To Örebro University

This study presents a comprehensive chemical and toxicological screening of chemicals extracted from WEEE (waste from electrical and electronic equipment) plastics. Chemical identification was conducted through suspect and target screening methods, revealing a diverse array of hazardous compounds including polycyclic aromatic compounds (PACs), organophosphate flame retardants (OPFRs), phthalates, benzotriazoles, and others. Toxicological endpoints included cell morphological phenotypes, inflammatory response, aryl hydrocarbon receptor (AhR) activation, activation of estrogenic receptor, and anti-androgenic activity. Results demonstrated that WEEE plastic chemicals significantly altered cell morphological phenotypes, particularly affecting the cytoskeleton, endoplasmic reticulum (ER), and mitochondrial measures. Moreover, WEEE chemicals induced inflammatory responses in resting human macrophages and altered ongoing inflammatory responses in lipopolysaccharide (LPS)-primed macrophages. Furthermore, WEEE chemicals exhibited potent AhR agonistic activity, activated estrogen receptor-α (ERα), and inhibited androgen receptor (AR) activation. The findings suggest that WEEE plastic chemicals exert their effects through multiple modes of action, targeting various subcellular sites. Thus, a combined approach utilizing non-target and target screening tools is essential for comprehensively assessing the toxic effects and health hazards associated with WEEE plastic chemicals.

A black substance exuding from fractures was observed in 2012 in Ytterby mine, Sweden, and identified in 2017 as birnessite with the composition Mx[Mn(III,IV)](2)O-4 center dot(H2O)n. M is usually calcium and sodium, with x around 0.5. The Ytterby birnessite is unique, with M being calcium, magnesium, and also rare earth elements (REEs) constituting up to 2% of the total metal content. The biogenic origin of the birnessite was established in 2018. Analysis of the microbial processes leading to the birnessite formation and the REE enrichment has continued since then. The process is fast and dynamic, as indicated by the depletion of manganese and of REE and other metals in the fracture water during the passage over the precipitation zone in the mine tunnel. Studies of the exchangeability of metals in the structure are the main objective of the present program. Exposure to solutions of sodium, calcium, lanthanum, and iron led to exchanges and altered distribution of the metals in the birnessite, however, generating phases with almost identical structures after the exchanges, and no new mineral phases were detected. Exchangeability was more efficient for trivalent elements (REE) over divalent (calcium) and monovalent (sodium) elements of a similar size (ionic radii 90-100 pm).

The influence of water hardness on copper (Cu) toxicity in Daphnia magna was studied using gene expression analysis. Exposing D. magna to Cu in water with increasing levels of hardness decreased the acute toxicity. Hardness did not affect the predicted Cu complexation. After 24 h, D. magna showed an increased level of genes related to metal homeostasis (mt) following exposure to 25 mu g Cu/L in hard water. Daphnids in soft and medium water responded to 25 mu g Cu/L by upregulation of antioxidant defense and mt genes, revealing oxidative stress as a mechanism of Cu toxicity in D. magna. D. magna exposed to 25 mu g Cu/L in soft water did not survive for 96 h. In contrast, those exposed to 25 mu g Cu/L in medium and hard water survived for 96 h with significantly higher levels of mt genes. The genes related to oxidative damage (heat shock protein and glutathione S-transferase) in these groups did not deviate from control levels, indicating the protective effect of hardness. Metallothionein genes were upregulated at 17 mu g Cu/L at both 24 h and 96 h. The expression of catalase and ferritin increased in this group in soft and hard water at 96 h. The protective effect of hardness (in the tested range) on survival was also observed at a concentration of 25 mu g/L. The results suggest metallothionein (A and B), catalase, and ferritin genes, as potential biomarkers for copper exposure in D. magna regardless of hardness.

Aqueous film-forming foams (AFFFs) are widely used to extinguish liquid fires due to their film-forming properties. AFFF formulation historically contains per- and polyfluoroalkyl substances (PFASs) that can be very persistent and pose a health risk to biota and humans. Detailed analysis of the chemical composition of AFFFs can provide a better understanding on the potential environmental impact of the ingredients. In this study, a novel workflow combining target analysis, nontarget screening analysis (NTA), total fluorine (TF) analysis, and inorganic fluoride (IF) analysis was applied to disclose the chemical composition of 24 foams intended for liquid fires. Foams marketed as containing PFASs as well as fluorine-free foams were included. By comparing the sum of targeted PFASs and total organofluorine concentrations, a mass balance of known and unknown organofluorine could be calculated. Known organofluorine accounted for <1% in most fluorine-containing AFFFs, and it was confirmed that the foams marketed as fluorine-free did not contain measurable amounts of organofluorine substances. Five fluorinated substances were tentatively identified, and non-fluorinated zwitterionic betaine compounds, which are considered to be replacement substances for PFASs, were tentatively identified in the organofluorine-free foams.

Uranium-stabilizing ligands can be useful complexing agents for uranium in aqueous solution. The discovery of novel ligand candidates for selective uranium capture in artificial and natural waters could provide scope for their use in water remediation and metal recovery from low- and high grade ores. In this study we used seven fungal strains, isolated from shale waste, to monitor the uranium retention capacity from an aqueous solution. After four weeks of incubation, suspensions containing the fungal strains were filtered, and up to 100% of the total uranium inventory was removed from a 10 mg L-1 solution. Approximately 70% of the total uranium removal is attributed to complexation and/or adsorption by particles in the malt extract and some 10% is adsorbed by the fungal biomass. The additional 20% uranium removed could be related to the excretion of fungal metabolites. From 58% to 90% of the uranium is removed within ten minutes. The formation of colloidal/particulate uranium is proposed to be controlled by organic ligands in the culture medium and organic ligands excreted by the fungi where phosphorus moieties seem to be important. Membrane fouling by the hydrocarbons is also suggested to contribute to a loss of uranium from the aqueous phase.

Silicon reduced Argon Oxygen Decarburization slag (Si-AOD) is a common by-product from manufacturing of stainless steel. In this work the possibility to use the slag as adsorbent for some selected metals (Cr, Ni, Cu, Zn and Pb) is tested. The slag was obtained from Outokumpu, Avesta, Sweden as one black, powder like, and one greenish, pumice-stone like. Due to its small grain size the black Si-AOD was not suitable as a filter material since it quickly clogged and formed almost impermeable layers. However, the greenish Si-AOD with its porous structure showed good permeability and seems to be good as a filter material. Its ability to remove the selected elements from an aqueous solution was tested at different metal concentrations, ionic strengths and pH. The absorption capacity was tested in columns each holding 30 gram of the greenish Si-AOD and 300 mL of the aqueous phase was passed through the material. Six fractions of 50 mL each were collected and analyzed with respect to pH and metal content to estimate the retention capacity. With an initial concentration of 10 mg/L (Ni, Cu and Zn) and 1 mg/L (Cr and Pb) an almost 100% adsorption was obtained. The adsorption seemed to follow the Freundlich adsorption isotherm and with a 1/n-value of 0.13 the adsorption process is probably chemical. The adsorption capacity of the surface was estimated to be at least 80 μeqv/g. Hence a liquid to solid ratio of up to 100 can be reached with the used metal solution before the retention capacity of the slag is depleted

Black shale was mined and processed for recovery of hydrocarbons in Kvarntorp, some 200 km SW of Stockholm, Sweden, during 1942–66. Remains from the mining period is a deposit with 40 Mm³ of crushed shale residues: Unprocessed 3ne-grained shale as well as processed shale. The deposit is still hot; oxidation of sulphides as well as burning of hydrocarbons are still in progress some 50 years a1er closure. Weathering of the shale leads to releases of metal-rich leachates which will increase with time. The release of metals from pristine shale as well as weathered shale (exposed to the atmosphere for 50 years) and two di2erent processed shale residues have been studied using water of di2erent pH as leaching solution, to simulate extreme pH-variations in environmental waters: 3.0 (determined by oxidation of iron sulphides), 5.5 (bu2ered by carbon dioxide), 8.5 (bu2ered by calcite) and 12.5 (bu2ered by calcium hydroxide). Extraction of cationic elements was substantial (several percent of the total content) for Ca and Mg, as well as Ni, Co and U at pH 3, and very high (up to 50–60 %) for anionic elements (V, Mo, As) at pH 12.5. Especially the high-temperature processed shale would be a potential source for As and Mo at high pH. The pH-dependence of the weathering processes should be considered when future remediation (or metal recovery) processes and strategies are designed.

Mining of black shale (alum shale) of Late Cambrium age for the extraction of alum started in the early 17th century in Sweden, and in the late 19th century there was an extensive use of shale, with its high content of organic carbon, as fuel in lime-burning processes. Full-scale recovery of hydrocarbons from shale took place in Kvarntorp during 1942-66, and recovery of uranium in Ranstad during 1965-76. Remains from the historic mining and processing of black shale are some 50 major deposits with processed and unprocessed shale residues, as well as water-filled pits, at the former mining sites. There are also large areas covered with crushed shale, e.g. as road filling material. Studies of the weathering of shale due to exposure to the atmosphere and water with pH within the natural range indicate a high leachability of cationic elements at low pH, as well as anionic elements at high pH. The presence of organic complexing acids of natural origin (microbial exudates and humic acids) may give an enhanced leaching, particularly at pH above 8, when hydroxy-groups would constitute active metal binding sites. Results from studies of weathering and leaching of processed and unprocessed black shale are presented, as well as the effects on the water quality observed at former mining sites and related environmental impact.

Analysis of dissolved metals in acid rock drainage (ARD) with an Agilent 4100 MP AES instrument that combines a nitrogen micro plasma with atomic emission detection (MP AES) was compared with an ICP-MS. Sample preparation consisted only of filtration, acidification (HNO3 1%) and addition of internal standard elements after appropriate dilution. In these complex matrices the systems gave identical results provided that care was taken to avoid ionization. This was easily done by addition of CsNO3 which eliminated the need for matrix matching of calibration solutions. The use of internal standards is only needed for elements with known spectral interferences.

Metal transport in small streams in boreal catchments is a function of weathering rate, water balance and redistribution mechanisms. Because of these highly dynamic processes long term water quality changes are difficult to determine but needed in order to assess the impact of several local and largescale changes on local water quality.

The field site is situated at Dyltabruk, some 20 km North of Örebro in South Central Sweden. The 4 km2 catchment has deciduous and coniferous species on a granitic moraine with some 20% ofmires and fens adjacent to the oldest sulphur mine in Sweden. Grab samples were collected weekly since 2006 but more frequent during periods with large changes in water balance. The samples were analysed for general hydrochemical parameters (temperature, electrical conductivity, pH, dissolved organic carbon (DOC), inorganic carbon (IC), fulvic and humic acids and dissolved oxygen), dissolved principal anions, principal and trace metals. Standardized analytical procedures were applied. Temperature, precipitation and other climatic parameters were recorded some 2 km from thesite every 15 minutes.

The results showed a general concentration pattern where the water balance had the largest single influence. The concentrations had a seasonality inversely related to the ground water level. Inter annual variations of one to two orders of magnitude were observed for group 1 and 2 elements. For transition metals with high affinity to solid matter as well as DOC the variation reached three to four orders of magnitude. Only aluminium and iron had concentrations that occasionally exceeded solubility limits which resulted in a similar inter annual variation.

During the study period the average annual temperature and precipitation were no different (p 0.05) from the previous ten years but rainfall intensities increased. In a long term perspective the concentrations for all metals except calcium had positive trends. The tendencies remained when normalizing against chloride. The same was found for DOC, nitrate and sulphate. Hence, there is an accelerating loss of most elements that is not limited by weathering. It is uncertain, however, if the positive trends for DOC depend on increased production or a balancing release from the supply in mires and fens. In addition, there is also an indication of increasing inter annual concentration changescwith time. Although not exclusively proven such phenome would occur as a result of increased rainfall intensity. It is therefore likely that the accelerating loss of elements is a result of increased weathering rather than increasing water discharge.

To establish vegetation on historical acidicmine waste and metal polluted soil has several environmental, physical and chemical advantages on metalrelease. Pot experiments with material from the Ljusnarsbergs mine waste deposit in Sweden showed that different kinds of refuse can be used to sustain germination and improve growth of Agrostiscapillariswhere it otherwise isimpossible. Bark compost increased the water holding capacity and an increase of pHin the top 50 mm by addition of water works granules made it possible for the grass to survive. An even better growth was obtained if those systems were also inoculated with mycorrhiza.

The use of nitrogen as plasma gas for microwave plasma atomic emission spectroscopy (MP AES) is an interesting development in analytical science since the running cost can be significantly reduced in comparison to the inductively coupled argon plasma. Here, we evaluate the performance of the Agilent 4100 MP AES instrument for the analysis of principal metals (Ca, K, Mg, and Na), lithogenic metals (Al, Fe, and Mn) and selected trace metals (As, Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, V, and Zn) in nitric acid plant digests. The digests were prepared by microwave-assisted dissolution of dry plant material from sunflower (Helianthus annuus) in concentrated nitric acid. Comparisons are made with analysis of the same solutions with ICP-MS (Agilent 7500cx) using the octopole reaction system (ORS) in the collision mode for As, Fe, and V.

The limits of detection were usually in the low μg L-1 range and all principal and lithogenic metals were successfully determined with the MP AES and provided almost identical results with the ICP-MS. The same applies for the selected trace metals except for As, Co and Mo where the concentrations were below the detection limit with the MP AES. For successful analysis we recommend that (i) only atom lines are used, (ii) ionization is minimized (e.g. addition of CsNO3) and (iii) the use of internal standards should be considered to resolve spectral interferences.

In order to establish plants on any kind of mine waste it is essential to determine its chemical properties, i.e. the potential to release elements. In this study we combine chemical extraction of six different solid metal species (water soluble, ion-exchangeable, carbonate, reducible, oxidizable acid leachable) on tailings from Zelazny Most, Poland. The results show that the plants encounter an environment with circumneutral pH and high availability of Ca, Na, and Cu. During reducing conditions there is also an increasing availability of As, Fe, Pb, and Zn.

Chemical and microlitter (ML) pollution in three Estonian coastal areas (Baltic Sea) was investigated using mussels (Mytilus trossulus). Polycyclic aromatic hydrocarbons (PAH) in mussel tissues were observed in moderate levels with high bioaccumulation factors for the more hydrophilic and low molecular weight PAH (LMW PAH), namely anthracene and fluorene. Tissue concentrations of polybrominated diphenyl ethers (PBDE) and cadmium within mussel populations exceeded the Good Environmental Status thresholds by more than 200% and 60%, respectively. Multiple contamination at the Muuga Harbour site by tributyltin, high molecular weight PAH, including the highly toxic benzo[c]fluorene and PBDE, coincided with the inhibition of acetylcholinesterase activity and a lower condition index of the mussels. The metabolization and removal of bioaccumulated LMW PAH, reflected in the dominance of oxy-PAH such as anthracene-9,10-dione, is likely associated with the increased activity of glutathione S-transferase in caged mussels. Only a few microplastic particles were observed among the ML in mussel tissues, with coloured cellulose-based microfibers being the most prevalent. The average concentration of ML in mussels was significantly higher at the harbour area than at other sites. The integrated biomarker response index values allowed for the differentiation of pollution levels across studied locations representing high, intermediate, and low pollution levels within the studied area.

This research evaluates the effect on herbal crops of mechanical stress induced by two specially developed robotic platforms. The changes in plant morphology, metabolite profiles, and element content are evaluated in a series of three empirical experiments, conducted in greenhouse and CNC growing bed conditions, for the case of basil plant growth. Results show significant changes in morphological features, including shortening of overall stem length by up to 40% and inter-node distances by up to 80%, for plants treated with a robotic mechanical stress-induction protocol, compared to control groups. Treated plants showed a significant increase in element absorption, by 20-250% compared to controls, and changes in the metabolite profiles suggested an improvement in plants' nutritional profiles. These results suggest that repetitive, robotic, mechanical stimuli could be potentially beneficial for plants' nutritional and taste properties, and could be performed with no human intervention (and therefore labor cost). The changes in morphological aspects of the plant could potentially replace practices involving chemical treatment of the plants, leading to more sustainable crop production.

Tire wear particles (TWP) stand out as a major contributor to microplastic pollution, yet their environmental impact remains inadequately understood. This study delves into the cocktail effects of TWP leachates, employing molecular, cellular, and organismal assessments on diverse biological models. Extracted in artificial seawater and analyzed for metals and organic compounds, TWP leachates revealed the presence of polyaromatic hydrocarbons and 4-tert-octylphenol. Exposure to TWP leachates (1.5 to 1000 mg peq L-1) inhibited algae growth and induced zebrafish embryotoxicity, pigment alterations, and behavioral changes. Cell painting uncovered pro-apoptotic changes, while mechanism-specific gene-reporter assays highlighted endocrine-disrupting potential, particularly antiandrogenic effects. Although heavy metals like zinc have been suggested as major players in TWP leachate toxicity, this study emphasizes water-leachable organic compounds as the primary causative agents of observed acute toxicity. The findings underscore the need to reduce TWP pollution in aquatic systems and enhance regulations governing highly toxic tire additives.

With this study, the removal mechanisms of arsenate by steel slag and its potential for treatment of contaminated water were elucidated. While original slag showed a poor fit to the Langmuir equation (R2 = 0.960), washed slag (the original slag is washed by low pH water solutions to remove readily soluble oxides) conformed better (R2 = 0.995). An initial pH of 2.0 give optimal adsorption, with a strong impact from the chemical speciation observed with highest efficiency for the fully protonated (OH)3AsO form. Adsorption capacity of the slag is 4.0 mg g−1, while together with precipitation the retention capacity reaches 13.7 mg g−1. However, removal by precipitation is a non-steady process due to re-dissolution of Ca3(AsO4)2(s). The washed slag shows a similar adsorption capacity to the original one but has not as strong alkaline properties. Batch experiment shows fast adsorption kinetics and column loading tests indicate an instant adsorption kinetics with 80 % As(V) removal for a 10 mg L−1 As(V) solution by 1.0 g of washed slag using a solution flowrate of 1 mL min−1. Common ions like sulfate, carbonate, chloride, iron(III), humic acid and fulvic acid do not significantly interfere with the removal efficiency. In combination with limited hazardous metals leaching, the slag is thus appropriate for use as a filter material for treatment of contaminated water and it has been successfully applied as filter material for treatment of arsenate spiked natural water sample with average removal efficiency of 84 % (solid to liquid ratio of 200).

Abatement of ARD with passive treatment systems can quite often rely only on pH-control if the iron content is high enough and to allow for the formation of ferric hydrous oxides, which act as efficient adsorbents. The stability of ferric hydrous oxides is sensitive to lowering of pH as well as Eh why they must be controlled. Hence, it would be favourable to use a well ordered adsorbent that is stable over time and under the chemical conditions of ARD. Municipal waste water sludge is a growing problem in many countries and incineration under oxidative conditions can be used to oxidize anthropogenic organic molecules which pose a threat to the environment. Sludge ashes rendering from wastewater treatment in which iron is used as a flocculation agent have high concentrations of calcium/ magnesium and ferric oxides, and should therefore, in theory be a suitable candidate for treatment of ARD. This study has therefore focused on the ability for these ashes to act as a sorbent for the removal of metals from ARD. The stability and potential release of metals from the material were quantified in batch experiments by extraction at pH 2-10, resulting in equilibrium concentrations (at pH 8) of 11.9, 0.08 and 24.1 mg L-1 for Al, Fe and Mn respectively. However, after washing with water the corresponding values were 0.01, 0.03 and 0.09 mgL(-1). In fact, after washing the sludge ash is stable from pH 4 to 10, with only slightly higher concentrations found at pH 2. Batch experiments on metal adsorption from ARD showed more than 99% sorption of Cr, Cu, Pb and V, corresponding values for Co, Ni and Zn were 56, 86 and 34% respectively. The overall results from this study show that sludge ashes are a promising solution for treatment of ARD.

Given the high efficiency in phosphorus removal at municipal wastewater treatment plants (MMWWTP), sewage sludge constitutes a promising resource for phosphorus (P) recovery. Sewage sludge is, however, a complex matrix and its direct use as fertiliser is limited by its content of metals/metalloids and organic pollutants. In order to increase its usability as a potential resource of P, there is a need for increased knowledge on phosphorus speciation in these matrices. The sludge composition is highly influenced by local conditions (i.e. wastewater composition and treatment method), and it is therefore important to study sludge from several MMWWTPs. In this study, three different protocols for sequential extraction were utilised to investigate the chemical speciation of phosphorus in sludge from three different MMWWTP sludges in Sweden, as well as in corresponding ashes following incineration. The results showed that the total amounts of phosphorus ranged from 26 to 32 mg g^-1 sludge (dry weight), of which 79-94% was inorganically bound (IP). In the sludge, 21-30% of the IP was associated with calcium (Ca-P), which is the preferred species for fertiliser production. Following incineration, this fraction increased to 54-56%, mainly due to transformation of iron-associated phosphorus (Fe-P), while aluminium-associated species of phosphorus (Al-P) remained unaltered. The results from this study confirm that incineration is a suitable treatment for sewage sludge in terms of potential phosphorus recovery.

Uranium contamination of soils and water is a worldwide problem due to geology or anthropogenic release such as mining, or use of inorganic fertilizers. In situ remediation of low and moderately contaminated sites is a complicated procedure due to the complex chemistry of uranium. This study demonstrates that at pH 3.5, a fungal strain isolated from unprocessed uranium bearing shale creates hydrochemical conditions that immobilize 97% of a total of 10 mg L^-1 dissolved uranium in a 0.20 μm pore system. The redistribution occurred within 10 minutes and remained for five weeks and just 12% of the inventory was retrieved in the biomass. Size exclusion chromatography of the dissolved phase identified organic substances in the range of more than 60 kD down to 100 D as a response to time of incubation. Geochemical modeling indicates formation of uranium-organic complexes where ligand size, coordination chemistry and their tendency to agglomerate determine the redistribution.

A greenhouse pot experiment was conducted to evaluate the feasibility of using Hieracium pilosella and soil microorganisms for phytostabilization of uranium-containing shale residues. Conductivity of leachates significantly decreased and pH increased when plants were grown on the substratum. H. pilosella has ability to change the hydrochemical parameters and to decrease the mobilization of uranium. Moreover, H. pilosella is able to accumulate significant amounts of uranium in the shoots.

Zinc is an essential trace metal required for the maintenance of multiple physiological functions. Due to this, organisms can experience both zinc deficiency and toxicity. Hardness is recognized as one of the main modifying physiochemical factors regulating zinc bioavailability. Therefore, the present study analyzed the effect of hardness on zinc toxicity using Daphnia magna. Endpoint parameters were acute-toxicity, development, reproduction, and expression data for genes involved in metal regulation and oxidative stress. In addition, the temporal expression profiles of genes during the initiation of reproduction and molting were investigated. Water hardness influenced the survival in response to exposures to zinc. A zinc concentration of 50μg/L in soft water (50 mg CaCO₃ /L) caused 73% mortality after 96h exposure, whereas the same zinc concentration in the hardest water did not cause any significant mortality. Moreover, increasing water hardness from 100 to 200mg CaCO₃ /L resulted in a reduced number of offspring. Fecundity was higher at first brood for groups exposed to higher Zn concentrations. The survival data was used to assess the precision of the bioavailability models (Bio-met) and the geochemical model (Visual MINTEQ). As the Bio-met risk predictions overestimated the Zn toxicity, a competition-based model to describe the effects of hardness on zinc toxicity is proposed. This approach can be used to minimize differences in setting environmental quality standards. Moreover, gene expression data showed that using the toxicogenomic approach was more sensitive than the physiological endpoints. Therefore, data presented in the study can be used to improve risk assessment for zinc toxicity.