title: Hydrogen-bonded adducts formed from platinum(II) and palladium(II) thiosalicylate complexes [(Ph₃E)₂M(SC₆H₄CO₂)] (E=P, As) and triethylammonium or pyridinium ions; X-ray crystal structure of [(Ph₃P)₂Pt(SC₆H₄CO₂) HNEt₃]⁺[BPh₄]⁻

authors: Henderson, William

subjects: palladium(II) thiosalicylate complexes

abstract: One-pot reactions of [MCl₂(cod)] (cod=cyclo-octa-1,5-diene; M=Pt, Pd) with two equiv of PPh₃ or AsPh₃, one equiv of thiosalicylic acid, and an excess of triethylamine base, followed by the addition of excess Na[BPh₄] to the hot reaction mixture gives complexes [(Ph₃E)₂M(SC₆H₄CO₂) HNEt₃]⁺[BPh4]⁻ (E=P, As). Analogous pyridinium and platinum–thioglycolate [(Ph₃P)₂Pt(SCH₂CO₂)] derivatives were also prepared. An X-ray crystal structure determination on [(Ph₃P)₂Pt(SC₆H₄CO₂) HNEt₃]⁺[BPh₄]⁻ reveals hydrogen-bonding between the NH proton and the carbonyl group of the thiosalicylate ligand, the major effect of which is to flatten the platinum–thiosalicylate moiety. NMR spectroscopic data indicate that the hydrogen-bonding interaction persists in solution.

text: Hydrogen-bonded adducts formed from platinum(II) and palladium(II) thiosalicylate complexes [(Ph₃E)₂M(SC₆H₄CO₂)] (E=P, As) and triethylammonium or pyridinium ions; X-ray crystal structure of [(Ph₃P)₂Pt(SC₆H₄CO₂) HNEt₃]⁺[BPh₄]⁻ One-pot reactions of [MCl₂(cod)] (cod=cyclo-octa-1,5-diene; M=Pt, Pd) with two equiv of PPh₃ or AsPh₃, one equiv of thiosalicylic acid, and an excess of triethylamine base, followed by the addition of excess Na[BPh₄] to the hot reaction mixture gives complexes [(Ph₃E)₂M(SC₆H₄CO₂) HNEt₃]⁺[BPh4]⁻ (E=P, As). Analogous pyridinium and platinum–thioglycolate [(Ph₃P)₂Pt(SCH₂CO₂)] derivatives were also prepared. An X-ray crystal structure determination on [(Ph₃P)₂Pt(SC₆H₄CO₂) HNEt₃]⁺[BPh₄]⁻ reveals hydrogen-bonding between the NH proton and the carbonyl group of the thiosalicylate ligand, the major effect of which is to flatten the platinum–thiosalicylate moiety. NMR spectroscopic data indicate that the hydrogen-bonding interaction persists in solution.

year: 2003-03-01

title: Toxicological effects of MV Rena pollutants to New Zealand fish and lobster

authors: Webby, Ashley Jade

subjects: Oil spill

abstract: As part of the Rena Long Term Environmental Recovery Programme commissioned by the Ministry for the Environment in response to the grounding of the MV Rena on Astrolabe Reef (Otaiti), an experimental study of ecotoxicological effects was initiated to examine potential effects of major pollutants discharged from or associated with the Rena shipwreck. This project is one of the first examinations of ship wreck and oil spill pollution in New Zealand. Research will aid responses to future oil pollution events such as ship groundings and oil industry pollution.
The container ship MV Rena ran aground on Astrolabe Reef in the Bay of Plenty in October 2011 and discharged approximately 350 tonnes of heavy fuel oil (HFO). During the response HFO was treated with approximately 3 m³ of the oil dispersant Corexit 9500 at sea. Other pollutants associated with the Rena grounding included general cargo and other goods classified as environmentally hazardous, in particular, 560 tonnes of sodium hexafluoroaluminate or cryolite. Given the almost total absence of toxicity data relevant to HFOs, Corexit 9500 and other contaminant mixtures on New Zealand marine species, this project sought to assess the acute sublethal toxicity of these contaminants to a range of culturally, ecologically and commercially important species.
Sub-adult snapper (Pagrus auratus), spotted wrasse (Notolabrus celidotus) and red rock lobster (Jasus edwardsii) were exposed to 1:1000 cryolite, 1:10000 HFO (HFO WAF), 1:400000 Corexit 9500 and 1:40 HFO/Corexit 9500 combination (HFO CEWAF: 1:10000 HFO, 1:400000 Corexit 9500) for up to 96 h followed by recovery for up to 10 d. These concentrations and exposure durations were viewed as being environmentally realistic. Fish were necropsied and examined for haematology and accumulation of polycyclic aromatic hydrocarbons (PAHs).
Exposure to toxicants caused no lethality but did indicate sub-lethal effects. Measurements of blood parameters indicated two main effects in fish of erythrocyte swelling and haemoconcentration. The overall pattern of response in fish appeared to be a greater degree of erythrocyte swelling in response to the HFO WAF treatment. HFO WAF and HFO CEWAF treatments caused changes in leukocyte differential counts indicating negative responses of immunosuppression in fish. Corexit 9500 and cryolite exposure caused negligible/minimal changes in haematology in all species. Haematological assessment of Jasus edwardsii indicated immune effects of HFO WAF, HFO CEWAF and cryolite exposure as evident by changes in differential haemocyte counts.
Bile PAHs in fish and red rock lobster reached levels several orders of magnitude higher than controls. Corexit 9500 increased PAH body burden when combined with oil, however in fish it also appeared to accelerate depuration of PAHs during post-exposure recovery. Depuration was not as evident in red rock lobster. Exposure to HFO appeared to stimulate an increase in melanomacrophages in the spleen of Pagrus auratus. Overall HFO exposure with or without the addition of Corexit 9500 caused apparent sublethal changes in haematology that mostly recovered by 10 d post-exposure.

text: Toxicological effects of MV Rena pollutants to New Zealand fish and lobster As part of the Rena Long Term Environmental Recovery Programme commissioned by the Ministry for the Environment in response to the grounding of the MV Rena on Astrolabe Reef (Otaiti), an experimental study of ecotoxicological effects was initiated to examine potential effects of major pollutants discharged from or associated with the Rena shipwreck. This project is one of the first examinations of ship wreck and oil spill pollution in New Zealand. Research will aid responses to future oil pollution events such as ship groundings and oil industry pollution.
The container ship MV Rena ran aground on Astrolabe Reef in the Bay of Plenty in October 2011 and discharged approximately 350 tonnes of heavy fuel oil (HFO). During the response HFO was treated with approximately 3 m³ of the oil dispersant Corexit 9500 at sea. Other pollutants associated with the Rena grounding included general cargo and other goods classified as environmentally hazardous, in particular, 560 tonnes of sodium hexafluoroaluminate or cryolite. Given the almost total absence of toxicity data relevant to HFOs, Corexit 9500 and other contaminant mixtures on New Zealand marine species, this project sought to assess the acute sublethal toxicity of these contaminants to a range of culturally, ecologically and commercially important species.
Sub-adult snapper (Pagrus auratus), spotted wrasse (Notolabrus celidotus) and red rock lobster (Jasus edwardsii) were exposed to 1:1000 cryolite, 1:10000 HFO (HFO WAF), 1:400000 Corexit 9500 and 1:40 HFO/Corexit 9500 combination (HFO CEWAF: 1:10000 HFO, 1:400000 Corexit 9500) for up to 96 h followed by recovery for up to 10 d. These concentrations and exposure durations were viewed as being environmentally realistic. Fish were necropsied and examined for haematology and accumulation of polycyclic aromatic hydrocarbons (PAHs).
Exposure to toxicants caused no lethality but did indicate sub-lethal effects. Measurements of blood parameters indicated two main effects in fish of erythrocyte swelling and haemoconcentration. The overall pattern of response in fish appeared to be a greater degree of erythrocyte swelling in response to the HFO WAF treatment. HFO WAF and HFO CEWAF treatments caused changes in leukocyte differential counts indicating negative responses of immunosuppression in fish. Corexit 9500 and cryolite exposure caused negligible/minimal changes in haematology in all species. Haematological assessment of Jasus edwardsii indicated immune effects of HFO WAF, HFO CEWAF and cryolite exposure as evident by changes in differential haemocyte counts.
Bile PAHs in fish and red rock lobster reached levels several orders of magnitude higher than controls. Corexit 9500 increased PAH body burden when combined with oil, however in fish it also appeared to accelerate depuration of PAHs during post-exposure recovery. Depuration was not as evident in red rock lobster. Exposure to HFO appeared to stimulate an increase in melanomacrophages in the spleen of Pagrus auratus. Overall HFO exposure with or without the addition of Corexit 9500 caused apparent sublethal changes in haematology that mostly recovered by 10 d post-exposure.

year: 2014

title: A cohort history of mortality in New Zealand

authors: Pool, Ian

abstract: This paper uses the generational life tables to track historical mortality experience for New Zealand Pakeha and Māori. The key research questions we seek to explore concern with why was Pakeha life expectation so high so early, and why did this survival advantage disappeared by the mid 20th century and what has happened since? For the Māori population what was the impact of contact on Māori mortality, what were the changes that have occurred and why, and what has happened to Māori mortality recently? A key finding from the cohort mortality analysis is that gains in survivorship have momentum effects that propel this advantage forward as survivors move up through the age-groups. That said, however, periods of gain may be followed later by cohort deterioration occurring among the same generations later in their life cycle, and even by further cycles of reprise and deterioration. These cycles of gain, deterioration, reprise etc are more evident for males, and particularly for Māori. Policy implications of these findings are discussed.

text: A cohort history of mortality in New Zealand This paper uses the generational life tables to track historical mortality experience for New Zealand Pakeha and Māori. The key research questions we seek to explore concern with why was Pakeha life expectation so high so early, and why did this survival advantage disappeared by the mid 20th century and what has happened since? For the Māori population what was the impact of contact on Māori mortality, what were the changes that have occurred and why, and what has happened to Māori mortality recently? A key finding from the cohort mortality analysis is that gains in survivorship have momentum effects that propel this advantage forward as survivors move up through the age-groups. That said, however, periods of gain may be followed later by cohort deterioration occurring among the same generations later in their life cycle, and even by further cycles of reprise and deterioration. These cycles of gain, deterioration, reprise etc are more evident for males, and particularly for Māori. Policy implications of these findings are discussed.

year: 2003