Sorption of Perfluorooctane sulfonate (PFOS) including its isomers on hydrargillite as a function of pH, humic substances and Na2SO4.

Perfluorooctane sulfonate (PFOS) is a persistent organic pollutant (POP) and emergent contaminant that are widespread in the environment. Understanding the mechanisms controlling the distribution of PFOS and its isomers between hydrargillite and the water phase is important in order to study their redistribution and mobility in the environment. This study investigated the effects of pH, humic acid, fulvic acid and Na2SO4 on sorption of PFOS isomers to hydrargillite. A mixture of PFOS isomers was spiked into water and hydrargillite was added to the system and shaken for one day; the system was tested with different aqueous composition. Concentrations of PFOS isomers in the aqueous phase were quantified using an ultra-performance liquid chromatograph coupled to a triple quadrupole mass spectrometer. Our results showed that the distribution coefficients of PFOS isomers were found to be 0.76, 0.71, 0.93 and 0.90 at pH 6.5, for 3-/4-/5- PFOS, 6-/2-PFOS, L-PFOS and total PFOS respectively. The distribution coefficients increased at lower pH and decreased at alkaline conditions. The presence of humic substances (HS) increased the sorption slightly at the environmental pH of 6.5, although a competition effect was observed during acidic conditions. A tendency of PFOS distribution to hydrargillite in the presence of Na2SO4 was like its behavior in the presence of HS although the mechanisms behind the sorption were interpreted differently. This study revealed that L-PFOS was readily sorbed when no other chemicals were added or in 20 mg/L FA or 100 mg/L Na2SO4. We suggest that an increase in PFOS sorption in the presence of HS may be due to hydrophobic mechanisms while Na2SO4 contributed to increased sorption through ionic strength effects.

Groundwater chemistry affected by trace elements (As, Mo, Ni, U and V) from a burning alum shale waste deposit, Kvarntorp, Sweden.

Worldwide, black shales and shale waste are known to be a potential source of metals to the environment. This project demonstrates ongoing weathering and evaluates leaching processes at a 100-m-high shale waste deposit closed in the 1960s. Some deep parts of the deposit are still burning with temperatures exceeding 500 °C. To demonstrate ongoing weathering and leaching, analyses of groundwater and solid samples of shale and shale waste have been undertaken. Largest impact on groundwater quality was observed downstream the deposit, where elevated temperatures also indicate a direct impact from the burning waste deposit. Groundwater quality is largely controlled by pH and redox conditions (e.g., for arsenic, nickel, molybdenum, uranium and vanadium), and the mixture of different waste materials, including pyrite (acidic leachates) and carbonates (neutralizing and buffering pH). Analyses of shale waste from the deposit confirm the expected pyrite weathering with high concentrations of iron, nickel and uranium in the leachates. No general time trends could be distinguished for the groundwater quality from the monitoring in 2004-2019. This study has shown that black shale waste deposits can have a complex long-term impact on the surrounding environment.

Sorption of PFOS isomers on goethite as a function of pH, dissolved organic matter (humic and fulvic acid) and sulfate.

Understanding the distribution of PFOS isomers between the aqueous phase and goethite is crucial, since it is an abundant sorbent and thus may have a large influence on the mobility of PFOS. This study was conducted to understand the effects of pH, humic acid (HA), fulvic acid (FA) and sulfate on sorption of PFOS isomers. The results will increase the understanding about what parameters may control the fate and transport of PFOS in surface and ground water. The study was conducted by adding PFOS spiked water to a goethite slurry with different aqueous chemistry. Levels of total PFOS and PFOS isomers were quantified using an Ultra-Performance Liquid Chromatograph coupled to a triple quadrupole mass spectrometer. Results showed that sorption of PFOS was mainly dependent on pH; sorption decreased as pH increased. Presence of HA increased log Kd from 1.29 to 2.03, 1.76 to 1.92 and 1.51 to 1.96 at pH 5.50-7.50 for 3-/4-/4-PFOS, 6-/2-PFOS and L-PFOS, respectively. Changes in the aqueous chemistry also affected the behaviour of PFOS as the addition of Na2SO4 enhanced the sorption of PFOS. Results showed that L-PFOS was more readily sorbed to goethite at pH < 4.35 both in the presence and in the absence of humic or fulvic acids. At pH > 4.5 the 3-/4-/5-PFOS isomer group was more associated to goethite. Besides electrostatic interactions, which controlled the sorption of PFOS, this study indicate that the presence of dissolved humic substances in the aqueous phase enhances the sorption via hydrophobic mechanisms.

Distribution and leaching characteristics of trace elements in ashes as a function of different waste fuels and incineration technologies.

Impact of waste fuels (virgin/waste wood, mixed biofuel (peat, bark, wood chips) industrial, household, mixed waste fuel) and incineration technologies on partitioning and leaching behavior of trace elements has been investigated. Study included 4 grate fired and 9 fluidized boilers. Results showed that mixed waste incineration mostly caused increased transfer of trace elements to fly ash; particularly Pb/Zn. Waste wood incineration showed higher transfer of Cr, As and Zn to fly ash as compared to virgin wood. The possible reasons could be high input of trace element in waste fuel/change in volatilization behavior due to addition of certain waste fractions. The concentration of Cd and Zn increased in fly ash with incineration temperature. Total concentration in ashes decreased in order of Zn>Cu>Pb>Cr>Sb>As>Mo. The concentration levels of trace elements were mostly higher in fluidized boilers fly ashes as compared to grate boilers (especially for biofuel incineration). It might be attributed to high combustion efficiency due to pre-treatment of waste in fluidized boilers. Leaching results indicated that water soluble forms of elements in ashes were low with few exceptions. Concentration levels in ash and ash matrix properties (association of elements on ash particles) are crucial parameters affecting leaching. Leached amounts of Pb, Zn and Cr in >50% of fly ashes exceeded regulatory limit for disposal. 87% of chlorine in fly ashes washed out with water at the liquid to solid ratio 10 indicating excessive presence of alkali metal chlorides/alkaline earths.

Trace element partitioning in ashes from boilers firing pure wood or mixtures of solid waste with respect to fuel composition, chlorine content and temperature.

Trace element partitioning in solid waste (household waste, industrial waste, waste wood chips and waste mixtures) incineration residues was investigated. Samples of fly ash and bottom ash were collected from six incineration facilities across Sweden including two grate fired and four fluidized bed incinerators, to have a variation in the input fuel composition (from pure biofuel to mixture of waste) and different temperature boiler conditions. As trace element concentrations in the input waste at the same facilities have already been analyzed, the present study focuses on the concentration of trace elements in the waste fuel, their distribution in the incineration residues with respect to chlorine content of waste and combustion temperature. Results indicate that Zn, Cu and Pb are dominating trace elements in the waste fuel. Highly volatile elements mercury and cadmium are mainly found in fly ash in all cases; 2/3 of lead also end up in fly ash while Zn, As and Sb show a large variation in distribution with most of them residing in the fly ash. Lithophilic elements such as copper and chromium are mainly found in bottom ash from grate fired facilities while partition mostly into fly ash from fluidized bed incinerators, especially for plants fuelled by waste wood or ordinary wood chips. There is no specific correlation between input concentration of an element in the waste fuel and fraction partitioned to fly ash. Temperature and chlorine content have significant effects on partitioning characteristics by increasing the formation and vaporization of highly volatile metal chlorides. Zinc and cadmium concentrations in fly ash increase with the incineration temperature.

Neutralisation of an acidic pit lake by alkaline waste products.

A former open pit where black shale (alum shale) was excavated during 1942-1965 has been water filled since 1966. The water chemistry was dominated by calcium and sulphate and had a pH of 3.2-3.4 until 1997-1998, when pH was gradually increasing. This was due to the intrusion of leachates from alkaline cement waste deposited close to the lake. A stable pH of around 7.5 was obtained after 6-7 years. The chemistry of the pit lake has changed due to the neutralisation. Concentrations of some dissolved metals, notably zinc and nickel, have gone down, as a result of adsorption/co-precipitation on solid phases (most likely iron and aluminium hydroxides), while other metals, notably uranium and molybdenum, are present at elevated levels. Uranium concentration is reaching a minimum of around pH 6.5 and is increasing at higher pH, which may indicate a formation of neutral and anionic uranyl carbonate species at high pH (and total carbonate levels around 1 mM). Weathering of the water-exposed shale is still in progress.

Learning about the history of landscape use for the future: consequences for ecological and social systems in Swedish Bergslagen.

Barriers and bridges to implement policies about sustainable development and sustainability commonly depend on the past development of social-ecological systems. Production of metals required integration of use of ore, streams for energy, and wood for bioenergy and construction, as well as of multiple societal actors. Focusing on the Swedish Bergslagen region as a case study we (1) describe the phases of natural resource use triggered by metallurgy, (2) the location and spatial extent of 22 definitions of Bergslagen divided into four zones as a proxy of cumulative pressure on landscapes, and (3) analyze the consequences for natural capital and society. We found clear gradients in industrial activity, stream alteration, and amount of natural forest from the core to the periphery of Bergslagen. Additionally, the legacy of top-down governance is linked to today's poorly diversified business sector and thus municipal vulnerability. Comparing the Bergslagen case study with other similar regions in Russia and Germany, we discuss the usefulness of multiple case studies.

Mobilisation of heavy metals by deicing salts in a roadside environment.

The seasonal variations of some selected heavy metals (Cd, Cu, Pb and Zn) and principal anions in soil solutions were monitored as a function of distance from the road at two field sites in Sweden. During the winter, the conductivity, concentrations of dissolved sodium and chloride increased dramatically due to the application of deicing agents (i.e. NaCl). Due to ion exchange, the pH decreased one unit in the soil solutions, whereas the concentrations of total organic carbon decreased due to coagulation and/or sorption to stationary solids. The heavy metal concentrations increased during the winter, but through different mechanisms. Cadmium concentrations in the aqueous phase increased as a response to ion exchange, possibly also enhanced by the formation of chloride complexes. Similarly, the concentrations of zinc increased, due to ion exchange, with calcium and protons. The mechanisms of mobilisation for copper and lead were not that clear probably due to association with coagulated or sorbed organic matter in combination with colloid dispersion.

Impact of fluoride and other aquatic parameters on radon concentration in natural waters.

Radon (222Rn) accumulation in water in relation to stable elements was studied for the purpose of determining factors influencing the transfer of 222Rn to and from water. In 72 groundwater samples, 222Rn and about 70 analytical parameters were analysed using radiometric and ICP-MS techniques. Using multivariate statistics (partial least squares), it was observed that 222Rn has a positive correlation with fluoride and uranium. The correlation with fluoride was further investigated by a laboratory time-scale experiment to measure the emanation of 222Rn from water as a function of fluoride, pH and carbonate. The transfer of 222Rn from water was measured by continuous monitoring in air in a closed loop set-up. It was observed that fluoride in water adhere or trap 222Rn preferably in acidic water (pH 3). It is suspected that natural physical processes (such as diffusion and microbubble phenomenon) are less effective to transport 222Rn in the presence of fluoride.

Metal leachability and anthropogenic signal in roadside soils estimated from sequential extraction and stable lead isotopes.

Several roadside soil samples were collected at two field sites in Sweden. They were analysed for total elemental content (using both ICP-MS and XRF) and stable lead isotopes. Extraction with deicing salt solution and sequential extraction were performed in order to elucidate the potential mobility due to the use of deicing agents. The total concentrations of elements, especially lead, have decreased and lead is presently almost at background concentrations (15-51 ppm for surface samples). However, the isotopic signature indicates that old gasoline lead still is left at the site constructed prior to 1975. The field site constructed in 1992 showed, however, no 206Pb/207Pb ratio below 1.14. Only minor amounts were leached using deicing salt solutions; for lead only 0.29%, on average, was extracted indicating that the mobile fraction already was released. Sequential extraction indicated that lead mainly was associated with reducible (34.4%) and oxidisable (35.4%) fractions. Exchangable and acid soluble fractions contained 20.3% while 10.0% was found in the residual fraction. The salt extraction released, however, very low concentrations indicating that most in fraction 1 is acid soluble (e.g. carbonates). Tungsten was also found at high concentrations indicating a possible impact from studded tires. For tungsten the following composition was obtained: residual (48.0%) > oxidisable (47.6%) > reducible (3.3%) > exchangeable/acid soluble (1.1%). From the isotopic studies it was also suggested that the order for incorporating anthropogenic lead into soils is exchangeable/carbonates > (hydr)oxides > organic matter > residual. The multivariate technique principal component analysis (PCA) seems promising for evaluating large sequential extraction datasets.

Multi-objective environmental management in constructed wetlands.

We examined multi-objective environmental management as applied to pursuing concurrent goals of water treatment, biodiversity and promotion of recreation in constructed wetlands. A case study of a wetland established to treat landfill leachate, increase biodiversity, and promote recreation was evaluated. The study showed that attempts to combine pollution management with activities promoting biodiversity or recreation are problematic in constructed wetlands. This could be because the typical single-objective focus of scientific research leads to contradictions when planning, implementing and assessing the multi-objective use of wetlands. In the specific case of wetland filters for landfill leachate treatment, biodiversity, and recreation, there is a need for further research that meet practical needs to secure positive outcomes.

Effects of a fulvic acid on the adsorption of mercury and cadmium on goethite.

The effects of an aquatic fulvic acid on the pH-dependent adsorption of Hg(II) and Cd(II) to particulate goethite (alpha-FeOOH) were studied in batch systems. The ionic medium consisted of 0.01 M HClO(4) and the total concentrations of mercury and cadmium were maintained at 10(-8) M with 203Hg and 109Cd as tracers. pH In the systems was varied in the range 3-10 by addition of HClO(4) and NaOH. All commercial chemicals were of analytical grade or better. An aquatic fulvic acid (20 ppm), previously isolated and characterised in detail, was used as a model for humic substances and its adsorption to goethite is included in this study. The adsorption of the fulvic acid (20 ppm) onto goethite decreased slowly from 90% at pH 3-7.5 to 10% at pH 10. In systems without fulvic acid the adsorption of mercury increased in a linear fashion from 10% at pH 3 to 70% at pH 10. In the presence of fulvic acid (20 ppm), the adsorption was almost quantitative in the intermediate pH range (pH 5-7), and exceeded 92% over the entire pH range. Thus, association between mercury and the fulvic acid enhanced adsorption in general although the largest impact was found at low pH. Adsorption of cadmium increased from nearly 0 to almost 100% at approximately pH 6. In the presence of fulvic acid, the adsorption increased below pH 7 and decreased above pH 7. The adsorption isotherm for mercury when the concentration was increased from 10(-8) to 1.8 x 10(-4) M showed a corresponding increase of K(d) (l/g) up to a total concentration at 10(-6) M. At higher mercury concentrations K(d) was lowered. In the presence of fulvic acid the corresponding relationship of K(d) was bi-modal, i.e. high values at low and intermediate concentrations of mercury. This behaviour suggests that in the absence of fulvic acid the adsorption follow the expected behaviour, i.e. adsorption sites with similar affinity for mercury. In the presence of fulvic acid, additional adsorption sites are available by the organic molecule (possibly sulfur groups) when it is associated to the goethite. The adsorption isotherm for cadmium indicates a lowering of K(d) at 10(-4) M. Cadmium had no competitive effect on mercury and vice versa. Zinc, however, affected the adsorption of cadmium but not the adsorption of mercury.

Diurnal variations of abiotic parameters in a stream, recipient for drainage water in Ranstad, southwest Sweden.

During 24 h, water samples were taken for determination of a number of key parameters in a water system containing high concentrations of FeII at circumneutral pH. None of the major constituents (Ca, Mg, Na, K and sulfate) showed diurnal variations, while dissolved oxygen and pH increased during the night. This increase could entirely be explained by the decrease in water temperature. However, the concentration of FeII slightly increased at constant concentration of total Fe during the night, opposite to earlier observations in other systems where the presence of FeII was shown to be controlled by photoreduction. Nocturnal peaks of FeII have also been observed in other systems with high iron concentrations, however, at acidic pH, but without obvious explanation. The mechanisms for this process therefore need further investigation.