Lanthanide-humic substances complexation. I. Experimental evidence for a lanthanide contraction effect

The interaction of the lanthanides (Ln) with humic substances (HS) was investigated with a novel chemical speciation tool, Capillary Electrophoresis-Inductively Coupled Plasma Mass Spectrometry (CE-ICP-MS). By using an EDTA-ligand competition method, a bi-modal species distribution of LnEDTA and LnHS is attained, separated by CE, and detected online by sector field ICP-MS. We quantified the binding of all 14 rare earth elements (REEs), Sc and Y with Suwannee river fulvic acid, Leonardite coal humic acid, and Elliot soil humic acid under environmental conditions (pH 6-9, 0.001-0.1 mol L⁻¹ NaNO₃, 1-1000 nmol L⁻¹ Ln, 10-20 mg L⁻¹ HS). Conditional binding constants for REE-HS interaction (K_c) ranged from 8.9 < log K_c < 16.5 under all experimental conditions, and display a lanthanide contraction effect, Δ_LK_c: a gradual increase in K_c from La to Lu by 2-3 orders of magnitude as a function of decreasing ionic radius. HS polyelectrolyte effects cause K_c to increase with increasing pH and decreasing ionic strength. Δ_LK_c increases significantly with increasing pH, and likely with decreasing ionic strength. Based on a strong correlation between Δ_LK_c values and denticity for organic acids, we suggest that HS form a range of tri- to tetra-dentate complexes under environmental conditions. These results confirm HS to be a strong complexing agent for Ln, and show rigorous experimental evidence for potential REE fractionation by HS complexation.     

A framework for dealing with uncertainty due to model structure error

Although uncertainty about structures of environmental models (conceptual uncertainty) is often acknowledged to be the main source of uncertainty in model predictions, it is rarely considered in environmental modelling. Rather, formal uncertainty analyses have traditionally focused on model parameters and input data as the principal source of uncertainty in model predictions. The traditional approach to model uncertainty analysis, which considers only a single conceptual model, may fail to adequately sample the relevant space of plausible conceptual models. As such, it is prone to modelling bias and underestimation of predictive uncertainty.     

An evaluation of the role of daphnids in controlling phytoplankton biomass in clear water versus turbid shallow lakes

Phytoplankton and zooplankton were monitored during 2 years in four eutrophic shallow lakes (two turbid and two clear water) from two wetland reserves in Belgium. In each wetland, phytoplankton biomass was significantly higher in the turbid lake than in the clear water lake. Although total macrozooplankton biomass and the contribution of daphnids to total zooplankton biomass was comparable in the clear water and the turbid lakes, the grazing pressure of macrozooplankton on phytoplankton as estimated from zooplankton to phytoplankton biomass ratios was higher in the clear water lakes. Estimated grazing by daphnids in the clear water lakes was always high in spring. In summer, however, daphnid biomass was low or daphnids were even absent during prolonged periods. During those periods phytoplankton was probably controlled by smaller macrozooplankton or by submerged macrophytes through nutrient competition, allelopathic effects or increased sedimentation rates in the macrophyte vegetation.     

Gully-head morphology and implications for gully development on abandoned fields in a semi-arid environment,Sierra de Gata,southeast Spain

In this paper we examine whether gully-head morphology can be used as an indicator for gully development and, hence, for sediment production. A survey was conducted at five hillslopes in the Sierra de Gata where different types of channel heads occur close to each other. The survey included measurements of morphologic and pedologic properties, ground surface, channel and catchment characteristics of every gully head present (n = 59). On the basis of the observed morphologies, the heads were subdivided into four types: gradual, transitional (a short inclined section), abrupt and rilled-abrupt. The analyses showed that it is possible to explain the differences of gully heads and the role of some environmental factors on the basis of their morphologies, at least for the gradual and the abrupt types. The results suggested that steep headcuts (abrupt) were formed from secondary headcuts in the channel, which migrated upstream. The abrupt headcuts were always formed in more than one soil layer of which one was a resistant (stony) layer. However, shear strength measurements (at saturation) showed that the top layer was not always the most resistant one. Width–depth relationships indicated that gradual type headcuts were controlled by fluvial processes and abrupt headcuts by a combination of fluvial and mass-wasting processes. Gradual types occurred more downslope than the abrupt types suggesting that the incisions started by fluvial processes and migrated upwards when knickpoints developed in the channel. The rilled-abrupt types are still actively retreating. Thus, the abrupt types correspond to slower retreat rates. Abrupt gully heads may deteriorate into transitional types when plunge-pool erosion becomes less effective. The conceptual model is supported by data from ephemeral gullies in two other study areas (Sierra de la Torrecilla, Spain, and Alentejo, Portugal). Copyright © 1999 John Wiley & Sons, Ltd.     

What is the role of the model in socio-hydrology? Discussion of “Prediction in a socio-hydrological world”*

Srinivasan et al. provide an interesting overview of the challenges for long-term socio-hydrological predictions. Although agreeing with most of the statements made, we argue for the need to take socio-hydrological analysis a step further and add some fundamental considerations, especially concerning the crucial importance of many (conscious and unconscious) assumptions made upfront of the modelling exercise. Eventual assumptions of technological determinism need correction: Models are not “value-free”, but uncertain, subjective and a product of the society in which they were shaped. It is important to acknowledge this uncertainty and bias when making decisions based on socio-hydrological models, considering also that these models are “social and political actors” in and by themselves. Furthermore, socio-hydrological models require a transdisciplinary approach, since physical water availability is only one of the boundary conditions for society. Last but not least, interaction with stakeholders remains important to enable understanding of what the variable of interest is.     

How to improve attribution of changes in drought and flood impacts

For the development of sustainable, efficient risk management strategies for the hydrological extremes of droughts and floods, it is essential to understand the temporal changes of impacts, and their respective causes and interactions. In particular, little is known about changes in vulnerability and their influence on drought and flood impacts. We present a fictitious dialogue between two experts, one in droughts and the other in floods, showing that the main obstacles to scientific advancement in this area are both a lack of data and a lack of commonly accepted approaches. The drought and flood experts “discuss” available data and methods and we suggest a complementary approach. This approach consists of collecting a large number of single or multiple paired-event case studies from catchments around the world, undertaking detailed analyses of changes in impacts and drivers, and carrying out a comparative analysis. The advantages of this approach are that it allows detailed context- and location-specific assessments based on the paired-event analyses, and reveals general, transferable conclusions based on the comparative analysis of various case studies. Additionally, it is quite flexible in terms of data and can accommodate differences between floods and droughts.     

A distribution law for relative humidity in the upper troposphere and lower stratosphere derived from three years of MOZAIC measurements

Data from three years of MOZAIC measurements made it possible to determine a distribution law for the relative humidity in the upper troposphere and lower stratosphere. Data amounting to 13.5% of the total were obtained in regions with ice supersaturation. Troposphere and stratosphere are distinguished by an ozone concentration of 130 ppbv as threshold. The probability of measuring a certain amount of ice supersaturation in the troposphere decreases exponentially with the degree of ice supersaturation. The probability of measuring a certain relative humidity in the stratosphere (both with respect to water and ice) decreases exponentially with the relative humidity. A stochastic model that naturally leads to the exponential distribution is provided. Mean supersaturation in the troposphere is about 15%, whereas ice nucleation requires 30% supersaturation on the average. This explains the frequency of regions in which aircraft induce persistent contrails but which are otherwise free of clouds. Ice supersaturated regions are 3-4 K colder and contain more than 50% more vapour than other regions in the upper troposphere. The stratospheric air masses sampled are dry, as expected, having mean relative humidity over water of 12% and over ice of 23%, respectively. However, 2% of the stratospheric data indicate ice supersaturation. As the MOZAIC measurements have been obtained on commercial flights mainly between Europe and North America, the data do not provide a complete global picture, but the exponential character of the distribution laws found is probably valid globally. Since water vapour is the most important greenhouse gas and since it might enhance the anthropogenic greenhouse effects via positive feedback mechanisms, it is important to represent its distribution correctly in climate models. The discovery of the distribution law of the relative humidity makes possible simple tests to show whether the hydrological cycle in climate models is represented in an adequate way or not.     

Chicxulub impact ejecta from Albion Island, Belize

Impact ejecta from the Albion Formation are exposed in northern Belize. The ejecta come from the outer portion of the continuous ejecta blanket of the Chicxulub crater, which is located 360 km to the northwest. The basal unit of the Albion Formation is a 1-m-thick clay and dolomite spheroid bed composed of up to four discrete flows. The clay spheroids are altered impact glass, and the dolomite spheroids are accretionary lapilli. The upper unit is a 15-m-thick coarse diamictite bed containing altered glass, large accretionary blocks, striated, polished, and impacted cobbles, and rare shocked quartz. The abundance of accretionary clasts, evidence for atmospheric drag sorting, and the presence of multiple flows in the Albion Formation indicate that atmospheres play an important role in the formation of the outer portions of continuous ejecta blankets of large craters.     

Coupled garnet Lu–Hf and monazite U–Pb geochronology constrain early convergent margin dynamics in the Ross orogen,Antarctica

The Ross orogen of Antarctica is an extensive (>3000 km‐long) belt of deformed and metamorphosed sedimentary rocks and granitoid batholiths, which formed during convergence and subduction of palaeo‐Pacific lithosphere beneath East Gondwana in the Neoproterozoic–early Palaeozoic. Despite its prominent role in Gondwanan convergent tectonics, and a well‐established magmatic record, relatively little is known about the metamorphic rocks in the Ross orogen. A combination of garnet Lu–Hf and monazite U–Pb (measured by laser‐ablation split‐stream ICP‐MS) geochronology reveals a protracted metamorphic history of metapelites and garnet amphibolites from a major segment of the orogen. Additionally, direct dating of a common rock‐forming mineral (garnet) and accessory mineral (monazite) allows us to test assumptions that are commonly used when linking accessory mineral geochronology to rock‐forming mineral reactions. Petrography, mineral zoning, thermobarometry and pseudosection modelling reveal a Barrovian‐style prograde path, reaching temperatures of ~610–680 °C. Despite near‐complete diffusional resetting of garnet major element zoning, the garnet retains strong rare earth element zoning and preserves Lu–Hf dates that range from c. 616–572 Ma. Conversely, monazite in the rocks was extensively recrystallized, with concordant dates that span from c. 610–500 Ma, and retain only vestigial cores. Monazite cores yield dates that overlap with the garnet Lu–Hf dates and typically have low‐Y and heavy rare earth element (HREE) concentrations, corroborating interpretations of low‐Y and low‐HREE monazite domains as records of synchronous garnet growth. However, ratios of REE concentrations in garnet and monazite do not consistently match previously reported partition coefficients for the REE between these two minerals. High‐Y monazite inclusions within pristine, crack‐free garnet yield U–Pb dates significantly younger than the Lu–Hf dates for the same samples, indicating recrystallization of monazite within garnet. The recrystallization of high‐Y and high‐HREE monazite domains over >50 Ma likely records either punctuated thermal pulses or prolonged residence at relatively high temperatures (up to ~610–680 °C) driving monazite recrystallization. One c. 616 Ma garnet Lu–Hf date and several c. 610–600 Ma monazite U–Pb dates are tentatively interpreted as records of the onset of tectonism metamorphism in the Ross orogeny, with a more robust constraint from the other Lu–Hf dates (c. 588–572 Ma) and numerous c. 590–570 Ma monazite U–Pb dates. The data are consistent with a tectonic model that involves shortening and thickening prior to widespread magmatism in the vicinity of the study area. The early tectonic history of the Ross orogen, recorded in metamorphic rocks, was broadly synchronous with Gondwana‐wide collisional Pan‐African orogenies.