A high-resolution TEM-AEM, pH titration, and modeling study of Zn coprecipitation with ferrihydrite

Experiments of Zn²⁺ and Fe³⁺ coprecipitation as a function of pH were conducted in the laboratory at ambient temperature and pressure. X-ray diffraction patterns of the coprecipitates show two broad peaks at 0.149 and 0.258 nm, which is consistent with published patterns for pure 2-line ferrihydrite. Zn²⁺ uptake occurred at pH ≥5 while Fe³⁺ precipitation occurred between pH 3 and 4, although both Zn²⁺ and Fe³⁺ were present in the same solution during the entire range of pH titration. High-resolution transmission electron microscopy shows that the coprecipitates are 2 to 6 nm sized single crystalline particles but aggregated to 50 to 400 nm sized clusters. Analytical electron microscopy indicated that the 5% atomic Zn with respect to Fe was homogeneously distributed. No segregated phases were found in the clusters or at single crystal edges, which is consistent with published extended X-ray absorption fine structure (EXAFS) results at similar Zn/(Zn + Fe) ratios. Hence, occlusion and surface precipitation may be excluded as possible coprecipitation mechanisms. The bulk solution Zn²⁺ sorption edge was fitted to both solid solution and generalized diffuse layer surface complexation models. However, a solid solution model is inconsistent with published EXAFS results that show tetrahedral polydentate Zn²⁺ complexes sharing apices with Fe³⁺octahedra.     

Understanding governance and networks: EU-US interactions and the regulation of genetically modified organisms

EU-US (European Union-United States) interactions in relation to the regulation of genetically modified organisms (GMOs) have been examined in detail in recent years. To do this scholars have tended to focus on a small number of high profile processes, such as the formal complaint of the US to the World Trade Organisation regarding the regulation of GMOs in the Europe. It is important to analyse developments of this kind but overemphasis on them has also lead to a distorted view of the case and a failure to appreciate the significance of other, less visible, types of interaction. In this paper we focus instead on trying to understand the roles played by various EU-US transnational networks—The Transatlantic Business Dialogue, The Transatlantic Economic Partnership, The Transatlantic Consumer Dialogue, The Transatlantic Environmental Dialogue and the EU-US Consultative Forum on Biotechnology. These networks have been trying to shape the regulation of GMOs in both jurisdictions since the mid 1990s. By analysing them through a ‘governance lens’ we find that we can better understand EU-US interactions and the dynamics and influences around the regulation of GMOs. This gives us valuable insights into processes of contemporary governance.     

A multi‐proxy record of changing environments from ca. 30 000 to 9000 cal. a BP: Onepoto maar palaeolake,Auckland, New Zealand

We present a high‐resolution record of lacustrine sedimentation spanning ca. 30 000 to 9000 cal. a BP from Onepoto maar, northern North Island, New Zealand. The multi‐proxy record of environmental change is constrained by tephrochronology and accelerator mass spectrometric ¹⁴C ages and provides evidence for episodes of rapid environmental change during the Last Glacial Coldest Period (LGCP) and Last Glacial–Interglacial Transition (LGIT) from northern New Zealand. The multi‐proxy palaeoenvironmental record from Onepoto indicates that the LGCP was cold, dry and windy in the Auckland region, with vegetation dominated by herb and grass in a beech forest mosaic between ca. 28 500 and 18 000 cal. a BP. The LGCP was accompanied by more frequent fires and influx of clastic sediment indicating increased erosion during the LGCP, with a mid‐LGCP interstadial identified between ca. 25 000 and 23 000 cal. a BP. Rapid climate amelioration at ca. 18 000 cal. a BP was accompanied by increased terrestrial biomass exemplified by the expansion of lowland podocarp forest, especially Dacrydium cupressinum. Increasing biomass production is reversed briefly by LGIT perturbations which are apparent in many of the proxies that span ca. 14 000–10 500 cal. a BP, suggesting generally increased wetness and higher in situ aquatic plant productivity with reduced terrestrial organic matter and terrigenous detrital influx. Furthermore, conditions at that time were probably warmer and frosts rare based on the increasing importance of Ascarina. The subsequent early Holocene is characterised by podocarp conifer forest and moist mild conditions. Postglacial sea‐level rise breached the crater rim and deposited 36 m of estuarine mud after ca. 9000 cal. a BP. Copyright © 2011 John Wiley & Sons, Ltd.     

Characterizing and classifying urban watersheds with compositional and structural attributes

Current land-use classifications used to assess urbanization effects on stream water quality date back to the 1980s when limited information was available to characterize watershed attributes that mediate non-point source pollution. With high resolution remote sensing and widely used GIS tools, there has been a vast increase in the availability and precision of geospatial data of built environments. In this study, we leverage geospatial data to expand the characterization of developed landscapes and create a typology that allows us to better understand the impact of complex developed landscapes across the rural to urban gradient. We assess the ability of the developed landscape typology to reveal patterns in stream water chemistry previously undetected by traditional land-cover based classification. We examine the distribution of land-cover, infrastructure, topography and geology across 3876 National Hydrography Dataset Plus catchments in the Piedmont region of North Carolina, USA. From this dataset, we generate metrics to evaluate the abundance, density and position of landscape features relative to streams, catchment outlets and topographic wetness metrics. While impervious surfaces are a key distinguishing feature of the urban landscape, sanitary infrastructure, population density and geology are better predictors of baseflow stream water chemistry. Unsupervised clustering was used to generate a distinct developed landscape typology based on the expanded, high-resolution landscape feature information. Using stream chemistry data from 37 developed headwater catchments, we compared the baseflow water chemistry grouped by traditional land-cover based classes of urbanization (rural, low, medium and high density) to our composition and structure-based classification (a nine-class typology). The typology based on 22 metrics of developed landscape composition and structure explained over 50% of the variation in NO₃⁻-N, TDN, DOC, Cl⁻, and Br⁻ concentration, while the ISC-based classification only significantly explained 23% of the variation in TDN. These results demonstrate the importance of infrastructure, population and geology in defining developed landscapes and improving discrete classes for water management.     

Late Quaternary sea‐level change and evolution of Belfast Lough,Northern Ireland: new offshore evidence and implications for sea‐level reconstruction

The interplay of eustatic and isostatic factors causes complex relative sea‐level (RSL) histories, particularly in paraglacial settings. In this context the past record of RSL is important in understanding ice‐sheet history, earth rheology and resulting glacio‐isostatic adjustment. Field data to develop sea‐level reconstructions are often limited to shallow depths and uncertainty exists as to the veracity of modelled sea‐level curves. We use seismic stratigraphy, 39 vibrocores and 26 radiocarbon dates to investigate the deglacial history of Belfast Lough, Northern Ireland, and reconstruct past RSL. A typical sequence of till, glacimarine and Holocene sediments is preserved. Two sea‐level lowstands (both max. ?40 m) are recorded at c. 13.5 and 11.5k cal a bp . Each is followed by a rapid transgression and subsequent periods of RSL stability. The first transgression coincides temporally with a late stage of Meltwater Pulse 1a and the RSL stability occurred between c. 13.0 and c. 12.2k cal a bp (Younger Dryas). The second still/slowstand occurred between c. 10.3 and c. 11.5k cal a bp . Our data provide constraints on the direction and timing of RSL change during deglaciation. Application of the Depth of Closure concept adds an error term to sea‐level reconstructions based on seismic stratigraphic reconstructions.     

Supraglacial weathering crust dynamics inferred from cryoconite hole hydrology

Water levels in cryoconite holes were monitored at high resolution over a 3‐week period on Austre Brøggerbreen (Svalbard). These data were combined with melt and energy balance modelling, providing insights into the evolution of the glacier's near‐surface hydrology and confirming that the hydrology of the near‐surface, porous ice known as the ‘weathering crust’ is dynamic and analogous to a shallow‐perched aquifer. A positive correlation between radiative forcing of melt and drainage efficiency was found within the weathering crust. This likely resulted from diurnal contraction and dilation of interstitial pore spaces driven by variations in radiative and turbulent fluxes in the surface energy balance, occasionally causing ‘sudden drainage events’. A linear decrease in water levels in cryoconite holes was also observed and attributed to cumulative increases in near‐surface ice porosity over the measurement period. The transport of particulate matter and microbes between cryoconite holes through the porous weathering crust is shown to be dependent upon weathering crust hydraulics and particle size. Cryoconite holes therefore yield an indication of the hydrological dynamics of the weathering crust and provide long‐term storage loci for cryoconite at the glacier surface. This study highlights the importance of the weathering crust as a crucial component of the hydrology, ecology and biogeochemistry of the glacier ecosystem and glacierized regions and demonstrates the utility of cryoconite holes as natural piezometers on glacier surfaces. Copyright © 2015 John Wiley & Sons, Ltd.     

Customary tenure systems under siege: contemporary access to land in Northern Ghana

Land in most of Africa is controlled under the customary tenure system which is governed by well intentioned social and cultural rules meant to grant equal access to families within groups with common interest in land. Rapid changes in the domestic situation of countries resulting from both refractions of policies and influences from the global economy and emerging complexities within the local socio-economic context has altered the traditional land tenure systems in most parts of Africa. In the rural setting and for agricultural purposes, the customary tenure system seems to be crumbling slowly, while in the urban centres and for housing, industrial and commercial purposes the system has collapsed in favour of a commoditised one. The emerging patterns of access in Northern Ghana show growing inequalities in access, control and ownership. There is the need for a new architecture of land rights negotiated by a participatory process and regulated by both state and traditional institutions.     

Assessment of spatial variations in water quality of Garra River at Shahjahanpur,Ganga Basin,India

Arabian Journal of Geosciences - A comprehensive study on the chemical considerations of thermal waters (springs and geothermal wells) on the performance of solute geothermometers in predicting the...