drug delivery via pH stimulation and biodegradation

A novel tri-block copolymer poly(oxopentanoate ethyl methacrylate)-block-poly(pyridyl disulfide ethyl acrylate)-block-poly(ethylene glycol acrylate) [poly(OEMA-b-PDEA-b-PEGA)], retaining active keto groups and pyridyl disulfide (PDS) side functionalities, was synthesized as a drug delivery vehicle using reversible addition-fragmentation chain transfer (RAFT) polymerization method. One mimic drug pyridine-2-thione (PT) was introduced into the monomer, PDEA for copolymerization. The other mimic drug O-benzylhydroxylamine (BHA) was conjugated with tri-block copolymer via efficient oxime coupling chemistry, followed by the attachment onto graphene via π-π stacking interaction to obtain a graphene/tri-block copolymer composite. 1H NMR, UV-vis absorption spectroscopy, fluorescence spectroscopy, gel permeation chromatography (GPC), atomic force microscope (AFM) and transmission electron microscope (TEM) were used to verify the successful step-wise preparation of the tri-block copolymer and drug loaded composite. In vitro release behaviors of BHA and PT from graphene/tri-block copolymer composite via dual drug release mechanisms were investigated. BHA can be released under acid environment, while PT will be released in the presence of reducing agents, such as dithiothreitol (DTT) or glutathione (GSH). It can be envisioned that this novel composite could be exploited as a novel intracellular drug delivery system via dual release mechanisms.

Anaerobic degradation of organic materials - significance of the substrate surface area

In anaerobic degradation of substrates containing mainly particulate organic matter, solids hydrolysis is rate-limiting. In these investigations, the particle size of various substrates was reduced by comminution to support hydrolysis. Two positive effects of comminution were observed. For substrates with high fibre content, which are particularly resistant to biodegradation, a significant improvement of the degradation degree was observed as a result of comminution. Secondly, for all substrates tested, and particularly for those rich in fibres, the degradation rate of comminuted samples was significantly higher. The first reason for both effects is an increase of the sample surface area. Several methods for measuring the specific surface area of organic materials, including particle size analysis, Nitrogen-adsorption and enzyme adsorption, were used and compared for the purpose of this study, where the surface area accessible to microbial enzymes is critical. The significance of the surface area in anaerobic degradation of particulate substrates was investigated through a kinetic model where the hydrolysis rate was based on the sample surface area. Good agreements were obtained between model and experiments carried out with samples of various specific surface areas. These results reinforced the significance of the sample surface area in anaerobic degradation processes. However, other effects of comminution responsible for the increased degradation degree and degradation rate were identified and discussed. These include: the increase of dissolved compounds due to cell rupture, exposition of surface areas previously inaccessible for microbial degradation, and alteration of the sample structure such as the lignin-cellulose arrangements.

Degradation of phenanthrene and pyrene in soil slurry reactors with immobilized bacteria Zoogloea sp.

The environmental fate of polycyclic aromatic hydrocarbons (PAHs) in soils is motivated by their wide distribution, high persistence, and potentially deleterious effect on human health. Polycyclic aromatic hydrocarbons constitute the largest group of environmental contaminants released in the environment. Therefore, the potential biodegradation of these compounds is of vital importance. A biocarrier suitable for the colonization by micro-organisms for the purpose of purifying soil contaminated by polycyclic aromatic hydrocarbons was developed. The optimized composition of the biocarrier was polyvinyl alcohol (PVA) 10%, sodium alginate (SA) 0.5%, and powdered activated carbon (PAC) 5%. There was no observable cytotoxicity of biocarriers on immobilized cells and a viable cell population of 1.86 × 10¹⁰ g^–1 was maintained for immobilized bacterium. Biocarriers made from chemical methods had a higher biodegradation but lower mechanical strengths. Immobilized bacterium Zoogloea sp. had an ideal capability of biodegradation for phenanthrene and pyrene over a relative wide concentration range. The study results showed that the biodegradation of phenanthrene and pyrene reached 87.0 and 75.4%, respectively, by using the optimal immobilized method of Zoogloea sp. cultivated in a sterilized soil. Immobilized Zoogloea sp. was found to be effective for biodegrading the soil contaminated with phenanthrene and pyrene. Even in "natural" (unsterilized) soil, the biodegradation of phenanthrene and pyrene using immobilized Zoogloea sp. reached 85.0 and 67.1%, respectively, after 168 h of cultivation, more than twice that achieved if the cells were not immobilized on the biocarrier. Therefore, the immobilization technology enhanced the competitive ability of introduced micro-organisms and represents an effective method for the biotreatment of soil contaminated with phenanthrene and pyrene.

Granular Activated Carbon (GAC) adsorption in tertiary wastewater treatment : experiments and models

Wastewater treatment has always been a major concern in the developed countries. Over the last few decades, activated carbon adsorption has gained importance as an alternative tertiary wastewater treatment and purification process. In this study, granular activated carbon (GAC) adsorption was evaluated in terms of total organic carbon (TOC) removal from low strength synthetic wastewater. This paper provides details on adsorption experiments conducted on synthetic wastewater to develop suitable adsorption isotherms. Although the inorganics used in the synthetic wastewater solution had an overall unfavourable effect on adsorption of organics, the GAC adsorption system was found to be effective in removing TOC from the wastewater. This study showed that equation of state (EOS) theory was able to fit the adsorption isotherm results more precisely than the most commonly used Freundlich isotherm. Biodegradation of the organics with time was the most crucial and important aspect of the system and it was taken into account in determining the isotherm parameters. Initial organic concentration of the wastewater was the determining factor of the model parameters, and hence the isotherm parameters were determined covering a wide range of initial organic concentrations of the wastewater. As such, the isotherm parameters derived using the EOS theory could predict the batch adsorption and fixed bed adsorption results of the multi-component system successfully. The isotherm parameters showed a significant effect on the determination of the mass transfer coefficients in batch and fixed bed systems.

Recent innovations in silk biomaterials

Silk contains a fibre forming protein, fibroin, which is biocompatible, particularly after removing the potentially immunogenic non-fibroin proteins. Silk can be engineered into a wide range of materials with diverse morphologies. Moreover, it is possible to regenerate fibroin with a desired amount of crystallinity, so that the biodegradation of silk materials can be controlled. These advantages have sparked new interest in the use of silk fibroin for biomedical applications, including tissue engineering scaffolds and carriers for sustained release of biologically active molecules. This article summarizes the current research related to the formation of silk materials with different morphologies, their biocompatibility, and examples of their biomedical applications. Recent work on the preparation of silk particles by mechanical milling and their applications in silk composite scaffolds is also discussed.