title: Identifying iron-binding antioxidants in New Zealand honeydew honey

authors: Omar, Syaliza Binti

subjects: antioxidants

abstract: Iron is an essential element for human physiological function. However, excess free iron could participate in the formation of reactive oxygen species via the Fenton reaction and is thought to be the primary mechanism for the pathogenesis of diseases related to iron excess. Prevention of the oxidative damage caused by reactive oxygen species can be accomplished by using selective iron-binding compounds. Beech honeydew honey has been found to have an exceptionally high level of iron-binding antioxidant activity. Due to that, the focus of the research in this thesis has been to isolate the compound(s) responsible for the activity and identify their molecular structure.
The stability of the antioxidants on exposure to heat and high and low pH was investigated to get a better understanding of the conditions which could be used when developing suitable techniques for the isolation of the iron-binding antioxidants. 
The isolation of the antioxidants was first attempted with XAD-2 resin. The results of solid phase extraction using XAD-2 resin showed that the activity is mainly found in the honey effluent, the fraction not retarded by the resin, indicating that hydrophilic components contributed to the iron-binding antioxidant activity. The phenolic compounds isolated from this resin did not exhibit iron-binding antioxidant activity.
When the antioxidants could not be isolated from the XAD-2 resin, size exclusion chromatography was used to separate the honey components based on their molecular sizes. The technique was successsful in separating antioxidants from free sugars in honey. However, size exclusion chromatography did not give any significant information regarding the identity of the antioxidants. Thus, two types of chromatography (reversed phase and anion exchange) were used in sequence to aid the separation of components of the active fraction from size exclusion chromatography. This procedure however was not compatible with subsequent mass spectrometry since a high level of sodium chloride existed in the final fraction, even after desalting using reversed phase column chromatography. Due to that, other means of chromatography were trialled in order to obtain a salt-free fraction prior to mass spectrometry. The first procedure was modified by switching the sequence of the columns used, and different mobile phases without salt were used. This second procedure was successful in isolating the antioxidants and the compounds have been characterised by mass spectrometry.
Mass spectrometry revealed that the antioxidants isolated were compounds of low molecular weight (i.e. 255, 283 and 227) which exhibited peaks with high intensity. Nuclear magnetic resonance (NMR) spectroscopy of the active fraction showed that the antioxidant may possess a 1,4-disubstituted aromatic ring. However, full elucidation of the structure of the compound was not possible because of the very low mass of the material that had been isolated. 
Other than the information gained from mass spectrometry and NMR, the antioxidant also could be characterised by forming the negative ion at pH 9.5–10. The UV absorbance at 220 and 280 nm, but not at 360 nm is indicative that the antioxidant possess a phenolic ring but not a flavonoid in the molecular structure.
Complete structural elucidation of the iron-binding antioxidants in honeydew honey could initiate a better understanding of the mechanism of action of the antioxidants. This could increase the use of honeydew honey in pharmaceutical and nutraceutical products as an iron-binding antioxidant. There is also the possibility that the identified compound(s) could be synthesised for pharmaceutical use, or serve as lead compounds for the development of other pharmaceutical iron-binding antioxidants.

text: Identifying iron-binding antioxidants in New Zealand honeydew honey Iron is an essential element for human physiological function. However, excess free iron could participate in the formation of reactive oxygen species via the Fenton reaction and is thought to be the primary mechanism for the pathogenesis of diseases related to iron excess. Prevention of the oxidative damage caused by reactive oxygen species can be accomplished by using selective iron-binding compounds. Beech honeydew honey has been found to have an exceptionally high level of iron-binding antioxidant activity. Due to that, the focus of the research in this thesis has been to isolate the compound(s) responsible for the activity and identify their molecular structure.
The stability of the antioxidants on exposure to heat and high and low pH was investigated to get a better understanding of the conditions which could be used when developing suitable techniques for the isolation of the iron-binding antioxidants. 
The isolation of the antioxidants was first attempted with XAD-2 resin. The results of solid phase extraction using XAD-2 resin showed that the activity is mainly found in the honey effluent, the fraction not retarded by the resin, indicating that hydrophilic components contributed to the iron-binding antioxidant activity. The phenolic compounds isolated from this resin did not exhibit iron-binding antioxidant activity.
When the antioxidants could not be isolated from the XAD-2 resin, size exclusion chromatography was used to separate the honey components based on their molecular sizes. The technique was successsful in separating antioxidants from free sugars in honey. However, size exclusion chromatography did not give any significant information regarding the identity of the antioxidants. Thus, two types of chromatography (reversed phase and anion exchange) were used in sequence to aid the separation of components of the active fraction from size exclusion chromatography. This procedure however was not compatible with subsequent mass spectrometry since a high level of sodium chloride existed in the final fraction, even after desalting using reversed phase column chromatography. Due to that, other means of chromatography were trialled in order to obtain a salt-free fraction prior to mass spectrometry. The first procedure was modified by switching the sequence of the columns used, and different mobile phases without salt were used. This second procedure was successful in isolating the antioxidants and the compounds have been characterised by mass spectrometry.
Mass spectrometry revealed that the antioxidants isolated were compounds of low molecular weight (i.e. 255, 283 and 227) which exhibited peaks with high intensity. Nuclear magnetic resonance (NMR) spectroscopy of the active fraction showed that the antioxidant may possess a 1,4-disubstituted aromatic ring. However, full elucidation of the structure of the compound was not possible because of the very low mass of the material that had been isolated. 
Other than the information gained from mass spectrometry and NMR, the antioxidant also could be characterised by forming the negative ion at pH 9.5–10. The UV absorbance at 220 and 280 nm, but not at 360 nm is indicative that the antioxidant possess a phenolic ring but not a flavonoid in the molecular structure.
Complete structural elucidation of the iron-binding antioxidants in honeydew honey could initiate a better understanding of the mechanism of action of the antioxidants. This could increase the use of honeydew honey in pharmaceutical and nutraceutical products as an iron-binding antioxidant. There is also the possibility that the identified compound(s) could be synthesised for pharmaceutical use, or serve as lead compounds for the development of other pharmaceutical iron-binding antioxidants.

year: 2013

title: Environmental offsets and water resource opportunities with Lake Onslow pumped storage

authors: Karaminik, Yasaman Maryam

abstract: As part of its transition toward an aspirational goal of 100% renewable electricity generation, New Zealand had been investigating an option of replacing the need for dry-year fossil fuel power generation with the world’s largest pumped storage scheme by energy storage measure. The scheme was to be located at Lake Onslow in the southern South Island. It would have an energy storage capacity up to 5 TWh for a construction cost of 16 billion dollars. However, the 2023 change of government means the scheme is not presently under active evaluation. Evaluation may well be restarted with a subsequent change of government, depending on party policy. 
While aiding emission reduction, there would be local environmental impact from expanding the existing Lake Onslow reservoir, which will flood over nearby wetlands. 
This study considers a range of potential environmental mitigation measures that might counterbalance the scheme's ecological impact. Consideration is also given to the large water volume in the Onslow reservoir potentially able to act as insurance against future extreme regional droughts that may arise from climate change.
The possible offsets include the restoration of two existing scenic hydro storage lakes – Lake Monowai and Lake Hawea. An argument is made that the large amount of new hydro storage capacity at Lake Onslow means that the relatively small storage contributions of these two lakes no longer justifies their inundation environmental impact. This would start a change in national thinking because to date no hydro storage lake in New Zealand has been restored for purely environmental reasons. 
In addition to lake restoration, discussion is also presented about the possibility of a hypothetical partial flow restoration of the depleted Waiau River. It was New Zealand’s second largest river by discharge prior to diversion into the Manapouri power station. It is tentatively suggested that new wind power in Southland buffered by Onslow pumped storage would enable partial closure of the Manapouri station, restoring about half of the original flow the lower Waiau River downstream of Lake Manapouri. 
Onslow water storage would involve cubic kilometres of water, so some water could be used to offset extreme droughts without impeding pumped storage energy functionality. A narrow-diameter rock tunnel could also be constructed between the expanded Lake Onslow and the Dunedin city water intake at Deep Creek. This would make Dunedin drought-resilient against climate change because presently the city water supply is derived just from small local catchments with little storage.
Some Onslow water might also be used to maintain water flow of the eastern Otago Taieri River in an extreme drought. However, this would raise cultural and ecological issues that would need to be considered prior to any water release.

text: Environmental offsets and water resource opportunities with Lake Onslow pumped storage As part of its transition toward an aspirational goal of 100% renewable electricity generation, New Zealand had been investigating an option of replacing the need for dry-year fossil fuel power generation with the world’s largest pumped storage scheme by energy storage measure. The scheme was to be located at Lake Onslow in the southern South Island. It would have an energy storage capacity up to 5 TWh for a construction cost of 16 billion dollars. However, the 2023 change of government means the scheme is not presently under active evaluation. Evaluation may well be restarted with a subsequent change of government, depending on party policy. 
While aiding emission reduction, there would be local environmental impact from expanding the existing Lake Onslow reservoir, which will flood over nearby wetlands. 
This study considers a range of potential environmental mitigation measures that might counterbalance the scheme's ecological impact. Consideration is also given to the large water volume in the Onslow reservoir potentially able to act as insurance against future extreme regional droughts that may arise from climate change.
The possible offsets include the restoration of two existing scenic hydro storage lakes – Lake Monowai and Lake Hawea. An argument is made that the large amount of new hydro storage capacity at Lake Onslow means that the relatively small storage contributions of these two lakes no longer justifies their inundation environmental impact. This would start a change in national thinking because to date no hydro storage lake in New Zealand has been restored for purely environmental reasons. 
In addition to lake restoration, discussion is also presented about the possibility of a hypothetical partial flow restoration of the depleted Waiau River. It was New Zealand’s second largest river by discharge prior to diversion into the Manapouri power station. It is tentatively suggested that new wind power in Southland buffered by Onslow pumped storage would enable partial closure of the Manapouri station, restoring about half of the original flow the lower Waiau River downstream of Lake Manapouri. 
Onslow water storage would involve cubic kilometres of water, so some water could be used to offset extreme droughts without impeding pumped storage energy functionality. A narrow-diameter rock tunnel could also be constructed between the expanded Lake Onslow and the Dunedin city water intake at Deep Creek. This would make Dunedin drought-resilient against climate change because presently the city water supply is derived just from small local catchments with little storage.
Some Onslow water might also be used to maintain water flow of the eastern Otago Taieri River in an extreme drought. However, this would raise cultural and ecological issues that would need to be considered prior to any water release.

year: 2024-03-18

title: Investment in Authentic Sustainable Cultural Tourism : Planning for the Future Benefit of Waikato-Tainui along the Waikato River, Case Studies at Tūrangawaewae and Te Awamārahi Marae

authors: Cooper, Mei Te Werawera Te Reokaha

abstract: “Tērā ōkū hoa kei ngā tōpito e whā o te ao - My friends will come from all parts of the world” – Kīngi Tāwhiao 1822-1894

This doctorate is guided by the visions of the second Māori king, Kīngi Tāwhiao, which reflect the importance of global connections, relationships (Turongo House, 2000:109) and investment to achieve the ultimate goal of authentic or ‘true’ sustainability throughout the world.  The strategic process will require a balance between humans and the natural environment to ensure long-term growth and survival.  This research will investigate whether investment in Authentic Sustainable Cultural Tourism (ASCT) will provide long-term and sustainable benefits for tribes throughout New Zealand, using a study of Waikato-Tainui.  ASCT, if practiced correctly, must be driven by whānau of marae, hapū and iwi alongside ideal long-term partners to ultimately achieve indigenous autonomy. ASCT prioritises the wellbeing of indigenous and local communities, cultural preservation and environmental sustainability while providing secure economic returns to key stakeholders. 

Today, tourism is New Zealand’s largest and fastest growing industry; total tourism expenditure is forecast to increase from $34.7b in 2016, an increase of 12.2% from the previous year, to $41b by 2025.  The natural landscape is the main reason why international travellers visit New Zealand, followed by an interest in Māori culture (Tourism Industry Association, 2015).  Unfortunately, there is sparse funding for Māori tourism development (New Zealand Māori Tourism, 2015; Goulter, 2015) compared to mainstream tourism and Māori are the most impoverished people in New Zealand (Statistics New Zealand, 2011).  Cultural tourism has existed in New Zealand for more than 150 years and has a vital role in New Zealand’s tourism industry.  Te Kīngitanga and the Waikato River are the main aspects that make Waikato unique in New Zealand, however, there is very little cultural tourism in the region.  As a descendant of Waikato-Tainui, I work with my people at the marae level to inform tribal governance about the significant opportunities available to whānau compared to current mainstream investments by the tribe. 

Using Kaupapa Māori and critical realism, the methods used in this research include an investigation of government tourism organisations, interviews with Waikato-Tainui governance groups, case studies at Tūrangawaewae and Te Awamārahi Marae, case studies at fourteen successful Māori tourism providers throughout New Zealand, and an international comparison of best practices in indigenous tourism.

text: Investment in Authentic Sustainable Cultural Tourism : Planning for the Future Benefit of Waikato-Tainui along the Waikato River, Case Studies at Tūrangawaewae and Te Awamārahi Marae “Tērā ōkū hoa kei ngā tōpito e whā o te ao - My friends will come from all parts of the world” – Kīngi Tāwhiao 1822-1894

This doctorate is guided by the visions of the second Māori king, Kīngi Tāwhiao, which reflect the importance of global connections, relationships (Turongo House, 2000:109) and investment to achieve the ultimate goal of authentic or ‘true’ sustainability throughout the world.  The strategic process will require a balance between humans and the natural environment to ensure long-term growth and survival.  This research will investigate whether investment in Authentic Sustainable Cultural Tourism (ASCT) will provide long-term and sustainable benefits for tribes throughout New Zealand, using a study of Waikato-Tainui.  ASCT, if practiced correctly, must be driven by whānau of marae, hapū and iwi alongside ideal long-term partners to ultimately achieve indigenous autonomy. ASCT prioritises the wellbeing of indigenous and local communities, cultural preservation and environmental sustainability while providing secure economic returns to key stakeholders. 

Today, tourism is New Zealand’s largest and fastest growing industry; total tourism expenditure is forecast to increase from $34.7b in 2016, an increase of 12.2% from the previous year, to $41b by 2025.  The natural landscape is the main reason why international travellers visit New Zealand, followed by an interest in Māori culture (Tourism Industry Association, 2015).  Unfortunately, there is sparse funding for Māori tourism development (New Zealand Māori Tourism, 2015; Goulter, 2015) compared to mainstream tourism and Māori are the most impoverished people in New Zealand (Statistics New Zealand, 2011).  Cultural tourism has existed in New Zealand for more than 150 years and has a vital role in New Zealand’s tourism industry.  Te Kīngitanga and the Waikato River are the main aspects that make Waikato unique in New Zealand, however, there is very little cultural tourism in the region.  As a descendant of Waikato-Tainui, I work with my people at the marae level to inform tribal governance about the significant opportunities available to whānau compared to current mainstream investments by the tribe. 

Using Kaupapa Māori and critical realism, the methods used in this research include an investigation of government tourism organisations, interviews with Waikato-Tainui governance groups, case studies at Tūrangawaewae and Te Awamārahi Marae, case studies at fourteen successful Māori tourism providers throughout New Zealand, and an international comparison of best practices in indigenous tourism.

year: 2018