Stable Cu and Zn isotope ratios as tracers of sources and transport of Cu and Zn in contaminated soil

Copper and Zn metals are produced in large quantities for different applications. During Cu production, large amounts of Cu and Zn can be released to the environment. Therefore, the surroundings of Cu smelters are frequently metal-polluted. We determined Cu and Zn concentrations and Cu and Zn stable isotope ratios (δ⁶⁵Cu, δ⁶⁶Zn) in three soils at distances of 1.1, 3.8, and 5.3 km from a Slovak Cu smelter and in smelter wastes (slag, sludge, ash) to trace sources and transport of Cu and Zn in soils. Stable isotope ratios were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) in total digests. Soils were heavily contaminated with concentrations up to 8087 μg g⁻¹ Cu and 2084 μg g⁻¹ Zn in the organic horizons. The δ⁶⁵Cu values varied little (−0.12‰ to 0.36‰) in soils and most wastes and therefore no source identification was possible. In soils, Cu became isotopically lighter with increasing depth down to 0.4 m, likely because of equilibrium reactions between dissolved and adsorbed Cu species during transport of smelter-derived Cu through the soil. The δ⁶⁶Zn_IRMM values were isotopically lighter in ash (−0.41‰) and organic horizons (−0.85‰ to −0.47‰) than in bedrock (−0.28‰) and slag (0.18‰) likely mainly because of kinetic fractionation during evaporation and thus allowed for separation of smelter-Zn from native Zn in soil. In particular in the organic horizons large variations in δ⁶⁶Zn values occur, probably caused by biogeochemical fractionation in the soil-plant system. In the mineral horizons, Zn isotopes showed only minor shifts to heavier δ⁶⁶Zn values with depth mainly because of the mixing of smelter-derived Zn and native Zn in the soils. In contrast to Cu, Zn isotope fractionation between dissolved and adsorbed species was probably only a minor driver in producing the observed variations in δ⁶⁶Zn values. Our results demonstrate that metal stable isotope ratios may serve as tracer of sources, vertical dislocation, and biogeochemical behavior in contaminated soil.     

A comparison between the fabric camera and texture goniometer methods of fabric analysis by X-ray diffraction

The effects of grain size on the analysis of fabrics by X-ray diffraction using both the fabric camera and the texture goniometer are discussed. Simple calculations show the interdependance between the mean grain diameter and the number of crystals which are measured by each instrument. The effects of both grain size and modal composition of the specimen are illustrated by comparative analyses. Both the fabric camera and texture goniometer are well suited to the analysis of specimens in which the mean grain diameter is between approximately 10 and 100 microns. The texture goniometer is more suitable when the grain size is less than this, while the fabric camera is better suited when the grain size is coarser, especially when the specimen is not monomineralic.     

The mesoscale convection life cycle: Building block or prototype for large-scale tropical waves?

A cumulonimbus cloud may ascend and spawn its anvil cloud, precipitation, and downdrafts within an hour or so. This paper inquires why a similar progression of events (life cycle) is observed for tropical weather fluctuations with time scales of hours, days, and even weeks. Regressions using point data illustrate the characteristic unit of rain production: the mesoscale convective system (MCS), covering tens of kilometers and lasting several hours, with embedded convective rain cells. Meanwhile, averages over larger spatial areas indicate a self-similar progression from shallow to deep convection to stratiform anvils on many time scales.Synthetic data exercises indicate that simple superpositions of fixed-structure MCS life cycles (the Building Block hypothesis) cannot explain why longer period life cycles are similar. Rather, it appears that an MCS may be a small analogue or prototype of larger scale waves. Multiscale structure is hypothesized to occur via a Stretched Building Block conceptual model, in which the widths (durations) of zones of shallow, deep, and stratiform anvil clouds in MCSs are modulated by larger scale waves.Temperature (T) and humidity (q) data are examined and fed into an entraining plume model, in an attempt to elucidate their relative roles in these large-scale convection zone variations. T profile variations, with wavelengths shorter than troposphere depth, appear important for high-frequency ( 2–5-day period) convectively coupled waves, as density directly links convection (via buoyancy) and large-scale wave dynamics (via restoring force). Still, the associated q anomalies are several times greater than adiabatic, suggesting a strong amplification by shallow convective feedbacks. For lower frequency (intraseasonal) variability, q anomalies are considerably larger compared to T, and may be dominant.     

Experimental characterization of the impact of temperature and humidity on the breakdown of soil water repellency in sandy soils and composts

Soil water repellency is a widespread phenomenon with the capacity to alter hydrological and geomorphological processes. Water repellency decays with time, and the consequences are only of concern during the timescale at which the water repellency persists. This study aimed to characterize the influence of temperature and humidity on the breakdown of water repellency. Apparent contact angle measurements were carried out on samples consisting of sand treated with stearic acid as well as naturally repellent dune sands and composts. Temperature and humidity were controlled using a cooled incubator and a purpose designed enclosed box in which humidity could be raised or lowered. Results showed the contact angle of the stearic‐acid‐treated sands decayed with time and that there was a significant increase with stearic acid concentration. For all samples, the decay in apparent contact angle could be described with a continuous breakdown model. The stearic‐acid‐treated sands showed a significant increase in contact angle with relative humidity at a temperature of 10 and 20 °C. These differences diminished with increasing temperature. Similar results were seen for the dune sands and composts. Despite the influence of temperature and humidity on contact angles, there was no significant change in the rate at which the contact angle decayed in any sample. Absolute humidity was found to provide a more relevant indicator than relative humidity when assessing the influence of humidity on repellency over a range of temperatures. The contact angle initially increased with absolute humidity before plateauing owing to the confounding effect of temperature. Copyright © 2014 John Wiley & Sons, Ltd.     

Towards more systematic perceptual model development: a case study using 3 Luxembourgish catchments

The synthesis of experimental understanding of catchment behaviour and its translation into qualitative perceptual models is an important objective of hydrological sciences. We explore this challenge by examining the cumulative understanding of the hydrology of three experimental catchments and how it evolves through the application of different investigation techniques. The case study considers the Huewelerbach, Weierbach and Wollefsbach headwater catchments of the Attert basin in Luxembourg. Subsurface investigations including bore holes and pits, analysis of soil samples and Electrical Resistivity Tomography measurements are presented and discussed. Streamflow and tracer data are used to gain further insights into the streamflow dynamics of the catchments, using end‐member mixing analysis and hydrograph separation based on dissolved silica and electrical conductivity. We show that the streamflow generating processes in all three catchments are controlled primarily by the subsolum and underlying bedrock. In the Huewelerbach, the permeable sandstone formation supports a stable groundwater component with little seasonality, which reaches the stream through a series of sources at the contact zone with the impermeable marls formation. In the Weierbach, the schist formation is relatively impermeable and supports a ‘fill and spill’‐type of flow mechanism; during wet conditions, it produces a delayed response dominated by pre‐event water. In the Wollefsbach, the impermeable marls formation is responsible for a saturation‐excess runoff generating process, producing a fast and highly seasonal response dominated by event water. The distinct streamflow generating processes of the three catchments are represented qualitatively using perceptual models. The perceptual models are in turn translated into quantitative conceptual models, which simulate the hydrological processes using networks of connected reservoirs and transfer functions. More generally, the paper illustrates the evolution of perceptual models based on experimental fieldwork data, the translation of perceptual models into conceptual models and the value of different types of data for processes understanding and model representation. Copyright © 2014 John Wiley & Sons, Ltd.     

New major element analyses of proximal tephras from the Azores and suggested correlations with cryptotephras in North-West Europe

The Azores Archipelago is one of the most active volcanic areas in the North Atlantic region. Approximately 30 eruptions have been reported over the last 600 years with some major VEI 5 (Volcanic Explosivity Index) eruptions further back in time. The geochemical composition of associated tephra-derived glass, however, is not well characterized. An Azorean origin of cryptotephras found in distal areas such as North Africa, the British Isles and Greenland has been suggested, but proximal data from the Azores are scarce and the correlations have only been tentative. These tephras have a traychtic composition, which excludes an Icelandic origin. In a previous study, we presented major element analyses of proximal tephra-derived glass from five Holocene eruptions on the Azores Islands. There is a striking geochemical similarity between tephras from volcanoes on São Miguel and Irish cryptotephras, and especially with eruptives from the Furnas volcano. Here we present new analyses of proximal tephras that confirm and strengthen a link between Furnas and cryptotephras found in south-west Ireland. We also suggest a correlation between a previously unsourced tephra found in a Swedish bog with an eruption of the Sete Cidades volcano c. 3880 a cal BP.     

Exploring hydroclimatic change disparity via the Budyko framework

The Budyko framework characterizes landscape water cycles as a function of climate. We used this framework to identify regions with contrasting hydroclimatic change during the past 50 years in Sweden. This analysis revealed three distinct regions: the mountains, the forests, and the areas with agriculture. Each region responded markedly different to recent climate and anthropogenic changes, and within each region, we identified the most sensitive subregions. These results highlight the need for regional differentiation in climate change adaptation strategies to protect vulnerable ecosystems and freshwater resources. Further, the Budyko curve moved systematically towards its water and energy limits, indicating augmentation of the water cycle driven by changing vegetation, climate and human interactions. This finding challenges the steady state assumption of the Budyko curve and therefore its ability to predict future water cycles. Copyright © 2013 John Wiley & Sons, Ltd.     

The Late Cretaceous Klepa basalts in Macedonia (FYROM)—Constraints on the final stage of Tethys closure in the Balkans

The waning stage(s) of the Tethyan ocean(s) in the Balkans are not well understood. Controversy centres on the origin and life‐span of the Cretaceous Sava Zone, which is allegedly a remnant of the last oceanic domain in the Balkan Peninsula, defining the youngest suture between Eurasia‐ and Adria‐derived plates. In order to investigate to what extent Late‐Cretaceous volcanism within the Sava Zone is consistent with this model we present new age data together with trace‐element and Sr–Nd–Pb isotope data for the Klepa basaltic lavas from the central Balkan Peninsula. Our new geochemical data show marked differences between the Cretaceous Klepa basalts (Sava Zone) and the rocks of other volcanic sequences from the Jurassic ophiolites of the Balkans. The Klepa basalts mostly have Sr–Nd–Pb isotopic and trace‐element signatures that resemble enriched within‐plate basalts substantially different from Jurassic ophiolite basalts with MORB, BAB and IAV affinities. Trace‐element modelling of the Klepa rocks indicates 2%–20% polybaric melting of a relatively homogeneously metasomatised mantle source that ranges in composition from garnet lherzolite to ilmenite+apatite bearing spinel–amphibole lherzolite. Thus, the residual mineralogy is characteristic of a continental rather than oceanic lithospheric mantle source, suggesting an intracontinental within‐plate origin for the Klepa basalts. Two alternative geodynamic models are internally consistent with our new findings: (1) if the Sava Zone represents remnants of the youngest Neotethyan Ocean, magmatism along this zone would be situated within the forearc region and triggered by ridge subduction; (2) if the Sava Zone delimits a diffuse tectonic boundary between Adria and Europe which had already collided in the Late Jurassic, the Klepa basalts together with a number of other magmatic centres represent volcanism related to transtensional tectonics.     

Effect of bed surface roughness on longitudinal dispersion in artificial open channels

In several empirical and modelling studies on river hydraulics, dispersion was negatively correlated to surface roughness. In this study, it was aimed to investigate the influence of surface roughness on longitudinal dispersion under controlled conditions. In artificial flow channels with a length of 104 m, tracer experiments with variations in channel bed material were performed. By use of measured tracer breakthrough curves, average flow velocity, mean longitudinal dispersion, and mean longitudinal dispersivity were calculated. Longitudinal dispersion coefficients ranged from 0·018 m² s^?1 in channels with smooth bed surface up to 0·209 m² s^?1 in channels with coarse gravel as bed material. Longitudinal dispersion was linearly related to mean flow velocity. Accordingly, longitudinal dispersivities ranged between 0·152 ± 0·017 m in channels with smooth bed surface and 0·584 ± 0·015 m in identical channels with a coarse gravel substrate. Grain size and surface roughness of the channel bed were found to correlate positively to longitudinal dispersion. This finding contradicts several existing relations between surface roughness and dispersion. Future studies should include further variation in surface roughness to derive a better‐founded empirical equation forecasting longitudinal dispersion from surface roughness. Copyright © 2011 John Wiley & Sons, Ltd.