title: Camphene-derived primary and hydroxymethyl phosphines

authors: Berrigan, Rebecca A.

subjects: Chemistry

abstract: Thermal disproportionation of (2,2-dimethylbicyclo[2.2.1]hept-3-ylmethyl)phosphinic acid (endo-8-camphanylphosphinic acid, camPO₂H₂) yields the primary phosphine (2,2-dimethylbicyclo[2.2.1]hept-3-ylmethyl)phosphine (camPH₂). The compound has been characterised by NMR spectroscopy, and as its tris(hydroxymethyl)phosphonium chloride salt [camP(CH₂OH)₃]Cl, synthesised by reaction with excess formaldehyde and hydrochloric acid. The X-ray crystal structure of this phosphonium salt is reported, confirming the endo position of the phosphonium group. On treatment with triethylamine base, camP(CH₂OH)₃ ⁺Cl⁻ is converted to the hydroxymethylphosphine camP(CH₂OH)₂. The sulfide and selenide of this phosphine have been prepared, together with the platinum(II) complex cis-[PtCl₂{camP(CH₂OH)₂}₂]. The gas-phase decomposition of camPH₂ has been investigated using the technique of IR laser powered homogeneous pyrolysis. Results indicate the initial elimination of phosphine, followed by the rearrangement and decomposition of camphene through two distinct pathways.

text: Camphene-derived primary and hydroxymethyl phosphines Thermal disproportionation of (2,2-dimethylbicyclo[2.2.1]hept-3-ylmethyl)phosphinic acid (endo-8-camphanylphosphinic acid, camPO₂H₂) yields the primary phosphine (2,2-dimethylbicyclo[2.2.1]hept-3-ylmethyl)phosphine (camPH₂). The compound has been characterised by NMR spectroscopy, and as its tris(hydroxymethyl)phosphonium chloride salt [camP(CH₂OH)₃]Cl, synthesised by reaction with excess formaldehyde and hydrochloric acid. The X-ray crystal structure of this phosphonium salt is reported, confirming the endo position of the phosphonium group. On treatment with triethylamine base, camP(CH₂OH)₃ ⁺Cl⁻ is converted to the hydroxymethylphosphine camP(CH₂OH)₂. The sulfide and selenide of this phosphine have been prepared, together with the platinum(II) complex cis-[PtCl₂{camP(CH₂OH)₂}₂]. The gas-phase decomposition of camPH₂ has been investigated using the technique of IR laser powered homogeneous pyrolysis. Results indicate the initial elimination of phosphine, followed by the rearrangement and decomposition of camphene through two distinct pathways.

year: 2001-01-01

title: The dynamics of ¹³C in several New Zealand lakes

authors: McCabe, Bruce

abstract: The main objectives of this study were to;
(i) Determine how the 𝜹¹³C of autochthonous production in fresh water lakes varies with productivity and trophic state.
(ii) Determine if such variations can be used for the investigation of lake palaeoenvironment.
(iii) Quantify the effect of anthropogenic activity on the productivity of Hamilton Basin lakes.
The viability of this project was assessed by monitoring the dissolved inorganic carbon chemistry of an eutrophic pond during a period of high insolation and algal productivity. These observations revealed that during the day, the Pc0₂ in the euphotic zone was reduced to levels low enough to affect. photosynthetic carbon isotopic fractionation, and hence plankton 𝜹¹³C values. The enrichment of ¹³C in the dissolved inorganic carbon (DIC) pool during periods of high
photosynthetic productivity also affects plankton 𝜹¹³C values. Analysis of diurnal changes in 𝜹¹³C and DIC concentration using the Rayleigh equation suggested that photosynthetic fractionation factors changed in response to changes in ambient P𝒸ₒ₂  levels.
The effect of lake trophic state on phytoplankton photosynthetic carbon isotopic fractionation was further investigated using closed system batch cultures of zooplankton-free natural algal populations collected from lakes of differing trophic state. The results indicated
that;
(i) There are considerable differences between algal communities, photosynthetic production and apparent CO₂  compensation points for cultures of algae from lakes of differing trophic state.
(ii) Plankton from a eutrophic lake were able to photosynthesise down to a low and had a variable photosynthetic carbon isotopic fractionation factor, (ep), which varied as a function of the P𝒸ₒ₂ .
(iii) Plankton from a mesotrophic lake were unable to reduce the Pc0₂   below 300ppm and exhibited a constant ∈p .
(iv) Carbon dioxide availability could be limiting plankton photosynthesis in productive eutrophic lakes, and may result in HCO₃⁻ use.
Phytoplankton 𝜹¹³C values and photosynthetic fractionation factors have the potential to be used to detect changes in plankton productivity and substrate use.
A study was made of the isotopic chemistry of the DIC and particulate organic matter, (POM), in six Hamilton Basin lakes with trophic states ranging from hypertrophic to oligotrophic-mesotrophic and dystrophic. From this study, it was concluded that;
(i) The isotopic chemistry of the DIC is a function of:
- catchment composition
- the relative amounts and 𝜹¹³C of inorganic carbon supplied from the atmosphere and biogenic sources.
- the mixing regime of the lake.
(ii) 𝜹¹³Cₚₒₘ varies seasonally in concert with changes in algal biomass.
(iii) Because variations in 𝜹¹³Cₚₒₘ result primarily from changes in the photosynthetic fractionation factor, ∆¹³C₍ₚₒₘ₋𝒸ₒ₂₍ₐq₎₎they can be used to detect changes in the productivity of lakes.
(i v) 𝜹¹³Cₚₒₘ values could not be used to rank lakes in order of increasing productivity because of the effect of systematic differences in the 𝜹¹³C 𝒸ₒ₂₍ₐq₎of different lakes.
(v) POM produced in the euphotic zone is incorporated in the sediment with only a small (-1%) change in its 𝜹¹³C, thus enabling sediment 𝜹¹³C values to be used to source organic carbon in the sediment and to investigate lake palaeoproductivity.
Large systematic variations were observed in sediment 𝜹¹³C values during the development of lakes. By assuming that the 𝜹¹³C 𝒸ₒ₂₍ₐq₎ had remained constant during lake development, an attempt was made to determine the palaeoenvironment of these lakes from sediment 𝜹¹³C values. It was concluded that the productivity of these lakes had undergone considerable changes during their development in response to climatically and anthropologically induced changes in the catchment vegetation. Low forest cover results in high or increased lake productivity, whilst dense forest cover led to low or reduced lake productivity. Lakes formed in the late glacial times had a high productivity, (low forest cover and high nutrient loading), which reduced as the forest cover developed. Peat development also affected some of the lakes.
An attempt was made to assess the effect of anthropogenic activity in the Hamilton Basin on the metabolism of the lakes from changes in the recent sediment 𝜹¹³C values and a comparison of present day 𝜹¹³Cₚₒₘ values with recent sediment 𝜹¹³C values. The results indicate that;
(i) Anthropogenic activity had a marked affect on lake metabolism, resulting in increased terrigenous inputs and/or increased productivity. This was particularly evident in Lake Hakanoa, where deforestation of the area by early Polynesian settlers resulted in a large increase in lake productivity.
(ii) Several of the lakes have very recently undergone a marked increase in their productivity, a result of European activity in the area. 
Thus, plankton productivity has a systematic affect on the 𝜹¹³C of the POM incorporated in lake sediments, which has the potential to be used in the investigation of lake palaeoproductivity, and in assessing the effect of anthropogenic activity on lake productivity.

text: The dynamics of ¹³C in several New Zealand lakes The main objectives of this study were to;
(i) Determine how the 𝜹¹³C of autochthonous production in fresh water lakes varies with productivity and trophic state.
(ii) Determine if such variations can be used for the investigation of lake palaeoenvironment.
(iii) Quantify the effect of anthropogenic activity on the productivity of Hamilton Basin lakes.
The viability of this project was assessed by monitoring the dissolved inorganic carbon chemistry of an eutrophic pond during a period of high insolation and algal productivity. These observations revealed that during the day, the Pc0₂ in the euphotic zone was reduced to levels low enough to affect. photosynthetic carbon isotopic fractionation, and hence plankton 𝜹¹³C values. The enrichment of ¹³C in the dissolved inorganic carbon (DIC) pool during periods of high
photosynthetic productivity also affects plankton 𝜹¹³C values. Analysis of diurnal changes in 𝜹¹³C and DIC concentration using the Rayleigh equation suggested that photosynthetic fractionation factors changed in response to changes in ambient P𝒸ₒ₂  levels.
The effect of lake trophic state on phytoplankton photosynthetic carbon isotopic fractionation was further investigated using closed system batch cultures of zooplankton-free natural algal populations collected from lakes of differing trophic state. The results indicated
that;
(i) There are considerable differences between algal communities, photosynthetic production and apparent CO₂  compensation points for cultures of algae from lakes of differing trophic state.
(ii) Plankton from a eutrophic lake were able to photosynthesise down to a low and had a variable photosynthetic carbon isotopic fractionation factor, (ep), which varied as a function of the P𝒸ₒ₂ .
(iii) Plankton from a mesotrophic lake were unable to reduce the Pc0₂   below 300ppm and exhibited a constant ∈p .
(iv) Carbon dioxide availability could be limiting plankton photosynthesis in productive eutrophic lakes, and may result in HCO₃⁻ use.
Phytoplankton 𝜹¹³C values and photosynthetic fractionation factors have the potential to be used to detect changes in plankton productivity and substrate use.
A study was made of the isotopic chemistry of the DIC and particulate organic matter, (POM), in six Hamilton Basin lakes with trophic states ranging from hypertrophic to oligotrophic-mesotrophic and dystrophic. From this study, it was concluded that;
(i) The isotopic chemistry of the DIC is a function of:
- catchment composition
- the relative amounts and 𝜹¹³C of inorganic carbon supplied from the atmosphere and biogenic sources.
- the mixing regime of the lake.
(ii) 𝜹¹³Cₚₒₘ varies seasonally in concert with changes in algal biomass.
(iii) Because variations in 𝜹¹³Cₚₒₘ result primarily from changes in the photosynthetic fractionation factor, ∆¹³C₍ₚₒₘ₋𝒸ₒ₂₍ₐq₎₎they can be used to detect changes in the productivity of lakes.
(i v) 𝜹¹³Cₚₒₘ values could not be used to rank lakes in order of increasing productivity because of the effect of systematic differences in the 𝜹¹³C 𝒸ₒ₂₍ₐq₎of different lakes.
(v) POM produced in the euphotic zone is incorporated in the sediment with only a small (-1%) change in its 𝜹¹³C, thus enabling sediment 𝜹¹³C values to be used to source organic carbon in the sediment and to investigate lake palaeoproductivity.
Large systematic variations were observed in sediment 𝜹¹³C values during the development of lakes. By assuming that the 𝜹¹³C 𝒸ₒ₂₍ₐq₎ had remained constant during lake development, an attempt was made to determine the palaeoenvironment of these lakes from sediment 𝜹¹³C values. It was concluded that the productivity of these lakes had undergone considerable changes during their development in response to climatically and anthropologically induced changes in the catchment vegetation. Low forest cover results in high or increased lake productivity, whilst dense forest cover led to low or reduced lake productivity. Lakes formed in the late glacial times had a high productivity, (low forest cover and high nutrient loading), which reduced as the forest cover developed. Peat development also affected some of the lakes.
An attempt was made to assess the effect of anthropogenic activity in the Hamilton Basin on the metabolism of the lakes from changes in the recent sediment 𝜹¹³C values and a comparison of present day 𝜹¹³Cₚₒₘ values with recent sediment 𝜹¹³C values. The results indicate that;
(i) Anthropogenic activity had a marked affect on lake metabolism, resulting in increased terrigenous inputs and/or increased productivity. This was particularly evident in Lake Hakanoa, where deforestation of the area by early Polynesian settlers resulted in a large increase in lake productivity.
(ii) Several of the lakes have very recently undergone a marked increase in their productivity, a result of European activity in the area. 
Thus, plankton productivity has a systematic affect on the 𝜹¹³C of the POM incorporated in lake sediments, which has the potential to be used in the investigation of lake palaeoproductivity, and in assessing the effect of anthropogenic activity on lake productivity.

year: 1985

title: Investigating Māori approaches to trauma informed care

authors: Pihama, Leonie

subjects: Māori health and wellbeing

abstract: This article gives an overview of a three-year Health Research Council funded research project “He Oranga Ngākau: Māori approaches to trauma-informed care”. The study is informed by Kaupapa Māori which provides both the theoretical and methodological foundation for understanding the world, exploring and conceptualising issues. The need for contextualised and culturally safe health and social services is well recognised within Aotearoa and particularly within Mental Health and Addiction Services. While trauma is an experience that can impact on all people, Māori experience trauma in distinct ways that are linked to the experience of colonisation, racism and discrimination, negative stereotyping and subsequent unequal rates of violence, poverty and ill health. Given that Māori are impacted by trauma in specific ways, it is important to explore and identify practice principles that contribute to the development of a framework that supports Māori Providers, counsellors, clinicians and healers in working with Māori. (Authors' abstract).

text: Investigating Māori approaches to trauma informed care This article gives an overview of a three-year Health Research Council funded research project “He Oranga Ngākau: Māori approaches to trauma-informed care”. The study is informed by Kaupapa Māori which provides both the theoretical and methodological foundation for understanding the world, exploring and conceptualising issues. The need for contextualised and culturally safe health and social services is well recognised within Aotearoa and particularly within Mental Health and Addiction Services. While trauma is an experience that can impact on all people, Māori experience trauma in distinct ways that are linked to the experience of colonisation, racism and discrimination, negative stereotyping and subsequent unequal rates of violence, poverty and ill health. Given that Māori are impacted by trauma in specific ways, it is important to explore and identify practice principles that contribute to the development of a framework that supports Māori Providers, counsellors, clinicians and healers in working with Māori. (Authors' abstract).

year: 2017