Detailed record of SO2 emissions from Pu'u `O`o between episodes 33 and 34 of the 1983–86 ERZ eruption,Kilauea, Hawaii

A tripod-mounted correlation spectrometer was used to measure SO₂ emissions from Pu`u `O`o vent, mid-ERZ, Kilauea, Hawaii between Episodes 33 and 34 (June 13 to July 6, 1985). In 24 repose days, 906 measurements were collected, averaging 38 determinations/day. Measurements reflect 13% of the total 576 hours of the repose and 42% of the bright daylight hours. The average SO<sub>2</sub> emission for the 24-day repose interval is 167±83 t/d, a total of 4000 tonnes emitted for the entire repose. The large standard deviation reflects the puffing character of the plume. The overall rate of SO<sub>2</sub> degassing gently decreased with a zero-intercept of 44–58 days and was interrupted by two positive peaks. The data are consistent with the gas emanating from a cylindrical conduit of 50 meter diameter and a length of 1700 meters which degasses about 50% of its SO<sub>2</sub> during 24 days. This is in support of the Pu'u `O`o model of Greenland et al. (1987). 36 hours before the onset of Episode 34 (July 5–6, 1985), elevated SO₂ emissions were detected while the magma column was extremely active ultimately spilling over during dome fountaining. A mid-repose anomaly of SO₂ emission (June 21–22, 1985) occurs two days before a sudden increase in the rate of summit inflation (on June 24, 1985), suggesting magma was simultaneously being injected in both the ERZ and summit reservoir until July 24 when it was channelled only to the summit reservoir. This implies degassing magma is sensitive to perturbations within the rift zone conduit system and may at times reflect these disturbances. Periods of 7–45 min are detected in the daily SO₂ emissions, which possibly reflect timing of convective overturn in the cylindrical magma body. If the 33–34 repose interval is considered representative of other repose periods, the ERZ reposes of Jan 1983–Jan 1986 ERZ activity, contributed 1.6 × 10⁵ tonnes of SO₂ to the atmosphere. Including summit fuming from non-eruptive fumaroles (2.7 × 10⁵ tonnes SO₂); 28% of the total SO₂ budget from Kilauea between Jan 1983 to Jan 1986 was contributed by quiescent degassing, and the remainder was released during explosive fountaining episodes.     

Redox potential measurements and Mössbauer spectrometry of Fe adsorbed onto Fe (oxyhydr)oxides

The redox properties of Fe^II adsorbed onto a series of Fe^III (oxyhydr)oxides (goethite, lepidocrocite, nano-sized ferric oxide hydrate (nano-FOH), and hydrous ferric oxide (HFO)) have been investigated by rest potential measurements at a platinum electrode, as a function of pH (−log₁₀[H⁺]) and surface coverage. Using the constant capacitance surface complexation model to describe Fe^II adsorption onto these substrates, theoretical values of the suspension redox potential (E_H) have been computed, under the assumption that Fe^II adsorption occurs at crystal growth sites of the substrate surface. Good agreement between calculated and experimental E_H values is observed for nano-FOH and HFO, however the redox potentials measured for lepidocrocite and goethite are significantly more oxidizing than predicted. Mössbauer spectroscopic analysis of ⁵⁷Fe^II adsorbed onto HFO and goethite shows that in both cases the adsorbed ⁵⁷Fe^II is incorporated into the crystal structure of the substrate, in broad agreement with the thermodynamic model, but is almost completely oxidized to ⁵⁷Fe^III. The mechanism by which the adsorbed ⁵⁷Fe^II is oxidized is not resolved in this work, but is thought to be due to electron transfer to the substrate, rather than a net oxidation of the suspension. The disagreement between experimental and calculated rest potential measurements in the goethite and lepidocrocite systems is thought to be due to the poor electrochemical equilibration of these suspensions with the platinum electrode, rather than a failure of the thermodynamic model. The model developed for the redox potential of adsorbed Fe^II allows direct assessment of the reactivity of this species towards oxidized pollutants.     

Lithium Isotope Composition of Marine Biogenic Carbonates and Related Reference Materials

In this study, the accuracy and the precision corresponding to Li isotopic measurements of low level samples such as marine and coastal carbonates are estimated. To this end, a total of fifty‐four analyses of a Li‐pure reference material (Li7‐N) at concentrations ranging from 1 to 6 ng ml^?1 were first performed. The average δ⁷Li values obtained for solutions with and without chemical purification were 30.3 ± 0.4‰ (2s, n = 19) and 30.2 ± 0.4‰ (2s, n = 36), respectively. These results show that the chosen Li chemical extraction and purification procedure did not induce any significant isotope bias. Two available carbonate reference materials (JCt‐1 and JCp‐1) were analysed, yielding mean δ⁷Li values of 18.0 ± 0.27‰ (2s, n = 6) and 18.8 ± 1.8‰ (2s, n = 9), respectively. Small powder aliquots (< 15 mg) of JCp‐1 displayed significant isotope heterogeneity and we therefore advise favouring JCt‐1 for interlaboratory comparisons. The second part of this study concerns the determination of δ⁷Li value for biogenic carbonate samples. We performed a total of twenty‐nine analyses of seven different tropical coral species grown under controlled and similar conditions (24.0 ± 0.1 °C). Our sample treatment prior to Li extraction involved removal of organic matter before complete dissolution in diluted HCl. Our results show (a) a constant δ⁷Li within each skeleton and between the different species (δ⁷Li = 17.3 ± 0.7‰), and (b) a Li isotope fractionation of ?2‰ compared with inorganic aragonite grown under similar conditions. Comparison with literature data suggests a significant difference between samples living in aquaria and those grown in natural conditions. Finally, we investigate ancient (fossil) carbonate material and foraminifera extracted from marine sedimentary records. Different leaching procedures were tested using various HCl molarities. Results indicate that carbonate preferential dissolution must be carried out at an acid molarity < 0.18 mol l^?1. Possible contamination from silicate minerals can be verified using the Al/Ca ratio, but the threshold value strongly depends on the carbonate δ⁷Li value. When the silicate/carbonate ratio is high in the sediment sample (typically > 2), contamination from silicates cannot be avoided, even at low HCl molarity (? 0.1 mol l^?1). Finally, bulk carbonate and foraminifera extracted from the same core sample exhibited significant discrepancies: δ⁷Li values of foraminifera were more reproducible but were significantly lower. They were also associated with lower Sr/Ca and higher Mn/Ca ratios, suggesting a higher sensitivity to diagenesis, although specific vital effects cannot be fully ruled out.     

Microbial deposits in the aftermath of the end‐Permian mass extinction: A diverging case from the Mineral Mountains (Utah,USA)

The Lower Triassic Mineral Mountains area (Utah, USA) preserves diversified Smithian and Spathian reefs and bioaccumulations that contain fenestral‐microbialites and various benthic and pelagic organisms. Ecological and environmental changes during the Early Triassic are commonly assumed to be associated with numerous perturbations (productivity changes, acidifica‐tion, redox changes, hypercapnia, eustatism and temperature changes) post‐dating the Permian–Triassic mass extinction. New data acquired in the Mineral Mountains sediments provide evidence to decipher the relationships between depositional environments and the growth and distribution of microbial structures. These data also help to understand better the controlling factors acting upon sedimentation and community turnovers through the Smithian–early Spathian. The studied section records a large‐scale depositional sequence during the Dienerian(?)–Spathian interval. During the transgression, depositional environments evolved from a coastal bay with continental deposits to intertidal fenestral–microbial limestones, shallow subtidal marine sponge–microbial reefs to deep subtidal mud‐dominated limestones. Storm‐induced deposits, microbialite–sponge reefs and shallow subtidal deposits indicate the regression. Three microbialite associations occur in ascending order: (i) a red beds microbialite association deposited in low‐energy hypersaline supratidal conditions where microbialites consist of microbial mats and poorly preserved microbially induced sedimentary structure; (ii) a Smithian microbialite association formed in moderate to high‐energy, tidal conditions where microbialites include stromatolites and associated carbonate grains (oncoids, ooids and peloids); and (iii) a Spathian microbialite association developed in low‐energy offshore conditions that is preserved as multiple decimetre thick isolated domes and coalescent domes. Data indicate that the morphologies of the three microbialite associations are controlled primarily by accommodation, hydrodynamics, bathymetry and grain supply. This study suggests that microbial constructions are controlled by changes between trapping and binding versus precipitation processes in variable hydrodynamic conditions. Due to the presence of numerous metazoans associated with microbialites throughout the Smithian increase in accommodation and Spathian decrease in accommodation, the commonly assumed anachronistic character of the Early Triassic microbialites and the traditional view of prolonged deleterious conditions during the Early Triassic time interval is questioned.     

The dissolution kinetics of a granite and its minerals—Implications for comparison between laboratory and field dissolution rates

The present study compares the dissolution rates of plagioclase, microcline and biotite/chlorite from a bulk granite to the dissolution rates of the same minerals in mineral-rich fractions that were separated from the granite sample. The dissolution rate of plagioclase is enhanced with time as a result of exposure of its surface sites due to the removal of an iron oxide coating. Removal of the iron coating was slower in the experiment with the bulk granite than in the mineral-rich fractions due to a higher Fe concentration from biotite dissolution. As a result, the increase in plagioclase dissolution rate was initially slower in the experiment with the bulk granite. The measured steady state dissolution rates of both plagioclase (6.2 ± 1.2 × 10⁻¹¹ mol g⁻¹ s⁻¹) and microcline (1.6 ± 0.3 × 10⁻¹¹ mol g⁻¹ s⁻¹) were the same in experiments conducted with the plagioclase-rich fraction, the alkali feldspar-rich fraction and the bulk granite.Based on the observed release rates of the major elements, we suggest that the biotite/chlorite-rich fraction dissolved non-congruently under near-equilibrium conditions. In contrast, the biotite and chlorite within the bulk granite sample dissolved congruently under far from equilibrium conditions. These differences result from variations in the degree of saturation of the solutions with respect to both the dissolving biotite/chlorite and to nontronite, which probably was precipitating during dissolution of the biotite and chlorite-rich fraction. Following drying of the bulk granite, the dissolution rate of biotite was significantly enhanced, whereas the dissolution rate of plagioclase decreased.The presence of coatings, wetting and drying cycles and near equilibrium conditions all significantly affect mineral dissolution rates in the field in comparison to the dissolution rate of fully wetted clean minerals under far from equilibrium laboratory conditions. To bridge the gap between the field and the laboratory mineral dissolution rates, these effects on dissolution rate should be further studied.     

The end of the Messinian Salinity Crisis in the western Mediterranean: Insights from the carbonate platforms of south-eastern Spain

How the Messinian Salinity Crisis (MSC) ended is still a matter of intense debate. The Terminal Carbonate Complex (TCC) is a late Messinian carbonate platform system that recorded western Mediterranean hydrological changes from the final stages of evaporite deposition till the advent of Lago-Mare fresh- to brackish water conditions at the very end of Messinian times. A multidisciplinary study has been carried out in three localities in south-eastern Spain to reconstruct the history of TCC platforms and elucidate their significance in the MSC. Overall, this study provides evidence that the TCC formed following a regional 4th order water level rise and fall concomitant with an opening-restriction trend. It can be subdivided into four 5th order depositional sequences (DS1 to DS4) recording two phases: (1) from DS1 to DS3, a tide-dominated ooidic to oobioclastic system with stenohaline faunas developed as a result of a 70 m water level rise. During this period, the TCC developed in a shallow sea with close to normal marine salinity; (2) in depositional sequence 4, a microbialite-dominated platform system developed. This is indicative of a significant environmental change and is attributed to a 30 to 40 m water level fall in the basins under study. These restricted conditions were coeval with intense evaporite deformation and brine recycling. The syn-sedimentary deformation of evaporites had a major impact on platform architecture and carbonate production, affecting the Messinian series throughout south-eastern Spain at the end of the TCC history. At that time, the TCC developed in a lake with fluctuating, brackish- to hypersaline water. These findings suggest a temporary restoration of marine conditions in the western Mediterranean marginal basins due to Atlantic water influxes prompted by a global sea level rise around 5.6 Ma. Whether marine conditions extended to the entire western Mediterranean still needs to be investigated.     

Simulating the Holocene climate evolution at northern high latitudes using a coupled atmosphere-sea ice-ocean-vegetation model

The response of the climate at high northern latitudes to slowly changing external forcings was studied in a 9,000-year long simulation with the coupled atmosphere-sea ice-ocean-vegetation model ECBilt-CLIO-VECODE. Only long-term changes in insolation and atmospheric CO₂ and CH₄ content were prescribed. The experiment reveals an early optimum (9–8 kyr BP) in most regions, followed by a 1–3°C decrease in mean annual temperatures, a reduction in summer precipitation and an expansion of sea-ice cover. These results are in general agreement with proxy data. Over the continents, the timing of the largest temperature response in summer coincides with the maximum insolation difference, while over the oceans, the maximum response is delayed by a few months due to the thermal inertia of the oceans, placing the strongest cooling in the winter half year. Sea ice is involved in two positive feedbacks (ice-albedo and sea-ice insulation) that lead regionally to an amplification of the thermal response in our model (7°C cooling in Canadian Arctic). In some areas, the tundra-taiga feedback results in intensified cooling during summer, most notably in northern North America. The simulated sea-ice expansion leads in the Nordic Seas to less deep convection and local weakening of the overturning circulation, producing a maximum winter temperature reduction of 7°C. The enhanced interaction between sea ice and deep convection is accompanied by increasing interannual variability, including two marked decadal-scale cooling events. Deep convection intensifies in the Labrador Sea, keeping the overall strength of the thermohaline circulation stable throughout the experiment.     

A case study of land cover change (1950-2003) and runoff in a Mediterranean catchment

Mediterranean environments have been subject to major land cover change since the end of the second world war. Housing, agricultural activities, forests, green spaces and other land uses have shifted due to urbanisation and tourism. These changes influence runoff, and municipal authorities often cannot estimate the net impact of complex land cover transitions. During this period, elected representatives have become increasingly sensitive to the risks of flooding and have implemented a number of channel management strategies. The main objective of this case study was to analyse the impact of land cover change on total storm runoff between 1950 and 2003 in a Mediterranean catchment near St Tropez, France. A secondary objective was to compare these changes to the impacts of channel management on bankfull discharge. Aerial photographs were used to classify land cover in 3 urban categories, vineyards and bare soil, forests, and green spaces. Stream discharge was estimated using a distributed event based total runoff approach. After validating the model for a large winter event (114 mm) for 1982, runoff was calculated for the same event for 1950 and 2003. Land cover changes occurred mainly in the alluvial plain area. Total gauge catchment urban area increased from 30.1 ha to 393.8 between 1950 and 2003 at the expense mainly of agricultural land, but this was compensated in part by an increase in grassed area. Some of the loss in vineyards was replaced by clearing forested land on the first hills close to the plain. Bank stabilisation and channel maintenance since the 1980’s reduced surface roughness and increased channel area, thereby greatly increasing bankfull discharge. While the impact of urbanisation on runoff was small, channel management effects increased bankfull discharge substantially. Flood damage from extreme events was not studied here.     

Laboratory methods for evaluating migrated high molecular weight hydrocarbons in marine sediments at naturally occurring oil seeps

A laboratory study has been conducted to determine the best methods for the detection of C₁₀–C₄₀ hydrocarbons at naturally occurring oil seeps in marine sediments. The results indicate that a commercially available method using n-C₆ to extract sediments and gas chromatography–flame ionization detection (GC–FID) to screen the resulting extract is effective at recognizing the presence of migrated hydrocarbons at concentrations from 50 to 5000 ppm. When non-biodegraded, the amount of oil charge is effectively tracked by the sum of n-alkanes in the gas chromatogram. However, once the charge oil becomes biodegraded, with the loss of n-alkanes and isoprenoids, the amount of oil is tracked by the quantification of the unresolved complex mixture (UCM). Gas chromatography–mass spectrometry (GC–MS) was also found to be very effective for the recognition of petroleum related hydrocarbons and results indicate that GC–MS would be a very effective tool for screening samples at concentrations below 50 ppm oil charge.     

The effect of dynamic–thermodynamic icebergs on the Southern Ocean climate in a three-dimensional model

Melting icebergs are a mobile source of fresh water as well as a sink of latent heat. In most global climate models, the spatio-temporal redistribution of fresh water and latent heat fluxes related to icebergs is parameterized by an instantaneous more or less arbitrary flux distribution over some parts of the oceans. It is uncertain if such a parameterization provides a realistic representation of the role of icebergs in the coupled climate system. However, icebergs could have a significant climate role, in particular during past abrupt climate change events which have been associated with armada’s of icebergs. We therefore present the interactive coupling of a global climate model to a dynamic thermodynamic iceberg model, leading to a more plausible spatio-temporal redistribution of fresh water and heat fluxes. We show first that our model is able to reproduce a reasonable iceberg distribution in both hemispheres when compared to recent data. Second, in a series of sensitivity experiments we explore cooling and freshening effects of dynamical icebergs on the upper Southern Ocean and we compare these dynamic iceberg results to the effects of an equivalent parameterized iceberg flux.In our model without interactive icebergs, the parameterized fluxes are distributed homogeneously South of 55°S, whereas dynamic icebergs are found to be concentrated closer to shore except for a plume of icebergs floating North–East from the tip of the Antarctic Peninsula. Compared to homogeneous fluxes, the dynamic icebergs lead to a 10% greater net production of Antarctic bottom water (AABW). This increased bottom water production involves open ocean convection, which is enhanced by a less efficient stratification of the ocean when comparing to a homogeneous flux distribution.Icebergs facilitate the formation of sea-ice. In the sensitivity experiments, both the fresh water and the cooling flux lead to a significant increase in sea-ice area of 12% and 6%, respectively, directly affecting the highly coupled and interactive air/sea/ice system. The consequences are most pronounced along the sea-ice edge, where this sea-ice facilitation has the greatest potential to affect ocean stratification, for example by heat insulation and wind shielding, which further amplifies the cooling and freshening of the surface waters.