Distinction between six- and fourfold coordinated silicon in SiO2 polymorphs via electron loss near edge structure (ELNES) spectroscopy

Si K-, L- and O K-edge ELNES spectra of natural α-quartz and synthetic coesite on one side and synthetic stishovite on the other show characteristic differences that can be related, by comparison with multiple-scattering (MS) calculations, to the fourfold vs. sixfold coordination of Si in these polymorphs of SiO₂. It is shown by MS calculations on large clusters that the outer shells contribute relatively little to the overall topologies of the spectra. Therefore, distinction between fourfold- and sixfold-coordinated Si is possible even on a nm scale and probably also in amorphous substances.     

Normal fault growth and early syn-rift sedimentology and sequence stratigraphy: Thal Fault, Suez Rift, Egypt

This paper investigates the tectono‐stratigraphic development of a major, segmented rift border fault (Thal Fault) during ca. 6 Myr of initial rifting in the Suez Rift, Egypt. The Thal Fault is interpreted to have evolved by the progressive linkage of at least four fault segments. We focus on two contrasting structural settings in its hangingwall: Gushea, towards the northern tip of the fault, and Musaba Salaama, ca. 20 km along‐strike to the south, towards the centre of the fault. The early syn‐rift stratigraphic succession passes upwards from continental facies, through a condensed marginal marine shell‐rich facies, into fully marine shoreface sandstone and offshore mudstone. Regionally correlatable stratal surfaces within this succession define time‐equivalent stratal units that exhibit considerable along‐strike variability in thickness and facies architecture. During the initial ca. 6 Myr of rifting, the thickest stratigraphy developed towards the centre of the array of fault segments that subsequently hard linked to form the Thal Fault. Thus, a displacement gradient existed between fault segments at the centre and tip of the fault array, suggesting that the fault segments interacted, and a fixed length was established for the fault array, at an early stage in rifting. Towards the centre of the Thal Fault the early syn‐rift succession shows pronounced thickening away from the fault and towards a series of intra‐block antithetic faults that were active for up to ca. 6 Myr. This indicates that a large proportion of fault‐controlled subsidence during the initial ca. 6 Myr of rifting occurred in the hangingwalls of antithetic intra‐block faults, and not the present‐day Thal Fault. The antithetic faults progressively switched off during rifting such that after ca. 6 Myr of rifting, fault‐activity had localised on the Thal Fault enabling it to accrue to the present‐day high level of displacement. Aspects of the development of the Thal Fault appear to be in contrast to many models of fault evolution that predict large‐displacement rift‐climax faults to have always had the greatest displacement during fault population evolution. This study has implications for tectono‐stratigraphic development during early rift basin evolution. In particular, we stress that caution must be taken when relating final rift‐climax fault structure to the early tectono‐stratigraphy, as these may differ considerably.     

Kinetic isotopic fractionation during carbonate dissolution in laboratory experiments: Implications for detection of microbial CO2 signatures using δC-DIC

Laboratory experiments on reagent-grade calcium carbonate and carbonate rich glacial sediments demonstrate previously unreported kinetic fractionation of carbon isotopes during the initial hydrolysis and early stages of carbonate dissolution driven by atmospheric CO₂. There is preferential dissolution of Ca¹²CO₃ during hydrolysis, resulting in δ¹³C-DIC values that are significantly lighter isotopically than the bulk carbonate. The fractionation factor for this kinetic isotopic effect is defined as ε_carb. ε_carb is greater on average for glacial sediments (−17.4‰) than for calcium carbonate (−7.8‰) for the < 63 μm size fraction, a sediment concentration of 5 g L⁻¹ and closed system conditions at 5°C. This difference is most likely due to the preferential dissolution of highly reactive ultra-fine particles with damaged surfaces that are common in subglacial sediments. The kinetic isotopic fractionation has a greater impact on δ¹³C-DIC at higher CaCO₃:water ratios and is significant during at least the first 6 h of carbonate dissolution driven by atmospheric CO₂ at sediment concentrations of 5 g L⁻¹. Atmospheric CO₂ dissolving into solution following carbonate hydrolysis does not exhibit any significant equilibrium isotopic fractionation for at least ∼ 6 h after the start of the experiment at 5°C. This is considerably longer than previously reported in the literature. Thus, kinetic fractionation processes will likely dominate the δ¹³C-DIC signal in natural environments where rock:water contact times are short <6-24 h (e.g., glacial systems, headwaters in fluvial catchments) and there is an excess of carbonate in the sediments. It will be difficult apply conventional isotope mass balance techniques in these types of environment to identify microbial CO₂ signatures in DIC from δ¹³C-DIC data.     

Sublethal effects of cupric ion activity on the grazing behaviour of three calanoid copepods

This research (1) characterized the effects of sublethal cupric ion activities on the grazing behavior of two estuarine copepods (Acartia tonsa, Acartia hudsonica) and one nearshore, neritic copepod (Temora longicornis) and (2) compared the sensitivity of short-term sublethal behavioral assays with that of longer-term acute toxicity tests. A nitrilotriacetate-trace-metal-ion buffer system at 27‰. S was used to quantify and control the free cupric ion activity. Acute toxicity tests were used to determine the mortality of A. tonsa and T. longicornis over 72 h within the approximate cupric ion activity range of 10⁻¹³ to 10^−9.5 M. 24 h survival was not affected within the approximate cupric ion activity range of 10⁻¹³ to 10^−9.7 M, the range used for subsequent grazing activity experiments after 24 h exposure to Cu. Grazing activity was significantly diminished at cupric ion activities of ≈ 10⁻¹⁰ M for A. tonsa and T. longicornis, and at ≈ 10⁻¹¹ M for A. hudsonica. A hormetic pattern of response in feeding activity was observed with A. tonsa and T. longicornis. Grazing activity was found to be a sensitive measure of sublethal Cu stress compared with the acute toxicity tests. Grazing activity was affected at environmentally relevant cupric ion activities.     

Land subsidence along the northeastern Texas Gulf coast: Effects of deep hydrocarbon production

The Texas Gulf of Mexico coast is experiencing high (5–11 mm/yr) rates of relative sea level (RSL) rise that are the sum of subsidence and eustatic sea level (ESL) rise. Even higher rates are associated with areas of groundwater pumping from confined aquifers. We investigate the possibility of deep petroleum production as a cause for the high regional rates of subsidence. The northeast Texas coast was chosen for the study because it has a high rate of RSL rise, very limited groundwater production, and a long history of petroleum production. We examine in detail the Big Hill and Fannett fields, for which adequate bottom hole pressure (BHP) and well log data are available. The hypothesis of deep petroleum production is tested in three ways. First, industry BHP tests show many of the fields are depressurized to far below hydrostatic pressures. Second, analysis of BHP data over time in the Big Hill and Fannett fields indicates that some Zones in these fields were below hydrostatic when production commenced. This indicates that depressurization from production in neighboring fields or zones within the same field is not limited to the production zone. Third, three models for subsidence (a general 1-D regional model, an intrareservoir model, and a reservoir bounding layer model), using reasonable hydrogeological parameters, predict subsidence within the inferred range of data. The latter two models use data from the Big Hill and Fannett fields. Additional verification of the hypothesis that deep petroleum production is causing or accelerating regional subsidence will require the collection and analysis of data on the subsurface hydrogeological parameters and detailed measurements of the spatial and temporal distribution of subsidence along the Texas Coast.