Magnetic polarity stratigraphy of a Plio-Pleistocene marine sequence of North Island, New Zealand

Thick sequences of relatively undisturbed Plio-Pleistocene sediments in the Wanganui Basin, North Island, New Zealand consist of well exposed silts, clayey silts, sandstones, rare limestones, and several tephras. Oriented specimens were collected from a section more than 2500 m thick and palaeomagnetic measurements were made using A.C. demagnetisations in fields up to 35 mT. With the aid of tephrochronology the age of the upper sequence is now well established and falls within the Matuyama epoch. The lower two-thirds of the section except for the basal 500 m is predominantly normally magnetised and is interpreted as a very extended sequence of the Gauss epoch. The lowest 500 m then represents the Gilbert epoch. The Plio-Pleistocene boundary, as defined at Vrica, Italy, falls within the upper part of the section studied, in the Upper Nukumaruan stage. For the first time a reliable correlation is made with the international boundary, using as intermediaries the palaeomagnetic and tephrostratigraphy of deep-sea cores from the southwest Pacific.

As a result of the high deposition rate (of the order of 1.2 m/ky) and the apparent lack of unconformities, the temporal resolution is high; short-lived magnetic events are detected, especially in the lower Matuyama and upper Gauss epochs. These generally correlate well with events reported from other extended sections.     

The hydrolysis of gold(I) in aqueous solutions to 600°c and 1500 bar

The solubility of gold has been measured in aqueous solutions at temperatures between 300 and 600°C and pressures from 500 to 1500 bar to determine the stability and stoichiometry of the hydroxy complexes of gold(I) in hydrothermal solutions. The experiments were carried out using a flow-through autoclave system. The solubilities, measured as total dissolved gold, were in the range 1.2 × 10⁻⁸ to 2.0 × 10⁻⁶ mol kg⁻¹ (0.002 to 0.40 mg kg⁻¹), in solutions of total dissolved sodium between 0.0 and 0.5 mol kg⁻¹, and total dissolved hydrogen between 4.0 × 10⁻⁶ and 4.0 × 10⁻⁴ mol kg⁻¹. At constant hydrogen molality, the solubility of gold increases with increasing temperature and decreases with increasing pressure. The solubilities were found to be independent of pH but increased with decreasing hydrogen molality at constant temperature and pressure. Consequently, gold dissolves in aqueous solutions of acidic to alkaline pH according to the reactionAu(s)+H₂O(l)=AuOH(aq)+0.5H₂(g) K_s,1The solubility constant, logK_s,1, increases with increasing temperature from a minimum of −8.76 (±0.18) at 300°C and 500 bar to a maximum of −7.50 (±0.11) at 500°C and 1500 bar and decreases to −7.61 (±0.08) at 600°C and 1500 bar. From the equilibrium solubility constant and the redox potential of gold, the formation constant to form AuOH(aq) was calculated. At 25°C the complex formation is characterised by an exothermic enthalpy and a positive entropy. With increasing temperature and decreasing pressure, the formation reaction becomes endothermic and is accompanied by a large positive entropy, indicating a greater electrostatic interaction between Au⁺ and OH⁻.     

The hydrothermal reaction kinetics of aspartic acid

Experimental data on the hydrothermal reaction kinetics of aspartic acid were acquired using a custom-built spectrophotometric reaction cell which permits in situ observation under hydrothermal conditions. The results of this study indicate that the reaction kinetics of dilute aspartic acid solutions are significantly different depending on the presence or absence of catalytic surfaces such as standard metal alloys. The spectroscopic data presented here represent the first direct observations, in situ and in real time, of an amino acid reacting in a hydrothermal solution. Quantitative kinetic information, including rate constants, concentration versus time profiles, and calculations of the individual component spectra, was obtained from the data using a chemometric approach based on factor analysis/principle component analysis which treats the rate expressions simultaneously as a system of differential algebraic equations (DAE) of index 1. Identification of the products was confirmed where possible by high pressure anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD). The reaction kinetics of aspartic acid under hydrothermal conditions was observed to be highly complex, in contrast to previous studies which indicated almost exclusively deamination. At lower temperatures (120-170 °C), several different reaction pathways were observed, including decarboxylation and polymerization, and the catalytic effects of reactor surfaces on the aspartic acid system were clearly demonstrated. At higher temperatures (above 170 °C), aspartic acid exhibited highly complex behaviour, with evidence indicating that it can simultaneously dimerize and cyclize, deaminate (by up to two pathways), and decarboxylate (by up to two pathways). These higher temperature kinetics were not fully resolvable in a quantitative manner due to the complexity of the system and the constraints of UV spectroscopy. The results of this study provide strong evidence that the reaction kinetics of aspartic acid are very sensitive to parameters such as temperature, reactor materials (i.e., reactive surfaces), and additives, and that previous observations on aspartic acid were specific to the choice of experimental conditions.     

Challenges Facing Environmentally Sustainable Ground Water Use in South Africa

In 1998, South Africa promulgated a Water Act that is widely regarded as one of the most progressive and enabling pieces of environmental legislation in the world. The environmental aspects of the Water Act are commonly referred to as “resource-directed measures.” These measures attempt to find the right balance between (1) leaving water in the resource (“nonconsumptive use”) to provide ecological goods and services for society and (2) taking the water out of the system for “consumptive” human use. These measures also attempt to ensure that both nonconsumptive and consumptive use is sustainable. This article discusses some of the challenges faced in using the measures to achieve environmentally sustainable ground water use. A major challenge is that misunderstanding still abounds regarding the environmental aims of this legislation. Other major challenges identified included a severe shortage of technical capacity, an inordinately long water use license application process, incorporating adaptive management to deal with uncertainty, incorporating the public participation process, and revising policy implementation processes to accommodate highly localized aquifers. Selecting appropriate scientific methodology—neither too simplistic nor too involved—is a recurring challenge. It is suggested that an important part of addressing these and the other challenges identified is a period of reflection and dialogue between the various sectors involved.     

The adsorption of gold(I) hydrosulphide complexes by iron sulphide surfaces

The adsorption of gold by pyrite, pyrrhotite, and mackinawite from solutions containing up to 40 mg/kg (8 μm) gold as hydrosulphidogold(I) complexes has been measured over the pH range from 2 to 10 at 25°C and at 0.10 m ionic strength (NaCl, NaClO₄). The pH of point of zero charge, pH_pzc, has been determined potentiometrically for all three iron sulphides and shown to be 2.4, 2.7, and 2.9 for pyrite, pyrrhotite, and mackinawite, respectively. In solutions containing hydrogen sulphide, the pH_pzc is reduced to values below 2. The surface charge for each sulphide is therefore negative over the pH range studied in the adsorption experiments. Adsorption was from 100% in acid solutions having pH < 5.5 (pyrite) and pH < 4 (mackinawite and pyrrhotite). At alkaline pH’s (e.g., pH = 9), the pyrite surface adsorbed 30% of the gold from solution, whereas the pyrrhotite and mackinawite surfaces did not adsorb.The main gold complex adsorbed is AuHS°, as may be deduced from the gold speciation in solution in combination with the surface charge. The adsorption of the negatively charged Au(HS)₂⁻ onto the negatively charged sulphide surfaces is not favoured. The X-ray photoelectron spectroscopic data revealed different surface reactions for pyrite and mackinawite surfaces. While no change in redox state of adsorbent and adsorbate was observed on pyrite, a chemisorption reaction has been determined on mackinawite leading to the reduction of the gold(I) solution complex to gold(0) and to the formation of surface polysulphides. The data indicate that the adsorption of gold complexes onto iron sulphide surfaces such as that of pyrite is an important process in the “deposition” of gold from aqueous solutions over a wide range of temperatures and pressures.     

The stability of chloride complexes of Silver in hydrothermal solutions up to 350°C

The solubility of silver chloride has been measured in sodium chloride solutions of 5×10^?5 ? 3.0 m over the temperature range from 100 to 353°C at the saturated vapour pressure of the system. The solubility product and the cumulative and stepwise formation constants have been calculated from the solubility data. With increasing temperature, there is a trend towards chlorosilver (I) complexes of low coordination number and charge. At T > 270°C, the species of maximum ligand number in concentrated solutions up to 3.0m sodium chloride, is the dichlorosilver (I) complex, AgCl₂. In addition, large endothermic enthalpies and large positive entropies, similar to those found for hardhard interactions at low temperature, accompany complex formation at elevated temperatures. It is concluded that chlorosilver (I) complexes play an important role in the transport and deposition of silver from hydrothermal ore solutions.     

Age of New Zealand Pleistocene substages by fission-track dating of glass shards from tephra horizons

Eleven tephras and two pumice-rich horizons interbedded in Pleistocene marine sediments of the Wanganui Basin have been dated using the fission-track method on glass shards. Ages of the lower boundaries of New Zealand Pleistocene marine Substages are 0.45 m.y. (Putikian), 1.06 m.y. (Okehuan), 1.55 m.y. (Marahauan). On the basis of sedimentation rates an estimation of 1.86 m.y. is obtained for the Plio-Pleistocene boundary (Hautawan).     

The reaction kinetics of alanine and glycine under hydrothermal conditions

Experimental data on the hydrothermal reaction kinetics of α-alanine, glycine, and β-alanine were acquired using a custom-built spectrophotometric reaction cell which permits in situ observation under hydrothermal conditions. Quantitative kinetic information, including rate constants, concentration versus time profiles, and calculations of the individual component spectra, was obtained from the data using a self-modeling chemometric approach based on factor analysis which treats the rate expressions simultaneously as a system of differential algebraic equations (DAE) of index 1. Experimental data collected at 120-165 °C and 20 bar indicates that aqueous α-alanine, glycine and β-alanine will preferentially undergo dimerization and subsequent cyclization when heated in an inert reactor. The results presented here lend further support to the roles of temperature, exposed reactive surfaces, and matrix additives in the reaction kinetics of the structurally simple amino acids examined in this study.