title: The Daldy Mcwilliams ‘Outrage’ of 1879

authors: Hart, Philip

abstract: In the later 1870s, conflicts developed near Paeroa between a small hapu, Ngati Hako, and other hapu over land sales and surveys. In 1879, after some members of Ngati Koi offered to sell the Pukehanga Block, at Rotokohu, between Paeroa and Te Aroha, to the Crown, surveyors were sent to determine the boundaries despite threats of violence from Ngati Hako. These threats became a reality with shots being fired, wounding a surveyor’s assistant, ‘Daldy’ McWilliams, who survived by playing dead. Despite Pakeha fury about a ‘weak’ response, officials reacted cautiously, fearing to provoke a wider conflict. 
Instead of trying to arrest the two men accused of the attempted murder, which would have been difficult, because Ngati Hako claimed their action was justified the Native Minister encouraged senior Hauraki rangatira to convene a rununga to examine their claim. Ngati Hako said that the block of land was theirs, and as previously other land had been surveyed without their permission they had taken this action. The government was criticized for paying advances on a block that had not been through the land court, and the rununga determined that although Ngati Hako had acted wrongfully, their action could be justified. When Ngati Hako refused to hand over the two accused to the authorities, the rununga claimed not to have the power to hand them over; Ngati Hako then constructed two pa to defend themselves.
Such actions provoked much frustration and criticisms of the government amongst Pakeha, but officials who investigated Ngati Hako’s complaints agreed that they had indeed lost land unjustly. Once the owners of a large domain, they had lost their land to the invading Marutuahu, whose slaves they became. When the two accused were arrested in 1882 one was found not guilty and the other was amnestied after eight months in prison because it was believed that, as rangatira, they probably had not fired the shots but had taken the responsibility for the actions of their hapu. As for McWilliams, he received what he considered inadequate compensation.
This ‘outrage’ was the first and only time in Hauraki that a Maori had shot a Pakeha, and the government’s cautious but firm response meant that the ‘peace of Hauraki’, although disturbed for a while, was maintained.

text: The Daldy Mcwilliams ‘Outrage’ of 1879 In the later 1870s, conflicts developed near Paeroa between a small hapu, Ngati Hako, and other hapu over land sales and surveys. In 1879, after some members of Ngati Koi offered to sell the Pukehanga Block, at Rotokohu, between Paeroa and Te Aroha, to the Crown, surveyors were sent to determine the boundaries despite threats of violence from Ngati Hako. These threats became a reality with shots being fired, wounding a surveyor’s assistant, ‘Daldy’ McWilliams, who survived by playing dead. Despite Pakeha fury about a ‘weak’ response, officials reacted cautiously, fearing to provoke a wider conflict. 
Instead of trying to arrest the two men accused of the attempted murder, which would have been difficult, because Ngati Hako claimed their action was justified the Native Minister encouraged senior Hauraki rangatira to convene a rununga to examine their claim. Ngati Hako said that the block of land was theirs, and as previously other land had been surveyed without their permission they had taken this action. The government was criticized for paying advances on a block that had not been through the land court, and the rununga determined that although Ngati Hako had acted wrongfully, their action could be justified. When Ngati Hako refused to hand over the two accused to the authorities, the rununga claimed not to have the power to hand them over; Ngati Hako then constructed two pa to defend themselves.
Such actions provoked much frustration and criticisms of the government amongst Pakeha, but officials who investigated Ngati Hako’s complaints agreed that they had indeed lost land unjustly. Once the owners of a large domain, they had lost their land to the invading Marutuahu, whose slaves they became. When the two accused were arrested in 1882 one was found not guilty and the other was amnestied after eight months in prison because it was believed that, as rangatira, they probably had not fired the shots but had taken the responsibility for the actions of their hapu. As for McWilliams, he received what he considered inadequate compensation.
This ‘outrage’ was the first and only time in Hauraki that a Maori had shot a Pakeha, and the government’s cautious but firm response meant that the ‘peace of Hauraki’, although disturbed for a while, was maintained.

year: 2016

title: Vital evidence: Change in the marine ¹⁴C reservoir around New Zealand (Aotearoa) and implications for the timing of Polynesian settlement.

authors: Petchey, Fiona

abstract: Precise and accurate radiocarbon chronologies are essential to achieve tight chronological control for the ~ 750-years since Polynesian settlement of New Zealand. This goal has, however, been elusive. While radiocarbon datasets in the region are typically dominated by marine and estuarine shell dates, such chronological information has been ignored by those interpreting the timing of key events because a detailed regional calibration methodology for marine shell, comparable to the highly precise Southern Hemisphere calibration curve, is lacking. In this paper, we present the first temporal ¹⁴C marine offset (ΔR) model for New Zealand based on paired estuarine/marine and terrestrial radiocarbon dates from 52 archaeological contexts. Our dataset displays significant offsets between the measured New Zealand data and the modelled global marine radiocarbon curve. These shifts are associated with oceanographic fluctuation at the onset of the Little Ice Age ~ AD 1350-1450 (650-500 BP). The application of a regional and temporal correction to archaeological shell dates provides complimentary information to terrestrial radiocarbon production and has the potential to add structure to the blurred chronology that has plagued archaeological theories about the colonization of New Zealand, and other Pacific islands, for decades.

text: Vital evidence: Change in the marine ¹⁴C reservoir around New Zealand (Aotearoa) and implications for the timing of Polynesian settlement. Precise and accurate radiocarbon chronologies are essential to achieve tight chronological control for the ~ 750-years since Polynesian settlement of New Zealand. This goal has, however, been elusive. While radiocarbon datasets in the region are typically dominated by marine and estuarine shell dates, such chronological information has been ignored by those interpreting the timing of key events because a detailed regional calibration methodology for marine shell, comparable to the highly precise Southern Hemisphere calibration curve, is lacking. In this paper, we present the first temporal ¹⁴C marine offset (ΔR) model for New Zealand based on paired estuarine/marine and terrestrial radiocarbon dates from 52 archaeological contexts. Our dataset displays significant offsets between the measured New Zealand data and the modelled global marine radiocarbon curve. These shifts are associated with oceanographic fluctuation at the onset of the Little Ice Age ~ AD 1350-1450 (650-500 BP). The application of a regional and temporal correction to archaeological shell dates provides complimentary information to terrestrial radiocarbon production and has the potential to add structure to the blurred chronology that has plagued archaeological theories about the colonization of New Zealand, and other Pacific islands, for decades.

year: 2020

title: Preparation of mesoporous solids containing encapsulated metal species of technological interest

authors: Xu, Sheng

subjects: mesoporous solids

abstract: The advent of mesoporous silicas such as MCM-41 has provided new opportunities for research into supported metal catalysis. The loading of metals into framework structures and particularly into the pores of porous molecular sieves, has long been of interest because of their potential catalytic activity. The larger pore sizes of mesoporous silicas allow for the possibility of preparing dispersions of metal/metal oxide particles within the pores while still allowing access by reagent molecule. In standard fabrication processes, metal particle size is not well controlled. Most studies of metal/metal oxide loaded mesoporous silicas report metal/metal oxide particles larger than the pore diameter. In the present work, new methods of preparing metal loaded systems have been developed to facilitate a more even dispersion of the metal. The metals were loaded as readily decomposed organometallic complexes so the chemistry involved in forming the metal/metal oxide particles minimized possible sintering effects. New synthetic routes were developed to facilitate loading into the pores or the framework of the silica matrix. An optimised acid synthetic route for preparing MCM-41 was used throughout. The acid concentration, surfactant concentration, reaction time and stirring rate, all of which have strong influence on the morphology and structure of the mesoporous materials under acidic synthetic conditions, were optimised to give systems of maximum surface area while exhibiting regular pore structures and good stability. The refined reaction conditions of high stirring speeds, low surfactant concentration, high acid concentrations and short reactions times developed in the present work represent important improvements in synthetic methodology giving stable, well ordered, small pore, thick walled and high surface area products. Single metal and mixed metal organometallic complexes were loaded into the preformed mesoporous supports by a modified imbibing method and then decomposed to prepare metal and mixed metal nanoparticles within the structures. However, loading by this method caused disordering and destruction of the MCM-41 porous supports, the broadening of the XRD diffraction lines, and the significant reduction of pore size, pore volume and specific surface area. A major contribution of the current work has been the development of two methods for controlling the loading of metals into the structures during synthesis. These methods offer the significant advantages of loading without structural effects and yielding producing systems where surface area increased rather than decreased with loading. By the M method, a hydrophobic organometallic complex was incorporated within the micelle system formed by the surfactant, cetyltrimethylammonium bromide. This micelle system containing the organometallic complex forms the template for the pores during the sol-gel formation of the mesoporous solids. Incorporation of the metal within the micelle facilitates the dispersion of the metal throughout the surfactant phase filling the pores of final precursor material. Calcining to remove the organic material favours leaving the metal or metal oxide in the form of small particles widely and uniformly dispersed in the mesoporous channels. By the T method, organometallic molecules are dissolved in the Si(OEt)4 of the synthesis mixture. Calcining the organic material from the resulting precursor favours leaving the metal or metal oxide in a widely and uniformly dispersed state in the walls of mesopores. The synthetic methods developed were extended to prepare mixed metal nanoparticles of defined composition using single-source mixed metal organometallic compounds. In this way novel mixed metal (Mo/Fe and Mo/Co) phases with compositions determined by the stoichiometry of the initial mixed metal complex were produced and characterised. The nature of the metal/metal oxide particles was studied by XRD and TEM. At the metal loadings obtained (ranging up to 4%) crystalline metal and metal oxide particles should be readily detected. The absence of well defined XRD peaks characteristic of the metal or metal oxides in any of the samples provided evidence that the metals after calcining were well dispersed, with particles sizes less than a few nm and too small to give diffraction signals. TEM studies revealed a clearly defined hexagonal pore structure with pore diameters of approximately 2 nm but gave no evidence of metal particles larger than the resolving power of the instrument (approximately 1 nm).

text: Preparation of mesoporous solids containing encapsulated metal species of technological interest The advent of mesoporous silicas such as MCM-41 has provided new opportunities for research into supported metal catalysis. The loading of metals into framework structures and particularly into the pores of porous molecular sieves, has long been of interest because of their potential catalytic activity. The larger pore sizes of mesoporous silicas allow for the possibility of preparing dispersions of metal/metal oxide particles within the pores while still allowing access by reagent molecule. In standard fabrication processes, metal particle size is not well controlled. Most studies of metal/metal oxide loaded mesoporous silicas report metal/metal oxide particles larger than the pore diameter. In the present work, new methods of preparing metal loaded systems have been developed to facilitate a more even dispersion of the metal. The metals were loaded as readily decomposed organometallic complexes so the chemistry involved in forming the metal/metal oxide particles minimized possible sintering effects. New synthetic routes were developed to facilitate loading into the pores or the framework of the silica matrix. An optimised acid synthetic route for preparing MCM-41 was used throughout. The acid concentration, surfactant concentration, reaction time and stirring rate, all of which have strong influence on the morphology and structure of the mesoporous materials under acidic synthetic conditions, were optimised to give systems of maximum surface area while exhibiting regular pore structures and good stability. The refined reaction conditions of high stirring speeds, low surfactant concentration, high acid concentrations and short reactions times developed in the present work represent important improvements in synthetic methodology giving stable, well ordered, small pore, thick walled and high surface area products. Single metal and mixed metal organometallic complexes were loaded into the preformed mesoporous supports by a modified imbibing method and then decomposed to prepare metal and mixed metal nanoparticles within the structures. However, loading by this method caused disordering and destruction of the MCM-41 porous supports, the broadening of the XRD diffraction lines, and the significant reduction of pore size, pore volume and specific surface area. A major contribution of the current work has been the development of two methods for controlling the loading of metals into the structures during synthesis. These methods offer the significant advantages of loading without structural effects and yielding producing systems where surface area increased rather than decreased with loading. By the M method, a hydrophobic organometallic complex was incorporated within the micelle system formed by the surfactant, cetyltrimethylammonium bromide. This micelle system containing the organometallic complex forms the template for the pores during the sol-gel formation of the mesoporous solids. Incorporation of the metal within the micelle facilitates the dispersion of the metal throughout the surfactant phase filling the pores of final precursor material. Calcining to remove the organic material favours leaving the metal or metal oxide in the form of small particles widely and uniformly dispersed in the mesoporous channels. By the T method, organometallic molecules are dissolved in the Si(OEt)4 of the synthesis mixture. Calcining the organic material from the resulting precursor favours leaving the metal or metal oxide in a widely and uniformly dispersed state in the walls of mesopores. The synthetic methods developed were extended to prepare mixed metal nanoparticles of defined composition using single-source mixed metal organometallic compounds. In this way novel mixed metal (Mo/Fe and Mo/Co) phases with compositions determined by the stoichiometry of the initial mixed metal complex were produced and characterised. The nature of the metal/metal oxide particles was studied by XRD and TEM. At the metal loadings obtained (ranging up to 4%) crystalline metal and metal oxide particles should be readily detected. The absence of well defined XRD peaks characteristic of the metal or metal oxides in any of the samples provided evidence that the metals after calcining were well dispersed, with particles sizes less than a few nm and too small to give diffraction signals. TEM studies revealed a clearly defined hexagonal pore structure with pore diameters of approximately 2 nm but gave no evidence of metal particles larger than the resolving power of the instrument (approximately 1 nm).

year: 2011