Experimental determination of activities in FeTiO3-MnTiO3 ilmenite solid solution by redox reversals

 Solid solutions of (Fe,Mn)TiO₃ were synthesized, mostly at 0.10 X_Mn intervals, at 1 bar, 900°C and log f _{O 2} = –17.50. Analysis by EMP indicate an ideal stoichiometry for the Fe-Mn ilmenites with (Fe+Mn) = Ti = 1.000 when normalized to 3 oxygens. Their unit cell volume increases linearly with X_Mn. The composition of Fe-Mn ilmenite coexisting with metallic Fe and rutile was reversed at 1 bar, 700–900°C and fixed f _{O 2} in a gas-mixing furnace. Oxygen fugacity was controlled by mixing CO₂ and H₂ gas and was continuously monitored with an yttrium-stabilized zirconia electrolyte. Solution properties of Fe-Mn ilmenite were derived from the experimental data by mathematical programming (Engi and Feenstra, in preparation) including notably the results of Fe-Mn exchange experiments between ilmenite and garnet (Feenstra and Engi, submitted) and anchoring the standard state properties to the updated thermodynamic dataset of Berman and Aranovich (1996). The thermodynamic analysis resulted in positive deviations from ideality for (Fe,Mn)TiO₃ ilmenite, which is well described by an asymmetric Margules model with W^H _FeFeMn = –9.703 and W^H _FeMnMn = –23.234 kJ/mol, W^S _FeFeMn = –19.65 and W^S _FeMnMn = –22.06 J/(K·mol). The excess free energy for Fe-Mn ilmenite derived from the redox reversals is larger than in the symmetric ilmenite model (W^G _FeMn = +2.2 kJ/mol) determined by O'Neill et al. from emf measurements on the assemblage iron-rutile-(Fe,Mn)ilmenite. Received: 10 January 1996 / Accepted: 11 July 1996     

Landscape controls on long‐term runoff in subhumid heterogeneous Boreal Plains catchments

We compared median runoff (R) and precipitation (P) relationships over 25 years from 20 mesoscale (50 to 5,000 km²) catchments on the Boreal Plains, Alberta, Canada, to understand controls on water sink and source dynamics in water‐limited, low‐relief northern environments. Long‐term catchment R and runoff efficiency (RP^?1) were low and varied spatially by over an order of magnitude (3 to 119 mm/year, 1 to 27%). Intercatchment differences were not associated with small variations in climate. The partitioning of P into evapotranspiration (ET) and R instead reflected the interplay between underlying glacial deposit texture, overlying soil‐vegetation land cover, and regional slope. Correlation and principal component analyses results show that peatland‐swamp wetlands were the major source areas of water. The lowest estimates of median annual catchment ET (321 to 395 mm) and greatest R (60 to 119 mm, 13 to 27% of P) were observed in low‐relief, peatland‐swamp dominated catchments, within both fine‐textured clay‐plain and coarse‐textured glacial deposits. In contrast, open‐water wetlands and deciduous‐mixedwood forest land covers acted as water sinks, and less catchment R was observed with increases in proportional coverage of these land covers. In catchments dominated by hummocky moraines, long‐term runoff was restricted to 10 mm/year, or 2% of P. This reflects the poor surface‐drainage networks and slightly greater regional slope of the fine‐textured glacial deposit, coupled with the large soil‐water and depression storage and higher actual ET of associated shallow open‐water marsh wetland and deciduous‐forest land covers. This intercatchment study enhances current conceptual frameworks for predicting water yield in the Boreal Plains based on the sink and source functions of glacial landforms and soil‐vegetation land covers. It offers the capability within this hydro‐geoclimatic region to design reclaimed catchments with desired hydrological functionality and associated tolerances to climate or land‐use changes and inform land management decisions based on effective catchment‐scale conceptual understanding.     

Quantifying fracture geometry with X-ray tomography: Technique of Iterative Local Thresholding (TILT) for 3D image segmentation

This paper presents a new method—the Technique of Iterative Local Thresholding (TILT)—for processing 3D X-ray computed tomography (xCT) images for visualization and quantification of rock fractures. The TILT method includes the following advancements. First, custom masks are generated by a fracture-dilation procedure, which significantly amplifies the fracture signal on the intensity histogram used for local thresholding. Second, TILT is particularly well suited for fracture characterization in granular rocks because the multi-scale Hessian fracture (MHF) filter has been incorporated to distinguish fractures from pores in the rock matrix. Third, TILT wraps the thresholding and fracture isolation steps in an optimized iterative routine for binary segmentation, minimizing human intervention and enabling automated processing of large 3D datasets. As an illustrative example, we applied TILT to 3D xCT images of reacted and unreacted fractured limestone cores. Other segmentation methods were also applied to provide insights regarding variability in image processing. The results show that TILT significantly enhanced separability of grayscale intensities, outperformed the other methods in automation, and was successful in isolating fractures from the porous rock matrix. Because the other methods are more likely to misclassify fracture edges as void and/or have limited capacity in distinguishing fractures from pores, those methods estimated larger fracture volumes (up to 80 %), surface areas (up to 60 %), and roughness (up to a factor of 2). These differences in fracture geometry would lead to significant disparities in hydraulic permeability predictions, as determined by 2D flow simulations.     

Tectonic Subsidence of California Estuaries Increases Forecasts of Relative Sea-Level Rise

Even along the generally uplifting coast of the Pacific US, local geologic structures can cause subsidence. In this study, we quantify Holocene-averaged subsidence rates in four estuaries (Carpinteria Slough, Goleta Slough, Campus Lagoon, and Morro Bay) along the southern and central California coast by comparing radiocarbon-dated estuarine material to a regional sea-level curve. Holocene-averaged rates of vertical motion range from subsidence of 1.4?±?2.4, 1.2±0.4, and 0.4?±?0.3 mm/year in Morro Bay, Carpinteria Slough, and Goleta Slough, respectively, to possible uplift in Campus Lagoon (?0.1?±?0.9 mm/year). The calculated rates of subsidence are of the same magnitude as rates of relative sea-level rise experienced over the late Holocene and effectively double the ongoing rates of relative sea-level rise experienced over the last five decades on other parts of the coast. The difference in rates of vertical motion among these four estuaries is attributed to their geological settings. Estuaries developed in subsiding geological structures such as synclines and fault-bounded basins are subsiding at much higher rates than those developed within flooded river valleys incised into marine terraces. Restoration projects accounting for future sea-level rise must consider the geologic setting of the estuaries and, if applicable, include subsidence in future sea-level rise scenarios, even along the tectonically uplifting US Pacific Coast.     

Back to the future: reflections and directions of South African marine bioinvasion research

Biological invasions continue to increase around the world, with impacts on many coastal marine systems. Here we review the South African marine invasion literature which, despite the field being relatively new, has grown to have significant presence in both the local and international arenas. Of the 79 papers reviewed, 70% focused on the establishment and spread of alien species, with modes of transport and introduction largely overlooked. An emphasis was also apparent towards field studies, in particular survey work, with few experimental studies. The overwhelming majority of papers focused on a single species, the Mediterranean mussel Mytilus galloprovincialis, reflecting the scale of this invasion and the tractable nature of rocky shores as study systems. With the exception of this one species, the impacts of marine alien species have rarely been quantified. We suggest that future research extends the taxonomic coverage of present work and develops a better understanding of the mechanisms of introduction, establishment and spread of marine alien species. Through an experimental approach, the drivers of altered ecological patterns and processes resulting from invasions should be addressed, providing insight into associated impacts. This approach will maintain the local applicability and international relevance of South African marine invasion research.     

Targeting carbon dioxide removal in the European Union

In principle, many climate policymakers have accepted that large-scale carbon dioxide removal (CDR) is necessary to meet the Paris Agreement’s mitigation targets, but they have avoided proposing by whom CDR might be delivered. Given its role in international climate policy, the European Union (EU) might be expected to lead the way. But among EU climate policymakers so far there is little talk on CDR, let alone action. Here we assess how best to ‘target’ CDR to motivate EU policymakers exploring which CDR target strategy may work best to start dealing with CDR on a meaningful scale. A comprehensive CDR approach would focus on delivering the CDR volumes required from the EU by 2100, approximately at least 50 Gigatonnes (Gt) CO₂, according to global model simulations aiming to keep warming below 2°C. A limited CDR approach would focus on an intermediate target to deliver the CDR needed to reach ‘net zero emissions’ (i.e. the gross negative emissions needed to offset residual positive emissions that are too expensive or even impossible to mitigate). We argue that a comprehensive CDR approach may be too intimidating for EU policymakers. A limited CDR approach that only addresses the necessary steps to reach the (intermediate) target of ‘net zero emissions’ is arguably more achievable, since it is a better match to the existing policy paradigm and would allow for a pragmatic phase-in of CDR while avoiding outright resistance by environmental NGOs and the broader public.

Key policy insights

• Making CDR an integral part of EU climate policy has the potential to significantly reshape the policy landscape.

• Burden sharing considerations would probably play a major role, with comprehensive CDR prolonging the disparity and tensions between progressives and laggards.

• Introducing limited CDR in the context of ‘net zero’ pathways would retain a visible primary focus on decarbonization but acknowledge the need for a significant enhancement of removals via ‘natural’ and/or ‘engineered’ sinks.

• A decarbonization approach that intends to lead to a low level of ‘residual emissions’ (to be tackled by a pragmatic phase-in of CDR) should be the priority of EU climate policy.

     

Ranking of Placer Gold Prospects in Chile Through Analytic Hierarchy Process

Chile has a rich, but poorly known history of placer gold mining. At present, this sector is almost nonexistent and there are some restrictions for its revival: disperse and partial information on existing resources and limited technical expertise to assess the potential of placer gold mine sites. This paper presents the background, methodology and results of the prioritization process of known prospects of this kind in Chile. This research was part of a publicly funded project aimed to incentivize the development of this industry. The ranking was carried out using the analytic hierarchy process, which allowed to include different quantitative and qualitative variables related to the economic potential, technical aspects, contextual viability and socioeconomic factors in the analysis. The results show that, despite the increasing relevance of environmental and community issues in mining development, the business potential and the economic/technical aspects are the main factors in the early selection of a site to advance in exploration and development activities. Both variables represented around 40% and 37% of weights in the final selection, respectively. In contrast, contextual viability and local socioeconomic impacts only accounted for the remaining 23%. This study also shows that the inclusion of experts with different backgrounds in the process enriches the analysis and does not significantly distort the final outcome of the prioritization. Finally, the relevance of using MCDM tools when assessing the attractiveness of mine sites for their development is highlighted, particularly when public funds for subsequent exploration activities are committed.

     

A simulation model of how life history strategies mediate pollution effects on fish populations

Pollution effects on fish populations were estimated with a simulation model, using Leslie matrices. Results from changing only first-year survival rate (S_o) have already been published (Schaaf et al. 1987). This paper explores the effects of perturbing both S_o and the adult survival rate (S_i) for 12 spatial-temporal stocks. Most stocks examined are more sensitive to permanent change in S_i than to changes in S_o. The relative importance of these two rates in determining the population growth rate (λ) depends upon the age distribution of the expected lifetime egg production of age i females (V_i). In turn, the vector V_i, as measured by its mean and standard deviation, is shown to vary among geographic or temporal stocks of a single species. Hence, we quantify the impact on population size of destroying a fixed percentage of habitat, relative to where and when it occurs (i.e., relative impact on S_i and S_o). For example, destroying 1% of the Atlantic menhaden habitat would reduce λ by 0.8% and the population by 8.0% in 10 yr, if the impact affected only adults (e.g., offshore in winter). If the 1% habitat destruction all occurred in the estuaries, affecting juveniles as well, λ would be reduced by almost 5%, and in 10 yr drive the population down to 58% of its former equilibrium. We show that knowledge of the mean and variance of the age distribution of V_i permits prediction of relative sensitivity among species to pollution. Within species, this knowledge of V_i permits comparison of the effects of impacting different life stages and at different times and places.     

Performance of the electrochemical ozone sonde OSR

Summary The accuracy of the electrochemical ozone sonde, type OSR, has been estimated by analysing tandem ozone soundings of the balloon-borne electrochemical ozone sonde OSR at the Lindenberg Observatory from May to November 1982. A negative bias, though not significant, has been observed above about 28 km for soundings having high single correction factors. Random errors are at their minimum just above the level of the maximum of ozone partial pressure, and reach their maximum in the troposphere. Except at heights above about 28 km the random error of ozone sondes is a factor 2 to 3 times less than the error of the short Umkehr method. Provided that soundings with too high correction factors are neglected, the ozone sonde OSR has an accuracy comparable to that of other Brewer type sondes.The maximum amount of information on the vertical ozone distribution can be drawn from sonde measurements in the lower stratosphere. A study is underway to improve the sensitivity of the sonde OSR and thus to further enhance its reliability.