A novel approach to peatlands as archives of total cumulative spatial pollution loads from atmospheric deposition of airborne elements complementary to EMEP data: priority pollutants (Pb, Cd, Hg).

A novel approach to using peatlands for assessment of cumulative contributions from long-range transport of pollutants (LRTP) - airborne trace elements - to spatial pollution was exemplified in evaluating retrospective atmospheric deposition of priority pollutants (Pb, Cd, Hg) in peat bogs in Norway in areas minor affected by local sources of pollution and in NW Poland located on the way of possible LRTP from Poland to Norway. Peat from the corresponding 14C-dated layers of five ombrotrophic bogs in each country, was analysed for trace element contents. Pollutant concentrations/load distribution along the peat profiles related to bulk density has given a clear evidence of uneven density-dependent temporal vertical migration of all studied elements that distorts the chronology of their deposition. Much higher loads of Pb, Cd and Hg in southern Norwegian bogs than in bogs located in NW Poland proved transboundary transport from neighbouring highly industrialized European countries to be much more significant contributor to high deposition of the priority pollutants in this area and rather excludes LRTP from Poland as a major source of total land pollution in southernmost Norway. The study showed excellent applicability of peat bogs for the exact assessment of retrospective cumulative pollutant loads from LRTP, but not for the identification of deposition chronology. Combining the use of ombrotrophic peat bogs as tools for retrospective monitoring of cumulative land pollution with airborne elements with current LRTP data within the Cooperative Programme for Monitoring and Evaluation of the Long-Range Transmission of Air Pollutants in Europe (EMEP) may provide a complete reliable picture of the effect of anthropogenic emissions on soil quality and create a foundation of optimum environmental policy and activities in this field.

Geotechnical properties of products of alternative fuel combustion and co-firing with hard coal in the context of their use as solidifying dense mixtures.

Efforts directed to reduction of greenhouse gas emissions have led to the introduction of new firing/co-firing technologies and alternative fuels in the coal-based power industry. This has resulted in the formation of combustion products with new properties that can affect the reuse of these wastes and/or pose a hazard to the environment. One of the power-plant fly ash (FA) reuse options is its application as a solidifying dense mixture with water for backfilling mine workings or in engineering constructions. In this comparative study, geotechnical properties of three groups of FA were evaluated: (i) weathered and freshly generated ash from hard coal combustion in conventional pulverized coal boilers without (C-PCA, C-PFA) and with selective non-catalytic reduction installations for NO x reduction (NC-PFA); (ii) FA from hard coal co-firing with alternative fuels: off gases (GC-PFA) or biomass (BC-PFA) in pulverized coal boilers; (iii) FA from coal (C-FFA) or biomass combustion (B-FFA) in fluidized-bed boilers. The transportability, bonding and solidification properties, uniaxial compression strength, and rewetting of dense mixtures were evaluated by measurements of volumetric density, fluidity, water retention capacity, bonding time, solidification time, uniaxial compression test, and slakeability at the background of the FA chemical composition. Calcareous C-FFA > B-FFA displayed the best geotechnical properties. Other materials showed poorer geotechnical properties than FFA and could be aligned in the order BC-PFA > GC-PFA > NC-PFA > C-PFA > C-PCA.

Impact of an iron mine and a nickel smelter at the Norwegian/Russian border close to the Barents Sea on surface soil magnetic susceptibility and content of potentially toxic elements.

An important problem in soil magnetometry is unraveling the soil contamination signal in areas with multiple emitters. Here, geophysical and geochemical measurements were performed at four sites on a north - south transect along the Pasvik River in the Barents Region (northern Norway). These sites are influenced by depositions from the Bjørnevatn iron mine and a Ni-Cu smelter in Nikel, Russia. To relate the degree and type of pollution from these sources to the corresponding magnetic signal, the topsoil concentrations of 12 Potentially Toxic Elements (PTEs) (As, Cd, Co, Cr, Cu, Fe, Mo, Ni, Pb, Se, Ti, Zn), were determined, magnetic hysteresis parameters and thermomagnetic properties were measured. In situ magnetic low-field susceptibility decreases from north to south with increasing distance from the iron mine. Relatively large magnetic multidomain grains of magnetite and/or titanomagnetite are responsible for the strong magnetic signal from the topsoil close to Bjørnevatn. These particles are related to increased enrichment factors of As, Mo and Cu, yielding high positive correlation coefficients with susceptibility values. At a site furthest away from the iron mine and located 7 km from the Ni-Cu smelter magnetic susceptibility values are much lower but significant positive correlations on the level of p < .1 with 8 PTEs (Ni, Cu, Co, Se, As, Zn, Cd, Cr) have been observed. The magnetic signal in this area is due to fine-grained primary sulphides and secondary fine-grained magnetite and/or maghemite.

Effect of weathering transformations of coal combustion residuals on trace elements mobility in view of the environmental safety and sustainability of their disposal and use. II. Element release.

This paper is the second one of two companion papers. It presents results of a study aimed at assessing the effect of real time weathering transformations of Coal Combustion Residuals (CCRs) on trace element binding/release and its environmental implications. The study is based on the chemical composition of pore solutions extracted from primary alkaline Class F CCRs, 0 to >40 years old, sampled from the surface layer and vertical profiles at four selected typical CCRs impoundments. The long-term weathering transformations were found to lead to gradual acidification to pH < 4 of this primary alkaline material, due to internal processes of mineral formation/dissolution. Direct analysis of the pore solutions and a statistical analysis have shown different susceptibility of many trace elements to release during internal acidification processes occurring at consecutive Wash-out I (pH > 8), Dissolution II (8 ≥ pH ≥ 7) and Delayed Release III (pH < 7) stages of weathering compared to that at external sources of pH. The elements occurring in the CCRs are represented by three major groups showing the highest release to pore water: (a) within the acidic pH range (Na, K, Zn, Fe, Cd, Mo, Cr, B, Mn, Be and Ni; (b) within the near-neutral pH range (Al, V, Ba, Cu and Ag) and also Sb, Hg and Co not analyzed at pH < 7; (c) within the alkaline pH range (Ca, Mg, Pb, As, Se, Tl). Elements whose concentrations exceeded the threshold values for good chemical status of groundwater (TVs) at all weathering stages over the entire pH range studied were K, Al, B, Cr, Mo, V, As, Se, Sb and Hg, while Na, Zn, Fe and Cd showed particularly high delayed release at pH < 7, thus confirming the need of a precautionary approach to CCRs uncontrolled disposal and bulk reuse as common fill in view of long term environmental safety and sustainability.

Effect of weathering transformations of coal combustion residuals on trace element mobility in view of the environmental safety and sustainability of their disposal and use. I. Hydrogeochemical processes controlling pH and phase stability.

Coal combustion residuals (CCRs) are one of the most abundant high-volume waste materials disposed in impoundments worldwide. Some methods of CCR recycling, e.g. their use as structural fill for low lying areas or as soil amendment, also expose this material to atmospheric conditions. Combustion processes result in concentration of trace elements in CCRs at about an order of magnitude compared to coal. In order to assess an effect of long-term weathering transformations of CCRs on trace element binding/release, a study has been carried out. It is based on the chemical composition of real pore solutions extracted from the most abundant primary alkaline Class F bituminous CCRs, 0 to >40 years old, sampled from the surface layer and vertical profiles at four different impoundments. In this part of the study, results of a hydrogeochemical simulation of the saturation state of real pore solutions with respect to mineral phases of CCRs with use of the PHREEQC program, related to actual pH values reflecting the full cycle of weathering transformations, have been discussed. This study is the first geochemical proof of the general trend towards a progressive acidification up to pH < 4 of primary alkaline CCRs due to release of protons during internal processes of formation of gibbsite and aluminosilicate minerals, buffered by carbonates at the alkaline - near-neutral stages, and followed by parallel dissolution and buffering by aluminosilicates at pH < 7 after carbonate depletion, to the level up to pH∼3.5-4.0. The intrinsic geochemical changes have resulted in the different susceptibility of trace elements to release and associated changes in risk to the environment at consecutive stages of weathering.