Lead coprecipitation with iron oxyhydroxide nano-particles

Pb²⁺ and Fe³⁺ coprecipitation was studied with sorption edge measurements, desorption experiments, sorbent aging, High Resolution Transmission and Analytical Electron Microscopy (HR TEM-AEM), and geochemical modeling. Companion adsorption experiments were also conducted for comparison. The macroscopic chemical and near atomic scale HRTEM data supplemented our molecule scale analysis with EXAFS (Kelly et al., 2008). Coprecipitation of Pb²⁺ with ferric oxyhydroxides occurred at ∼pH 4 and is more efficient than adsorption in removing Pb²⁺ from aqueous solutions at similar sorbate/sorbent ratios and pH. X-ray Diffraction (XRD) shows peaks of lepidocrocite and two additional broad peaks similar to fine particles of 2-line ferrihydrite (2LFh). HRTEM of the Pb-Fe coprecipitates shows a mixture of 2-6 nm diameter spheres and 8-20 by 200-300 nm needles, both uniformly distributed with Pb²⁺. Geochemical modeling shows that surface complexation models fit the experimental data of low Pb:Fe ratios when a high site density is used. Desorption experiments show that more Pb²⁺ was released from loaded sorbents collected from adsorption experiments than from Pb to Fe coprecipitates at dilute EDTA concentrations. Desorbed Pb²⁺ versus dissolved Fe³⁺ data show a linear relationship for coprecipitation (CPT) desorption experiments but a parabolic relationship for adsorption (ADS) experiments.Based on these results, we hypothesize that Pb²⁺ was first adsorbed onto the nanometer-sized, metastable, iron oxyhydroxide polymers of 2LFh with domain size of 2-3 nm. As these nano-particles assembled into larger particles, some Pb²⁺ was trapped in the iron oxyhydroxide structure and re-arranged to form solid solutions. Therefore, the CPT contact method produced more efficient removal of Pb²⁺ than the adsorption contact method, and Pb²⁺ bound in CPT solids represent a more stable sequestration of Pb²⁺ in the environment than Pb²⁺ adsorbed on iron oxyhydroxide surfaces.     

Predictability of the mid-latitude Atlantic meridional overturning circulation in a multi-model system

Assessing the skill of the Atlantic meridional overturning circulation (AMOC) in decadal hindcasts (i.e. retrospective predictions) is hampered by a lack of observations for verification. Models are therefore needed to reconstruct the historical AMOC variability. Here we show that ten recent oceanic syntheses provide a common signal of AMOC variability at 45°N, with an increase from the 1960s to the mid-1990s and a decrease thereafter although they disagree on the exact magnitude. This signal correlates with observed key processes such as the North Atlantic Oscillation, sub-polar gyre strength, Atlantic sea surface temperature dipole, and Labrador Sea convection that are thought to be related to the AMOC. Furthermore, we find potential predictability of the mid-latitude AMOC for the first 3–6 year means when we validate decadal hindcasts for the past 50 years against the multi-model signal. However, this predictability is not found in models driven only by external radiative changes, demonstrating the need for initialization of decadal climate predictions.     

An inter-hemispheric comparison of the tropical storm response to global warming

Model studies do not agree on future changes in tropical cyclone (TC) activity on regional scales. We aim to shed further light on the distribution, frequency, intensity, and seasonality of TCs that society can expect at the end of the twenty-first century in the Southern hemisphere (SH). Therefore, we investigate TC changes simulated by the atmospheric model ECHAM5 with T213 (~60 km) horizontal resolution. We identify TCs in present-day (20C; 1969–1990) and future (21C; 2069–2100) time slice simulations, using a tracking algorithm based on vorticity at 850 hPa. In contrast to the Northern hemisphere (NH), where tropical storm numbers reduce by 6 %, there is a more dramatic 22 % reduction in the SH, mainly in the South Indian Ocean. While an increase of static stability in 21C may partly explain the reduction in tropical storm numbers, stabilization cannot alone explain the larger SH drop. Large-scale circulation changes associated with a weakening of the Tropical Walker Circulation are hypothesized to cause the strong decrease of cyclones in the South Indian Ocean. In contrast the decrease found over the South Pacific appears to be partly related to increased vertical wind shear, which is possibly associated with an enhanced meridional sea surface temperature gradient. We find the main difference between the hemispheres in changes of the tropical cyclones of intermediate strength with an increase in the NH and a decrease in the SH. In both hemispheres the frequency of the strongest storms increases and the frequency of the weakest storms decreases, although the increase in SH intense storms is marginal.     

The structure of circumstellar envelopes

Copious mass loss on the Asymptotic Giant Branch dominates the late stages of stellar evolution. Maps of extended circumstellar envelopes provide a history of mass loss and trace out anisotropic mass loss. This review concentrates on observations of millimeter wavelength molecular line emission, on high resolution maps of maser emission and on observations of submillimeter, millimeter and radio wavelength continuum emission. Radio continuum observations show that AGB stars are larger at radio than at optical wavelengths. The extended chromospheres indicated by these observations extend to distances from the star large enough for dust to form, thereby initiating mass loss. Molecular line maps have found time-variable mass loss for some stars, including detached shells indicating interrupted mass loss and evidence for a rapid increase in the mass loss rate at the end of the AGB phase. Maps of circumstellar envelopes show evidence of flattening, bipolar outflow and angular variations in both the mass loss rate and the outflow velocity. As stars evolve away from the AGB and planetary nebula formation begins, these structures become more pronounced, and fast bipolar molecular winds are observed. The time scales derived from the dynamical times of these winds and from the expansion rates of the central planetary nebulae are very rapid in some cases, about 100 years, in agreement with the predictions of stellar evolution theory.     

Desperately seeking niches: Grassroots innovations and niche development in the community currency field

The sustainability transitions literature seeks to explain the conditions under which technological innovations can diffuse and disrupt existing socio-technical systems through the successful scaling up of experimental ‘niches’; but recent research on ‘grassroots innovations’ argues that civil society is a promising but under-researched site of innovation for sustainability, albeit one with very different characteristics to the market-based innovation normally considered in the literature. This paper aims to address that research gap by exploring the relevance of niche development theories in a civil society context. To do this, we examine a growing grassroots innovation – the international field of community currencies – which comprises a range of new socio-technical configurations of systems of exchange which have emerged from civil society over the last 30 years, intended to provide more environmentally and socially sustainable forms of money and finance. We draw on new empirical research from an international study of these initiatives comprising primary and secondary data and documentary sources, elite interviews and participant observation in the field. We describe the global diffusion of community currencies, and then conduct a niche analysis to evaluate the utility of niche theories for explaining the development of the community currency movement. We find that some niche-building processes identified in the existing literature are relevant in a grassroots context: the importance of building networks, managing expectations and the significance of external ‘landscape’ pressures, particularly at the level of national-type. However, our findings suggest that existing theories do not fully capture the complexity of this type of innovation: we find a diverse field addressing a range of societal systems (money, welfare, education, health, consumerism), and showing increasing fragmentation (as opposed to consolidation and standardisation); furthermore, there is little evidence of formalised learning taking place but this has not hampered movement growth. We conclude that grassroots innovations develop and diffuse in quite different ways to conventional innovations, and that niche theories require adaptation to the civil society context.     

Isotopic composition of a large photosymbiotic foraminifer: Evidence for hypersaline environments across the Great Australian Bight during the late Pleistocene

Analysis of carbon and oxygen isotopic compositions of large benthic foraminifera tests (Marginopora vertebralis) that lived in the Great Australian Bight during the late Pleistocene, reveal that the tests are enriched by 1 to 3‰ in both ¹⁸O and ¹³C relative to modern specimens from the same region. The intolerance of M. vertebralis for cool waters negates lower ocean water temperature as an explanation for such high δ¹⁸O values. The oxygen isotopic compositions are thus interpreted to reflect tests secreted in hypersaline waters of up to 56 ppt salinity, concentrated from seawater by evaporation. M. vertebralis thrives today in waters of similar salinity at Shark Bay, Western Australia. The Pleistocene sedimentary assemblage supports an interpretation that environments broadly similar to those in outer modern-day Shark Bay were wide spread across the Great Australian Bight during portions of marine isotope stages 2, 3 and 4. The high δ¹³C values of the Pleistocene M. vertebralis are interpreted to reflect enhanced photosynthetic activity that depletes dissolved carbonate in ¹²C in such shallow, saline settings. These hypersaline environments formed during periods of lower sea-level when shallow-waters (< 20 m depth) extended from the shoreline over ~ 100 km across what is currently a relatively deep shelf. This study indicates that shelf bathymetry was a critical determinant of past environments of deposition across the Great Australian Bight.