First results of operating and monitoring an innovative design of a permeable reactive barrier for the remediation of chromate contaminated groundwater

An innovative setup of a permeable reactive barrier (PRB) was installed in Willisau, Switzerland to remediate chromate contaminated groundwater. Instead of a conventional continuous barrier, this PRB consists of cylinders installed in rows: a single row for lower expected Cr^VI-concentrations and an offset double row for higher expected Cr^VI-concentrations. The cylinders are filled with reactive grey cast-Fe shavings mixed with gravel to prevent extensive precipitation of secondary phases in the pore space. The treatment of the contaminants takes place both within the cylinders and in the dissolved Fe^II plume generated downstream of the barrier. Monitoring of the contamination situation over a period of 3 a provided evidence of the mobilization, transport and behavior of the contaminants in the aquifer. Groundwater and reactive material were sampled upstream, within and downstream of the barrier by a Multi-Port Sampling System (MPSS) that revealed the geochemical processes as a function of time and space. Comprehensive chemical analyses included sensitive parameters such as Cr^VI, Fe^II/Fe^III, redox potential, dissolved O₂ and pH. Several campaigns using multiple optical tracers revealed a rather complex hydrological regime at different scales, thereby complicating the barrier performance.     

A chromate-contaminated site in southern Switzerland – Part 2: Reactive transport modeling to optimize remediation options

A 2D horizontal reactive transport model of a chromate-contaminated site near Rivera, Switzerland, was developed using the computer code CrunchFlow to evaluate site remediation strategies. Transport processes were defined according to the results of an existing hydrological model, and the definition of geochemical (reactive) processes is based on the results of a detailed mineralogical and geochemical site characterization leading to a comprehensive conceptual site model. Kinetics of naturally occurring Cr(VI) reduction by Fe(II) and natural solid organic matter is quantified by fitting measured Cr isotope ratios to a modeled 1D section along the best constrained flow line. The simulation of Cr isotope fractionation was also incorporated into the 2D model. Simulation of the measured present day Cr(VI) plume and δ⁵³Cr value distribution was used for the 2D model calibration and corresponds to a situation where only monitored natural attenuation (MNA) is occurring. Other 2D model runs simulate alternate excavation scenarios. The simulations show that with an excavation of the top 2–4 m the groundwater Cr(VI) plume can be minimized, and that a deeper excavation depth only diminishes the plume if all the contaminants can be removed. A combination of an excavation of the top 2–4 m and monitoring of the ongoing natural Cr(VI) reduction is suggested as the most ecological and economical remediation strategy, even though a remaining time period with ongoing subsoil Cr(VI) contamination in the order of 1 ka is predicted.     

Impact cratering in sandstone: The MEMIN pilot study on the effect of pore water

Abstract– Planetary surfaces are subjected to meteorite bombardment and crater formation. Rocks forming these surfaces are often porous and contain fluids. To understand the role of both parameters on impact cratering, we conducted laboratory experiments with dry and wet sandstone blocks impacted by centimeter‐sized steel spheres. We utilized a 40 m two‐stage light‐gas gun to achieve impact velocities of up to 5.4 km s^?1. Cratering efficiency, ejection velocities, and spall volume are enhanced if the pore space of the sandstone is filled with water. In addition, the crater morphologies differ substantially from wet to dry targets, i.e., craters in wet targets are larger, but shallower. We report on the effects of pore water on the excavation flow field and the degree of target damage. We suggest that vaporization of water upon pressure release significantly contributes to the impact process.     

Abundance of 17 trace elements in carbonaceous chondrites

Seventeen trace elements (Ag, Au, Bi, Br, Cd, Cs, Ge, In, Ir, Rb, Re, Sb, Se, Te, Tl, U and Zn) were measured by neutron activation analysis in 8 C1 samples (1 Alais, 3 Ivuna, 4 Orgueil) and in 3 C2 samples (one each of Mighei, Murchison, Murray). The results show far less scatter than earlier literature data. The standard deviation of a single measurement from the mean of 8 C1 samples lies between 2 and 14 per cent, except for the following 4 elements: Au ±18 per cent, Ag ±22 per cent, Rb ±19 per cent and Br ±33 per cent. The first two probably reflect contamination and sample heterogeneity, the last two, analytical error. Apparently C1 chondrites have a far more uniform composition than some authors have claimed.The new data suggest significant revisions in cosmic abundance for the following elements (old values in parentheses): Zn 1250 (1500), Cd 1.51 (2.12), Ir 0.72 (0.43) atoms/10⁶ Si atoms. The Br value is also lower, 6.8 vs 20.6, but may be affected by analytical error.Relative to C1 chondrites, the C2 chondrites Mighei, Murchison and Murray are depleted in volatile elements by a factor of 0.508 ± 0.038, much more constant than indicated by oldor data. Ordinary chondrites also show a more uniform depletion relative to the new C1 data. The mean depletion factor of Sb, F, Cu, Ga, Ge, Sn, S, Se, Te and Ag is 0.227 ± 0.027 in H-chondrites. This constancy further strengthens the case for the two-component model of chondrite formation.     

A chromate-contaminated site in southern Switzerland – Part 1: Site characterization and the use of Cr isotopes to delineate fate and transport

The risk of groundwater contamination by chromate at a former chromite ore processing industrial site in Rivera (Switzerland) was assessed by determining subsoil Cr(VI) concentrations and tracking naturally occurring Cr(VI) reduction with Cr isotopes. Using a hot alkaline extraction procedure, a total Cr(VI) contamination of several 1000 kg was estimated. Jarosite, KFe₃((SO₄)_x(CrO₄)_1−x)₂(OH)₆, and chromatite (CaCrO₄) were identified as Cr(VI) bearing mineral phases using XRD, both limiting groundwater Cr(VI) concentrations. To track assumed Cr(VI) reduction at field scale δ⁵³Cr values of contaminated subsoil samples in addition to groundwater δ⁵³Cr data are used for the first time. The measurements showed a fractionation of groundwater δ⁵³Cr values towards positive values and subsoil δ⁵³Cr towards negative values confirming reduction of soluble Cr(VI) to insoluble Cr(III). Using a Rayleigh fractionation model, a current Cr(VI) reduction efficiency of approximately 31% along a 120 m long flow path was estimated at an average linear groundwater velocity of 3.3 m/d. Groundwater and subsoil δ⁵³Cr values were compared with a site specific Rayleigh fractionation model proposing that subsoil δ⁵³Cr values can possibly be used to track previous higher Cr(VI) reduction efficiency during the period of industrial activity. The findings strongly favor monitored natural attenuation to be part of the required site remediation measures.     

ALH 82102: An Antarctic meteorite embedded partly in ice

Abstract We measured the concentrations of F, Cl, Br and I in two different aliquots of the meteorite ALH 82102. This H5 chondrite was recovered at the Allan Hills region, while it was partially embedded in the ice. One aliquot was taken from that part of the surface of the meteorite that was still in the ice, and the other one was taken from the side, which was poking out of the ice. Both aliquots are highly, and nearly to the same degree, contaminated with halogens. The observed enrichments occurred mainly during the time the meteorite was lying on the surface of the ice by deposition and/or adsorption of aerosols, salts, and gaseous components. A contamination during the time it was covered by the ice is unlikely. We conclude, therefore, that this meteorite was not always buried in the ice during its “residence time” on Earth. In order to accumulate the observed contamination, it had to be on the surface of the ice part of the time between its fall onto the Earth and its collection. The age of the ice surrounding the meteorite cannot be equal to the measured terrestrial age of ALH 82102.     

The MEMIN research unit: Scaling impact cratering experiments in porous sandstones

Abstract– The MEMIN research unit (Multidisciplinary Experimental and Modeling Impact research Network) is focused on analyzing experimental impact craters and experimental cratering processes in geological materials. MEMIN is interested in understanding how porosity and pore space saturation influence the cratering process. Here, we present results of a series of impact experiments into porous wet and dry sandstone targets. Steel, iron meteorite, and aluminum projectiles ranging in size from 2.5 to 12 mm were accelerated to velocities of 2.5–7.8 km s^?1, yielding craters with diameters between 3.9 and 40 cm. Results show that the target’s porosity reduces crater volumes and cratering efficiency relative to nonporous rocks. Saturation of pore space with water to 50% and 90% increasingly counteracts the effects of porosity, leading to larger but flatter craters. Spallation becomes more dominant in larger‐scale experiments and leads to an increase in cratering efficiency with increasing projectile size for constant impact velocities. The volume of spalled material is estimated using parabolic fits to the crater morphology, yielding approximations of the transient crater volume. For impacts at the same velocity these transient craters show a constant cratering efficiency that is not affected by projectile size.     

On the morphological characteristics of overdeepenings in high‐mountain glacier beds

Overdeepenings, i.e. closed topographic depressions with adverse slopes in the direction of flow, are characteristic for glacier beds and glacially sculpted landscapes. Quantitative information about their morphological characteristics, however, has so far hardly been available. The present study provides such information by combining the analysis of (a) numerous bed overdeepenings below still existing glaciers of the Swiss Alps and the Himalaya‐Karakoram region modelled with a robust shear stress approximation and (b) detailed bathymetries from recently exposed lakes in the Peruvian Andes. The investigated overdeepenings exist where glacier surface slopes are low (< 5°–10°), occur in bedrock or morainic material and are most commonly a fraction of a kilometre squared in surface area, hundreds of metres long, about half the length in width and tens of metres deep. They form under conditions of low to high basal shear stresses, at cirque, confluence, trunk valley and terminus positions. The most striking phenomenon, however, is the high variability of their geometries: Depths, surface areas, lengths and widths of the overdeepenings vary over orders of magnitude and are only weakly – if at all – interrelated. Inclinations of adverse slopes do not differ significantly from those of forward slopes and are in many cases higher than so far assumed theoretical limits for supercooling of ascending water and corresponding closure of sub‐glacial channels. Such steep adverse slopes are a robust observation and in support of recently developed new concepts concerning the question about where supercooling of sub‐glacial water and closure of ice channels can or must occur. However, the question of when and under what climatic, topographic and ice conditions the overdeepenings had formed remains unanswered. This open question constitutes a key problem concerning the interpretation of observed overdeepenings, the understanding of the involved glacio‐hydraulic processes and the possibility of realistic predictive modelling of overdeepening formation. Copyright © 2016 John Wiley & Sons, Ltd.