Case study on the strategy and application of enhancement solutions to improve remediation of soils contaminated with Cu, Pb and Zn by means of electrodialysis

Numerous studies have been conducted with electrochemical removal of heavy metals from spiked kaolinite. Meanwhile, when moving from kaolinite to real soils, new factors must be taken into account—factors influencing, e.g., the buffering capacity of the soil against acidification and the adsorption/desorption processes of the heavy metals. The present study gives some examples where it is necessary to use an enhancement solution to aid desorption of Cu, Zn and Pb during electrodialytic treatment. Dependent on the composition of the pollution, different choices can be made. In the case of a Cu-polluted calcareous soil, ammonia may be used as enhancement solution, due to the formation of charged complexes between ammonia and Cu. Thus, Cu is mobile at high pH when ammonia is added and Cu can be removed without dissolving the calcareous parts. Zn is also mobilized by ammonia, but to a lesser extent than Cu. In the case of Cu, Zn and Pb at the same time, alkaline ammonium citrate may be a solution. It was shown that this enhancement solution could mobilize these three pollutants, but optimization of concentration and pH of the ammonium citrate is still needed. When choosing a remediation scheme for electrochemical treatment of an actual industrially polluted soil, this scheme must be chosen on basis of characterization of soil and pollution combination.     

Scour below pipelines and around vertical piles due to second-order random waves plus a current

This paper provides a method by which the scour depth below pipelines and around single vertical piles for combined random waves plus current including effects of second-order wave asymmetry can be derived. Here the empirical formulas proposed by Sumer and Fredsøe [1996. Scour below pipelines in combined waves and current. In: Proceedings of the 15th OMAE Conference, Florence, Italy. Vol. 5, ASME, New York, pp. 595–602] for pipelines, and by Sumer and Fredsøe [2002. The mechanics of scour in the marine environment. World Scientific, Singapore] for vertical piles are used together with Stokes second-order wave theory by assuming the basic harmonic wave motion to be a stationary Gaussian narrow-band random process. Comparisons are made with the Sumer and Fredsøe [1996. Scour below pipelines in combined waves and current. In: Proceedings of the 15th OMAE Conference, Florence, Italy. Vol. 5, ASME, New York, pp. 595–602; 2001. Scour around pile in combined waves and current. Journal of Hydraulic Engineering, 127(5), 403–411] data for linear random waves plus current. An example of calculation is also presented.     

A micro-Mössbauer study of chromites included in diamond and other mantle-related rocks

Oxygen fugacity ( $ f_{{{\text{O}}_{ 2} }} $ f O 2 ) is a fundamental but little known intensive variable in mantle processes. It influences the P/T position of a mantle solidus and the composition of mantle-derived melts and fluids and constrains mantle-core equilibria and a number of geophysical properties of the mantle. An important source of information on oxidation states is the ferric–ferrous iron ratio in mantle spinels. Since the magnetite component is low in mantle spinels, normal analytical errors translate into considerable $ f_{{{\text{O}}_{ 2} }} $ f O 2 uncertainties. In this study, we analyzed the Fe³⁺–Fe_tot ratio of chromites present as inclusions in diamond and other mantle-related occurrences by point-source Mössbauer spectroscopy using single-crystal absorbers as well as conventional Mössbauer spectroscopy using powder absorbers. The studied spinels have been previously analyzed by single-crystal X-ray diffraction and electron microprobe. The ferric–ferrous ratios found are normally similar to the different techniques apart from some samples where a large number of grains have been used for the analyses (powder absorbers). The general agreement between the different techniques allows us to conclude that the studied chromites are stoichiometric. However, conventional Mössbauer spectroscopy on powder absorbers should be conducted with great care, since the method requires a relatively large amount of sample material. Spinel frequently occurs as small grains, and the large number of crystals required may possess different degrees of oxidation/alteration and, consequently, different ferric–ferrous ratio leading to possible errors in the interpretation of the results.     

Benthic Carbon Mineralization and Nutrient Turnover in a Scottish Sea Loch: An Integrative In Situ Study

Based on in situ microprofiles, chamber incubations and eddy covariance measurements, we investigated the benthic carbon mineralization and nutrient regeneration in a ~65-m-deep sedimentation basin of Loch Etive, UK. The sediment hosted a considerable amount of infauna that was dominated by the brittle star A. filiformis. The numerous burrows were intensively irrigated enhancing the benthic in situ O₂ uptake by ~50 %, and inducing highly variable redox conditions and O₂ distribution in the surface sediment as also documented by complementary laboratory-based planar optode measurements. The average benthic O₂ exchange as derived by chamber incubations and the eddy covariance approach were similar (14.9 ± 2.5 and 13.1 ± 9.0 mmol m^?2 day^?1) providing confidence in the two measuring approaches. Moreover, the non-invasive eddy approach revealed a flow-dependent benthic O₂ flux that was partly ascribed to enhanced ventilation of infauna burrows during periods of elevated flow rates. The ratio in exchange rates of ΣCO₂ and O₂ was close to unity, confirming that the O₂ uptake was a good proxy for the benthic carbon mineralization in this setting. The infauna activity resulted in highly dynamic redox conditions that presumably facilitated an efficient degradation of both terrestrial and marine-derived organic material. The complex O₂ dynamics of the burrow environment also concurrently stimulated nitrification and coupled denitrification rates making the sediment an efficient sink for bioavailable nitrogen. Furthermore, bioturbation mediated a high efflux of dissolved phosphorus and silicate. The study documents a high spatial and temporal variation in benthic solute exchange with important implications for benthic turnover of organic carbon and nutrients. However, more long-term in situ investigations with like approaches are required to fully understand how environmental events and spatio-temporal variations interrelate to the overall biogeochemical functioning of coastal sediments.     

Detecting the near-surface redox front in crystalline bedrock using fracture mineral distribution,geochemistry and U-series disequilibrium

Oxidizing conditions normally prevail in surface waters and near-surface groundwaters, but there is usually a change to reducing conditions in groundwater at greater depth. Dissolved O₂ originally present is consumed through biogenic and inorganic reactions along the flow paths. Fracture minerals participate in these reactions and the fracture mineralogy and geochemistry can be used to trace the redox front. An important task in the safety assessment of a potential repository for the disposal of nuclear waste in crystalline bedrock, at an approximate depth of 500 m in Sweden, is to demonstrate that reducing conditions can be maintained for a long period of time. Oxygen may damage the Cu canisters that host nuclear waste; additionally, in the event of a canister failure, oxidizing conditions may increase the mobility of some radionuclides. The present study of the near-surface redox front is based on mineralogical (redox-sensitive minerals), geochemical (redox-sensitive elements) and U-series disequilibrium investigations of mineral coatings along open fractures. The fractures have been sampled along drill cores from closely spaced, 100 m deep boreholes, which were drilled during the site investigation work in the Laxemar area, south-eastern Sweden, carried out by the Swedish Nuclear Fuel and Waste Management Co. (SKB). The distribution of the redox-sensitive minerals pyrite and goethite in open fractures shows that the redox front (switch from mainly goethite to mainly pyrite in the fractures) generally occurs at about 15–20 m depth. Calcite leaching by recharging water is indicated in the upper 20–30 m and positive Ce-anomalies suggest oxidation of Ce down to 20 m depth. The U-series radionuclides show disequilibrium in most of the samples, indicating mobility of U during the last 1 Ma. In the upper 20 m, U is mainly removed (due to oxidation) or has experienced complex removal and/or deposition. At depths of 35–55 m, both deposition and removal of U are indicated. Below 55 m, recent deposition of U is generally indicated which suggests removal of U near surface (oxidation) and deposition of U below the redox front. Scattered goethite occurrences below the general redox front (down to ca 80 m) and signs of U removal at 35–55 m mostly correlate with sections of high transmissivity (and/or high fracture frequencies). This shows that highly transmissive fractures are generally required to allow oxygenated groundwaters at depth greater than ca 30 m. Removal of U (oxidation) below 55 m within the last 300 ka is not observed. Although penetration of glacial waters to great depths has been confirmed in the study area, their potential O₂ load seems to have been reduced near the surface.     

Honey, I cooled the cods: Modelling the effect of temperature on the structure of Boreal/Arctic fish ecosystems

Historically colder regions of the North Atlantic had fisheries dominated by only a few fish species; principally cod and capelin. Possible population dynamic mechanisms that lead to such dominance are investigated by considering how a charmingly simple published multispecies model of the North Sea would react if the system operated at a lower temperature. The existing model equations were modified to describe temperature effects on growth, fecundity and recruitment and the model was rerun based on typical temperatures for the North Sea and a colder system. The results suggest that total fish biomass in the colder system increases but the community is more vulnerable to a given rate of fishing mortality. In the colder system, within species density dependence is reduced but relative predation rates are higher. Consequently, intermediate-sized species are vulnerable to relatively high levels of predation throughout their life history and tend to be excluded, leading to a system dominated by small and large species. The model helps to explain how temperature may govern coexistence and competitive exclusion in fish communities and accounts for the observed dominance of small and large species in Boreal/Arctic ecosystems.