(U-Th)/He and 40Ar/39Ar Geochronology of Weathering, Hamersley Province, Australia: Implications for weathering history and landscape Evolution

(U–Th)/He dating of goethite, when combined with quantification of diffusive 4He loss by the 4He/3He methodology, provides reliable corrected ages for minerals precipitated in weathering profiles. We have combined (U–Th)/He dating of supergene goethite with 40Ar/39Ar dating of supergene manganese oxides to study the weathering history and landscape evolution in the Hamersley Province, northwestern Australia. Incremental heating 40Ar/39Ar analysis of 187 grains of Mn oxides from 65 samples (44 hand specimens) collected from weathering profiles at seven field sites across the Hamersley Province yield precipitation ages ranging from 63.4 ± 0.9 to 1.5 ± 0.2 Ma. These results, combined with previous results of 40Ar/39Ar dating of Mn oxides (Vasconcelos, 1998 Vasconcelos, P.V., 1998. Unpub. report, pp. 1–278.Vasconcelos, 1998 and Cochrane, 2003), reveal a protracted and episodic history of weathering and landscape evolution, which was already ongoing in Late Cretaceous and spans the Palaeogene and Neogene. Seventy-three grains of goethite from 39 samples extracted from 21 hand specimens, collected from the same field sites where the Mn oxides originated, were dated by the (U–Th)/He method. Internally consistent (U–Th)/He ages, which range from 84.3 ± 12.2 to 3.3 ± 0.5 Ma, have been obtained for most samples when corrections are applied for 10% helium diffusive loss. The geochronological results obtained show remarkable similarity in the distribution of ages associated with supergene mineral precipitation. The widespread occurrence of iron oxides such as goethite in soils and weathering profiles and the successful application of (U–Th)/He dating of goethite offers great opportunities for extracting the wealth of palaeoclimatic and palaeoenvironmental information recorded by these profiles on the surface of terrestrial planets such as Earth and Mars.

Innovative measurement methodology in the study of weathering of automotive coatings

An initial aim of this project was to evaluate the conventional techniques used in the analysis of newly prepared environmentally friendly water-borne automotive coatings and compare them with solvent-borne coatings having comparable formulations. The investigation was carried out on microtuned layers as well as on complete automotive multi-layer paint systems. Methods used included the very traditional methods of gloss and hardness and the commonly used photo-oxidation index (from FTIR spectral analysis). All methods enabled the durability to weathering of the automotive coatings to be initially investigated. However, a primary aim of this work was to develop methods for analysing the early stages of chemical and property changes in both the solvent-borne and water-borne coating systems that take place during outdoor natural weathering exposures and under accelerated artificial exposures. This was achieved by using dynamic mechanical analysis (DMA), in both tension mode on the microtomed films (on all depths of the coating systems from the uppermost clear-coat right down to the electron-coat) and bending mode of the full (unmicrotomed) systems, as well as MALDI-Tof analysis on the movement of the stabilisers in the full systems. Changes in glass transition temperature and relative cross-link density were determined after weathering and these were related to changes in the chemistries of the binder systems of the coatings after weathering. Concentration profiles of the UV-stabilisers (UVA and HALS) in the coating systems were analysed as a consequence of migration in the coating systems in separate microtomed layers of the paint samples (depth profiling) after weathering and diffusion co-efficient and solubility parameters were determined for the UV stabilisers in the coating systems. The methods developed were used to determine the various physical and chemical changes that take place during weathering of the different (water-borne and solvent-borne) systems (photoxidation). The solvent-borne formulations showed less changes after weathering (both natural and accelerated) than the corresponding water-borne formulations due to the lower level of cross-links in the binders of the water-borne systems. The silver systems examined were more durable than the blue systems due to the reflecting power of the aluminium and the lower temperature of the silver coatings.

The effect of weathering processes on the vertical turbulent dispersion characteristics of crude oil spilled on the sea

Since the Exxon Valdez accident in 1987, renewed interest has come forth to better understand and predict the fate and transport of crude oil lost to marine environments. The short-term fate of an Arabian Crude oil was simulated in laboratory experiments using artificial seawater. The time-dependent changes in the rheological and chemical properties of the oil under the influence of natural weathering processes were characterized, including dispersion behavior of the oil under simulated ocean turbulence. Methodology included monitoring the changes in the chemical composition of the oil by Gas Chromatography/Mass Spectrometry (GCMS), toxicity evaluations for the oil dispersions by Microtox analysis, and quantification of dispersed soluble aromatics by fluorescence spectrometry. Results for this oil show a sharp initial increase in viscosity, due to evaporative losses of lower molecular weight hydrocarbons, with the formation of stable water-in-oil emulsions occurring within one week. Toxicity evaluations indicate a decreased EC-50 value (higher toxicity) occurring after the oil has weathered eight hours, with maximum toxicity being observed after weathering seven days. Particle charge distributions, determined by electrophoretic techniques using a Coulter DELSA 440, reveal that an unstable oil dispersion exists within the size range of 1.5 to 2.5 um, with recombination processes being observed between sequential laser runs of a single sample.

Radiogenic isotope record of Arctic Ocean circulation and weathering inputs of the past 15 million years

Lead (Pb), neodymium (Nd), and strontium (Sr) isotopic analyses were carried out on sediment leachates (reflecting the isotope composition of past seawater) and digests of the bulk residues (reflecting detrital continental inputs) of Integrated Ocean Drilling Program (IODP) Leg 302 and core PS2185 from the Lomonosov Ridge (Arctic Ocean). Our records are interpreted to reflect changes in continental erosion and oceanic circulation, driven predominantly by tectonic forcing on million-year timescales in the older (pre-2 Ma) part of the record and by climatic forcing of weathering and erosion of the Eurasian continental margin on thousand-year timescales in the younger (post-2 Ma) part. These data, covering the past ~15 Ma, show that continental inputs to the central Arctic Ocean have been more closely linked to glacial and hydrological processes occurring on the Eurasian margin than on continental North America and Greenland. The constancy of the detrital input signatures supports the early existence of an Arctic sea ice cover, whereas the major initiation of Northern Hemisphere glaciation at 2.7 Ma appears to have had little impact on the weathering regime of the Eurasian continental margin.

Weathering characteristics and lithology of samples from the Rauer Group, Antarctica, obtained in February/March 2007, and conducted with field support of POLARSTERN cruise ANT-XXIII/9

The presence of glacial sediments across the Rauer Group indicates that the East Antarctic ice sheet formerly covered the entire archipelago and has since retreated at least 15 km from its maximum extent. The degree of weathering of these glacial sediments suggests that ice retreat from this maximum position occurred sometime during the latter half of the last glacial cycle. Following this phase of retreat, the ice sheet margin has not expanded more than ~1 km seaward of its present position. This pattern of ice sheet change matches that recorded in Vestfold Hills, providing further evidence that the diminutive Marine Isotope Stage 2 ice sheet advance in the nearby Larsemann Hills may have been influenced by local factors rather than a regional ice-sheet response to climate and sea-level change.

Weathering the crisis? Managing democracy at a national broadcaster

With post-2008 political and economic crises as its backdrop, this inquiry into the political roles and functions of public service broadcasting (PSB) in Ireland is principally concerned with examining the capacities for and actuality of critical and counter-hegemonic professional journalistic and institutional mediations of crisis. Recognising the diversity of influences on the normative identity of Irish PSB, the dissertation adopts a sociological approach that acknowledges the systemic embedding of media institutions in the broader field of power. An initial tracing of the formative impacts of endogenous and exogenous forces on the democratic horizons of PSB suggests that the present crisis conjuncture does not represent promising terrain for engendering critical crisis and recovery imaginaries. A methodologically diverse intra-institutional empirical research agenda aims to explore at close hand Irish PSB’s contingent navigation of crisis, encompassing ethnographic observation in the newsroom, practitioner interviews and textual analysis of broadcast output. These methods afford close analysis of practices of journalistic production and reflexivity, self-conceptions of the journalistic habitus, and ideological affinities of crisis framings in broadcast output. These analyses are supplemented by a participant observation study of the possibilities for public agenda-building in a key institutional venue of public participation in broadcasting governance. The findings offer an evidential basis for the arguments that the crisis has prompted only minimal changes to professional norms and practices of representation and inclusion; that journalistic crisis framings tend toward effecting hegemonic repair by lending support to neoliberal crisis and recovery imaginaries; and that the institutional openings for the building of public counterpower are highly constrained. The overall conclusion is made that the normative democratic orientation embedded in the professional and institutional projects of public service broadcasting help render it ill-equipped to act as a re-democratising countervailing power against the democratic regressions engendered by the present crisis of democratic capitalism.

Stone temperature and moisture variability under temperate environmental conditions: implications for sandstone weathering

Temperature and moisture conditions are key drivers of stone weathering processes in both natural and built environments. Given their importance in the breakdown of stone, a detailed understanding of their temporal and spatial variability is central to understanding present-day weathering behaviour and for predicting how climate change may influence the nature and rates of future stone decay.
Subsurface temperature and moisture data are reported from quarry fresh Peakmoor Sandstone samples exposed during summer (June–July) and late autumn / early winter (October–December) in a mid-latitude, temperate maritime environment. These data demonstrate that the subsurface thermal response of sandstone comprises numerous short-term (minutes), low magnitude fluctuations superimposed upon larger-scale diurnal heating and cooling cycles with distinct aspect-related differences. The short-term fluctuations create conditions in the outer 5–10 mm of stone that are much more ‘energetic’ in comparison to the more subdued thermal cycling that occurs deeper within the sandstone samples.
Data show that moisture dynamics are equally complex with a near-surface region (5–10 mm) in which frequent moisture cycling takes place and this, combined with the thermal dynamism exhibited by the same region may have significant implications for the nature and rate of weathering activity. Data indicate that moisture input from rainfall, particularly when it is wind-driven, can travel deep into the stone where it can prolong the time of wetness. This most often occurs during wetter winter months when moisture input is high and evaporative loss is low but can happen at any time during the year when the hydraulic connection between near-surface and deeper regions of the stone is disrupted with subsequent loss of moisture from depth slowing as it becomes reliant on vapour diffusion alone.
These data illustrate the complexity of temperature and moisture conditions in sandstone exposed to the ‘moderate’ conditions of a temperate maritime environment. They highlight differences in thermal and moisture cycling between near-surface (5–10 mm) and deeper regions within the stone and contribute towards a better understanding of the development of structural and mineralogical heterogeneity between the stone surface and substrate.