Freezing as a method of sample preservation for the analysis of dissolved inorganic nutrients in seawater

It is often desirable or necessary to store collected seawater samples prior to analysis for dissolved inorganic nutrients. It is therefore important to establish preservation and storage techniques that will ensure sample integrity and will not alter the precision or accuracy of analysis. We have performed a series of experiments on the storage of nutrient samples collected at the oligotrophic North Pacific benchmark Station ALOHA, using both standard autoanalyses and low-level techniques. Our results reveal that for oligotrophic oceanic waters, the immediate freezing of an unfiltered water sample in a clean polyethylene bottle is a suitable preservation method. This procedure is simple, it avoids potentially contaminating sample manipulations and chemical additions, and it adequately preserves the concentrations of nitrate + nitrite, soluble reactive phosphate, and soluble reactive silicate within a single water sample.     

Raman spectra from the Al2SiO5 polymorphs at high pressures and room temperature

Raman spectra of the three Al₂SiO₅ polymorphs; andalusite, sillimanite and kyanite were recorded as a function of pressure at room temperature. All the Raman active bands which could be observed from the high-pressure cell showed a linear pressure dependence for each of the three Al₂SiO₅ polymorphs and no phase changes were observed over the pressure ranges used in this study. In andalusite and to a lesser extent in sillimanite, vibrations which could be correlated with internal motions of the SiO₄ tetrahedra were generally well separated from the lattice modes and showed a greater pressure dependence than that observed for other modes. The distinct pressure dependence of the internal SiO₄ modes is less evident in kyanite, probably due to the lack of continuous tetrahedral chains and the fact that the rigid SiO₄ tetrahedra now form an integral part of the structural network. At ambient pressure, kyanite also exhibits two fluorescence bands at 705 and 706.2 nm which are due to small amounts of Cr³⁺ in the kyanite crystals. These fluorescence bands showed a non-linear frequency shift as pressure was increased.     

Gold ore-forming fluids of the Tanami region, Northern Australia

Fluid inclusion studies have been carried out on major gold deposits and prospects in the Tanami region to determine the compositions of the associated fluids and the processes responsible for gold mineralization. Pre-ore, milky quartz veins contain only two-phase aqueous inclusions with salinities ≤19 wt% NaCl eq. and homogenization temperatures that range from 110 to 410°C. In contrast, the ore-bearing veins typically contain low to moderate salinity (<14 wt% NaCl eq.), H₂O + CO₂ ± CH₄ ± N₂-bearing fluids. The CO₂-bearing inclusions coexist with two-phase aqueous inclusions that exhibit a wider range of salinities (≤21 wt% NaCl eq.). Post-ore quartz and carbonate veins contain mainly two-phase aqueous inclusions, with a last generation of aqueous inclusions being very CaCl₂-rich. Salinities range from 7 to 33 wt% NaCl eq. and homogenization temperatures vary from 62 to 312°C. Gold deposits in the Tanami region are hosted by carbonaceous or iron-rich sedimentary rocks and/or mafic rocks. They formed over a range of depths at temperatures from 200 to 430°C. The Groundrush deposit formed at the greatest temperatures and depths (260–430°C and ≤11 km), whereas deposits in the Tanami goldfield formed at the lowest temperatures (≥200°C) and at the shallowest depths (1.5–5.6 km). There is also evidence in the Tanami goldfield for late-stage isothermal mixing with higher salinity (≤21 wt% NaCl eq.) fluids at temperatures between 100 and 200°C. Other deposits (e.g., The Granites, Callie, and Coyote) formed at intermediate depths and at temperatures ranging from 240 to 360°C. All ore fluids contained CO₂ ± N₂ ± CH₄, with the more deeply formed deposits being enriched in CH₄ and higher level deposits being enriched in CO₂. Fluids from deposits hosted mainly by sedimentary rocks generally contained appreciable quantities of N₂. The one exception is the Tanami goldfield, where the quartz veins were dominated by aqueous inclusions with rare CO₂-bearing inclusions. Calculated δ ¹⁸O values for the ore fluids range from 3.8 to 8.5‰ and the corresponding δD values range from −89 to −37‰. Measured δ ¹³C values from CO₂ extracted from fluid inclusions ranged from −5.1 to −8.4‰. These data indicate a magmatic or mixed magmatic/metamorphic source for the ore fluids in the Tanami region. Interpretation of the fluid inclusion, alteration, and structural data suggests that mineralization may have occurred via a number of processes. Gold occurs in veins associated with brittle fracturing and other dilational structures, but in the larger deposits, there is also an association with iron-rich rocks or carbonaceous sediments, suggesting that both structural and chemical controls are important. The major mineralization process appears to be boiling/effervescence of a gas-rich fluid, which leads to partitioning of H₂S into the vapor phase resulting in gold precipitation. However, some deposits also show evidence of desulfidation by fluid–rock interaction and/or reduction of the ore-fluid by fluid mixing. These latter processes are generally more prevalent in the higher crustal-level deposits.     

Decadal- to interannual-scale source water variations in the Caribbean Sea recorded by Puerto Rican coral radiocarbon

Water that forms the Florida Current, and eventually the Gulf Stream, coalesces in the Caribbean from both subtropical and equatorial sources. The equatorial sources are made up of, in part, South Atlantic water moving northward and compensating for southward flow at depth related to meridional overturning circulation. Subtropical surface water contains relatively high amounts of radiocarbon (¹⁴C), whereas equatorial waters are influenced by the upwelling of low ¹⁴C water and have relatively low concentrations of ¹⁴C. We use a 250 year record of Δ¹⁴C in a coral from southwestern Puerto Rico along with previously published coral Δ¹⁴C records as tracers of subtropical and equatorial water mixing in the northern Caribbean. Data generated in this study and from other studies indicate that the influence of either of the two water masses can change considerably on interannual to interdecadal time scales. Variability due to ocean dynamics in this region is large relative to variability caused by atmospheric ¹⁴C changes, thus masking the Suess effect at this site. A mixing model produced using coral Δ¹⁴C illustrates the time varying proportion of equatorial versus subtropical waters in the northern Caribbean between 1963 and 1983. The results of the model are consistent with linkages between multidecadal thermal variability in the North Atlantic and meridional overturning circulation. Ekman transport changes related to tradewind variability are proposed as a possible mechanism to explain the observed switches between relatively low and high Δ¹⁴C values in the coral radiocarbon records.     

Paleoproterozoic gold deposits in the Bald Hill and Coyote areas, Western Tanami, Western Australia

Significant gold deposits in the western Tanami region of Western Australia include deposits in the Bald Hill and Coyote areas. The ca. 1,864 Ma Bald Hill sequence of turbiditic and mafic volcanic rocks hosts the Kookaburra and Sandpiper deposits and a number of smaller prospects. The ca. 1,835 Ma turbiditic Killi Killi Formation hosts the Coyote deposit and several nearby prospects. The Kookaburra deposit forms as a saddle reef within a syncline, and the Sandpiper deposit is localized within graphitic metasedimentary rocks along a limb of an anticline. Gold in these deposits is hosted by anastomosing quartz–(–pyrite–arsenopyrite) veins within quartz–sericite schist with disseminated arsenopyrite, pyrite, and marcasite (after pyrrhotite). Based on relative timing relationships with structural elements, the auriferous veins are interpreted to have been emplaced before or during the ca. 1,835–1,825 Ma Tanami Orogeny (regional D₁). Gold deposition is thought to have been caused by pressure drops associated with saddle reef formation (Kookaburra) and chemical reactions with graphitic rocks (Sandpiper). The Coyote deposit, the largest in the western Tanami region, consists of a number of ore lenses localized along the limbs of the Coyote Anticline, which formed during the Tanami Orogeny. The largest lenses are associated with the Gonzalez Fault, which is located along the steeply dipping southern limb of this fold. Gold was introduced at ca. 1,790 Ma into dilatant zones that formed in local perturbations along this fault during later reactivation (regional D₅) towards the end of a period of granite emplacement. Gold is associated with quartz–chlorite–pyrite–(arsenopyrite–galena–sphalerite) veins with narrow (<?5 mm) chloritic selvages. A quartz–muscovite–biotite–K–feldspar–(tourmaline–actinolite–arsenopyrite) assemblage, which is interpreted to relate to granite emplacement, overprints the regional greenschist facies metamorphic assemblage. The mineralogical similarity between this overprinting assemblage and the vein assemblage suggests that the auriferous veins at the Coyote deposit are associated with the granite-related metamorphic–metasomatic assemblage. Gold deposition is thought to have been caused by pressure drops within dilatant zones.     

Exact Boltzmann-Gas Filled Bianchi Type V Space-Times

Bianchi type V cosmological models are studied that contain a relativistic ideal Boltzmann gas. The effect of a cosmological constant upon the space-time geometry is also considered. In both high and low temperature limit the general solution of the Einstein gravitational field equations can be expressed in an exact closed parametric form. At final stages, depending on the presence or absence of the cosmological constant, cosmologies are driven to an isotropic inflationary open de Sitter type Universe or to an isotropic open Friedmann era.     

Effects of bottom sediments on the survival of Enterobacter aerogenes in seawater

The survival of the coliform bacterium Enterobacter aerogenes in seawater was greatly affected by the underlying bottom sediments. The presence of sediments which contained higher concentrations of organic nutrients than the overlaying seawater prolonged the survival and even enabled growth of the bacterial cells. Results obtained from chemical analysis indicated that sediments of fine-grained, silt-clay type contained highest amounts of organic nutrients as compared with sediments with larger particle sizes such as silt and sand grains. Thus, nutrient contents of the sediments were found to be inversely proportional to sediment particle size. The degree of prolonged survival of E. aerogenes was also found to be inversely proportional to the size of the sediment particles presented. Release of the bound nutrients which became available to cells of E. aerogenes from sediments by action of waves and human activities can explain, at least in part, why high counts of coliform bacteria are obtained in coastal and beach waters.     

Temperature dependence of Raman spectra of the quartz- and rutile-types of GeO2

The temperature dependence (at ambient pressure) of the Raman spectra of both the quartz- and rutile-types of GeO₂ has been studied from 109 to 874?K. All spectra were corrected for the effects of temperature and are presented in their reduced form to allow a direct comparison of intensities at all temperatures. In the quartz-type GeO₂, the Raman bands above 400?cm^?1 exhibited relatively larger temperature dependences and at least four of the bands in this region vary nonlinearly with increasing temperature. Deconvolution of the most intense Raman band at 700?cm^?1 in the rutile-type GeO₂ revealed the presence of a previously unreported band at 684?cm^?1 at 298?K which may arise from splitting of the A_1g mode. A nonlinear temperature dependence was observed for all the Raman bands above 600?cm^?1 in the rutile-type GeO₂ with the new band at 684?cm^?1 exhibiting the largest curvature. In common with previous studies of rutile-type oxides, the B_1g mode at 171?cm^?1 showed anomalous behaviour by increasing linearly in frequency with increasing temperature. In a separate experiment, the oxidation of metallic germanium in air demonstrated that the quartz-type GeO₂ is the preferred form of germanium oxide at temperatures above 745?K at atmospheric pressure. Thermodynamic calculations predict that the rutile-form of GeO₂ should be the stable species under these conditions. This suggests that atmospheric gases may have a marked effect on the kinetics and stability of the quartz and rutile forms of GeO₂.     

Irreversible Matter Creation in Inflationary Cosmology

Irreversible matter creation is investigated in a two-component (scalar field and ordinary matter) cosmological fluid in a homogeneous spatially flat and isotropic Friedmann-Robertson-Walker (FRW) inflationary Universe during its reheating era. The thermodynamics of open systems as applied together with the gravitational field equations to the two-component cosmological fluid leads to a generalisation of the elementary reheating theory in which the decay (creation) pressures are explicitly considered as parts of the fluid stress-energy tensor. Particular models describing coherently oscillating scalar waves and leading to a high particle production at the beginning of the oscillatory period are considered too. This revised version was published online in July 2006 with corrections to the Cover Date.