title: Estimating the abundance of banded kokopu (galaxias fasciatus gray) in small streams by nocturnal counts under spotlight illumination

authors: Hicks, Brendan J.

subjects: biology

abstract: The abundance of banded kokopu (Galaxias fasciatus Gray) in small streams has usually been determined by the labour intensive and invasive method of electric fishing. Recently, nocturnal counts under spotlight illumination have been used to determine presence or absence and relative abundance of banded kokopu, but the proportion of the population seen was unknown. We compared 20 spotlight counts of banded kokopu in approximately 20 m reaches in streams in the North Island, New Zealand, to population estimates determined by removal electric
fishing in the same reaches. Spotlight counts were related to population estimates
over a range of densities, and on average, spotlight counts were 64% of the population estimates. Though we tried to separate age-0 fish from older fish visually in the spotlight counts, the size frequency distribution of the fish caught by electric fishing showed that the visual separation was not reliable. In addition, visual counts were generally inefficient for age-0 fish (40-70 mm total length), as only about 40% were observed. Banded kokopu were also recorded in streams using time-lapse video recordings with a camera sensitive to low light levels. Diel activity showed two major peaks, one in the early morning from 0400 h to 0900 h, and the other in the afternoon
and evening from 1300 h to 1900 h. Fish were less disturbed by the observer.s approach after dark than during the day, so we suggest that from dusk to about 2200 h is the best time for visual counts of banded kokopu by spotlight in summer months.

text: Estimating the abundance of banded kokopu (galaxias fasciatus gray) in small streams by nocturnal counts under spotlight illumination The abundance of banded kokopu (Galaxias fasciatus Gray) in small streams has usually been determined by the labour intensive and invasive method of electric fishing. Recently, nocturnal counts under spotlight illumination have been used to determine presence or absence and relative abundance of banded kokopu, but the proportion of the population seen was unknown. We compared 20 spotlight counts of banded kokopu in approximately 20 m reaches in streams in the North Island, New Zealand, to population estimates determined by removal electric
fishing in the same reaches. Spotlight counts were related to population estimates
over a range of densities, and on average, spotlight counts were 64% of the population estimates. Though we tried to separate age-0 fish from older fish visually in the spotlight counts, the size frequency distribution of the fish caught by electric fishing showed that the visual separation was not reliable. In addition, visual counts were generally inefficient for age-0 fish (40-70 mm total length), as only about 40% were observed. Banded kokopu were also recorded in streams using time-lapse video recordings with a camera sensitive to low light levels. Diel activity showed two major peaks, one in the early morning from 0400 h to 0900 h, and the other in the afternoon
and evening from 1300 h to 1900 h. Fish were less disturbed by the observer.s approach after dark than during the day, so we suggest that from dusk to about 2200 h is the best time for visual counts of banded kokopu by spotlight in summer months.

year: 2002

title: The synthesis and metal ion catalysed hydrolysis of methyl 4,5-diaminopentanoate

authors: Beresford, Geoffrey Derrick

abstract: The diamino acid ester, methyl 4, 5-diaminopentanoate has been prepared for the first time. The successful five step synthesis starting from 4-hydroxybutanoic acid lactone, and two other possible pathways via ethyl 3-formylpropanoate, are described. 
pKₐ values for 4,5-diaminopentanoic acid dihydrochloride and its a methyl ester dihydrochloride (determined by potentiometric titration at 25°C and I= 0.10molℓ⁻¹) are discussed in relation to those for other 1,2-diamines.
Stability constants of Cu(II) complexes of 4,5-diaminopentanoic acid and its methyl ester were evaluated from potentiometric titration data by the program SCOGS on a PDP 11/70 computer. Both compounds form high stability constant 1:1 and 1:2 complexes with Cu(II). (For 4,5-diaminopentanoic acid log K₁ = 10.94, log K₂ = 9.40 and for methyl 4,5-diaminopentanoate log K₁ = 9.84, log K₂ = 8.51, at 25°C and I= 0.10molℓ⁻¹). A variety of protonated complexes were also present at lower pH. 
pH-stat and spectrophotometric investigations showed that in the alkaline hydrolysis of methyl 4,5-diaminopentanoate, the simple Bᴀс2 reaction is slow and masked by a competing, extremely rapid, pair of intramolecular aminolysis (lactamisation) reactions. These involve competition between five and six membered lactam ring closure. Overall constants of the order 10³ℓmol⁻¹s⁻¹ at 25°C and I = 0.10molℓ⁻¹ are observed.
The Cu(II) catalysed hydrolysis of methyl 4,5-diaminopentanoate was studied at constant pH using a pH-stat. The kinetics of hydrolysis of solutions containing a 1:2 mole ratio of Cu(II): ester are consistent with the two consecutive second order (pseudo-first-order at constant pH) reactions (1) and (2) (where E is the ester and A⁻ the anion, of 4 ,5-diaminopentanoic acid).
CuE₂²⁺ + OH⁻ → CuEA⁺ + CH₃OH 	1
CuEA⁺ + OH⁻ → CUA₂ + CH₃OH 		2
The relative values for the two rate constants obtained (k (CuE₂²⁺) = 2.41ℓmol⁻¹s⁻¹ and k (CuEA⁺) = 0.80ℓmol⁻¹s⁻¹ at 25°C and I = 0.10molℓ⁻¹) can be explained by charge and statistical effects. The value of k(CuEA⁺) was confirmed independently from studies on solutions containing a 2.5:1:4 mole ratio of Cu(II): ester: acid. The value of k(CuEen²⁺) = 0.96ℓmol⁻¹s⁻¹ obtained from solutions containing Cu(II): ester: 1,2-diaminoethane = 2.5:1:4 is approximately k(CuE₂²⁺)/2 as expected statistically. 1:1 Solutions of Cu(II) and methyl 4,5-diaminopentanoate disproportionate, so no values for k(CuE²⁺) could be measured.
The absolute values for the Cu(II) catalysed rate constants are discussed in comparison with those for methyl 2,3-diaminopropanoate and other diamino acid esters. The results for methyl 4,5-diaminopentanoate can be explained by the attenuation of inductive and positive charge effects of the metal ion by the additional methylene groups of the methyl 4,5-diaminopentanoate alkyl chain. Direct methoxycarbonyl-metal ion interaction, presumably absent in methyl 4,5-diaminopentanoate must, therefore, be unimportant in the Cu(II) catalysed hydrolysis of methyl 2,3-diarninopropanoate.

text: The synthesis and metal ion catalysed hydrolysis of methyl 4,5-diaminopentanoate The diamino acid ester, methyl 4, 5-diaminopentanoate has been prepared for the first time. The successful five step synthesis starting from 4-hydroxybutanoic acid lactone, and two other possible pathways via ethyl 3-formylpropanoate, are described. 
pKₐ values for 4,5-diaminopentanoic acid dihydrochloride and its a methyl ester dihydrochloride (determined by potentiometric titration at 25°C and I= 0.10molℓ⁻¹) are discussed in relation to those for other 1,2-diamines.
Stability constants of Cu(II) complexes of 4,5-diaminopentanoic acid and its methyl ester were evaluated from potentiometric titration data by the program SCOGS on a PDP 11/70 computer. Both compounds form high stability constant 1:1 and 1:2 complexes with Cu(II). (For 4,5-diaminopentanoic acid log K₁ = 10.94, log K₂ = 9.40 and for methyl 4,5-diaminopentanoate log K₁ = 9.84, log K₂ = 8.51, at 25°C and I= 0.10molℓ⁻¹). A variety of protonated complexes were also present at lower pH. 
pH-stat and spectrophotometric investigations showed that in the alkaline hydrolysis of methyl 4,5-diaminopentanoate, the simple Bᴀс2 reaction is slow and masked by a competing, extremely rapid, pair of intramolecular aminolysis (lactamisation) reactions. These involve competition between five and six membered lactam ring closure. Overall constants of the order 10³ℓmol⁻¹s⁻¹ at 25°C and I = 0.10molℓ⁻¹ are observed.
The Cu(II) catalysed hydrolysis of methyl 4,5-diaminopentanoate was studied at constant pH using a pH-stat. The kinetics of hydrolysis of solutions containing a 1:2 mole ratio of Cu(II): ester are consistent with the two consecutive second order (pseudo-first-order at constant pH) reactions (1) and (2) (where E is the ester and A⁻ the anion, of 4 ,5-diaminopentanoic acid).
CuE₂²⁺ + OH⁻ → CuEA⁺ + CH₃OH 	1
CuEA⁺ + OH⁻ → CUA₂ + CH₃OH 		2
The relative values for the two rate constants obtained (k (CuE₂²⁺) = 2.41ℓmol⁻¹s⁻¹ and k (CuEA⁺) = 0.80ℓmol⁻¹s⁻¹ at 25°C and I = 0.10molℓ⁻¹) can be explained by charge and statistical effects. The value of k(CuEA⁺) was confirmed independently from studies on solutions containing a 2.5:1:4 mole ratio of Cu(II): ester: acid. The value of k(CuEen²⁺) = 0.96ℓmol⁻¹s⁻¹ obtained from solutions containing Cu(II): ester: 1,2-diaminoethane = 2.5:1:4 is approximately k(CuE₂²⁺)/2 as expected statistically. 1:1 Solutions of Cu(II) and methyl 4,5-diaminopentanoate disproportionate, so no values for k(CuE²⁺) could be measured.
The absolute values for the Cu(II) catalysed rate constants are discussed in comparison with those for methyl 2,3-diaminopropanoate and other diamino acid esters. The results for methyl 4,5-diaminopentanoate can be explained by the attenuation of inductive and positive charge effects of the metal ion by the additional methylene groups of the methyl 4,5-diaminopentanoate alkyl chain. Direct methoxycarbonyl-metal ion interaction, presumably absent in methyl 4,5-diaminopentanoate must, therefore, be unimportant in the Cu(II) catalysed hydrolysis of methyl 2,3-diarninopropanoate.

year: 1977

title: Ngā Pakanga mō Wāhi Tapu: Battles over sacred places

authors: Joseph, Robert

abstract: Wāhi tapu are the sacred places of Māori in Aotearoa New Zealand. All cultures have sacred sites such as cemeteries, significant battlefields, and places of spiritual significance. Standout examples internationally include the ‘Weeping Wall’ in the Holy Land, Stonehenge in Britain, Maraeātea in the Pacific, and Intihuatana at Macchu Picchu in Peru. But unlike these sites, wāhi tapu are rarely a visible structure but rather a site or area within the landscape with values so significant that restrictions are warranted. In law, wāhi tapu are defined as a ‘place of special significance according to tikanga Māori’
 and ‘a place sacred to Māori in the traditional, spiritual, religious, ritual, or mythological sense’.
As the aphorism above emphasises, Māori historically were willing to die for land (and for women of course!), and wāhi tapu are the most sacred of places. Many battles have been fought over actual or proposed transgressions of their sacredness. In earlier years, blood was shed and men did die; today battles tend to occur in the Environment Court, but are just as passionate. Recent decades have seen conflicts where wāhi tapu were threatened by new highways, railroads, airports, prisons, residential and commercial developments, wind farms, power stations and waste dumps.
In this chapter, I discuss a number of the battles that have been fought over the development or preservation of wāhi tapu from first European contact up until the present time. I highlight the growing legal recognition of tikanga Māori in relation to these sacred landscapes, and conclude with a proposed pragmatic solution for all New Zealanders when negotiating developments over wāhi tapu. Having a
background in law and tribal affiliations, I discuss these tensions from both legal and kaupapa Māori perspectives.

text: Ngā Pakanga mō Wāhi Tapu: Battles over sacred places Wāhi tapu are the sacred places of Māori in Aotearoa New Zealand. All cultures have sacred sites such as cemeteries, significant battlefields, and places of spiritual significance. Standout examples internationally include the ‘Weeping Wall’ in the Holy Land, Stonehenge in Britain, Maraeātea in the Pacific, and Intihuatana at Macchu Picchu in Peru. But unlike these sites, wāhi tapu are rarely a visible structure but rather a site or area within the landscape with values so significant that restrictions are warranted. In law, wāhi tapu are defined as a ‘place of special significance according to tikanga Māori’
 and ‘a place sacred to Māori in the traditional, spiritual, religious, ritual, or mythological sense’.
As the aphorism above emphasises, Māori historically were willing to die for land (and for women of course!), and wāhi tapu are the most sacred of places. Many battles have been fought over actual or proposed transgressions of their sacredness. In earlier years, blood was shed and men did die; today battles tend to occur in the Environment Court, but are just as passionate. Recent decades have seen conflicts where wāhi tapu were threatened by new highways, railroads, airports, prisons, residential and commercial developments, wind farms, power stations and waste dumps.
In this chapter, I discuss a number of the battles that have been fought over the development or preservation of wāhi tapu from first European contact up until the present time. I highlight the growing legal recognition of tikanga Māori in relation to these sacred landscapes, and conclude with a proposed pragmatic solution for all New Zealanders when negotiating developments over wāhi tapu. Having a
background in law and tribal affiliations, I discuss these tensions from both legal and kaupapa Māori perspectives.

year: 2011