Experiments and modelling of phenanthrene biodegradation in the aqueous phase by a mixed culture

Pollution by polycyclic aromatic hydrocarbons(PAHs) is widespread due to unsuitable disposal of industrial waste. They are mostly defined as priority pollutants by environmental protection authorities worldwide. Phenanthrene, a typical PAH, was selected as the target in this paper. The PAH-degrading mixed culture, named ZM, was collected from a petroleum contaminated river bed. This culture was injected into phenanthrene solutions at different concentrations to quantify the biodegradation process. Results show near-complete removal of phenanthrene in three days of biodegradation if the initial phenanthrene concentration is low. When the initial concentration is high, the removal rate is increased but 20%-40% of the phenanthrene remains at the end of the experiment. The biomass shows a peak on the third day due to the combined effects of microbial growth and decay. Another peak is evident for cases with a high initial concentration, possibly due to production of an intermediate metabolite. The pH generally decreased during biodegradation because of the production of organic acid. Two phenomenological models were designed to simulate the phenanthrene biodegradation and biomass growth. A relatively simple model that does not consider the intermediate metabolite and its inhibition of phenanthrene biodegradation cannot fit the observed data. A modified Monod model that considered an intermediate metabolite (organic acid) and its inhibiting reversal effect reasonably depicts the experimental results.

Constitutive model for long term municipal solid waste mechanical behavior

This paper presents some improvements in the model proposed by Machado et al. [Machado SL, Carvalho MF, Vilar OM. Constitutive model for municipal solid waste. J Geotech Geoenviron Eng ASCE 2002; 128(11):940-51] now considering the influence of biodegradation of organic matter in the mechanical behavior of municipal solid waste. The original framework considers waste as composed of two component groups; fibers and organic paste. The particular laws of behavior are assessed for each component group and then coupled to represent waste behavior. The improvements introduced in this paper take into account the changes in the properties of fibers and mass loss due to organic matter depletion over time. Mass loss is indirectly calculated considering the MSW gas generation potential through a first order decay model. It is shown that as the biodegradation process occurs the proportion of fibers increases, however, they also undergo a degradation process which tends to reduce their ultimate tensile stress and Young modulus. The way these changes influence the behavior of MSW is incorporated in the final framework which captures the main features of the MSW stress-strain behavior under different loading conditions. (C) 2007 Elsevier Ltd. All rights reserved.

Ironporphyrin immobilized onto montmorillonite as a bimimetical model for azo dye oxidation

In this work, we studied the oxidation of the azo dye Disperse orange 3 (DO3) by hydrogen peroxide, catalyzed by 5,10,15, 20-tetrakis(4-N-methylpyridyl)porphyrin iron(III) chloride immobilized onto montmorillonite K10, FeP-K10. Results showed that the FeP-K10/H2O2 system is efficient for discoloration of the DO3 dye, especially at pH 3.0. The catalyst was shown to be relatively stable and could be recycled many times, leading to good yields. DO3 oxidation products were analyzed by gas chromatography and mass spectrometry, being 4-nitroaniline the main product. Tert-butylhydroperoxide and iodosylbenzene were also used as oxidants, giving rise to 4-nitroaniline as product too. The studied system is a good biomimetic model of oxidative enzymes, being a promising discoloring agent for azo dyes. (C) 2007 Elsevier Ltd. All rights reserved.

Three-dimensional model for multi-component reactive transport with variable density groundwater flow

PHWAT is a new model that couples a geochemical reaction model (PHREEQC-2) with a density-dependent groundwater flow and solute transport model (SEAWAT) using the split-operator approach. PHWAT was developed to simulate multi-component reactive transport in variable density groundwater flow. Fluid density in PHWAT depends not on only the concentration of a single species as in SEAWAT, but also the concentrations of other dissolved chemicals that can be subject to reactive processes. Simulation results of PHWAT and PHREEQC-2 were compared in their predictions of effluent concentration from a column experiment. Both models produced identical results, showing that PHWAT has correctly coupled the sub-packages. PHWAT was then applied to the simulation of a tank experiment in which seawater intrusion was accompanied by cation exchange. The density dependence of the intrusion and the snow-plough effect in the breakthrough curves were reflected in the model simulations, which were in good agreement with the measured breakthrough data. Comparison simulations that, in turn, excluded density effects and reactions allowed us to quantify the marked effect of ignoring these processes. Next, we explored numerical issues involved in the practical application of PHWAT using the example of a dense plume flowing into a tank containing fresh water. It was shown that PHWAT could model physically unstable flow and that numerical instabilities were suppressed. Physical instability developed in the model in accordance with the increase of the modified Rayleigh number for density-dependent flow, in agreement with previous research. (c) 2004 Elsevier Ltd. All rights reserved.

Applied models to biodegradation kinetics of lubricant and vegetable oils in wastewater

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Phenol biodegradation by a microbial consortium: application of artificial neural network (ANN) modelling

In this study, an effective microbial consortium for the biodegradation of phenol was grown under different operational conditions, and the effects of phosphate concentration (1.4 g L-1, 2.8 g L-1, 4.2 g L-1), temperature (25 degrees C, 30 degrees C, 35 degrees C), agitation (150 rpm, 200 rpm, 250 rpm) and pH (6, 7, 8) on phenol degradation were investigated, whereupon an artificial neural network (ANN) model was developed in order to predict degradation. The learning, recall and generalization characteristics of neural networks were studied using data from the phenol degradation system. The efficiency of the model generated by the ANN was then tested and compared with the experimental results obtained. In both cases, the results corroborate the idea that aeration and temperature are crucial to increasing the efficiency of biodegradation.

Halogenated aliphatic and aromatic aerobic biodegradation via direct metabolism and cometabolism: batch and continuous tests

In this thesis the application of biotechnological processes based on microbial metabolic degradation of halogenated compound has been investigated. Several studies showed that most of these pollutants can be biodegraded by single bacterial strains or mixed microbial population via aerobic direct metabolism or cometabolism using as a growth substrates aromatic or aliphatic hydrocarbons. The enhancement of two specific processes has been here object of study in relation with its own respective scenario described as follow: 1st) the bioremediation via aerobic cometabolism of soil contaminated by a high chlorinated compound using a mixed microbial population and the selection and isolation of consortium specific for the compound. 2nd) the implementation of a treatment technology based on direct metabolism of two pure strains at the exact point source of emission, preventing dilution and contamination of large volumes of waste fluids polluted by several halogenated compound minimizing the environmental impact. In order to verify the effect of these two new biotechnological application to remove halogenated compound and purpose them as a more efficient alternative continuous and batch tests have been set up in the experimental part of this thesis. Results obtained from the continuous tests in the second scenario have been supported by microbial analysis via Fluorescence in situ Hybridisation (FISH) and by a mathematical model of the system. The results showed that both process in its own respective scenario offer an effective solutions for the biological treatment of chlorinate compound pollution.

Perchlorate remediation technologies: A systematic review of solely biodegradation versus a combination of ion-exchange and biodegradation technologies

A systematic review was performed in order to evaluate perchlorate remediation technologies. The two included technologies were ion-exchange concerted with biodegradation and solely biodegradation. A meta-analysis was completed and subsequently, a regression model was formed to conduct a degradation rate analysis and to depict the association between rate and various dependent variables (salinity/sali, nitrate concentration/nitc and carbon source concentration/csou). The outcome of the model analysis suggested that salt concentration did have an effect on the degradation rate in the ion-exchange process and that with a salt concentration greater than or equal to 18.6 g/L, the biodegradation process will produce a greater reduction of perchlorate than ion-exchange concerted with biodegradation. However, when a t-test examined the difference in perchlorate degradation rate between the two cleanup methods, there was no significant difference seen (p=0.7351, α = 0.05).^

THE CHLOREX TREATABILITY STUDY: ENVIRONMENTAL FATE IN FACULTATIVE ANAEROBIC AND AEROBIC WASTE STABILIZATION PONDS (BIODEGRADATION, VOLATILIZATION, SORPTION, PRIORITY POLLUTANTS)

The efficacy of waste stabilization lagoons for the treatment of five priority pollutants and two widely used commercial compounds was evaluated in laboratory model ponds. Three ponds were designed to simulate a primary anaerobic lagoon, a secondary facultative lagoon, and a tertiary aerobic lagoon. Biodegradation, volatilization, and sorption losses were quantified for bis(2-chloroethyl) ether, benzene, toluene, naphthalene, phenanthrene, ethylene glycol, and ethylene glycol monoethyl ether. A statistical model using a log normal transformation indicated biodegradation of bis(2-chloroethyl) ether followed first-order kinetics. Additionally, multiple regression analysis indicated biochemical oxygen demand was the water quality variable most highly correlated with bis(2-chloroethyl) ether effluent concentration. ^

Biodegradation of naphthalene-2-sulfonic acid present in tannery wastewater by bacterial isolates Arthrobacter sp 2AC and Comamonas sp 4BC

Two bacterial strains, 2AC and 4BC, both capable of utilizing naphthalene-2-sulfonic acid (2-NSA) as a sole source of carbon, were isolated from activated sludges previously exposed to tannery wastewater. Enrichments were carried out in mineral salt medium (MSM) with 2-NSA as the sole carbon source. 16S rDNA sequencing analysis indicated that 2AC is an Arthrobacter sp. and 4BC is a Comamonas sp. Within 33 h, both isolates degraded 100% of 2-NSA in MSM and also 2-NSA in non-sterile tannery wastewater. The yield coefficient was 0.33 g biomass dry weight per gram of 2-NSA. A conceptual model, which describes the aerobic transformation of organic matter, was used for interpreting the biodegradation kinetics of 2-NSA. The half-lives for 2-NSA, at initial concentrations of 100 and 500 mg/l in MSM, ranged from 20 h (2AC) to 26 h (4BC) with lag-phases of 8 h (2AC) and 12 h (4BC). The carbon balance indicates that 75-90% of the initial TOC (total organic carbon) was mineralized, 5-20% remained as DOC (dissolved organic carbon) and 3-10% was biomass carbon. The principal metabolite of 2-NSA biodegradation (in both MSM and tannery wastewater) produced by Comamonas sp. 4BC had a MW of 174 and accounted for the residual DOC (7.0-19.0% of the initial TOC and 66% of the remaining TOC). Three to ten percent of the initial TOC (33% of the remaining TOC) was associated with biomass. The metabolite was not detected when Arthrobacter sp. 2AC was used, and a lower residual DOC and biomass carbon were recorded. This suggests that the two strains may use different catabolic pathways for 2-NSA degradation. The rapid biodegradation of 2-NSA (100 mg/l) added to non-sterile tannery wastewater (total 2-NSA, 105 mg/l) when inoculated with either Arthrobacter 2AC or Comamonas 4BC showed that both strains were able to compete with the indigenous microorganisms and degrade 2-NSA even in the presence of alternate carbon sources (DOC in tannery wastewater = 91 mg/l). The results provide information useful for the rational design of bioreactors for tannery wastewater treatment.

A dynamic model for the activated sludge treatment of coke oven effluents

This is an Inter-Disciplinary Higher Degree (IHD) thesis about Water Pollution Control in the Iron and Steel Industry. After examining the compositions, and various treatment methods, for the major effluent streams from a typical Integrated Iron and Steel works, it was decided to concentrate investigative work on the activated-sludge treatment of coke-oven effluents. A mathematical model of this process was developed in an attempt to provide a tool for plant management that would enable improved performance, and enhanced control of Works Units. The model differs from conventional models in that allowance is made for the presence of two genera of microorganisms, each of which utilises a particular type of substrate as its energy source. Allowance is also made for the inhibitive effect of phenol on thiocyanate biodegradation, and for the self-toxicity of the bacteria when present in a high substrate concentration environment. The enumeration of the kinetic characteristics of the two groups of micro-organisms was shown to be of major importance. Laboratory experiments were instigated in an attempt to determine accurate values of these coefficients. The use of the Suspended Solids concentration was found to be too insensitive a measure of viable active mass. Other measures were investigated, and Adenosine Triphosphate concentration was chosen as the most effective measure of bacterial populations. Using this measure, a model was developed for phenol biodegradation from experimental results which implicated the possibility of storage of substate prior to metabolism. A model for thiocyanate biodegradation was also developed, although the experimental results indicate that much work is still required in this area.

Trichloroethylene fate and transport studies and biodegradation kinetics in the saturated zone

Permeable reactive barriers (PRB) are constructed from soil solid amendments to support the growth of bacteria that are capable of degrading organic contaminants. The objective of this study was to identify low-cost soil solid amendments that could retard the movement of trichloroethylene (TCE) while serving as long-lived carbon sources to foster its biodegradation in shallow groundwater through the use of a PRB. The natural amendments high in organic carbon content such as eucalyptus mulch, compost, wetland peat, organic humus were compared based on their geophysical characteristics, such as pHw, porosity and total organic carbon (TOC), and as well as TCE sorption potentials. The pHw values were within neutral range except for pine bark mulch and wetland peat. All other geophysical characteristics of the amendments showed suitability for use in a PRB. While the Freundlich model showed better fit for compost and pine bark mulch, the linear sorption model was adequate for eucalyptus mulch, wetland peat and Everglades muck within the concentration range studied (0.2-0.8 mg/L TCE). According to these results, two composts and eucalyptus mulch were selected for laboratory column experiments to evaluate their effectiveness at creating and maintaining conditions suitable for TCE anaerobic dechlorination. The columns were monitored for pH, ORP, TCE degradation, longevity of nutrients and soluble TOC to support TCE dechlorination. Native bacteria in the columns had the ability to convert TCE to DCEs; however, the inoculation with the TCE-degrading culture greatly increased the rate of biodegradation. This caused a significant increase in by-product concentration, mostly in the form of DCEs and VC followed by a slow degradation to ethylene. Of the tested amendments eucalyptus mulch was the most effective at supporting the TCE dechlorination. The experimental results of TCE sequential dechlorination took place in eucalyptus mulch and commercial compost from Savannah River Site columns were then simulated using the Hydrus-1D model. The simulations showed good fit with the experimental data. The results suggested that sorption and degradation were the dominant fate and transport mechanisms for TCE and DCEs in the column, supporting the use of these amendments in a permeable reactive barrier to remediate the TCE.

DEVELOPMENT OF A 2-DIMENSIONAL FINITE VOLUME MODEL TO ASSESS HYDRODYNAMIC AND MICROBIAL CONTROLS ON DNAPL DISSOLUTION AND DETOXIFICATION

Tetrachloroethene (PCE) and trichloroethene (TCE) form dense non-aqueous phase liquids (DNAPLs), which are persistent groundwater contaminants. DNAPL dissolution can be "bioenhanced" via dissolved contaminant biodegradation at the DNAPL-water interface. This research hypothesized that: (1) competitive interactions between different dehalorespiring strains can significantly impact the bioenhancement effect, and extent of PCE dechlorination; and (2) hydrodynamics will affect the outcome of competition and the potential for bioenhancement and detoxification. A two-dimensional coupled flowtransport model was developed, with a DNAPL pool source and multiple microbial species. In the scenario presented, Dehalococcoides mccartyi 195 competes with Desulfuromonas michiganensis for the electron acceptors PCE and TCE. Simulations under biostimulation and low velocity (vx) conditions suggest that the bioenhancement with Dsm. michiganensis alone was modestly increased by Dhc. mccartyi 195. However, the presence of Dhc. mccartyi 195 enhanced the extent of PCE transformation. Hydrodynamic conditions impacted the results by changing the dominant population under low and high vx conditions.

Integrated Proteomics Identified Up-regulated Focal Adhesion-mediated Proteins In Human Squamous Cell Carcinoma In An Orthotopic Murine Model.

Understanding the molecular mechanisms of oral carcinogenesis will yield important advances in diagnostics, prognostics, effective treatment, and outcome of oral cancer. Hence, in this study we have investigated the proteomic and peptidomic profiles by combining an orthotopic murine model of oral squamous cell carcinoma (OSCC), mass spectrometry-based proteomics and biological network analysis. Our results indicated the up-regulation of proteins involved in actin cytoskeleton organization and cell-cell junction assembly events and their expression was validated in human OSCC tissues. In addition, the functional relevance of talin-1 in OSCC adhesion, migration and invasion was demonstrated. Taken together, this study identified specific processes deregulated in oral cancer and provided novel refined OSCC-targeting molecules.

Electronic And Structural Study Of Pt-modified Au Vicinal Surfaces: A Model System For Pt-au Catalysts.

Two single crystalline surfaces of Au vicinal to the (111) plane were modified with Pt and studied using scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS) in ultra-high vacuum environment. The vicinal surfaces studied are Au(332) and Au(887) and different Pt coverage (θPt) were deposited on each surface. From STM images we determine that Pt deposits on both surfaces as nanoislands with heights ranging from 1 ML to 3 ML depending on θPt. On both surfaces the early growth of Pt ad-islands occurs at the lower part of the step edge, with Pt ad-atoms being incorporated into the steps in some cases. XPS results indicate that partial alloying of Pt occurs at the interface at room temperature and at all coverage, as suggested by the negative chemical shift of Pt 4f core line, indicating an upward shift of the d-band center of the alloyed Pt. Also, the existence of a segregated Pt phase especially at higher coverage is detected by XPS. Sample annealing indicates that the temperature rise promotes a further incorporation of Pt atoms into the Au substrate as supported by STM and XPS results. Additionally, the catalytic activity of different PtAu systems reported in the literature for some electrochemical reactions is discussed considering our findings.