Assessing the redox properties of iron-bearing clay minerals using homogeneous electrocatalysis

Iron-bearing clay minerals are ubiquitous in the environment and have been shown to play important roles in several biogeochemical processes. Previous efforts to characterize the Fe²⁺–Fe³⁺ redox couple in clay minerals using electrochemical techniques have been limited by experimental difficulties due to inadequate reactivity between clay minerals and electrodes. The current work overcomes this limitation by utilizing organic electron transfer mediators that rapidly transfer electrons with both the Fe-bearing clay minerals and electrodes. Here, an Fe-rich source clay mineral (ferruginous smectite, SWa-1) is examined with respect to what fraction of structural Fe participates in oxidation/reduction reactions and the relationship between bulk Fe²⁺/Fe³⁺ ratios to the reduction potential (E_h).     

Soil erosion due to rainfall impact with no inflow: a numerical solution with spatial and temporal effects of sediment settling velocity characteristics

Dynamic changes take place in the nature of sediment eroded from bare soil at low slopes by rainfall impact when there is no inflow of water at the top of the eroding slope. This relates initially to fine soil sediment not settling back onto the soil after the rainfall impact. Coupled partial differential equations describing such dynamic changes have been solved numerically for a bed of soil, bounded at its upper end, and subject to a constant rainfall rate. This solution allows prediction of the change with time and downslope distance in the concentration and settling velocity (or size) characteristics of eroding sediment, allowing critical evaluation of the assumption of space-independent sediment characteristics made in prior approximate analytical solutions of the equations involved. Following the determination of as yet unpredictable soil-related parameters in the equations, the solution was tested by comparison with experimented data on two soils of contrasting structural stability, namely a vertosol [The Australian Soil Classification (1996)] and a aridisol. Investigations included the determination of a minimum number of sediment size classes required to adequately describe the settling velocity characteristics, based on the shape of the underlying basic settling velocity characteristic, which is used to predict the dynamics of sediment deposition. The effect on the solution of observed structural breakdown in soil aggregation due to rainfall impact was investigated, leading to more accurate predictions of the settling velocity characteristics of eroded sediment. Other sources of discrepancy between theory and observation remain to be determined.     

A late Pleistocene record of aeolian sedimentation in Blanche Cave, Naracoorte, South Australia

We provide geochemical analyses and grain size data for a clearly layered, 80 cm thick sedimentary deposit close to a roof collapse in Blanche Cave near Naracoorte in SE South Australia. This deposit contains aeolian material deposited between 40 ka and 14 ka cal BP and which yields airborne sediments spanning the Last Glacial Maximum, a period of time with little information for the Australian continent. The deposit also contains abundant vertebrate fossil material derived from owl pellets, accumulation and pitfall entrapment. Below the studied profile, large vertebrate remains are found but are not discussed here. No Holocene sedimentation occurred at the site examined in the cave, and the top of the sequence is capped with a layer that has been anthropologically disturbed and contains exotic Pinus pollen. Chronologies of the deposit were obtained using two dating techniques: single stage accelerator mass spectrometer (SSAMS) ¹⁴C analysis of 23 charcoal samples and optically stimulated luminescence (OSL) dating of quartz from 6 sediment samples. The ¹⁴C chronology is preferred to describe the history of the deposits since the OSL chronology, which consistently overestimates the associated radiocarbon dates, may be inaccurate due to complexities in calculating dose rates, and may in addition represent the timing of sediment deposition through the cave opening rather than sediment transport to the deposit site. Morphological analysis of single quartz grains and grain size analysis indicate different provenance that is confirmed through the geochemical analyses of bulk sediment. Major elements were measured by X-ray Fluorescence (XRF), trace and rare earth elements by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA ICP-MS), and Neodymium isotopic ratios were obtained using a Thermal Ionisation Mass Spectrometer (TIMS).Our results indicate that the aeolian material deposited in Blanche Cave over the 40–14 ka cal BP period originated from different sources across South Australia, although Nd isotopes clearly indicate a close association with sediments of the Kanmantoo Group outcropping along the eastern portion of the Mount Lofty Ranges and the Padthaway Ridge further south, both being located to the NW and NNW of the cave. During the latter part of Marine Isotope Stage 3, conditions were wetter and windblown sediment came from the coastal region just north and south of the Coorong Lagoon, with winds originating from the north-northwest. At that time, woody taxa appear to have vegetated the landscape. During the drier phases, especially the Last Glacial Maximum, sediment came from further inland, thus suggesting a different predominant wind direction, more from the northwest. The deglaciation saw material originating from a more northerly direction.     

Mercury mobilization by oxidative dissolution of cinnabar (α-HgS) and metacinnabar (β-HgS)

Cinnabar (α-HgS) and metacinnabar (β-HgS) dissolved at environmentally significant rates in oxygenated slurry experiments simulating a low-flow fluvial system. Based on SO₄²⁻ production, cinnabar dissolution rates were 2.64 to 6.16 μmol (SO₄²⁻) m^− 2 day^− 1, and metacinnabar dissolution rates were 1.20 to 1.90 μmol (SO₄²⁻) m^− 2 day^− 1. Monodentate-bound thiosulfate (S₂O₃²⁻) was identified as an oxidation product on the HgS surface by ATR-IR spectroscopy based on strong infrared absorption bands in the 1140–1145 cm^− 1 and 1006–1014 cm^− 1 regions. The presence of sulfide oxidation intermediates on the HgS surface indicates that SO₄²⁻ concentration underestimates α-HgS and β-HgS dissolution in this setting. Mercury release rates during dissolution were more than two orders of magnitude less than SO₄²⁻ production, but were significant: 0.47 mg (Hg) m^− 2 y^− 1 from cinnabar [6.45 nmol (Hg) m^− 2 day^− 1], and 0.17 mg (Hg) m^− 2 y^− 1 from metacinnabar [2.29 nmol (Hg) m^− 2 day^− 1]. The Hg mobilized during α-HgS and β-HgS dissolution is sufficient to form natural Au–Hg amalgam in downstream placer settings. The proportion of mercury that is not remobilized during α-HgS and β-HgS dissolution likely adsorbs to the dissolving mercuric sulfide. Adsorption of Hg²⁺ to cinnabar was detected in situ by anodic stripping voltammetry using a cinnabar-modified carbon paste electrode following accumulation of Hg²⁺ on the electrode at open circuit potential.     

Coarse clast ridge sequences as suitable archives for past storm events? Case study on the Houtman Abrolhos,Western Australia

Prehistoric storm records are relatively scarce in most parts of the world. This article presents storm records derived from coral rubble‐based geological archives of the Houtman Abrolhos Archipelago located off the west coast of Australia, where the southernmost coral reefs of the Indian Ocean are found. Winter storm swell from the circum‐Antarctic ‘Brave Westerlies’, as well as tropical cyclone waves, have left numerous ridge systems on dozens of islands of the archipelago, all composed of coral rubble from adjacent reefs. At three islands, seven ridge systems were dated by three different methods: U‐series (68 dates), radiocarbon (64 dates), electron spin resonance (7 dates); 139 radiometric dates span the last 5500 years of the Holocene. In contrast to the geomorphological interpretation, the age sequences show ‘inversions’, hiatuses and different ages for the same ridge, all pointing to complicated ridge formation processes. Time gaps, some exceeding 1000 years, are interpreted as phases of erosion and not as phases without storm activity. Copyright © 2012 John Wiley & Sons, Ltd.     

Über einige Innsbrucker Institutsarbeiten seit 1940

Ohne Zusammenfassung     

The land cover and carbon cycle consequences of large-scale utilizations of biomass as an energy source

The use of modern biomass for energy generation has been considered in many studies as a possible measure for reducing or stabilizing global carbon dioxide (CO₂) emissions. In this paper we assess the impacts of large-scale global utilization of biomass on regional and grid scale land cover, greenhouse gas emissions, and carbon cycle. We have implemented in the global environmental change model IMAGE the LESS biomass intensive scenario, which was developed for the Second Assessment Report of IPCC. This scenario illustrates the potential for reducing energy related emission by different sets of fuel mixes and a higher energy efficiency. Our analysis especially covers different consequences involved with such modern biomass scenarios. We emphasize influences of CO₂ concentrations and climate change on biomass crop yield, land use, competition between food and biomass crops, and the different interregional trade patterns for modern biomass based energy. Our simulations show that the original LESS scenario is rather optimistic on the land requirements for large-scale biomass plantations. Our simulations show that 797 Mha is required while the original LESS scenario is based on 550 Mha. Such expansion of agricultural land will influence deforestation patterns and have significant consequenses for environmental issues, such as biodiversity. Altering modern biomass requirements and the locations where they are grown in the scenario shows that the outcome is sensitive for regional emissions and feedbacks in the C cycle and that competition between food and modern biomass can be significant. We conclude that the cultivation of large quantities of modern biomass is feasible, but that its effectiveness to reduce emissions of greenhouse gases has to be evaluated in combination with many other environmental land use and socio-economic factors.     

Effective and geographically balanced? An output-based assessment of non-state climate actions

At COP21 in Paris, governments reiterated the importance of ‘non-Party’ contributions, placing big bets that the efforts of cities, regions, investors, companies, and other social groups will help keep average global warming limited to well under 2°C. However, there is little systematic knowledge concerning the performance of non-state and subnational efforts. We established a database of 52 climate actions launched at the 2014 UN Climate Summit in New York to assess output performance – that is, the production of relevant outputs – to understand whether they are likely to deliver social and environmental impacts. Moreover, we assess to which extent climate actions are implemented across developed and developing countries. We find that climate actions are starting to deliver, and output performance after one year is higher than one might expect from previous experiences with similar actions. However, differences exist between action areas: resilience actions have yet to produce specific outputs, whereas energy and industry actions perform above average. Furthermore, imbalances between developing and developed countries persist. While many actions target low-income and lower-middle-income economies, the implementation gap in these countries remains greater. More efforts are necessary to mobilize and implement actions that benefit the world’s most vulnerable people.

Policy relevance

Climate actions by non-state and subnational actors are an important complement to the multilateral climate regime and the associated contributions made by national governments. Although such actions hold much potential, we still know very little about how they could deliver in practice. This article addresses this knowledge gap, by showing how 52 climate actions announced at the UN Climate Summit in 2014 have performed thus far. Based on our analysis, we argue that the post-Paris action agenda for non-state and subnational climate action should (1) find more effective ways to incentivize private sector actors to engage in transnational climate governance through actions that seek to reduce greenhouse gas emissions and promote climate resilience in a tangible manner; (2) identify factors underlying effectiveness, to take appropriate measures to support underperforming climate actions; and (3) address the large implementation gap of climate actions in developing countries.