Stable isotope coherence in the earlywood and latewood of tree-line conifers

Annually resolved and replicated tree-ring stable isotope series have the potential to reconstruct growing season environmental parameters over multi-millennial timescales. As this archive may require only minimal statistical detrending, it has the potential to preserve a large portion of low frequency climate signals. To date, many studies have utilised only the latewood portion of the tree ring, in an attempt to minimize carry-over effects from previous year reserves and maximise the annual nature of the climate signal preserved. However, the old trees from tree-line locations, necessary to build long chronologies, often display narrow ring-widths (< 0.5 mm), making accurate earlywood–latewood separation difficult and particular time consuming. The resulting samples may also be too small for efficient cellulose purification or multiple isotopic determinations. As photosynthates from the current year are predominantly used in conifer ring formation at marginal sites with short growing seasons, latewood separation may not be especially advantageous in determining a useful climate signal and therefore unnecessary where resources are limited. To test this hypothesis, Scots pine from Northern Norway and European larch from the Swiss Alps are used. Both sites are tree-line locations where growth is predominantly temperature limited. Tree rings were cut and extracted to cellulose for both the earlywood and latewood of each annual growth ring and stable carbon isotope ratios were measured. Our results demonstrate a very high common carbon isotope signal between earlywood and latewood in both species (r_larch = 0.68 and r_pine = 0.79), which also show high correlations with summer temperature over the investigated period (AD 1980–2004 for larch and AD 1929–1978 for pine). High turnover rates and small reserve pools at these tree-line locations may account for these high common signals. These results suggest that for European tree-line conifers, the separation of earlywood from latewood is unnecessary to resolve an annual isotopic signal and make a reliable climate calibration. Using the whole ring may provide additional analytical advantages and consequently even improve climate calibrations.     

Isotopic evidence (Sr/Sr, δLi) for alteration of the oceanic crust at deep-rooted mud volcanoes in the Gulf of Cadiz, NE Atlantic Ocean

The chemical and isotopic composition of pore fluids is presented for five deep-rooted mud volcanoes aligned on a transect across the Gulf of Cadiz continental margin at water depths between 350 and 3860 m. Generally decreasing interstitial Li concentrations and ⁸⁷Sr/⁸⁶Sr ratios with increasing distance from shore are attributed to systematically changing fluid sources across the continental margin. Although highest Li concentrations at the near-shore mud volcanoes coincide with high salinities derived from dissolution of halite and late-stage evaporites, clayey, terrigenous sediments are identified as the ultimate Li source to all pore fluids investigated. Light δ⁷Li values, partly close to those of hydrothermal vent fluids (δ⁷Li: +11.9‰), indicate that Li has been mobilized during high-temperature fluid/sediment or fluid/rock interactions in the deep sub-surface. Intense leaching of terrigenous clay has led to radiogenic ⁸⁷Sr/⁸⁶Sr ratios (∼0.7106) in pore fluids of the near-shore mud volcanoes. In contrast, non-radiogenic ⁸⁷Sr/⁸⁶Sr ratios (∼0.7075) at the distal locations are attributed to admixing of a basement-derived fluid component, carrying an isotopic signature from interaction with the basaltic crust. This inference is substantiated by temperature constraints from Li isotope equilibrium calculations suggesting exchange processes at particularly high temperatures (>200 °C) for the least radiogenic pore fluids of the most distal location.Advective pore fluids in the off-shore reaches of the Gulf of Cadiz are influenced by successive exchange processes with both oceanic crust and terrigenous, fine-grained sediments, resulting in a chemical and isotopic signature similar to that of fluids in near-shore ridge flank hydrothermal systems. This suggests that deep-rooted mud volcanoes in the Gulf of Cadiz represent a fluid pathway intermediate between mid-ocean ridge hydrothermal vent and shallow, marginal cold seep. Due to the thicker sediment coverage and slower fluid advection rates, the overall geochemical signature is shifted towards the sediment-diagenetic signal compared to ridge flank hydrothermal environments.     

Risk acceptance criterion for tanker oil spill risk reduction measures

This paper is aimed at investigating whether there is ample support for the view that the acceptance criterion for evaluating measures for prevention of oil spills from tankers should be based on cost-effectiveness considerations. One such criterion can be reflected by the Cost of Averting a Tonne of oil Spilt (CATS) whereas its target value is updated by elaborating the inherent uncertainties of oil spill costs and establishing a value for the criterion’s assurance factor. To this end, a value of $80,000/t is proposed as a sensible CATS criterion and the proposed value for the assurance factor F = 1.5 is supported by the retrieved Protection and Indemnity (P&I) Clubs’ Annual Reports. It is envisaged that this criterion would allow the conversion of direct and indirect costs into a non-market value for the optimal allocation of resources between the various parties investing in shipping. A review of previous cost estimation models on oil spills is presented and a probability distribution (log-normal) is fitted on the available oil spill cost data, where it should be made abundantly clear that the mean value of the distribution is used for deriving the updated CATS criterion value. However, the difference between the initial and the updated CATS criterion in the percentiles of the distribution is small. It is found through the current analysis that results are partly lower than the predicted values from the published estimation models. The costs are also found to depend on the type of accident, which is in agreement with the results of previous studies. Other proposals on acceptance criteria are reviewed and it is asserted that the CATS criterion can be considered as the best candidate. Evidence is provided that the CATS approach is practical and meaningful by including examples of successful applications in actual risk assessments. Finally, it is suggested that the criterion may be refined subject to more readily available cost data and experience gained from future decisions.     

Dolomite Controls on Phanerozoic Seawater Chemistry

We investigate the potential role of dolomite as a long-term buffer on Phanerozoic seawater composition. Using a comprehensive model of Phanerozoic geochemical cycling, we show how variations in the formation rate of sedimentary marine dolomite have buffered seawater saturation state. The total inventory of inorganic carbon reflects the sum of fluxes derived from continental weathering, basalt-seawater exchange, alumino-silicate diagenesis (reverse weathering), and global deposition of calcium carbonate. Although these fluxes are approximately balanced, model results indicate that seawater saturation state is sensitive to the marine dolomite depositional flux. This conclusion is consistent with and constrained by independent proxy data for seawater ion ratios, paleo-atmospheric CO₂ concentrations, and paleo-pH data, and dolomite mass-age distribution through Phanerozoic time. Abundant research indicates that dolomite’s occurrence in marine sediments is sensitive to many factors: temperature, seawater composition, paleogeographic setting, continental organization, etc. Although the complexity of the process of dolomite formation prevents a complete understanding of the relative role of these factors, our model results clearly underscore the importance of this mineral in the chemical history of Phanerozoic seawater.     

Computations with finite element methods for the Brinkman problem

Various finite element families for the Brinkman flow (or Stokes–Darcy flow) are tested numerically. Particularly, the effect of small permeability is studied. The tested finite elements are the MINI element, the Taylor–Hood element, and the stabilized equal order methods. The numerical tests include both a priori analysis and adaptive methods.     

Tentative kinetic model for dolomite precipitation rate and its application to dolomite distribution

The dolomite problem has a long history and remains one of the most intensely studied and debated topics in geology. Major amounts of dolomite are not directly forming today from seawater. This observation has led many investigators to develop geochemical/hydrologic models for dolomite formation in diagenetic environments. A fundamental limitation of the current models for the growth of sedimentary dolomite is the dearth of kinetic information for this phase, in contrast to that available for calcite and aragonite.We present a simple kinetic model describing dolomite growth as a function of supersaturation using data from published high temperature synthesis experiments and our own experimental results. This model is similar in form to empirical models used to describe precipitation and dissolution rates of other carbonate minerals. Despite the considerable uncertainties and assumptions implicit in this approach, the model satisfies a basic expectation of classical precipitation theory, i.e., that the distance from equilibrium is a basic driving force for reaction rate. The calculated reaction order is high (~ 3), and the combined effect of high order and large activation energy produces a very strong dependence of the rate on temperature and the degree of supersaturation of aqueous solutions with respect to this phase.Using the calculated parameters, we applied the model to well-documented case studies of sabkha dolomite at Abu Dhabi (Persian Gulf), and organogenic dolomite from the Gulf of California. Growth rates calculated from the model agree with independent estimates of the age of these dolomites to well within an order of magnitude. A comparison of precipitation rates in seawater also shows the rate of dolomite precipitation to converge strongly with that of calcite with increasing temperature. If correct, this result implies that dolomite may respond to relatively modest warming of surface environments by substantial increases in accumulation rate, and suggests that the distribution of sedimentary dolomite in the rock record may be to some extent a temperature signal.     

New safety issues when moving from liquid fuels to natural gas

Natural gas (NG) is produced whenever organic matter is decomposed in the absence of oxygen. The main constituent of natural gas is methane. In contrast to liquid fuels, methane has a boiling point far below normal ambient temperatures. Even the critical temperature is well below ambient. Therefore natural gas must be stored either as compressed natural gas (CNG) at very high pressures at ambient temperatures, or as liquefied natural gas (LNG) at very low temperatures. The basic safety issues are caused by loss of confinement of either CNG or LNG. In both cases the issues are: global greenhouse effects of natural gas (methane); local fire and explosion hazards; and local asphyxiation hazard due to reduced oxygen content in the atmosphere breathed when air is mixed with methane.