Improving the way we think about projecting future energy use and emissions of carbon dioxide

A variety of decision makers need projections of future energy demand, CO₂ emissions and similar factors that extend many decades into the future. The past performance of such projections has been systematically overconfident. Analysts have often used scenarios based on detailed story lines that spell out “plausible alternative futures” as a central tool for evaluating uncertainty. No probabilities are typically assigned to such scenarios. We argue that this practice is often ineffective. Rather than expanding people’s judgment about the range of uncertainty about the future, scenario-based analysis is more likely to lead to systematic overconfidence, to an underestimate of the range of possible future outcomes. We review relevant findings from the literature on human judgment under uncertainty and discuss their relevance to the task of making probabilistic projections. The more detail that one adds to the story line of a scenario, the more probable it will appear to most people, and the greater the difficulty they likely will have in imagining other, equally or more likely, ways in which the same outcome could be reached. We suggest that scenario based approaches make analysts particularly prone to such cognitive biases, and then outline a strategy by which improved projections, tailored to the needs of specific decision makers, might be developed.     

Surface complexation of Pb(II) by hexagonal birnessite nanoparticles

Natural hexagonal birnessite is a poorly crystalline layer type Mn(IV) oxide precipitated by bacteria and fungi which has a particularly high adsorption affinity for Pb(II). X-ray spectroscopic studies have shown that Pb(II) forms strong inner-sphere surface complexes mainly at two sites on hexagonal birnessite nanoparticles: triple corner-sharing (TCS) complexes on Mn(IV) vacancies in the interlayers and double edge-sharing (DES) complexes on lateral edge surfaces. Although the TCS surface complex has been well characterized by spectroscopy, some important questions remain about the structure and stability of the complexes occurring on the edge surfaces. First-principles simulation techniques such as density functional theory (DFT) offer a useful way to address these questions by providing complementary information that is difficult to obtain by spectroscopy. Following this computational approach, we used spin-polarized DFT to perform total-energy-minimization geometry optimizations of several possible Pb(II) surface complexes on model birnessite nanoparticles similar to those that have been studied experimentally. We first validated our DFT calculations by geometry optimizations of (1) the Pb-Mn oxyhydroxide mineral, quenselite (PbMnO₂OH), and (2) the TCS surface complex, finding good agreement with experimental structural data while uncovering new information about bonding and stability. Our geometry optimizations of several protonated variants of the DES surface complex led us to conclude that the observed edge-surface species is very likely to be this complex if the singly coordinated terminal O that binds to Pb(II) is protonated. Our geometry optimizations also revealed that an unhydrated double corner-sharing (DCS) species that has been proposed as an alternative to the DES complex is intrinsically unstable on nanoparticle edge surfaces, but could become stabilized if the local coordination environment is well-hydrated. A significant similarity exists in the structural parameters for the TCS complex and those for a DCS edge-surface complex that is protonated in the same manner as the optimal DES complex, which could complicate detecting the DCS complex in X-ray absorption spectra.     

Silver in the subarctic northeast Pacific Ocean: Explaining the basin scale distribution of silver

Five vertical profiles of silver (Ag) in the subarctic northeast Pacific are presented. Dissolved (< 0.2 μm) Ag concentrations within the surface mixed layer range from 6–25 pM, with the highest observed values at the most coastal site. Elevated Ag concentrations at this station are most likely attributable to the estuarine circulation in the Juan de Fuca Strait. One open-ocean station (P20) exhibited a strong surface Ag maximum. The station was located at the edge of a Haida eddy which raises the possibility that such eddies transport Ag seaward from the coastal zone. Ag concentrations in the deep waters ranged from 60–80 pM. These measurements are consistent with other recent Ag data collected in the Pacific. Ag profiles throughout the Pacific Ocean yield a strong positive correlation between Ag concentration and dissolved silicic acid concentration. However, Ag is depleted relative to silicic acid at intermediate depths where dissolved O₂ concentrations are low, implying a possible removal of Ag from oxygen-depleted waters by scavenging and/or precipitation.     

Development and deployment of a deep-sea Raman probe for measurement of pore water geochemistry

We have developed, deployed, and tested a novel probe for study of the geochemistry of sediment pore waters based upon Raman spectroscopy. The Raman technique has already been used successfully for in situ measurements of targets of scientific interest including gas and hydrothermal vents and complex gas hydrates, but sediment geochemistry has so far been an intractable problem since the sediments themselves are strongly fluorescent and typically only very small sample volumes are obtainable. The 35 cm long probe extracts pore fluids through a 10 μm sintered metallic frit and draws the sample through a 2 mm diameter channel into a sapphire windowed optical cell within which the laser beam is focused and the spectrum recorded. The dead volume of the system is ～1 ml and the instrument is ROV deployable with activation of probe insertion and sample withdrawal under direct operator control. The unique features of this mode of detection include observation of the sulfate gradient in marine pore waters as an indicator of diagenesis, direct measurement of the dissolved sulfide species H₂S and HS^?, and measurement of dissolved methane; all of which are of primary geochemical interest. Quantitative analysis is achieved by area ratio to known water peaks and from standard calibration curves with a precision of ±5%. We find only very small fluorescence from pore waters measured in situ, but observe rapid increases in fluorescence from cores returned to the surface and exposed to oxygen.     

The Hydraulic Effects of Lost Circulation and the Implications for Contaminant Migration During Drilling

The impact of lost circulation during rotary drilling near an existing monitoring well cluster was evaluated by periodic measurements of water levels and contaminant concentrations at the well cluster. Due to regulatory concerns, changes in water levels or VOC concentration in the well cluster during drilling would trigger monitoring well redevelopment. The borehole was drilled approximately 30 feet northeast of four nested monitoring wells that screen Devonian and Silurian carbonate bedrock at depths of 15, 60, 130, and 190 feet. Following complete circulation loss at depths of 177 and 1 S3 feet in the borehole, a rapid decrease in water levels was observed in the upper three monitoring wells. The water level in the well that was screened through the lost circulation zones increased slightly.
Decreasing water levels in formations located above the point of circulation loss appear to occur in response to a sudden decrease in borehole fluid pressure caused by the flow of drilling fluid into the formation. The relative contribution of contaminated formation water lo the borehole can be estimated by using the time-drawdown relationship and estimates of transmissivity. At the point of circulation loss, significant dilution of contaminant concentrations occurs from the loss of drilling fluid into the contaminated zone. Contaminated formation water entering the borehole during periods of complete lost circulation may mobilize contaminants from upper lo lower formations. Lost circulation into a formation would be signaled by a water level increase in monitoring wells. The wells would subsequently require development to remove the volume of fluid lost to the formation, including both drilling fluid and contaminated formation water. Monitoring wells exhibiting declining water levels following lost circulation would not require development since drilling water has not entered the zones screened by these wells.     

Defence and the environment: An economic approach

Abtract The environmental impacts of defence is a neglected and under-researched area for economists. This article presents a conceptual approach outlining some of the economic issues involved in the environmental impacts of defence spending and the activities of the armed forces. It reviews the economics and politics of externalities and then considers beneficial and harmful externalities and concludes by identifying some of the environmental costs of disarmanent.     

A review of the geochemistry of methane in natural gas hydrate

The largest accumulations on Earth of natural gas are in the form of gas hydrate, found mainly offshore in outer continental margin sediment and, to a lesser extent, in polar regions commonly associated with permafrost. Measurements of hydrocarbon gas compositions and of carbon-isotopic compositions of methane from natural gas hydrate samples, collected in subaquatic settings from around the world, suggest that methane guest molecules in the water clathrate structures are mainly derived by the microbial reduction of CO₂ from sedimentary organic matter. Typically, these hydrocarbon gases are composed of > 99% methane, with carbon-isotopic compositions (δ¹³C_PDB) ranging from − 57 to − 73‰. In only two regions, the Gulf of Mexico and the Caspian Sea, has mainly thermogenic methane been found in gas hydrate. There, hydrocarbon gases have methane contents ranging from 21 to 97%, with δ¹³C values ranging from − 29 to − 57‰. At a few locations, where the gas hydrate contains a mixture of microbial and thermal methane, microbial methane is always dominant. Continental gas hydrate, identified in Alaska and Russia, also has hydrocarbon gases composed of > 99% methane, with carbon-isotopic compositions ranging from − 41 to − 49‰. These gas hydrate deposits also contain a mixture of microbial and thermal methane, with thermal methane likely to be dominant. Published by Elsevier Science Ltd