The microbial ecology of sulphidogenic lignocellulose degradation
- Authors: Clarke, Anna Maria
- Date: 2007
- Subjects: Microbial ecology , Lignocellulose , Sulfides , Lignin , Lignocellulose -- Biodegradation , Mines and mineral resources -- Waste disposal , Acid mine drainage
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4094 , http://hdl.handle.net/10962/d1008181
- Description: Acid mine drainage is a well known environmental pollutant, not only in South Africa, but throughout the world, and the use of microbial processes in the treatment of these wastes has been the subject of investigation over past decades. Lignocellulose packed-bed reactors have been used in passive treatment systems, and, although effective initially, they show early decline in performance while the packing material remains largely un-utilized. Little is known about this phenomenon which remains a severe constraint in the development of efficient passive mine water treatment systems. It has been proposed that the degradation pathways of the complex lignocellulose substrate may be limited in some way in these systems during the manifestation of this effect. This study has addressed the problem using a molecular microbial ecology methodology in an attempt to relate trophic functions of the microbial population to the physico-chemical data of the system. A field-scale lignocellulose packed-bed reactor located at Vryheid Coronation Colliery (Northern Kwa-Zulu Natal province, South Africa) was monitored for six years and the results showed the classic profile of performance decline related to a slowdown in sulphate reduction and alkalinity production. The reactor was decommissioned , comprehensive samples were collected along the depth profile and the microbial populations investigated by means of 16S rRNA gene methodology. The population was found to include cellulolytic Clostridia spp., CytophagaIFlavobacterlBacteroidetes, Sphingomonadaceae and as yet uncultured microorganisms related to microbiota identified in the rumen and termite gut. These are all known to be involved as primary fermenters of cellulose. Oesulphosporosinus was present as sulphate reducer. A comparison of substrata sampling and population distribution suggested that spatial and temporal gradients within the system may become established over the course of its operation. Based on these findings, a laboratory-scale reactor was constructed to simulate the performance of the packed-bed reactor under controlled experimental conditions. The laboratory-scale reactor was operated for 273 days and showed comparable performance to that in the field in both biomolecular and physicochemical data. Clearly defined trophic niches were observed. These results suggested that a sequence of events does occur in lignocellulose degradation over time. Based on the spatial and temporal column studies, a descriptive model was proposed to account for these events. It was found that fermentative organisms predominate in the inlet zone of the system using easily extractable compounds from the wood, thus providing feedstock for sulphate reduction occurring in the succeeding compartments. Production of sulphide and alkalinity appears to be involved in the enhancement of lignin degradation and this, in turn, appears to enhance access to the cellulose fraction. However, once the readily extractables are exhausted, the decline in sulphide and alkalinity production leads inexorably to a decline in the overall performance of the system as a sulphate reducing unit operation. These observations led to the proposal that with the addition of a limited amount of a readily available carbon source, such as molasses, in the initial zone of the the reactor, the ongoing generation of sulphide would be sustained and this in turn would sustain the microbial attack on the lignocellulose complex. This proposal was tested in scale-up studies and positive results indicate that the descriptive model may, to some extent, provide an account of events occurring in these systems. The work on sustaining lignocellulose degradation through the maintenance of sulphate reduction in the initial stages of the reactor flow path has led to the development of the Degrading Packed-bed Reactor concept and that, has subsequently been successfully evaluated in the field.
- Full Text:
- Date Issued: 2007
- Authors: Clarke, Anna Maria
- Date: 2007
- Subjects: Microbial ecology , Lignocellulose , Sulfides , Lignin , Lignocellulose -- Biodegradation , Mines and mineral resources -- Waste disposal , Acid mine drainage
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4094 , http://hdl.handle.net/10962/d1008181
- Description: Acid mine drainage is a well known environmental pollutant, not only in South Africa, but throughout the world, and the use of microbial processes in the treatment of these wastes has been the subject of investigation over past decades. Lignocellulose packed-bed reactors have been used in passive treatment systems, and, although effective initially, they show early decline in performance while the packing material remains largely un-utilized. Little is known about this phenomenon which remains a severe constraint in the development of efficient passive mine water treatment systems. It has been proposed that the degradation pathways of the complex lignocellulose substrate may be limited in some way in these systems during the manifestation of this effect. This study has addressed the problem using a molecular microbial ecology methodology in an attempt to relate trophic functions of the microbial population to the physico-chemical data of the system. A field-scale lignocellulose packed-bed reactor located at Vryheid Coronation Colliery (Northern Kwa-Zulu Natal province, South Africa) was monitored for six years and the results showed the classic profile of performance decline related to a slowdown in sulphate reduction and alkalinity production. The reactor was decommissioned , comprehensive samples were collected along the depth profile and the microbial populations investigated by means of 16S rRNA gene methodology. The population was found to include cellulolytic Clostridia spp., CytophagaIFlavobacterlBacteroidetes, Sphingomonadaceae and as yet uncultured microorganisms related to microbiota identified in the rumen and termite gut. These are all known to be involved as primary fermenters of cellulose. Oesulphosporosinus was present as sulphate reducer. A comparison of substrata sampling and population distribution suggested that spatial and temporal gradients within the system may become established over the course of its operation. Based on these findings, a laboratory-scale reactor was constructed to simulate the performance of the packed-bed reactor under controlled experimental conditions. The laboratory-scale reactor was operated for 273 days and showed comparable performance to that in the field in both biomolecular and physicochemical data. Clearly defined trophic niches were observed. These results suggested that a sequence of events does occur in lignocellulose degradation over time. Based on the spatial and temporal column studies, a descriptive model was proposed to account for these events. It was found that fermentative organisms predominate in the inlet zone of the system using easily extractable compounds from the wood, thus providing feedstock for sulphate reduction occurring in the succeeding compartments. Production of sulphide and alkalinity appears to be involved in the enhancement of lignin degradation and this, in turn, appears to enhance access to the cellulose fraction. However, once the readily extractables are exhausted, the decline in sulphide and alkalinity production leads inexorably to a decline in the overall performance of the system as a sulphate reducing unit operation. These observations led to the proposal that with the addition of a limited amount of a readily available carbon source, such as molasses, in the initial zone of the the reactor, the ongoing generation of sulphide would be sustained and this in turn would sustain the microbial attack on the lignocellulose complex. This proposal was tested in scale-up studies and positive results indicate that the descriptive model may, to some extent, provide an account of events occurring in these systems. The work on sustaining lignocellulose degradation through the maintenance of sulphate reduction in the initial stages of the reactor flow path has led to the development of the Degrading Packed-bed Reactor concept and that, has subsequently been successfully evaluated in the field.
- Full Text:
- Date Issued: 2007
Preparation and evaluation of Lignocellulose-Montmorillonite nanocomposites for the adsorption of some heavy metals and organic dyes from aqueous solution
- Authors: Bunhu, Tavengwa
- Date: 2011
- Subjects: Lignocellulose , Lignocellulose -- Biodegradation , Water -- Purification , Adsorption , Separation (Technology) , Dyes and dyeing , Montmorillonite
- Language: English
- Type: Thesis , Doctoral , PhD (Chemistry)
- Identifier: vital:11333 , http://hdl.handle.net/10353/535 , Lignocellulose , Lignocellulose -- Biodegradation , Water -- Purification , Adsorption , Separation (Technology) , Dyes and dyeing , Montmorillonite
- Description: The need to reduce the cost of adsorption technology has led scientists to explore the use of many low cost adsorbents especially those from renewable resources. Lignocellulose and montmorillonite clay have been identified as potentially low cost and efficient adsorbent materials for the removal of toxic heavy metals and organic substances from contaminated water. Montmorillonite clay has good adsorption properties and the potential for ion exchange. Lignocellulose possesses many hydroxyl, carbonyl and phenyl groups and therefore, both montmorillonite and lignocellulose are good candidates for the development of effective and low cost adsorbents in water treatment and purification. The aim of this study was to prepare composite materials based on lignocellulose and montmorillonite clay and subsequently evaluate their efficacy as adsorbents for heavy metal species and organic pollutants in aqueous solution. It was also important to assess the adsorption properties of the modified individual (uncombined) lignocellulose and montmorillonite. Lignocellulose and sodium-exchanged montmorillonite (NaMMT) clay were each separately modified with methyl methacrylate (MMA), methacrylic acid (MAA) and methacryloxypropyl trimethoxysilane (MPS) and used as adsorbents for the removal of heavy metals and dyes from aqueous solution. The lignocellulose and NaMMT were modified with MMA, MAA and MPS through free radical graft polymerisation and/or condensation reactions. NaMMT was also modified through Al-pillaring to give AlpMMT. The materials were characterised by fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and small angle X-ray scattering (SAXS) and characterisation results showed that the modification of the montmorillonite with MAA, MMA and MPS was successful. The modified lignocellulose and montmorillonite materials were evaluated for the adsorption of heavy metal ions (Cd2+ and Pb2+) from aqueous solution by the batch method. The adsorption isotherms and kinetics of both Cd2+ and Pb2+ onto the NaMMT clay, AlpMMT and lignocellulose materials are presented. The Langmuir isotherm was found to be the best fit for the adsorption of both heavy metals onto all the adsorbents. AlpMMT showed very poor uptake for heavy metals (both Cd2+ and Pb2+). PMMAgMMT, PMAAgMMT, PMAAgLig and PMPSgLig showed improved adsorption for both heavy metals. The mechanism of heavy metal adsorption onto the adsorbents was best represented by the pseudo second-order kinetic model. PMPSgLig, NaMMT and AlpMMT showed relatively high adsorption capacities for methyl orange, while the adsorption of neutral red was comparable for almost all the adsorbents. Neither the Langmuir model nor the Freundlich model was found to v adequately describe the adsorption process of dyes onto all the adsorbents. The pseudo second-order model was found to be the best fit to describe the adsorption mechanism of both dyes onto all the adsorbents. The modification of lignocellulose and montmorillonite with suitable organic groups can potentially produce highly effective and efficient adsorbents for the removal of both heavy metals and dyes from contaminated water. Novel adsorbent composite materials based on lignocellulose and montmorillonite clay (NaMMT) were also prepared and evaluated for the removal of pollutants (dyes and heavy metals) from aqueous solution. The lignocellulose-montmorillonite composites were prepared by in situ intercalative polymerisation, using methyl methacrylate, methacrylic acid and methacryloxypropyl trimethoxysilane (MPS) as coupling agents. The composite materials were characterised by FTIR, TGA, TEM and SAXS. SAXS diffractograms showed intercalated nanocomposites of PMMAgLig-NaMMT and PMAAgLig-NaMMT, whereas PMPSgLig-NaMMT showed a phase-separated composite and the same results were confirmed by TEM. The lignocellulose-montmorillonite composites were assessed for their adsorption properties for heavy metal ions (Cd2+ and Pb2+) and dyes (methyl orange and neutral red) from aqueous solution. Among these composite materials, only PMAAgLig-NaMMT showed a marked increase in the uptake of both Cd2+ and Pb2+ relative to lignocellulose and montmorillonite when used independently. The adsorption data were fitted to the Langmuir and Freundlich isotherms, as well as to the pseudo first-order and pseudo second-order kinetic models. The data were best described by the Langmuir isotherm and the pseudo second-order kinetic model. On the adsorption of dyes, only PMPSgLig-NaMMT showed enhanced adsorption of methyl orange (MetO) compared with lignocellulose and montmorillonite separately. The enhanced adsorption was attributed to the synergistic adsorption due to the presence of MPS, lignocellulose and NaMMT. Competitive adsorption studies were carried out from binary mixtures of MetO and Cd2+ or Pb2+ in aqueous solution. The adsorption process of MetO onto the composite material was found to follow the Freundlich adsorption model, while the mechanism of adsorption followed both the pseudo first-order and pseudo second-order models. This particular composite can be used for the simultaneous adsorption of both heavy metals and organic dyes from contaminated water. The adsorption of neutral red to the composite materials was comparable and the pseudo second-order kinetic model best described the adsorption mechanism.
- Full Text:
- Date Issued: 2011
- Authors: Bunhu, Tavengwa
- Date: 2011
- Subjects: Lignocellulose , Lignocellulose -- Biodegradation , Water -- Purification , Adsorption , Separation (Technology) , Dyes and dyeing , Montmorillonite
- Language: English
- Type: Thesis , Doctoral , PhD (Chemistry)
- Identifier: vital:11333 , http://hdl.handle.net/10353/535 , Lignocellulose , Lignocellulose -- Biodegradation , Water -- Purification , Adsorption , Separation (Technology) , Dyes and dyeing , Montmorillonite
- Description: The need to reduce the cost of adsorption technology has led scientists to explore the use of many low cost adsorbents especially those from renewable resources. Lignocellulose and montmorillonite clay have been identified as potentially low cost and efficient adsorbent materials for the removal of toxic heavy metals and organic substances from contaminated water. Montmorillonite clay has good adsorption properties and the potential for ion exchange. Lignocellulose possesses many hydroxyl, carbonyl and phenyl groups and therefore, both montmorillonite and lignocellulose are good candidates for the development of effective and low cost adsorbents in water treatment and purification. The aim of this study was to prepare composite materials based on lignocellulose and montmorillonite clay and subsequently evaluate their efficacy as adsorbents for heavy metal species and organic pollutants in aqueous solution. It was also important to assess the adsorption properties of the modified individual (uncombined) lignocellulose and montmorillonite. Lignocellulose and sodium-exchanged montmorillonite (NaMMT) clay were each separately modified with methyl methacrylate (MMA), methacrylic acid (MAA) and methacryloxypropyl trimethoxysilane (MPS) and used as adsorbents for the removal of heavy metals and dyes from aqueous solution. The lignocellulose and NaMMT were modified with MMA, MAA and MPS through free radical graft polymerisation and/or condensation reactions. NaMMT was also modified through Al-pillaring to give AlpMMT. The materials were characterised by fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and small angle X-ray scattering (SAXS) and characterisation results showed that the modification of the montmorillonite with MAA, MMA and MPS was successful. The modified lignocellulose and montmorillonite materials were evaluated for the adsorption of heavy metal ions (Cd2+ and Pb2+) from aqueous solution by the batch method. The adsorption isotherms and kinetics of both Cd2+ and Pb2+ onto the NaMMT clay, AlpMMT and lignocellulose materials are presented. The Langmuir isotherm was found to be the best fit for the adsorption of both heavy metals onto all the adsorbents. AlpMMT showed very poor uptake for heavy metals (both Cd2+ and Pb2+). PMMAgMMT, PMAAgMMT, PMAAgLig and PMPSgLig showed improved adsorption for both heavy metals. The mechanism of heavy metal adsorption onto the adsorbents was best represented by the pseudo second-order kinetic model. PMPSgLig, NaMMT and AlpMMT showed relatively high adsorption capacities for methyl orange, while the adsorption of neutral red was comparable for almost all the adsorbents. Neither the Langmuir model nor the Freundlich model was found to v adequately describe the adsorption process of dyes onto all the adsorbents. The pseudo second-order model was found to be the best fit to describe the adsorption mechanism of both dyes onto all the adsorbents. The modification of lignocellulose and montmorillonite with suitable organic groups can potentially produce highly effective and efficient adsorbents for the removal of both heavy metals and dyes from contaminated water. Novel adsorbent composite materials based on lignocellulose and montmorillonite clay (NaMMT) were also prepared and evaluated for the removal of pollutants (dyes and heavy metals) from aqueous solution. The lignocellulose-montmorillonite composites were prepared by in situ intercalative polymerisation, using methyl methacrylate, methacrylic acid and methacryloxypropyl trimethoxysilane (MPS) as coupling agents. The composite materials were characterised by FTIR, TGA, TEM and SAXS. SAXS diffractograms showed intercalated nanocomposites of PMMAgLig-NaMMT and PMAAgLig-NaMMT, whereas PMPSgLig-NaMMT showed a phase-separated composite and the same results were confirmed by TEM. The lignocellulose-montmorillonite composites were assessed for their adsorption properties for heavy metal ions (Cd2+ and Pb2+) and dyes (methyl orange and neutral red) from aqueous solution. Among these composite materials, only PMAAgLig-NaMMT showed a marked increase in the uptake of both Cd2+ and Pb2+ relative to lignocellulose and montmorillonite when used independently. The adsorption data were fitted to the Langmuir and Freundlich isotherms, as well as to the pseudo first-order and pseudo second-order kinetic models. The data were best described by the Langmuir isotherm and the pseudo second-order kinetic model. On the adsorption of dyes, only PMPSgLig-NaMMT showed enhanced adsorption of methyl orange (MetO) compared with lignocellulose and montmorillonite separately. The enhanced adsorption was attributed to the synergistic adsorption due to the presence of MPS, lignocellulose and NaMMT. Competitive adsorption studies were carried out from binary mixtures of MetO and Cd2+ or Pb2+ in aqueous solution. The adsorption process of MetO onto the composite material was found to follow the Freundlich adsorption model, while the mechanism of adsorption followed both the pseudo first-order and pseudo second-order models. This particular composite can be used for the simultaneous adsorption of both heavy metals and organic dyes from contaminated water. The adsorption of neutral red to the composite materials was comparable and the pseudo second-order kinetic model best described the adsorption mechanism.
- Full Text:
- Date Issued: 2011
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