Kristine B. Pedersen

Multivariate methods for evaluating the efficiency of electrodialytic removal of heavy metals from polluted harbour sediments

Chemometrics was used to develop a multivariate model based on 46 previously reported electrodialytic remediation experiments (EDR) of five different harbour sediments. The model predicted final concentrations of Cd, Cu, Pb and Zn as a function of current density, remediation time, stirring rate, dry/wet sediment, cell set-up as well as sediment properties. Evaluation of the model showed that remediation time and current density had the highest comparative influence on the clean-up levels. Individual models for each heavy metal showed variance in the variable importance, indicating that the targeted heavy metals were bound to different sediment fractions. Based on the results, a PLS model was used to design five new EDR experiments of a sixth sediment to achieve specified clean-up levels of Cu and Pb. The removal efficiencies were up to 82% for Cu and 87% for Pb and the targeted clean-up levels were met in four out of five experiments. The clean-up levels were better than predicted by the model, which could hence be used for predicting an approximate remediation strategy; the modelling power will however improve with more data included.

Chemometric analysis for pollution source assessment of harbour sediments in Arctic locations.

Pollution levels, pollutant distribution and potential source assessments based on multivariate analysis (chemometrics) were made for harbour sediments from two Arctic locations; Hammerfest in Norway and Sisimiut in Greenland. High levels of heavy metals were detected in addition to organic pollutants. Preliminary assessments based on principal component analysis (PCA) revealed different sources and pollutant distribution in the sediments of the two harbours. Tributyltin (TBT) was, however, found to originate from point source(s), and the highest concentrations of TBT in both harbours were found adjacent to the former shipyards. Polyaromatic hydrocarbons (PAH) ratios and PCA plots revealed that the predominant source in both harbours was pyrogenic related to coal/biomass combustion. Comparison of commercial polychlorinated biphenyls (PCB) mixtures with PCB compositions in the sediments indicated relation primarily to German, Russian and American mixtures in Hammerfest; and American, Russian and Japanese mixtures in Sisimiut. PCA was shown to be an important tool for identifying pollutant sources and differences in pollutant composition in relation to sediment characteristics.

Screening of variable importance for optimizing electrodialytic remediation of heavy metals from polluted harbour sediments

Using multivariate design and modelling, the optimal conditions for electrodialytic remediation (EDR) of heavy metals were determined for polluted harbour sediments from Hammerfest harbour located in the geographic Arctic region of Norway. The comparative importance of the variables, current density, remediation time, light/no light, the liquid–solid ratio and stirring rate of the sediment suspension, was determined in 15 laboratory-scale EDR experiments by projection to latent structures (PLS). The relation between the X matrix (experimental variables) and the Y matrix (removal efficiencies) was computed and variable importance in the projection was used to assess the influence of the experimental variables. Current density and remediation time proved to have the highest influence on the remediation of the heavy metals Cr, Cu, Ni, Pb and Zn in the studied experimental domain. In addition, it was shown that excluding the acidification time improved the PLS model, indicating the importance of applying a limited experimental domain that covers the removal phases of each heavy metal in the specific sediment. Based on PLS modelling, the optimal conditions for remediating the Hammerfest sediment were determined; operating in the experimental domain of 0.5–0.8 mA/cm2 and a remediation time after acidification of 450–570 h met acceptable levels according to Norwegian sediment quality guidelines. GRAPHICAL ABSTRACT

The impact of submarine copper mine tailing disposal from the 1970s on Repparfjorden, northern Norway

We investigate the state of sedimentological environment and contaminant status of Repparfjorden (N Norway) impacted by submarine disposal of mine tailings during the 1970s using sedimentological and geochemical properties of seventeen sediment cores. The impact of tailings disposal is mainly restricted to the inner fjord where the discharge occurred. Sediment cores retrieved from the inner fjord contain layers of mine tailings up to 9-cm thick, 3-9cm below the seafloor. Spreading of the tailing-related metal Cu and particles is limited to the inner fjord and to a 2cm layer in one core from the outer fjord. Two interrelated factors, fjord morphology and sedimentation rate, controlled the distribution of contaminant-laden tailings in the fjord. The mobility of Cu from buried contaminated sediments to the sediment-water interface in the inner fjord indicates that benthic communities have been continuously exposed to elevated Cu concentrations for nearly four decades.

Simultaneous electrodialytic removal of PAH, PCB, TBT and heavy metals from sediments

Contaminated sediments are remediated in order to protect human health and the environment, with the additional benefit of using the treated sediments for other activities. Common for many polluted sediments is the contamination with several different pollutants, making remediation challenging with the need of different remedial actions for each pollutant. In this study, electrodialytic remediation (EDR) of sediments was found effective for simultaneous removal of heavy metals and organic pollutants for sediments from Arctic regions - Sisimiut in Greenland and Hammerfest in Norway. The influence of sediment properties and experimental settings on the remediation process was studied by employing multivariate analysis. The importance of the variables studied varied with the pollutant and based on these results it was possible to assess removal processes for the different pollutants. Desorption was found to be important for the removal of heavy metals and TBT, while photolysis was significant for removal of PAH, PCB and TBT. In addition, dechlorination was found to be important for the removal of PCB. The highest removal efficiencies were found for heavy metals, TBT and PCB (>40%) and lower removal efficiencies for PAH (<35%).

Applying Chemometrics to Determine Dispersion of Mine Tailing-Affected Sediments from Submarine Tailing Disposal in Bøkfjorden, Northern Norway

Mine tailing management is one of the largest environmental issues related to mining operation. This study uses chemometrics to assess the dispersion of iron mine tailing-affected sediments in Bøkfjorden, Northern Norway. Metal concentrations (Al, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Zn) and physico-chemical sediment characteristics (conductivity, organic matter, sulphate, chloride, grain size, CaCO3, pH) were analysed in seven sediment cores collected in a transect out of the fjord along with two reference cores. Results of hierarchical cluster analysis and principal component analysis allowed to distinguish between mine tailing-affected and non-affected sediments. Non-affected sediments were especially characterised by high levels of organic matter whilst mine tailing-affected sediments varied significantly in sediment characteristics depending on location in the fjord. Crucial parameters to reveal mine tailing-affected sediments varied between the target metal Fe along with metals of Cd and Mn, albeit less significant. Variations in mine tailing-affected sediment characteristics could be attributed to other anthropogenic activities in the fjord. Despite potential disturbances, chemometrics made it possible to identify dispersion of mine tailing-affected sediments to cover the inner and middle parts of the fjord. The study demonstrates the advantage of applying chemometrics on complex fjord systems, which in this case was used to distinguish mine tailing-affected sediments from areas with elevated levels of metals not necessarily related to the mine.

Applying multivariate analysis for optimising the electrodialytic removal of Cu and Pb from shooting range soils

Multivariate analysis was applied to simultaneously evaluate the influence of soil properties and experimental variables on electrodialytic removal of Cu and Pb from three shooting range soils. Both stationary and stirred set-ups in laboratory scale were tested, representing in-situ and ex-situ remediation conditions, respectively. Within the same experimental space, higher removal of the targeted metals, Cu and Pb, were observed in the stirred set-up (9-81%) compared to the stationary set-up (0-41%). Multivariate analysis (projections onto latent structures) revealed that the influence of soil type on the remediation efficiency was dependent on the metal and varied in the stationary and stirred set-ups. Optimising the removal of Cu by adjusting the experimental settings was easier to achieve in the stirred set-up and could be done by increasing the current density. Optimising the removal of Pb could be done by prolonging the treatment and in the stirred set-up also by increasing the current density.

The influence of Magnafloc10 on the acidic, alkaline, and electrodialytic desorption of metals from mine tailings

Repparfjorden in northern Norway has been partly designated for submarine mine tailings disposal when the adjacent Cu mine re-opens in 2019. In order to increase sedimentation, the flocculant, Magnafloc10 is planned to be added to the mine tailings prior to discharge into the fjord. This study investigated the feasibility of reducing the Cu concentrations (375 mg/kg) in the mine tailings by applying electrodialytic extraction, including potential optimisation by adding Magnafloc10. In the acidic electrodialytic treatment (pH < 2), Magnafloc10 increased the extraction of Cu from the mine tailings particles from 76 to 86%, and the flocs with adsorbed metals were separated from the tailings solids by the electric field (1 mA/cm2). The electric energy consumption increased with the use of Magnafloc10 (from 17 to 30 kWh/g Cu extracted), due to lower conductivity in the liquid phase and clogging of the membrane by the flocs. In the alkaline electrodialytic treatment (pH > 12), Magnafloc10 reduced the extraction of Cu from 17% to 0.7%, due to the flocs remaining in the tailing slurries. The electric energy consumption per extracted Cu was similar in the acidic and alkaline electrodialytic treatments without the addition of Magnafloc10. In the alkaline electrodialytic treatment, the extraction of other metals was low (<2%), however longer treatment time is necessary to achieve similar Cu extraction as in the acidic electrodialysis. Depending on the target and timescale for treatment, acidic and alkaline electrodialysis can be employed to reduce the Cu concentration in the mine tailings thereby reducing the metal toxicity potential.

Influence of electrode placement for mobilising and removing metals during electrodialytic remediation of metals from shooting range soil

Electrodialytic remediation was applied to a shooting range soil to investigate the influence of electrode placement on the removal and binding of metals during the treatment. The set-up was based on a 2-compartment cell, in which the cathode was separated from the soil by a cation exchange membrane and the anode was placed directly in the soil, thereby introducing protons and oxygen directly in the soil. Mobilisation of metals from less available fractions (oxidisable and residual) in the soil occurred, due to oxidation/dissolution of insoluble/soluble organic matter and possibly metal oxides in the residual fraction. The transport via electromigration out of the soil and/or re-precipitation in other fractions of the soil (oxidisable, reducible, exchangeable) depended on the metal. More than 30% of the initial content of Mn, Cd, Cu, Pb and Zn and less than 20% of the initial content of Al, Fe, K, Mg, As, Cr and Ni was transported out of the soil. By decreasing the distance between the electrodes from 3.0 to 1.5 cm, the removal of the targeted metal for remediation, Pb, was improved by more than 200%, from 14 to 31%. A similar removal could be achieved in experiments with long distance between electrodes (3.0 cm) by increasing the current intensity from 4 to 10 mA and/or the remediation time from 7 to 35 d. The experiments showed that the design and optimisation of electrodialytic remediation depends on the targeted metal and metal partitioning.