Effects of anthropogenic seawater acidification on acid-base balance in the sea urchin Psammechinus miliaris

The purple-tipped sea urchin, Psammechinus miliaris, was exposed to artificially acidified seawater treatments (pH(w) 6.16, 6.63 or 7.44) over a period of 8 days. Urchin mortality of 100% was observed at pH(w) 6.16 after 7 days and coincided with a pronounced hypercapnia in the coelomic fluid producing an irrecoverable acidosis. Coelomic fluid acid-base measures showed that an accumulation of CO(2) and a significant reduction in pH occurred in all treatments compared with controls. Bicarbonate buffering was employed in each case, reducing the resultant acidosis, but compensation was incomplete even under moderate environmental hypercapnia. Significant test dissolution was inferred from observable increases in the Mg(2+) concentration of the coelomic fluid under all pH treatments. We show that a chronic reduction of surface water pH to below 7.5 would be severely detrimental to the acid-base balance of this predominantly intertidal species; despite its ability to tolerate fluctuations in pCO(2) and pH in the rock pool environment. The absence of respiratory pigment (or any substantial protein in the coelomic fluid), a poor capacity for ionic regulation and dependency on a magnesium calcite test, make echinoids particularly vulnerable to anthropogenic acidification. Geological sequestration leaks may result in dramatic localised pH reductions, e.g. pH 5.8. P. miliaris is intolerant of pH 6.16 seawater and significant mortality is seen at pH 6.63.     

Mechanisms of iron oxide transformations in hydrothermal systems

Coexistence of magnetite and hematite in hydrothermal systems has often been used to constrain the redox potential of fluids, assuming that the redox equilibrium is attained among all minerals and aqueous species. However, as temperature decreases, disequilibrium mineral assemblages may occur due to the slow kinetics of reaction involving the minerals and fluids. In this study, we conducted a series of experiments in which hematite or magnetite was reacted with an acidic solution under H₂-rich hydrothermal conditions (T = 100-250 °C, ) to investigate the kinetics of redox and non-redox transformations between hematite and magnetite, and the mechanisms of iron oxide transformation under hydrothermal conditions. The formation of euhedral crystals of hematite in 150 and 200 °C experiments, in which magnetite was used as the starting material, indicates that non-redox transformation of magnetite to hematite occurred within 24 h. The chemical composition of the experimental solutions was controlled by the non-redox transformation between magnetite and hematite throughout the experiments. While solution compositions were controlled by the non-redox transformation in the first 3 days in a 250 °C experiment, reductive dissolution of magnetite became important after 5 days and affected the solution chemistry. At 100 °C, the presence of maghemite was indicated in the first 7 days. Based on these results, equilibrium constants of non-redox transformation between magnetite and hematite and those of non-redox transformation between magnetite and maghemite were calculated. Our results suggest that the redox transformation of hematite to magnetite occurs in the following steps: (1) reductive dissolution of hematite to and (2) non-redox transformation of hematite and to magnetite.     

Probable Neolithic footprints preserved in inter-tidal peat at Kenfig, South Wales (UK)

Holocene footprints have been reported from several locations around the UK coast preserved within inter-tidal sediments. These sediments are normally fine-grained silts, sands and clays. Here we report potential human footprints preserved in the lower of two inter-tidal peat units exposed on the foreshore at Kenfig in South Wales. The lower peat layer pre-dates 3810 ± 40 BP and its maximum age is constrained by two dates, one of 4930 ± 50 BP and another of 5110 ± 50 BP. The prints may have formed at any point within this time interval. Both peat units formed in a salt marsh, or fen environment, as indicated by the analysis of both diatoms and pollen and have been tentatively assigned to the middle Wentlooge Formation within the Holocene lithostratigraphy established for the Severn Estuary Holocene sequence. The footprints were digitised using an optical laser scanner and are compared to other Holocene human footprints exposed on the Sefton Coast in North West England. In comparison the Kenfig prints have poor anatomical form which may be the result of both the substrate and post-depositional modification. The paper demonstrates the value of using optical laser scanning in the data capture and analysis of transitory archaeological and geological trace evidence.     

An EPR study of native radiation-induced paramagnetic defects in sudoite (di–trioctahedral Al–Mg chlorite) from the alteration halo related to unconformity-type uranium deposits

Natural radiation-induced defects were identified in specimens of sudoite (Al–Mg di-trioctahedral chlorite) related to unconformity-type uranium deposits at the base of the Athabasca Group (Saskatchewan, Canada), using electron paramagnetic resonance (EPR) spectroscopy at X- and Q-band frequencies. X-band spectra indicate the presence of a main native defect, named the A_s-center, whose EPR signal is dominated by an axially distorted spectrum with apparent principal components as follows: g _// = 2,051 and g _⊥ = 2,005, and a secondary defect with apparent component g = 2,025. The study of oriented specimens shows that the main defect has its g _// component perpendicular to the (ab) plane of sudoite. The A_s-center corresponds to an electron hole located on oxygen atoms of the structure and is likely associated with Si, according to the lack of hyperfine structure. The A_s-center in sudoite has EPR parameters similar to the A-center in kaolinite and dickite, and the A_i-center in illite. The saturation behavior of EPR spectra as a function of power demonstrates that native defects of sudoite are different from those known in other clays, such as kaolinite, dickite or smectite, but are similar to those of illite. The isochronal annealing data suggest that the main defect in sudoite is stable to more than 300°C. The corresponding defects characterized in sudoite may have the potential for tracing past radionuclide migration around unconformity-type uranium deposits.     

Temperature response to future urbanization and climate change

This study examines the impact of future urban expansion on local near-surface temperature for Sydney (Australia) using a future climate scenario (A2). The Weather Research and Forecasting model was used to simulate the present (1990–2009) and future (2040–2059) climates of the region at 2-km spatial resolution. The standard land use of the model was replaced with a more accurate dataset that covers the Sydney area. The future simulation incorporates the projected changes in the urban area of Sydney to account for the expected urban expansion. A comparison between areas with projected land use changes and their surroundings was conducted to evaluate how urbanization and global warming will act together and to ascertain their combined effect on the local climate. The analysis of the temperature changes revealed that future urbanization will strongly affect minimum temperature, whereas little impact was detected for maximum temperature. The minimum temperature changes will be noticeable throughout the year. However, during winter and spring these differences will be particularly large and the increases could be double the increase due to global warming alone at 2050. Results indicated that the changes were mostly due to increased heat capacity of urban structures and reduced evaporation in the city environment.     

Late Miocene sedimentary architecture of the Ebro Continental Margin (Western Mediterranean): implications to the Messinian Salinity Crisis

The Messinian Salinity Crisis (MSC) resulted from a significant multi-phase drop and subsequent reflooding of the Mediterranean Sea from 5.96 to 5.33 Ma. Well-developed drainage networks, characterized by step-like profiles and abrasion platforms, are associated to this event. The Ebro Continental Margin (Western Mediterranean) presents an additional complexity since the capture of the drainage of the adjacent subaerial Ebro Basin took place sometime prior to the Messinian stage. Using 3D seismic reflection data, this work provides new insights into the origin of the step-like profile of the Messinian erosional surface (MES) and timing of the capture of the subaerial Ebro Basin. The results obtained indicate a sedimentary-active continental slope and delta progradation during Middle-Late Miocene, in a normal regressive context associated to a pre-Messinian proto-Ebro River. The mature development attained by the Messinian Ebro River network during the MSC corroborates that the capture of the Ebro Basin occurred prior to the MSC. The configuration of the clinoforms below the MES suggests that deltaic sediments of the Messinian Paleo-Ebro River deposited during the Tortonian and initial Messinian sea-level drawdown. The MES formed at the top of the Tortonian Highstand, where a fluvial network was deeply carved, and in the topset region of the Messinian Falling Stage Systems Tract, where minor erosion occurred. Fluvial deposits are outstandingly preserved on the main valleys of the MES. Therefore, the step-like profile of the MES was not created during Zanclean inundation, but during the latest stages of the main Messinian sea-level fall and lowstand.     

Correcting lateral boundary biases in regional climate modelling: the effect of the relaxation zone

Climate Dynamics - Regional climate models (RCM) are an important tool for simulating atmospheric information at finer resolutions often of greater relevance to local scale climate change impact...     

Structure Inclination Angles in the Convective Atmospheric Surface Layer

Two-point correlations of the fluctuating streamwise velocity are examined in the atmospheric surface layer over the salt flats of Utah’s western desert, and corresponding structure inclination angles are obtained for neutral, stable and unstable conditions. The neutral surface-layer results supplement evidence for the invariance of the inclination angle given in Marusic and Heuer (Phys Rev Lett 99:114504, 2007). In an extension of those results it is found that the inclination angle changes drastically under different stability conditions in the surface layer, varying systematically with the Monin–Obukhov stability parameter in the unstable regime. The variation is parametrized and subsequently can be used to improve existing near-wall models in the large-eddy simulation of the atmospheric surface layer.     

The amino acid composition of the Sutter's Mill CM2 carbonaceous chondrite

We determined the abundances and enantiomeric compositions of amino acids in Sutter's Mill fragment #2 (designated SM2) recovered prior to heavy rains that fell April 25–26, 2012, and two other meteorite fragments, SM12 and SM51, that were recovered postrain. We also determined the abundance, enantiomeric, and isotopic compositions of amino acids in soil from the recovery site of fragment SM51. The three meteorite stones experienced terrestrial amino acid contamination, as evidenced by the low d/l ratios of several proteinogenic amino acids. The d/l ratios were higher in SM2 than in SM12 and SM51, consistent with rain introducing additional l‐ amino acid contaminants to SM12 and SM51. Higher percentages of glycine, β‐alanine, and γ‐amino‐n‐butyric acid were observed in free form in SM2 and SM51 compared with the soil, suggesting that these free amino acids may be indigenous. Trace levels of d +l‐ β‐aminoisobutyric acid (β‐AIB) observed in all three meteorites are not easily explained as terrestrial contamination, as β‐AIB is rare on Earth and was not detected in the soil. Bulk carbon and nitrogen and isotopic ratios of the SM samples and the soil also indicate terrestrial contamination, as does compound‐specific isotopic analysis of the amino acids in the soil. The amino acid abundances in SM2, the most pristine SM meteorite analyzed here, are approximately 20‐fold lower than in the Murchison CM2 carbonaceous chondrite. This may be due to thermal metamorphism in the Sutter's Mill parent body at temperatures greater than observed for other aqueously altered CM2 meteorites.