Spectrophotometric determination of pH in seawater off Taiaroa Head,Otago, New Zealand: Full-spectrum modelling and prediction of pCO2 levels

Accurate measurement of seawater pH has long been sought by marine chemists (for example: [Dickson, A.G. 1993a. The measurement of sea water pH. Marine Chemistry, 44, 131–142, Dickson, A.G. 1993b. pH buffers for sea water media based on the total hydrogen ion concentration scale. Deep-Sea Research, 40, 107–118; Zhang, 1996; Tapp, M., Hunter, K.A., Currie, K. and Macaskill, B. 2000. Apparatus of continuous-flow underway spectrophotometric measurement of surface water pH. Marine Chemistry 72(2–4), 193–202; Friis, K., Koetzinger, A., Wallace, D.W.R. 2004. Spectrophotometric pH measurement in the ocean: Requirements, design and testing of an autonomous charge-coupled device detector system. Limnology and Oceanography: Methods 2, 126–136]. Recently, such attempts have taken on greater significance as anthropogenic carbon dioxide emissions may create rapidly changing oceanic pH. Spectrophotometric techniques have been accepted generally as the best for determination of seawater pH. Here we report a new technique using thymol blue as the indicator dye and fitting the entire spectrum from 400 to 900 nm rather than measuring the absorbance values at only two or three points in the spectrum. This full-spectrum modelling enables a reduction in signal to noise over other techniques. In the laboratory, we find with seawater samples a pH precision increase of five-fold “within” a sample and seven-fold “between” samples when comparing the full spectrum to the three-point method of analysis [Zhang, H., Byrne, R.H. 1996. Spectrophotometric pH measurements of surface seawater at in-situ conditions: absorbance and protonation behaviour of thymol blue. Marine Chemistry 52, 17–25].     

Regional trends in crude birth,death, and natural increase rates in Russia and the USSR: 1897-1989

"This paper establishes and discusses briefly regional patterns and trends in crude birth, death, and natural increase rates in Russia and the USSR from the turn of the century to 1989. The study is based on a comparable regional framework and placed in the context of the demographic transition theory. It discusses sources, collection, and quality of data, as well as necessary estimating procedures. An attempt also is made to examine briefly regional age-standardized rates."     

Primodial retention of carbon by the terrestrial planets

Chemical equilibrium calculations on the stability of pure and dissolved graphite and cohenite (Fe₃C), several other carbides, and several carbonates have been carried out for a system with solar elemental abundances over a very wide range of temperature and pressure. The calculated abundances of condensed carbon compounds are similar to the observed inventories on Earth and Venus, but fully 10 times smaller than the minimum carbon abundance found in ordinary chondrites. The total carbon content of most iron meteorites is compatible with their origin as a cooling FeNiCSP solution which was saturated with dissolved carbon at the solidus, such as would be produced by melting an ordinary chondrite, not by direct condensation from or equilibrium with the primitive solar nebula. It is argued that the carbon content of Mars need not be appreciably greater than that of the Earth. Material with even lower formation temperatures than Mars, such as the primitive material in the asteroid belt, may retain substantially more carbon as disequilibrium polymeric organic matter, possibly by the Fischer-Tropsch mechanism favored by Anders. Carbonates are not found as equilibrium products in a solar-composition system, and are probably secondary alteration products. CaCO₃ might, however, persist in a solar-composition gas at temperatures below 460°K and pressures below 10^?6.6 bar. The most stable condensed carbon compounds are found to be graphite, Fe₃C, and possibly TiC, all in solid solution in the metal phase.     

Thermodynamics of selected trace elements in the Jovian atmosphere

The thermochemistry of several hundred compounds of twelve selected trace elements (Ge, Se, Ga, As, Te, Pb, Sn, Cd, Sb, Tl, In, and Bi) has been investigated for solar composition material along a Jupiter adiabat. The results indicate that AsF₃, InBr, TlI, and SbS, in addition to CO, PH₃, GeH₄, AsH₃, H₂Se, HCl, HF, and H₃BO₃ proposed by Barshay and Lewis (1978), may be potential chemical tracers of atmospheric dynamics. The reported observations of GeH₄ is interpreted on the basis of new calculations as implying rapid vertical transport from levels where T ? 800°K. Upper limits are also set on the abundances of many gaseous compounds of the elements investigated.     

Mass-radius relationships and constraints on the composition of Pluto,II

A new estimate of Pluto's mass within the range of possible masses considered in an earlier work has enabled us to refine our model of Pluto's interior.     

Numerical simulation of the final stages of terrestrial planet formation

Three representative numerical simulations of the growth of the terrestrial planets by accretion of large protoplanets are presented. The mass and relative-velocity distributions of the bodies in these simulations are free to evolve simultaneously in response to close gravitational encounters and occasional collisions between bodies. The collisions between bodies, therefore, arise in a natural way and the assumption of expressions for the relative velocity distribution and the gravitational collision cross section is unnecessary. These simulations indicate that the growth of bodies with final masses approaching those of Venus and the Earth is possible, at least for the case of a two-dimensional system. Simulations assuming an initial uniform distribution of orbital eccentricities on the interval from 0 to e_max are found to produce final states containing too many bodies with masses which are too small when e_max < 0.10, while simulations with e_max > 0.20 result in too many catastrophic collisions between bodies thus preventing rapid accretion of planetary-size bodies. The e_max = 0.15 simulation ends with a state surprisingly similar to that of the present terrestrial planets and, therefore, provides a rough estimate of the range of radial sampling to be expected for the terrestrial planets.     

Stable isotope (O and C) and pollen trends in eastern Lake Erie,evidence for a locally-induced climatic reversal of Younger Dryas age in the Great Lakes basin

A cool period from about 11000 to 10 500 BP (11 to 10.5 ka) is recognized in pollen records from the southern Great Lakes area by the return of Picea and Abies dominance and by the persistence of herbs. The area of cooling appears centred on the Upper Great Lakes. A high-resolution record (ca. 9 mm/y) from a borehole in eastern Lake Erie reveals, in the same time interval, this pollen anomaly, isotope evidence of meltwater presence (a — 3 per mil shift in ¹⁸O and a +1.1 per mil shift in ¹³C), increased sand, and reduced detrital calcite content, all suggesting concurrent cooling of Lake Erie. The onset of cooling is mainly attributed to the effect of enhanced meltwater inflow on the relatively large upstream Main Lake Algonquin during the first eastward discharge of glacial Lake Agassiz. Termination of the cooling coincides with drainage of Lake Algonquin, and is attributed to loss of its cooling effectiveness associated with a substantial reduction in its surface area. It is hypothesized that the cold extra inflow effectively prolonged the seasonal presence of lake ice and the period of spring overturn in Lake Algonquin. The deep mixing would have greatly increased the thermal conductive capacity of this extensive lake, causing suppression of summer surface lakewater temperatures and reduction of onshore growing-degree days. Alternatively, a rapid flow of meltwater, buoyed on sediment-charged (denser) lakewater, may have kept the lake surface cold in summer. Other factors such as wind-shifted pollen deposition and possible effects from the Younger Dryas North Atlantic cooling could have contributed to the Great Lakes climatic reversal, but further studies are needed to resolve their relative significance.Contribution to Climo Locarno — Past and Present Climate Dynamics; Conference September 1990, Swiss Academy of Sciences — National Climate ProgramGeological Survey of Canada Contribution 58 890     

The observed limb effect in Fraunhofer lines,I

The absolute limb effect is presented for Fei lines 3767 and 3969; for five Tii lines of multiplet 42 near 4535 and one Tiii line at 4534; two lines of Mgi, 4571 and 5172; two lines of Baii at 5854 and 6497. The scattered light of the McMath solar telescope is illustrated by several figures but not applied to the limb-effect observations. It is suggested that the supergravity shift at the limb is the result of scattering of the atoms in anisotropic velocity field.Operated by the Association of Universities for Research in Astronomy, Inc. (AURA) under cooperative agreement with the National Science Foundation.     

Noble gases in the Allende and Abee meteorites and a gas-rich mineral fraction: investigation by stepwise heating

Noble gases in three meteoritic samples were examined by stepwise heating, in an attempt to relate peaks in the outgassing curves to specific minerals: NeKrXe in Allende (C3V) and an Allende residue insoluble in HF-HCl, and Xe in Abee (E4). In Allende, chromite and carbon contain most of the trapped Ne (²⁰Ne/²²Ne ≈ 8.7) and anomalous Xe enriched in light and heavy isotopes, and release it at ~850°C (bulk meteorite) or 1000°C (residue). Mineral Q, containing most of the trapped Ar, Kr, Xe as well as some Ne (²⁰Ne/²²Ne ≈ 10.4), releases its gases mainly between 1200 and 1600°C, well above the release temperatures of organic polymers (300–500°) or amorphous carbon (800–1000°). The high noble-gas release temperature, ready solubility in oxidizing acids, and correlation with acid-soluble Fe and Cr all point to an inorganic rather than carbonaceous nature of Q.All the radiogenic ¹²⁹Xe is contained in HCl, HF-soluble minerals, and is distributed as follows over the peaks in the release curve: Attend 1000° (75%), 1300° (25%); Abee (data of Hohenberg and Reynolds, 1969) ~850° (15%), 1100° (60%), 1300° (25%). No conclusive identifications of host phases can yet be given; possible candidates are troilite and silicates for Allende, and djerfisherite, troilite and silicates for Abee.Mineral Q strongly absorbs air xenon, and releases some of it only at 800–1000°C. Dilution by air Xe from Q and other minerals may explain why temperature fractions from bulk meteorites often contain less ^124–130Xe for a given enrichment in heavy isotopes than does xenon from etched chromitecarbon samples, although chromite-carbon is the source of the anomalous xenon in either case. Air xenon contamination thus is an important source of error in the derivation of fission xenon spectra.