title: Ab initio molecular dynamics investigation of beryllium complexes

authors: Raymond, Onyekachi

subjects: Science & Technology

abstract: Structures of aqueous [Be(H₂O)₄]²⁺, its outer-sphere and inner-sphere complexes with F⁻, Cl⁻, and SO₄²⁻, and dinuclear complexes with a [Be₂(κ-OH)(κ-SO₄)]⁺ core have been studied through Car–Parrinello molecular dynamics (CPMD) simulations with the BLYP functional. According to constrained CPMD/BLYP simulations and pointwise thermodynamic integration, the free energy of deprotonation of [Be(H₂O)₄]²⁺ and its binding free energy with F⁻ are 9.6 and −6.2 kcal/mol, respectively, in good accord with available experimental data. The computed activation barriers for replacing a water ligand in [Be(H₂O)₄]²⁺ with F⁻ and SO₄²⁻, 10.9 and 13.6 kcal/mol, respectively, are also in good qualitative agreement with available experimental data. These ligand-substitution reactions are indicated to follow associative interchange mechanisms with backside (SN2-like) attack of the anion relative to the aquo ligand it is displacing. Outperforming static density functional theory computations of the salient kinetic and thermodynamic quantities involving simple polarizable continuum solvent models, CPMD simulations are validated as a promising tool for studying the structures and speciation of beryllium complexes in aqueous solution.

text: Ab initio molecular dynamics investigation of beryllium complexes Structures of aqueous [Be(H₂O)₄]²⁺, its outer-sphere and inner-sphere complexes with F⁻, Cl⁻, and SO₄²⁻, and dinuclear complexes with a [Be₂(κ-OH)(κ-SO₄)]⁺ core have been studied through Car–Parrinello molecular dynamics (CPMD) simulations with the BLYP functional. According to constrained CPMD/BLYP simulations and pointwise thermodynamic integration, the free energy of deprotonation of [Be(H₂O)₄]²⁺ and its binding free energy with F⁻ are 9.6 and −6.2 kcal/mol, respectively, in good accord with available experimental data. The computed activation barriers for replacing a water ligand in [Be(H₂O)₄]²⁺ with F⁻ and SO₄²⁻, 10.9 and 13.6 kcal/mol, respectively, are also in good qualitative agreement with available experimental data. These ligand-substitution reactions are indicated to follow associative interchange mechanisms with backside (SN2-like) attack of the anion relative to the aquo ligand it is displacing. Outperforming static density functional theory computations of the salient kinetic and thermodynamic quantities involving simple polarizable continuum solvent models, CPMD simulations are validated as a promising tool for studying the structures and speciation of beryllium complexes in aqueous solution.

year: 2020

title: Biology of common bully (Gobiomorphus cotidianus) populations in the Tarawera and Rangitaiki Rivers: Reproductive isolation by inland distance or effluent discharges?

authors: Bleackley, Natalie Anne

subjects: Gobiomorphus cotidianus

abstract: Previous research identified distinct genetic, life-history and reproductive differences between populations of common bully (Gobiomorphus cotidianus) upstream and downstream of a pulp and paper mill outfall on the Tarawera River in the Bay of Plenty, New Zealand. This thesis sought to investigate the distribution of amphidromous and non-amphidromous common bully in the Tarawera River by examining fish collected from upstream (37 km inland) and downstream (20 km inland) locations and comparing them to fish from similar inland locations (40 km and 17 km inland, respectively) in the nearby Rangitaiki River. Otolith microchemistry revealed life-history differences between upstream and downstream populations and stable isotope analysis ensured long-term site residency. Amphidromy dominated in the downstream river populations, while the disappearance of diadromous fish generally occurred with inland distance. A mixture of diadromous and non-diadromous fish were found in the upstream Rangitaiki, while a complete absence of diadromous recruits was found in the upstream Tarawera River. A reduction in oculoscapular canal structures also coincided with loss of diadromy in fish from both rivers. Temporal reproductive divergence was investigated through track annual trends in gonadosomatic index.

The Tarawera River receives significant inputs from numerous industrial, municipal and natural sources, most notably from two pulp and paper mills. In the absence physical barriers in the Tarawera, it has been hypothesised that the lack of diadromous recruits in the upstream Tarawera River may be related to aquatic discharges in the downstream river. A behavioural study was performed to examine the hypothesis that pulp and paper mill effluent may be acting as a chemical barrier to fish migration within the river. A dual-choice chamber was employed to examine the responses of common bully exposed to a range of effluent concentrations (100, 50, 25, 12.5, 0% v/v). Fish exhibited significant avoidance responses when exposed to 100 and 50% effluent concentration, while no avoidance was observed at effluent concentrations below 50% This study demonstrated that common bully show a strong preference for river water when simultaneously exposed to effluent, albeit at environmentally unrealistic concentrations (i.e. greater than 15%), implicating potential for this effluent to act as a chemical barrier in the Tarawera River.
Following the establishment of reproductive timing of common bully in the Tarawera River, a wild fish health assessment was undertaken to investigate the effects of long-term effluent exposure in situ. Adult common bully were sampled downstream of the mill influence and compared to an appropriate reference population from the downstream Rangitaiki River. Male and female fish from the Tarawera River demonstrated 6- to 9-fold greater ethoxyresorufin-O¬-deethylase (EROD) activity compared to reference fish, indicating exposure to organic contaminants in this river. Tarawera females showed some minor variation in hematological variables including decreased mean cell volume (MCV), mean cell haemoglobin (MCH) and increased total white blood cell count (WBCC) suggestive of an immune response. Slightly greater ovarian follicular steroid production in Tarawera fish potentially indicates some form of endocrine alteration. However, this response may also be related to differences in reproductive synchrony and gonadal development between the two fish populations.

text: Biology of common bully (Gobiomorphus cotidianus) populations in the Tarawera and Rangitaiki Rivers: Reproductive isolation by inland distance or effluent discharges? Previous research identified distinct genetic, life-history and reproductive differences between populations of common bully (Gobiomorphus cotidianus) upstream and downstream of a pulp and paper mill outfall on the Tarawera River in the Bay of Plenty, New Zealand. This thesis sought to investigate the distribution of amphidromous and non-amphidromous common bully in the Tarawera River by examining fish collected from upstream (37 km inland) and downstream (20 km inland) locations and comparing them to fish from similar inland locations (40 km and 17 km inland, respectively) in the nearby Rangitaiki River. Otolith microchemistry revealed life-history differences between upstream and downstream populations and stable isotope analysis ensured long-term site residency. Amphidromy dominated in the downstream river populations, while the disappearance of diadromous fish generally occurred with inland distance. A mixture of diadromous and non-diadromous fish were found in the upstream Rangitaiki, while a complete absence of diadromous recruits was found in the upstream Tarawera River. A reduction in oculoscapular canal structures also coincided with loss of diadromy in fish from both rivers. Temporal reproductive divergence was investigated through track annual trends in gonadosomatic index.

The Tarawera River receives significant inputs from numerous industrial, municipal and natural sources, most notably from two pulp and paper mills. In the absence physical barriers in the Tarawera, it has been hypothesised that the lack of diadromous recruits in the upstream Tarawera River may be related to aquatic discharges in the downstream river. A behavioural study was performed to examine the hypothesis that pulp and paper mill effluent may be acting as a chemical barrier to fish migration within the river. A dual-choice chamber was employed to examine the responses of common bully exposed to a range of effluent concentrations (100, 50, 25, 12.5, 0% v/v). Fish exhibited significant avoidance responses when exposed to 100 and 50% effluent concentration, while no avoidance was observed at effluent concentrations below 50% This study demonstrated that common bully show a strong preference for river water when simultaneously exposed to effluent, albeit at environmentally unrealistic concentrations (i.e. greater than 15%), implicating potential for this effluent to act as a chemical barrier in the Tarawera River.
Following the establishment of reproductive timing of common bully in the Tarawera River, a wild fish health assessment was undertaken to investigate the effects of long-term effluent exposure in situ. Adult common bully were sampled downstream of the mill influence and compared to an appropriate reference population from the downstream Rangitaiki River. Male and female fish from the Tarawera River demonstrated 6- to 9-fold greater ethoxyresorufin-O¬-deethylase (EROD) activity compared to reference fish, indicating exposure to organic contaminants in this river. Tarawera females showed some minor variation in hematological variables including decreased mean cell volume (MCV), mean cell haemoglobin (MCH) and increased total white blood cell count (WBCC) suggestive of an immune response. Slightly greater ovarian follicular steroid production in Tarawera fish potentially indicates some form of endocrine alteration. However, this response may also be related to differences in reproductive synchrony and gonadal development between the two fish populations.

year: 2008

title: A Māori homeless woman

authors: Groot, Shiloh Ann Maree

subjects: Māori

abstract: Indigenous peoples are overrepresented in homeless populations in many countries. As part of a larger ethnographic project, this case study draws upon interviews and photoelicitation projects with a homeless Māori woman, Ariā. The actions of this Māori woman exemplify how Indigenous cultural practices can shape a person’s efforts to retain a positive sense of self and place while homeless. Māori cultural concepts relating to caring, leadership, unity, relationships, spirituality, history and place provide a basis for interpreting Ariā’s actions. This article demonstrates the appropriateness of cultural concepts indigenous to a group for conducting ethnographic research into homelessness within that group.

text: A Māori homeless woman Indigenous peoples are overrepresented in homeless populations in many countries. As part of a larger ethnographic project, this case study draws upon interviews and photoelicitation projects with a homeless Māori woman, Ariā. The actions of this Māori woman exemplify how Indigenous cultural practices can shape a person’s efforts to retain a positive sense of self and place while homeless. Māori cultural concepts relating to caring, leadership, unity, relationships, spirituality, history and place provide a basis for interpreting Ariā’s actions. This article demonstrates the appropriateness of cultural concepts indigenous to a group for conducting ethnographic research into homelessness within that group.

year: 2011-09