Distribution of barium and fulvic acid at the mica-solution interface using in-situ X-ray reflectivity

The interfacial structures of the basal surface of muscovite mica in solutions containing (1) 5 × 10⁻³ m BaCl₂, (2) 500 ppm Elliott Soil Fulvic Acid I (ESFA I), (3) 100 ppm Elliott Soil Fulvic Acid II (ESFA II), (4) 100 ppm Pahokee Peat Fulvic Acid I (PPFA), and (5) 5 × 10⁻³ m BaCl₂ and 100 ppm ESFA II were obtained with high resolution in-situ X-ray reflectivity. The derived electron-density profile in BaCl₂ shows two sharp peaks near the mica surface at 1.98(2) and 3.02(4) Å corresponding to the heights of a mixture of Ba²⁺ ions and water molecules adsorbed in ditrigonal cavities and water molecules coordinated to the Ba²⁺ ions, respectively. This pattern indicates that most Ba²⁺ ions are adsorbed on the mica surface as inner-sphere complexes in a partially hydrated form. The amount of Ba²⁺ ions in the ditrigonal cavities compensates more than 90% of the layer charge of the mica surface. The electron-density profiles of the fulvic acids (FAs) adsorbed on the mica surface, in the absence of Ba²⁺, had overall thicknesses of 4.9-10.8 Å and consisted of one broad taller peak near the surface (likely hydrophobic and positively-charged groups) followed by a broad humped pattern (possibly containing negatively-charged functional groups). The total interfacial electron density and thickness of the FA layer increased as the solution FA concentration increased. The sorbed peat FA which has higher ash content showed a higher average electron density than the sorbed soil FA. When the muscovite reacted with a pre-mixed BaCl₂-ESFA II solution, the positions of the two peaks nearest the surface matched those in the BaCl₂ solution. However, the occupancy of the second peak decreased by about 30% implying that the hydration shell of surface-adsorbed Ba²⁺ was partially substituted by FA. The two surface peaks were followed by a broad less electron-dense layer suggesting a sorption mechanism in which Ba²⁺ acts dominantly as a bridging cation between the mica surface and FA. When the muscovite reacted first with FA and subsequently with BaCl₂, more Ba²⁺ could be adsorbed on the FA-coated mica surface. The peak closest to the mica included Ba²⁺ ions adsorbed directly on the mica in an amount similar to that in the BaCl₂ solution but more broadly distributed. A second peak observed within the FA layer suggests that the FA coating provides additional sites for Ba²⁺ sorption. The results indicate that enhanced uptake of heavy metals can occur when an organic coating already exists on a mineral surface.     

Factors triggering landslide occurrence on the Zemun loess plateau,Belgrade area,Serbia

Among the numerous factors that trigger landslide events, the anthropogenic impact caused by inadequate planning and faulty land use in urban areas is increasing. The Zemun settlement on the northern outskirts of Belgrade has experienced a number of landslides in the last three decades, endangering buildings and roads, and claiming human lives, particularly in the case of the 2010/2011 landslides. Selected meteorological parameters were used to calculate rainfall erosivity indices such as Precipitation Concentration Index and Modified Fournier Index over the period 1991–2015. Drought indices, Lang aridity index and Palfai Drought Index were calculated as well. Mann–Kendall trend test was applied to identify potential rising and/or declining trends both in meteorological parameters and calculated indices. Trend analysis of the annual and seasonal scales yielded a statistically significant trend in the spring time series. Stable arid and pronounced drought conditions were recorded. The modified Fournier index based on monthly mean values yields moderate aggressiveness, with several extreme values indicating very high erosivity classes, especially for 2010/2011. The geological substrate is predominantly loess and hence highly susceptible to erosion and slope failure when climatological conditions are suitable. Accelerated urbanization at the end of the last century reduced vegetation cover, intensified pressure on the vertical loess slope, and lacked suitable rain drainage systems so that surface-water runoff was directed into the porous loess, thereby endangering slope stability. We proposed a geomorphic model to describe the nature of the erosional processes on the loess cliffs of the Zemun loess plateau. Results from this study have implications for mitigation strategies.     

Salinization: the ultimate threat to temperate lakes,with particular reference to Southeastern Wisconsin (USA)

Many lakes in Southeastern Wisconsin(the metropolitan-Milwaukee area) are gradually becoming increasingly "salty".While these waterbodies would not be considered presently to be saline lakes,there has been a rapid increase in the chloride concentrations in most of these lakes over the last 30 years,with the lakes increasing from a mean chloride concentration of about 19 mg/L to over 100 mg/L in some cases.While ecological impacts can be expected when chloride values exceed 250 mg/L,the rate of increase presents a basis for concern,especially since the underlying geology of the region is based on limestone/dolomite which is deficient in chlorides.Thus,the origin of the chlorides is anthropogenic:human and industrial wastewaters(treatment of which has effected improvements in trophic status but has not affected other water-borne contaminants) and winter de-icing practices based upon large quantities of sodium chloride are major contributors to the increasing concentrations of chloride in the region's waterways.Without taking remedial measures,the rate of salinization is expected to continue to increase,resulting,ultimately,in the alteration of the freshwater systems in the region.     

Characterization of Mason Gully (H5): The second recovered fall from the Desert Fireball Network

Mason Gully, the second meteorite recovered using the Desert Fireball Network (DFN), is characterized using petrography, mineralogy, oxygen isotopes, bulk chemistry, and physical properties. Geochemical data are consistent with its classification as an H5 ordinary chondrite. Several properties distinguish it from most other H chondrites. Its 10.7% porosity is predominantly macroscopic, present as intergranular void spaces rather than microscopic cracks. Modal mineralogy (determined via PS‐XRD, element mapping via energy dispersive spectroscopy [EDS], and X‐ray tomography [for sulfide, metal, and porosity volume fractions]) consistently gives an unusually low olivine/orthopyroxene ratio (0.67?0.76 for Mason Gully versus ~1.3 for typical H5 ordinary chondrites). Widespread “silicate darkening” is observed. In addition, it contains a bright green crystalline object at the surface of the recovered stone (diameter ≈ 1.5 mm), which has a tridymite core with minor α‐quartz and a rim of both low‐ and high‐Ca pyroxene. The mineralogy allows the calculation of the temperatures and ?(O₂) characterizing thermal metamorphism on the parent body using both the two‐pyroxene and the olivine‐chromite geo‐oxybarometers. These indicate that MG experienced a peak metamorphic temperature of ~900 °C and had a similar ?(O₂) to Kernouvé (H6) that was buffered by the reaction between olivine, metal, and pyroxene. There is no evidence for shock, consistent with the observed porosity structure. Thus, while Mason Gully has some unique properties, its geochemistry indicates a similar thermal evolution to other H chondrites. The presence of tridymite, while rare, is seen in other OCs and likely exogenous; however, the green object itself may result from metamorphism.     

Sensitivity-guided reduction of parametric dimensionality for multi-objective calibration of watershed models

Problem complexity for watershed model calibration is heavily dependent on the number of parameters that can be identified during model calibration. This study investigates the use of global sensitivity analysis as a screening tool to reduce the parametric dimensionality of multi-objective hydrological model calibration problems while maximizing the information extracted from hydrological response data. This study shows that by expanding calibration problem formulations beyond traditional, statistical error metrics to also include metrics that capture indices or signatures of hydrological function, it is possible to reduce the complexity of calibration while maintaining high quality model predictions. The sensitivity-guided calibration is demonstrated using the Sacramento Soil Moisture Accounting (SAC-SMA) conceptual rainfall–runoff model of moderate complexity (i.e., up to 14 freely varying parameters). Using both statistical and hydrological metrics, optimization results demonstrate that parameters controlling at least 20% of the model output variance (through individual effects and interactions) should be included in the calibration process. This threshold generally yields 30–40% reductions in the number of SAC-SMA parameters requiring calibration – setting the others to a priori values – while maintaining high quality predictions. Two parameters are recommended to be calibrated in all cases (percent impervious area and lower zone tension water storage), three parameters are needed in drier watersheds (additional impervious area, riparian zone vegetation, and percent of percolation going to tension storage), and the lower zone parameters are crucial unless the watershed is very dry. Overall, this study demonstrates that a coupled, multi-objective sensitivity and calibration analysis better captures differences between watersheds during model calibration and serves to maximize the value of available watershed response time series. These contributions are particularly important given the ongoing development of more complex integrated models, which will require new tools to address the growing discrepancy between the information content of hydrological data and the number of model parameters that have to be estimated.     

Trends in eutrophication research and control

Eutrophication is the natural ageing process of lakes. It is characterized by a geologically slow shift from in-lake biological production driven by allochthonous (external to the water body) loading of nutrients, to production driven by autochthonous (in-lake) processes. This shift typically is accompanied by changes in species and biotic community composition, as an aquatic ecosystem is ultimately transformed into a terrestrial biome. However, this typically slow process can be greatly accelerated by human intervention in the natural biogeochemical cycling of nutrients within a watershed; the resulting cultural eutrophication can create conditions inimical to the continued use of the water body for human-driven economic purposes. Excessive algal and rooted plant growth, degraded water quality, extensive deoxygenation of the bottom water layers and increased fish biomass accompanied by decreased harvest quality, are some features of this process. Following the Second World War, concern with cultural eutrophication achieved an intensity that spurred a significant research effort, culminating in the identification of phosphorus as the single most significant, and controllable, element involved in driving the eutrophication process. During the late 1960s and throughout the 1970s, much effort was devoted to reducing phosphorus in wastewater effluents, primarily in the developed countries of the temperate zone. These efforts generally resulted in the control of eutrophication in these countries, albeit with varying degrees of success. The present effort in the temperature zone, comprising mostly developed nations, has now shifted to the control of diffuse sources of a broader spectrum of contaminants that impact human water use. In the developing countries of the inter-tropical zone, however, rapidly expanding populations, a growing industrial economy and extensive urbanization have only recently reached an intensity at which cultural eutrophication can no longer be ignored. Further, initial attempts at applying temperate zone control measures in this region have been largely unsuccessful. Modification of the temperate zone eutrophication paradigm will be needed, especially to address the differing climatic and hydrological conditions, if cultural eutrophication is to be contained in this region, where eutrophication-related diseases continue to be a primary cause of human distress.     

Organic carbon and nutrient fluxes to the coastal zone from the Sepik River outflow

The Sepik River is a major contributor of water, sediment and associated organic loads to the coastal waters of northern New Guinea and the Bismarck Sea. We compare dissolved and particulate organic carbon data from September 1997 during an extremely dry El Nino year with those from 1996, 1999 and 2000 during La Nina wet season discharges. Estimated Sepik River flux of DOC is 3.2×10¹⁰ mol yr⁻¹ and POC is 1.1×10¹¹ mol yr⁻¹. The estimates for total river nutrient fluxes to the sea are 1.1×10¹⁰ mol yr⁻¹ for nitrogen and 4.6×10⁸ mol yr⁻¹ for phosphorus. The Sepik DOC flux is about equal to that combined from all four major rivers that enter the Gulf of Papua on the south coast of PNG. The Sepik inorganic PIC flux is low (1.4×10⁸ mol yr⁻¹) as the river does not drain carbonate soils. With a narrow continental shelf, and strong coastal currents, much of this exported material is available for long distance transport into the coastal Bismarck Sea and beyond.     

Hypoxia impairs embryo development and survival in black bream (Acanthopagrus butcheri)

Coastal environments are threatened by the increasing frequency, extent and severity of hypoxic events. Hypoxia affects vast areas around the world and often causes fish kills, reduced abundance, altered distribution, low benthic biomass and declines in fisheries. In Australia, many fisheries are based on sparid fishes and in the southern states black bream (Acanthopagrus butcheri) is important to both the recreational and commercial sectors. This species completes its entire life cycle in estuaries and annual recruitment is highly variable and very likely influenced by environmental conditions during the spawning season.In a laboratory-based experiment, fertilised black bream eggs (embryos) were exposed to five different levels of dissolved oxygen (DO). The DO levels were maintained in small test wells using nitrogen gas in a novel chamber design. Embryo development was assessed over a 2-day period and hatched larvae were observed until Day 2 post-hatch. Significant differences (p < 0.05) were observed in embryonic development and survival as a function of DO level. In severely hypoxic conditions (30% saturation) survival to 1 day was reduced and no hatching occurred. In moderately hypoxic conditions (45–55%S), both precocious and delayed hatching was observed and hatch rates were reduced, whilst the number of hatched larvae with deformities increased, resulting in reduced larval lengths. No larvae survived to Day 2 post-hatch when held in hypoxic conditions (<55%S). This study demonstrates the detrimental effect that severe hypoxia can have on the early development of black bream which could result in reduced recruitment and lowered abundance. Other species that share similar early life histories may also be at risk.