Seawater nutrient and carbonate ion concentrations recorded as P/Ca, Ba/Ca, and U/Ca in the deep-sea coral Desmophyllum dianthus

As paleoceanographic archives, deep sea coral skeletons offer the potential for high temporal resolution and precise absolute dating, but have not been fully investigated for geochemical reconstructions of past ocean conditions. Here we assess the utility of skeletal P/Ca, Ba/Ca and U/Ca in the deep sea coral D. dianthus as proxies of dissolved phosphate (remineralized at shallow depths), dissolved barium (trace element with silicate-type distribution) and carbonate ion concentrations, respectively. Measurements of these proxies in globally distributed D. dianthus specimens show clear dependence on corresponding seawater properties. Linear regression fits of mean coral Element/Ca ratios against seawater properties yield the equations: P/Ca_coral (μmol/mol) = (0.6 ± 0.1) P/Ca_sw(μmol/mol) - (23 ± 18), R² = 0.6, n = 16 and Ba/Ca_coral(μmol/mol) = (1.4 ± 0.3) Ba/Ca_sw(μmol/mol) + (0 ± 2), R² = 0.6, n = 17; no significant relationship is observed between the residuals of each regression and seawater temperature, salinity, pressure, pH or carbonate ion concentrations, suggesting that these variables were not significant secondary dependencies of these proxies. Four D. dianthus specimens growing at locations with Ω_arag ? 0.6 displayed markedly depleted P/Ca compared to the regression based on the remaining samples, a behavior attributed to an undersaturation effect. These corals were excluded from the calibration. Coral U/Ca correlates with seawater carbonate ion: U/Ca_coral(μmol/mol) = (−0.016 ± 0.003) (μmol/kg) + (3.2 ± 0.3), R² = 0.6, n = 17. The residuals of the U/Ca calibration are not significantly related to temperature, salinity, or pressure. Scatter about the linear calibration lines is attributed to imperfect spatial-temporal matches between the selected globally distributed specimens and available water column chemical data, and potentially to unresolved additional effects. The uncertainties of these initial proxy calibration regressions predict that dissolved phosphate could be reconstructed to ±0.4 μmol/kg (for 1.3-1.9 μmol/kg phosphate), and dissolved Ba to ±19 nmol/kg (for 41-82 nmol/kg Ba_sw). Carbonate ion concentration derived from U/Ca has an uncertainty of ±31μmol/kg (for ). The effect of microskeletal variability on P/Ca, Ba/Ca, and U/Ca was also assessed, with emphasis on centers of calcification, Fe-Mn phases, and external contaminants. Overall, the results show strong potential for reconstructing aspects of water mass mixing and biogeochemical processes in intermediate and deep waters using fossil deep-sea corals.     

Evaluation of Subsurface Oxygen Sensors for Remediation Monitoring

Continuous remediation monitoring using sensors is potentially a more effective and inexpensive alternative to current methods of sample collection and analysis. Gaseous components of a system are the most mobile and easiest to monitor. Continuous monitoring of soil gases such as oxygen, carbon dioxide, and contaminant vapors can provide important quantitative information regarding the progress of bioremediation efforts and the area of influence of air sparging or soil venting. Laboratory and field tests of a commercially available oxygen sensor show that the subsurface oxygen sensor provides rapid and accurate data on vapor phase oxygen concentrations. The sensor is well suited for monitoring gas flow and oxygen consumption in the vadose zone during air sparging and bioventing. The sensor performs well in permeable, unsaturated soil environments and recovers completely after being submerged during temporary saturated conditions. Calibrations of the in situ oxygen sensors were found to be stable after one year of continuous subsurface operation. However, application of the sensor in saturated soil conditions is limited. The three major advantages of this sensor for in situ monitoring arc as follows: (1) it allows data acquisition at any specified time interval; (2) it provides potentially more accurate data by minimizing disturbance of subsurface conditions; and (3) it minimizes the cost of field and laboratory procedures involved in sample retrieval and analysis.     

Thermal history of the Rio Muni (West Africa)–NE Brazil margins during continental breakup

We document the thermal record of breakup of the conjugate Rio Muni (West Africa) and NE Brazil margins using apatite fission track analysis, vitrinite reflectance data and stratigraphic observations from both margins. These results permit determination of the timing of four cooling episodes, and the temperature of samples at the onset of each episode. All samples are interpreted to have experienced higher temperatures in the geological past due to i) elevated basal heatflow (palaeogeothermal gradient in Rio Muni-1 well decaying from 58 °C/km during the Mid Cretaceous to 21.5 °C/km in the Late Cenozoic) and ii) progressive exhumation from formerly greater burial depth. A well constrained history of changing palaeogeothermal gradient allows for much more precise quantification of the thickness of eroded section (exhumation) than if a constant heatflow is assumed. Cooling episodes identified from the palaeotemperature data at 110–95 Ma (both margins) and 85–70 Ma (Rio Muni only) coincide with major unconformities signifying, respectively, the cessation of rifting (breakup) and compressional shortening that affected the African continent following the establishment of post-rift sedimentation (drift). The interval between these separate unconformities is occupied by allochthonous rafts of shallow-water carbonates recording gravitational collapse of a marginal platform. The rift shoulder uplift that triggered this collapse was enhanced by local transpression associated with the obliquely divergent Ascension Fracture Zone, and thermal doming due to the coeval St Helena and Ascension Plumes. The data also reveal a c.45–35 Ma cooling episode, attributed to deep sea erosion at the onset of Eo-Oligocene ice growth, and a c.15–10 Ma episode interpreted as the record of Miocene exhumation of the West African continental margin related to continent-wide plume development. Integration of thermal history methods with traditional seismic- and stratigraphy-based observations yields a dynamic picture of kilometre-scale fluctuations in base level through the breakup and early drift phases of development of these margins. Major unconformities at ocean margins are likely to represent composite surfaces recording not only eustasy, but also regional plate margin-generated deformation, local ‘intra-basinal’ reorganization, and the amplifying effect of negative feedbacks between these processes.     

High-order kernels for Riemannian wavefield extrapolation

Riemannian wavefield extrapolation is a technique for one‐way extrapolation of acoustic waves. Riemannian wavefield extrapolation generalizes wavefield extrapolation by downward continuation by considering coordinate systems different from conventional Cartesian ones. Coordinate systems can conform with the extrapolated wavefield, with the velocity model or with the acquisition geometry. When coordinate systems conform with the propagated wavefield, extrapolation can be done accurately using low‐order kernels. However, in complex media or in cases where the coordinate systems do not conform with the propagating wavefields, low order kernels are not accurate enough and need to be replaced by more accurate, higher‐order kernels. Since Riemannian wavefield extrapolation is based on factorization of an acoustic wave‐equation, higher‐order kernels can be constructed using methods analogous to the one employed for factorization of the acoustic wave‐equation in Cartesian coordinates. Thus, we can construct space‐domain finite‐differences as well as mixed‐domain techniques for extrapolation. High‐order Riemannian wavefield extrapolation kernels improve the accuracy of extrapolation, particularly when the Riemannian coordinate systems does not closely match the general direction of wave propagation.