The degassing behavior of Au, Tl, As, Pb, Re, Cd and Bi from silicate liquids: Experiments and applications

We investigate the degassing of volatile heavy metals from natural basalt and dacite and synthetic rhyolite melts doped with Bi, Pb, Tl, Au, Re, Sb, Sn, Cd, Mo, As, Cu in Pt capsules over a range of temperatures (1200-1430 °C) exposed to air at 0.1 MPa. We also investigated the effects of ligands on degassing by adding known concentrations of Cl and S. During the experiments concentration gradients normal to the melt/gas interface arose for the trace metals Au, Tl, As, Cd, Re, Bi and Pb, as shown by measurements by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) on the quenched glasses. In contrast, erratic concentration gradients occurred for Cu, Mo, Sn, Sb due to the development of compositional cords in the glass for those elements. The diffusivities for Au, Tl, As, Cd, Re, Bi and Pb (in decreasing order of volatility) followed an Arrhenius relationship with log D at 1260 °C varying from −12 to −17. The addition of Cl and S were shown to increase by two-to five-fold the volatilities of all metals, with S having a more profound effect. Diffusivities from the experiments were applied in a bubble growth model to examine the behavior of Tl and Pb in volcanic gases. The Tl/Pb ratio in gases shows much greater variation than can be explained by partitioning and magma composition alone, with diffusion serving to drastically enrich or deplete the Tl/Pb of gases to values significantly different from that of the melt.     

Recurrent spring‐fed rivers in a Middle to Late Pleistocene semi‐arid grassland: Implications for environments of early humans in the Lake Victoria Basin,Kenya

The effect of changing palaeoclimate and palaeoenvironment on human evolution during the Pleistocene is debated, but hampered by few East African records directly associated with archaeological sites prior to the Last Glacial Maximum. Middle to Late Pleistocene deposits on the shoreline of eastern Lake Victoria preserve abundant vertebrate fossils and Middle Stone Age arte‐facts associated with riverine tufas at the base of the deposits, which are ideal for palaeoenvironmental reconstructions. New data from tufas identified on Rusinga Island and on the mainland near Karungu, Kenya are provided from outcrop, thin sections, mineralogical, stable isotopic and U‐series dating analyses. Tufa is identified in four sites: Nyamita (94·0 ± 3·3 and 111·4 ± 4·2 ka); Kisaaka, Aringo (455 ± 45 ka); and Obware. The age ranges of these tufa deposits demonstrate that spring‐fed rivers were a recurrent, variably preserved feature on the Pleistocene landscape for ca 360 kyr. Poor sorting of clastic facies from all sites indicates flashy, ephemeral discharge, but these facies are commonly associated with barrage tufas, paludal environments with δ¹³C values of ca 10‰ indicative of C₃ plants and fossil Hippopotamus, all of which indicate a perennial water source. Other tufa deposits from Nyamita, Obware and Aringo have a mixed C₃/C₄ signature consistent with a semi‐arid C₄ grassland surrounding these spring‐fed rivers. The δ¹⁸O values of tufa from Nyamita are on average ca 1‰ more negative than calcite precipitated from modern rainfall in the region, suggesting greater contribution of depleted monsoonal input, similar to the Last Glacial Maximum. Microdebitage and surface‐collected artefacts indicate that early modern humans were utilizing these spring‐fed rivers. The presence of spring?fed rivers would have afforded animals a reliable water source, sustaining a diverse plant and animal community in an otherwise arid environment.     

Albedo distribution on Io's surface

A visual albedo distribution model for all hemispheres of Io's surface has been synthesized from available Earth-based and spacecraft image and photometric data. The resulting model indicates some interesting patterns and symmetries on Io's surface: The dark polar caps are shifted off Io's rotational axis and are eliptical rather than circular in shape, with extensions toward the sub-Jupiter and anti-Jupiter points on Io; equatorial bright areas are located approximately on a great circle about Io, the plane of which is tilted approximately 15° toward Io longitude 60°. These and other indicated features may be clues to understanding the endogenic and exogenic processes that have resulted in Io's present observed surface characteristics.     

Seasonal and Interannual Variability in the Distribution of Surface Nutrients and Dissolved Inorganic Carbon in the Northern North Pacific: Influence of El Niño

The seasonal and interannual changes in surface nutrients, dissolved inorganic carbon (DIC) and total alkalinity (TA) were recorded in the North Pacific (30–54°N) from 1995 to 2001. This study focuses on the region north of the subarctic boundary (∼40°N) where there was extensive monthly coverage of surface properties. The nutrient cycles showed large interannual variations in the eastern and western subarctic gyres. In the Alaska Gyre the seasonal depletion of nitrate (ΔNO₃) increased from 8–14 μmol kg⁻¹ in 1995–1999 to 21.5 μmol kg⁻¹ in 2000. In the western subarctic the shifts were similar in amplitude but more frequent. The large ΔNO₃ levels were associated with high silicate depletions, indicating enhanced diatom production. The seasonal DIC:NO₃ drawdown ratios were elevated in the eastern and central subarctic due to calcification. In the western subarctic and the central Bering Sea calcification was significant only during 1997 and/or 1998, two El Ni?o years. Regional C/N stoichiometric molar ratios of 5.7 to 7.0 (>40°N) were determined based on the years with negligible or no calcification. The annual new production (NP_a) based on ΔNO₃ and these C/N ratios showed large interannual variations. NP_a was usually higher in the western than in the eastern subarctic. However, values of 84 gC m⁻²yr⁻¹ were found in the Alaska Gyre in 2000 which is similar to that in the most productive provinces of the northern North Pacific. There were also large increases in NP_a around the Alaska Peninsula in 1997 and 1998. Finally, the net removal of carbon by the biological pump was estimated as 0.72 Gt C yr⁻¹ in the North Pacific (>30°N). This revised version was published online in August 2006 with corrections to the Cover Date.     

Organochlorines and other environmental contaminants in muscle tissues of sportfish collected from San Francisco Bay

Edible fish species were collected from 13 locations throughout San Francisco Bay, during the spring of 1994, for determination of contaminant levels in muscle tissue. Species collected included white croaker, surfperch, leopard and brown smoothhound sharks, striped bass, white sturgeon and halibut. 66 composite tissue samples were analysed for the presence of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (P0CBs), pesticides, trace elements and dioxin/furans. The US EPA approach to assessing chemical contaminant data for fish tissue consumption was used for identifying the primary chemicals of concern. Six chemicals or chemical groups were found to exceed screening values (SVs) established using the US EPA approach. PCBs (as total Aroclors) exceeded the screening level of 3 ng g⁻¹ in all 66 muscle tissue samples, with the greatest concentrations (638 ng g⁻¹) found near San Francisco's industrial areas. Mercury was elevated (> 0.14 μg g⁻¹) in 40 of 66 samples with the greatest concentrations (1.26 μg g⁻¹) occurring in shark muscle tissues. Concentrations of the organochlorine pesticides dieldrin, total chlordane and total dichlorodiphenyltri-chloroethane (DDT) exceeded screening levels in a number of samples. Dioxin/furans (as toxic equivalent concentrations (TEQ's)) were elevated (> 0.15 pg g⁻¹) in 16 of the 19 samples analysed. Fish with high lipid content (croaker and surfperch) in their muscle tissue generally exhibited higher organic contaminant levels while fish with low lipid levels (halibut and shark) exhibited lower organic contaminant levels. Tissue samples taken from North Bay stations most often exhibited high levels of chemical contamination. The California Office of Health Hazard Assessment is currently evaluating the results of this study and has issued an interim Health Advisory concerning the human consumption of fish tissue from San Francisco Bay.     

Heavy ion formation in Titan's ionosphere: Magnetospheric introduction of free oxygen and a source of Titan's aerosols?

Discovery by Cassini's plasma instrument of heavy positive and negative ions within Titan's upper atmosphere and ionosphere has advanced our understanding of ion neutral chemistry within Titan's upper atmosphere, primarily composed of molecular nitrogen, with ~2.5% methane. The external energy flux transforms Titan's upper atmosphere and ionosphere into a medium rich in complex hydrocarbons, nitriles and haze particles extending from the surface to 1200 km altitudes. The energy sources are solar UV, solar X-rays, Saturn's magnetospheric ions and electrons, solar wind and shocked magnetosheath ions and electrons, galactic cosmic rays (GCR) and the ablation of incident meteoritic dust from Enceladus’ E-ring and interplanetary medium. Here it is proposed that the heavy atmospheric ions detected in situ by Cassini for heights >950 km, are the likely seed particles for aerosols detected by the Huygens probe for altitudes <100 km. These seed particles may be in the form of polycyclic aromatic hydrocarbons (PAH) containing both carbon and hydrogen atoms C_nH_x. There could also be hollow shells of carbon atoms, such as C₆₀, called fullerenes which contain no hydrogen. The fullerenes may compose a significant fraction of the seed particles with PAHs contributing the rest. As shown by Cassini, the upper atmosphere is bombarded by magnetospheric plasma composed of protons, H₂⁺ and water group ions. The latter provide keV oxygen, hydroxyl and water ions to Titan's upper atmosphere and can become trapped within the fullerene molecules and ions. Pickup keV N₂⁺, N⁺ and CH₄⁺ can also be implanted inside of fullerenes. Attachment of oxygen ions to PAH molecules is uncertain, but following thermalization O+ can interact with abundant CH₄ contributing to the CO and CO₂ observed in Titan's atmosphere. If an exogenic keV O+ ion is implanted into the haze particles, it could become free oxygen within those aerosols that eventually fall onto Titan's surface. The process of freeing oxygen within aerosols could be driven by cosmic ray interactions with aerosols at all heights. This process could drive pre-biotic chemistry within the descending aerosols. Cosmic ray interactions with grains at the surface, including water frost depositing on grains from cryovolcanism, would further add to abundance of trapped free oxygen. Pre-biotic chemistry could arise within surface microcosms of the composite organic-ice grains, in part driven by free oxygen in the presence of organics and any heat sources, thereby raising the astrobiological potential for microscopic equivalents of Darwin's “warm ponds” on Titan.     

Negative ions in the Enceladus plume

During Cassini’s Enceladus encounter on 12th March 2008, the Cassini Electron Spectrometer, part of the CAPS instrument, detected fluxes of negative ions in the plumes from Enceladus. It is thought that these ions include negatively charged water group cluster ions associated with the plume and forming part of the ‘plume ionosphere’. In this paper we present our observations, argue that these are negative ions, and present preliminary mass identifications. We also suggest mechanisms for production and loss of the ions as constrained by the observations. Due to their short lifetime, we suggest that the ions are produced in or near the water vapour plume, or from the extended source of ice grains in the plume. We suggest that Enceladus now joins the Earth, Comet Halley and Titan as locations in the Solar System where negative ions have been directly observed although the ions observed in each case have distinctly different characteristics.