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Soil pollution constitutes one of the major threats to public health, where spreading to groundwater is one of several critical aspects. In most internationally adopted frameworks for routine risk assessments of contaminated land, generic models and soil guideline values are cornerstones. In order to protect the groundwater at contaminated sites, a common practice worldwide today is to depart from health risk-based limit concentrations for groundwater, and use generic soil-to-groundwater spreading models to back-calculate corresponding equilibrium levels (concentration limits) in soil, which must not be exceeded at the site. This study presents an extensive survey of how actual soil and groundwater concentrations, compiled for all high-priority contaminated sites in Sweden, relate to the national model for risk management of contaminated sites, with focus on As, Cu, Pb and Zn. Results show that soil metal concentrations, as well as total amounts, constitute a poor basis for assessing groundwater contamination status. The evaluated model was essentially incapable of predicting groundwater contamination (i.e. concentrations above limit values) based on soil data, and erred on the unsafe side in a significant number of cases, with modelled correlations not being conservative enough. Further, the risk of groundwater contamination was almost entirely independent of industry type. In essence, since neither soil contaminant loads nor industry type is conclusive, there is a need for a supportive framework for assessing metal spreading to groundwater accounting for site-specific, geochemical conditions.

Accurate prediction of the sorption of perfluoroalkyl substances (PFASs) in soils is essential for environmental risk assessment. We investigated the effect of solution pH and calculated soil organic matter (SOM) net charge on the sorption of 14 PFASs onto an organic soil as a function of pH and added concentrations of Al3+, Ca2+ and Na+. Often, the organic C-normalized partitioning coefficients (KOC) showed a negative relationship to both pH (Δlog KOC/ΔpH = −0.32 ± 0.11 log units) and the SOM bulk net negative charge (Δlog KOC = −1.41 ± 0.40 per log unit molc g−1). Moreover, perfluorosulfonic acids (PFSAs) sorbed more strongly than perfluorocarboxylic acids (PFCAs) and the PFAS sorption increased with increasing perfluorocarbon chain length with 0.60 and 0.83 log KOC units per CF2 moiety for C3–C10 PFCAs and C4, C6, and C8 PFSAs, respectively. The effects of cation treatment and SOM bulk net charge were evident for many PFASs with low to moderate sorption (C5–C8 PFCAs and C6 PFSA). However for the most strongly sorbing and most long-chained PFASs (C9–C11 and C13 PFCAs, C8 PFSA and perfluorooctane sulfonamide (FOSA)), smaller effects of cations were seen, and instead sorption was more strongly related to the pH value. This suggests that the most long-chained PFASs, similar to other hydrophobic organic compounds, are preferentially sorbed to the highly condensed domains of the humin fraction, while shorter-chained PFASs are bound to a larger extent to humic and fulvic acid, where cation effects are significant., QC 20180529

This study addresses the reactivity and risks of metals (Ba, Cd, Co, Cr, Cu, Ni, Pb, Zn, As and Sb) at a Swedish site with large glass waste deposits. Old glassworks sites typically have high total metal concentrations, but as the metals are mainly bound within the glass waste and considered relatively inert, environmental investigations at these kinds of sites are limited. In this study, soil and landfill samples were subjected to a sequential chemical extraction procedure. Data from batch leaching tests and groundwater upstream and downstream of the waste deposits were also interpreted. The sequential extraction revealed that metals in <2 mm soil/waste samples were largely associated with geochemically active fractions, indicating that metals are released from pristine glass and subsequently largely retained in the surrounding soil and/or on secondary mineral coatings on fine glass particles. From the approximately 12,000 m(3) of coarse glass waste at the site, almost 4000 kg of Pb is estimated to have been lost through corrosion, which, however, corresponds to only a small portion of the total amount of Pb in the waste. Metal sorption within the waste deposits or in underlying soil layers is supported by fairly low metal concentrations in groundwater. However, elevated concentrations in downstream groundwater and in leachates of batch leaching tests were observed for several metals, indicating on-going leaching. Taken together, the high metal concentrations in geochemically active forms and the high amounts of as yet uncorroded metal-rich glass, indicate considerable risks to human health and the environment.

Det övergripande målet med denna publikation är att tillsynsmyndigheter (kommuner, länsstyrelser och Generalläkaren), konsulter och problemägare ska få ett stöd i sin bedömning av miljö-och hälsorisker av områden som är förorenade med PFAS. Riktvärden behövs även för prioriteringar och bedömning av åtgärdsbehovet av PFAS-förorenade områden. Metodiken kan även användas för framtagning av generella och platsspecifika riktvärden för olika PFAS-föreningar. I publikationen ges förslag på preliminära riktvärden för perfluoroktansulfonat (PFOS) i mark och grundvatten. För mark har två riktvärden beräknats, ett för känslig markanvändning och ett för mindre känslig markanvändning.

Chromium is a common soil contaminant, and it often exists as chromium(III). However, limited information exists on the coordination chemistry and stability of chromium(III) complexes with natural organic matter (NOM). Here, the complexation of chromium(III) to mor layer material and to Suwannee River Fulvic Acid (SRFA) was investigated using EXAFS spectroscopy and batch experiments. The EXAFS results showed a predominance of monomeric chromium(III)-NOM complexes at low pH (<5), in which only Cr··C and Cr-O-C interactions were observed in the second coordination shell. At pH > 5 there were polynuclear chromium(III)-NOM complexes with Cr···Cr interactions at 2.98 Å and for SRFA also at 3.57 Å, indicating the presence of dimers (soil) and tetramers (SRFA). The complexation of chromium(III) to NOM was intermediate between that of iron(III) and aluminum(III). Chromium(III) complexation was slow at pH < 4: three months or longer were required to reach equilibrium. The results were used to constrain chromium-NOM complexation in the Stockholm Humic Model (SHM): a monomeric complex dominated at pH < 5, whereas a dimeric complex dominated at higher pH. The optimized constant for the monomeric chromium(III) complex was in between those of the iron(III) and aluminum(III) NOM complexes. Our study suggests that chromium(III)-NOM complexes are important for chromium speciation in many environments., QC 20140313

Nitrogen deposition and increasing temperature are two of the major large-scale changes projected for coming decades and the effect of this change on dissolved organic matter is largely unknown. We have utilized a long-term fertilization and soil warming experiment in Northern Sweden to study the effects of increased nutrient levels and increased temperature on DOC transport under the O horizon. The site is N limited and mean annual temperature 2. °C. Experimental fertilization with ammonium nitrate and a physiological mixture of other macro- and micro-nutrients has been going on for 22. years and soil warming, 5. °C above ambient soil temperature for 14. years, prior to the study. Experimental plots have been irrigated to avoid drying and we also studied the effect of this long-term irrigation on DOC by establishing control plots receiving no irrigation.DOC concentrations and fluxes under the O horizon were approximately 50% higher in fertilized plots than in non-fertilized control plots. We did not find any statistically significant effect of soil warming. There was a statistically significant effect of long-term irrigation on DOC with higher DOC concentration and fluxes in irrigated plots than in plots without irrigation. There were no major effects on DOC quality measured by specific UV absorbance. Fertilization approximately doubled soil organic matter stocks in the O horizon, whereas there were no such effects of warming or irrigation on soil organic matter amounts. There was no statistically significant treatment effect on DOC collected from the B horizon. We hypothesize that the positive effect of fertilization on DOC is related to increased soil C stocks., QC 20131122

In order to manage municipal solid waste incineration (MSWI) bottom ash safely, risk assessments, including the prediction of leaching under different field conditions, are necessary. In this study, the influence of salt or dissolved organic matter (DOM) in the influent on metal leaching from MSWI bottom ash was investigated in a column experiment. The presence of salt (0.1 M NaCI) resulted in a small increase of As leaching, whereas no impact on leachate concentration was found when lakewater DOM (35.1 mg/I dissolved organic carbon) was added. Most of the added DOM was retained within the material. Further, X-ray spectroscopy revealed that Cu(II) was the dominating form of Cu and that it probably Occurred as a CuO-type mineral. The CU2+ activity in the MSWI bottom ash leachate was most likely determined by the dissolution of CuO together with the formation of Cu-DOM complexes and possibly also by adsorption to (hydr)oxide minerals. The addition of lake DOM in the influent resulted in lower saturation indices for CuO in the leachates. which may be due to slow CuO dissolution kinetics in combination with strong Cu-DOM complexation., QC 20100525

This paper comprises data from an extensive cross-disciplinary research project aiming to elucidate the environmental fate of corrosion-induced zinc release from external structures. It includes an exposure assessment that provide long-term runoff rates, concentrations and chemical speciation of zinc, from 14 zinc-based materials exposed during 5 years in Stockholm, Sweden, and an effect assessment including bioavailability and ecotoxicity measurements, both at the immediate release situation and after soil interaction.Runoff rates of total zinc ranged from 0.07 to 2.5g Znm(-2) yr(-1) with zinc primarily released as the free ion for all materials investigated. The average effect concentration, causing a 50% growth reduction after 72h to the green algae Raphidocelis subcapitata, was at the immediate release situation 69 mu g ZnL-1. Upon interaction of runoff water with soil, which simulated 18 to 34years of exposure, the total zinc concentration was significantly reduced, from milligram per litre to microgram per litre levels. Simultaneously, the most bioavailable fraction of zinc in runoff, the hydrated zinc(II)-ion, decreased from more than 95% to about 30%. The major fraction, 98-99%, of the introduced total zinc concentration in the runoff water was retained within the soil. As long as the soil retention capacity was not reached, this resulted in zinc concentrations in the percolate water transported through the soil layer, close to background values and below growth inhibition concentrations for the green algae investigated. Zinc retained in soil was to a large extent (85-99.9%) extractable with EDTA, and available for plant uptake after 5 to 7months of ageing., QC 20100901. Tidigare titel: Occurrence and environmental fate of corrosion-induced zinc in runoff water from external structures. Titel ändrad och uppdaterad från Submitted till Published 20100901.

QC 20120302

Models are available for simulations of proton dissociation and cation binding by natural organic matter; two examples are the NICA-Donnan and Stockholm Humic (SHM) models. To model proton and metal binding, it is necessary to properly account for the ionic strength dependence of proton dissociation. In previous applications of the models for soils it was assumed that the electrostatic interactions for solid-phase humic substances were the same as in solution;this assumption was recently challenged. Therefore, we reanalyzed previously published acid-base titrations of acid-washed Sphagnum peat, and we produced additional data sets for two Sphagnum peats and two Spodosol Oe horizons. For the soil suspensions, the original NICA-Donnan and SHM models, which were developed for dissolved humic substances, underestimated the observed salt dependence considerably. When a fixed Donnan volume of 1 L kg(-1) for humic substances in the solid phase was used, the NICA-Donnan model fits were much improved. Also for SHM, slight changes produced improved model fits. The models also produced acceptable simulations of the dissolved Ca, Mg, and Cd concentrations, provided that cation selectivity was introduced. In conclusion, the proposed extensions to the NICA-Donnan and SHM models were shown to predict the salt dependence of solid-phase humic substances more satisfactorily than earlier model versions., QC 20100525

The solubility of aluminium (Al) in many acidic soils is controlled by complexation reactions with soil organic matter. In such soils, Al solubility is theoretically a function of the pool size of active Al, i.e., the total amount of Al that equilibrates with the sod solution within a defined period of time. To date, no reliable measurements of active Al in soil materials exist. In this study, we determined the isotopically exchangeable pool of Al (E-A1) as an operationally defined assessment of active Al in acidic mineral soils. The suitability of CuCl2 and pyrophosphate (Na4P2O7) as extractants for active Al was also evaluated. Eleven samples, mostly from spodic B horizons, were spiked with carrier-free Al-26 and equilibrated for different time periods (1-756 h). The size of the Al pool with which the Al-26 tracer exchanged increased with time during the whole experimental period. Thus, contact time between solid and solution phases needs to be defined when assessing the active Al pool. Values of E-A1 obtained after I to 5 d of equilibration were equal to the amount of CuCl2 extractable Al, but considerably smaller than the Na4P2O7-extractable pool. Equilibration times greater than 5 d resulted in CuCl2 extractable Al concentrations that under-estimated the active Al pool. Three of the investigated samples were rich in imogolite-type materials (ITM). In these samples, 30-50 % of the added Al-26 rapidly became associated with soil constituents in forms that could not be extracted by Na4P2O7, indicating that a part of ITM may be in a dynamic state., QC 20100525

The solubility of aluminium (Al) in many acidic soils is controlled by complexation reactions with soil organic matter. In such soils, Al solubility is theoretically a function of the pool size of "active" Al, i.e., the total amount of Al that equilibrates with the soil solution within a defined period of time. To date, no reliable measurements of "active" Al in soil materials exist. In this study, we determined the isotopically exchangeable pool of Al (EAl) as an operationally defined assessment of "active" Al in acidic mineral soils. The suitability of CuCl2 and pyrophosphate (Na4P2 O7) as extractants for "active" Al was also evaluated. Eleven samples, mostly from spodic B horizons, were spiked with carrier-free 26Al and equilibrated for different time periods (1-756 h). The size of the Al pool with which the 26Al tracer exchanged increased with time during the whole experimental period. Thus, contact time between solid and solution phases needs to be defined when assessing the "active" Al pool. Values of EAl obtained after 1 to 5 d of equilibration were equal to the amount of CuCl2 extractable Al, but considerably smaller than the Na4P2O7-extractable pool. Equilibration times greater than 5 d resulted in CuCl2 extractable Al concentrations that under-estimated the "active" Al pool. Three of the investigated samples were rich in imogolite-type materials (ITM). In these samples, 30-50 % of the added 26Al rapidly became associated with soil constituents in forms that could not be extracted by Na4P2 O7, indicating that a part of ITM may be in a dynamic state.

Some areas within ice sheet boundaries retain pre-existing landforms and thus either remained as ice free islands (nunataks) during glaciation, or were preserved under ice. Differentiating between these alternatives has significant implications for paleoenvironment, ice sheet surface elevation, and ice volume reconstructions. In the northern Swedish mountains, in situ cosmogenic 10Be and 26Al concentrations from glacial erratics on relict surfaces as well as glacially eroded bedrock adjacent to these surfaces, provide consistent last deglaciation exposure ages (~8-13 kyr), confirming ice sheet overriding as opposed to ice free conditions. However, these ages contrast with exposure ages of 34-61 kyr on bedrock surfaces in these same relict areas, demonstrating that relict areas were preserved with little erosion through multiple glacial cycles. Based on the difference in radioactive decay between 26Al and 10Be, the measured nuclide concentration in one of these bedrock surfaces suggests that it remained largely unmodified for a minimum period of 845+461-418 kyr. These results indicate that relict areas need to be accounted for as frozen bed patches in basal boundary conditions for ice sheet models, and in landscape development models. Subglacial preservation also implies that source areas for glacial sediments in ocean cores are considerably smaller than the total area covered by ice sheets. These relict areas also have significance as potential long-term subglacial biologic refugia.

Despite spectacular landform evidence of a dominant role for glacial action in shaping landscapes under former northern hemisphere ice sheets, there is little quantitative evidence for rates and patterns of erosion associated with specific glaciations. Here we use cosmogenic nuclide data to assess rates of subglacial erosion underneath the Fennoscandian ice sheet. By testing whether there are remnant nuclide concentrations in samples taken from sites that include both relict areas and features and landscapes typically associated with vigorous glacial erosion, we can constrain the level and pattern of modification that resulted from the last glaciation. Cosmogenic 10Be and 36Cl data from the Torneträsk region confirm the temporal and spatial variability of glacial erosion suggested by geomorphological mapping. At some sites, glacial erosion estimates in what appear to be heavily scoured areas indicate erosion of only c. 2 ± 0.4 m of bedrock, based on cosmogenic nuclide inheritance. This implies that the generation of severely scoured terrain in this study area required multiple glaciations. The overall modification produced by ice sheets along glacial corridors may be more restricted than previously thought, or may have occurred preferentially during earlier Quaternary glacial periods.