New typologies for estuarine morphology

New theories to explain how tides and river flow determine estuarine bathymetries have been developed. The range of validity of these theories has been subsequently assessed against a recently available observational data set.Success in reproducing the evolution of estuarine bathymetries that has occurred over the last 10 000 years provides the basis for the translation, here, of these theories into new typologies. These then provide reference frameworks to enhance our perspective on existing morphologies and identify ‘anomalous’ estuaries. Further refinement of these new theories requires analyses of causal factors responsible for such anomalies drawing on classical morphological experience. These frameworks can also be used for calculating likely future bathymetric adjustments for prescribed changes in mean sea level, tidal amplitudes, river flow and sediment supply.     

A chronological assessment of Lake Okeechobee (Florida) sediments using multiple dating markers

Reconstructing recent limnological history often relies on lead-210 dating to accurately ascribe a chronology to a sediment profile. In Lake Okeechobee, Florida, a large, shallow subtropical lake that may experience severe mixing, multiple dating methods are required to confirm that conformable sedimentation has been preserved and that the assumptions of the ²¹⁰Pb method are satisfied. This study uses stratigraphic profiles of heavy metals, ¹³⁷Cs, PCBs and pollen as independent dating markers to validate the sediment chronology as determined by ²¹⁰Pb for three cores from the central mud zone of the lake. Unsupported ²¹⁰Pb and most dating markers show distinct concentration/depth profiles, suggesting that the sediments have not been severely mixed for at least the last 75 years. Onset and maximum activity of the radioisotope ¹³⁷Cs in the cores coincides with the ²¹⁰Pb-dated interval of 1945–1970. This agrees well with the known timing of atmospheric deposition of ¹³⁷Cs that resulted from above-ground nuclear testing during late 1940s until 1963. Sediment core profiles of atmospherically deposited metals such as Zn and Pb, which reflect regional increases during industrialization and decreases after regulation in the 1970s, exhibit expected concentration increases and peaks coinciding within 5–15 years of the predicted ²¹⁰Pb dates. Uranium, a contaminant in some phosphate fertilizers, shows large concentration increases at core depths dated to be about 1950 by ²¹⁰Pb, matching the intensification of agriculture after WWII. PCBs, which are expected to peak in the early 1970s, were measured in one core, and the observed peak corresponds to a ²¹⁰Pb date of about 1960. Pollen makers were unable to verify specific events, but increases in disturbance taxa and declines in native types correspond generally with the expected dates assigned by ²¹⁰Pb dating. Conformity between the ²¹⁰Pb defined dates and independent markers of < ±15 years confirm that Lake Okeechobee sediments do preserve a sequential and reliable stratigraphic history of the lake, useful for reconstructing past limnological conditions.     

Quantification of karst aquifer discharge components during storm events through end-member mixing analysis using natural chemistry and stable isotopes as tracers

Karst aquifer components that contribute to the discharge of a water supply well in the Classical Karst (Kras) region (Italy/Slovenia) were quantitatively estimated during storm events. Results show that water released from storage within the epikarst may comprise as much as two-thirds of conduit flow in a karst aquifer following rainfall. Principal components analysis (PCA) and end-member mixing analysis (EMMA) were performed using major ion chemistry and the stable isotopes of water (δ¹⁸O, δ²H) and of dissolved inorganic carbon (δ¹³C_DIC) to estimate mixing proportions among three sources: (1) allogenic river recharge, (2) autogenic recharge, and (3) an anthropogenic component stored within the epikarst. The sinking river most influences the chemical composition of the water-supply well under low-flow conditions; however, this proportion changes rapidly during recharge events. Autogenic recharge water, released from shallow storage in the epikarst, displaces the river water and is observed at the well within hours after the onset of precipitation. The autogenic recharge end member is the second largest component of the well chemistry, and its contribution increases with higher flow. An anthropogenic component derived from epikarstic storage also impacts the well under conditions of elevated hydraulic head, accounting for the majority of the chemical response at the well during the wettest conditions.     

Synchrotron IR study of hydrous ringwoodite (γ-Mg2SiO4) up to 30 GPa

High-pressure synchrotron infrared (IR) absorption spectra were collected between 650 and 4,000 cm⁻¹ at ambient temperature for hydrous Mg-ringwoodite (γ-Mg₂SiO₄) up to 30 GPa. The main feature in the OH⁻ stretching region is an extremely broad band centred at 3,150 cm⁻¹. The hydrogen bond is strong for most protons and the most probable site for protonation is the tetrahedral edge. With increasing pressure, this band shifts downward while decreasing its integrated intensity until disappearance at a pressure of 25 GPa. Only one band at 2,450 cm⁻¹ and an absorption plateau persist with a maximum wavenumber of 3,800 cm⁻¹. This behaviour is reversible upon pressure release. We interpret this as a second-order phase transition occurring in hydrated Mg-ringwoodite at high pressure (beyond ∼ 25 GPa). This result is compatible with the observation by Kleppe et al. (Phys Chem Miner 29:473–476, 2002a) who suggested the presence of Si–O–Si linkages and/or partial increase in the coordination of Si. Beyond the phase transition, the protons are delocalized and their environment on the ringwoodite structure is probably quite different from that at low pressure. Data obtained in situ at high pressures and temperatures are needed to better understand the effect of protonation on the structure and to better constrain this phase transition.     

Spatial process and data models: Toward integration of agent-based models and GIS

The use of object-orientation for both spatial data and spatial process models facilitates their integration, which can allow exploration and explanation of spatial-temporal phenomena. In order to better understand how tight coupling might proceed and to evaluate the possible functional and efficiency gains from such a tight coupling, we identify four key relationships affecting how geographic data (fields and objects) and agent-based process models can interact: identity, causal, temporal and topological. We discuss approaches to implementing tight integration, focusing on a middleware approach that links existing GIS and ABM development platforms, and illustrate the need and approaches with example agent-based models.     

Up to what temperature is petroleum stable? New insights from a 5200 free radical reactions model

The discovery of crude oils and condensates at ever higher temperatures casts doubt on the validity of the usual geochemical modelling approach, that uses empirical reactions and rate constants. The solution used to account for such a high thermal stability is presently to adjust the rate parameters, but the physical meaning and scientific value of such a strategy can be questioned. We have developed a mechanistic model consisting of 5200 lumped free radical reactions to describe the thermal evolution of a mixture of 52 organic species meant to represent light petroleum. Rate constants used are those available in the literature or estimated using well established thermochemistry-reactivity correlations. Chemical structures included in the model are linear, branched and cyclic hydrocarbons, hydro- and alkyl-aromatics, PAHs, and three heteroatomic compounds. Reactions include cracking and alkylation chains and inhibiting and accelerating reactions from the various reactants. This model has been applied to several mixtures with various proportions of reaction inhibitors and accelerators, and to a composition representing a light mature oil. From the results obtained, we conclude that mature oils will be stable up to 240–260 °C, depending on their composition, and that the thermal cracking of oil to gas is not possible under reasonable basin conditions. The kinetics of petroleum cracking are thus much slower than generally recognized.     

Anhydrite-bearing rocks from the Rožná district (Moldanubian zone,Czech Republic): high-grade metamorphosed exhalites?

Several types of anhydrite-bearing rocks have been found in the amphibolite-facies metamorphosed rocks at the north-eastern margin of the Moldanubian Zone. Anhydrite either forms monomineralic bands up to 40 cm thick, or occurs in the form of disseminated grains in surrounding calc-silicate gneiss together with feldspar, scapolite, amphibole, pyroxene, epidote and pyrite. The isotopic composition of sulphur ('³⁴S=30.6 to 32.3‰) and strontium (⁸⁷Sr/⁸⁶Sr=0.70797 to 0.70781) in anhydrite may indicate a marine source of sulphate. The isotopic ratio of strontium is in the same range as that of metamorphosed strata-bound barite-sulphide ores, which have been previously described in the same area. The '³⁴S values of coexisting pyrite range from 21.4 to 22.5‰, the (³⁴S_{anhydrite-pyrite} corresponding to the metamorphic temperature of 600 to 660 °C. In contrast to many submarine-exhalative deposits, the oxygen isotopic compositions of anhydrite ('¹⁸O=9.3 to 10.2‰) are lighter than that of barite ('¹⁸O=10.4 to 13.8‰). This indicates that the both minerals are not in isotopic equilibrium. Therefore, it is probable that anhydrite and barite from the Ro—ná district were deposited from fluids that contained different proportions of seawater and hydrothermal fluids or from hydrothermal fluids that underwent variable extent of oxygen isotope exchange with seafloor rocks. The '¹³C values in calcite ('¹³C=-17.2 to -18.7‰) from anhydrite-bearing rock are lower than those in distant marbles. As graphite is absent in anhydrite- and calcite-bearing rocks, impoverishment in the ¹³C isotope cannot be attributed to the graphite-carbonate isotopic exchange during metamorphism. It is proposed that low '¹³C values in carbonates are caused by pre-metamorphic oxidation of organic matter in course of hydrothermal processes. Anhydrite and anhydrite-bearing calc-silicate gneiss from the north-eastern part of the Moldanubian Zone are interpreted to be the high-grade metamorphosed analogue of anhydrite-rich exhalites commonly found in submarine-exhalative hydrothermal deposits.