Uranium Repartitioning during Microbial Driven Reductive Transformation of U(VI)-Sorbed Schwertmannite and Jarosite.

This study exposes U(VI)-sorbed schwertmannite and jarosite to biotic reductive incubations under field-relevant conditions and examines the changes in aqueous and solid-phase speciation of U, Fe, and S as well as associated microbial communities over 180 days. The chemical, X-ray absorption spectroscopy, X-ray diffraction, and microscopic data demonstrated that the U(VI)-sorbed schwertmannite underwent a rapid reductive dissolution and solid-phase transformation to goethite, during which the surface-sorbed U(VI) was partly reduced and mostly repartitioned to monomeric U(VI)/U(IV) complexes by carboxyl and phosphoryl ligands on biomass or organic substances. Furthermore, the microbial data suggest that these processes were likely driven by the consecutive developments of fermentative and sulfate- and iron- reducing microbial communities. In contrast, the U(VI)-sorbed jarosite only stimulated the growth of some fermentative communities and underwent very limited reductive dissolution and thus, remaining in its initial state with no detectable mineralogical transformation and solid-phase U reduction/repartitioning. Accordingly, these two biotic incubations did not induce increased risk of U reliberation to the aqueous phase. These findings have important implications for understanding the interactions of schwertmannite/jarosite with microbial communities and colinked behavior and fate of U following the establishment of reducing conditions in various acidic and U-rich settings.

Cumulative Impacts of Oil Pollution, Ocean Warming, and Coastal Freshening on the Feeding of Arctic Copepods.

The Arctic is undergoing rapid changes, and biota are exposed to multiple stressors, including pollution and climate change. Still, little is known about their joint impact. Here, we investigated the cumulative impact of crude oil, warming, and freshening on the copepod species Calanus glacialis and Calanus finmarchicus. Adult females were exposed to ambient conditions (control; 0 °C + 33 psu) and combined warming and freshening: 5 °C + 27 psu (Scenario 1), 5 °C + 20 psu (Scenario 2) for 6 days. All three conditions were tested with and without dispersed crude oil. In Scenario 1, fecal pellet production (FPP) significantly increased by 40-78% and 42-122% for C. glacialis and C. finmarchicus, respectively. In Scenario 2, FPP decreased by 6-57% for C. glacialis, while it fluctuated for C. finmarchicus. For both species, oil had the strongest effect on FPP, leading to a 68-83% reduction. This overshadowed the differences between climatic scenarios. All variables (temperature, salinity, and oil) had significant single effects and several joint effects on FPP. Our results demonstrate that Arctic copepods are sensitive to environmentally realistic concentrations of crude oil and climate change. Strong reductions in feeding can reduce the copepods' energy content with potential large-scale impacts on the Arctic marine food web.

Influence of water hardness on zinc toxicity in Daphnia magna.

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 50 µg/l in soft water (50 mg CaCO3 /L) caused 73% mortality after 96 h exposure, whereas the same zinc concentration in the hardest water did not cause any significant mortality. Moreover, increasing water hardness from 100 to 200 mg 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 were 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.

Phosphorus speciation in sewage sludge from three municipal wastewater treatment plants in Sweden and their ashes after incineration.

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.

Characterization of the Chemical Contents of Fluorinated and Fluorine-Free Firefighting Foams Using a Novel Workflow Combining Nontarget Screening and Total Fluorine Analysis.

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.

Cocktail effects of tire wear particles leachates on diverse biological models: A multilevel analysis.

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.

A case study on microlitter and chemical contaminants: Assessing biological effects in the southern coast of the Gulf of Finland (Baltic sea) using the mussel Mytilus trossulus as a bioindicator.

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.

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.

Development of novel robotic platforms for mechanical stress induction, and their effects on plant morphology, elements, and metabolism.

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.

Microbiomes in a manganese oxide producing ecosystem in the Ytterby mine, Sweden: impact on metal mobility.

Microbe-mediated precipitation of Mn-oxides enriched in rare earth elements (REE) and other trace elements was discovered in tunnels leading to the main shaft of the Ytterby mine, Sweden. Defining the spatial distribution of microorganisms and elements in this ecosystem provide a better understanding of specific niches and parameters driving the emergence of these communities and associated mineral precipitates. Along with elemental analyses, high-throughput sequencing of the following four subsystems were conducted: (i) water seeping from a rock fracture into the tunnel, (ii) Mn-oxides and associated biofilm; referred to as the Ytterby Black Substance (YBS) biofilm (iii) biofilm forming bubbles on the Mn-oxides; referred to as the bubble biofilm and (iv) fracture water that has passed through the biofilms. Each subsystem hosts a specific collection of microorganisms. Differentially abundant bacteria in the YBS biofilm were identified within the Rhizobiales (e.g. Pedomicrobium), PLTA13 Gammaproteobacteria, Pirellulaceae, Hyphomonadaceae, Blastocatellia and Nitrospira. These taxa, likely driving the Mn-oxide production, were not detected in the fracture water. This biofilm binds Mn, REE and other trace elements in an efficient, dynamic process, as indicated by substantial depletion of these metals from the fracture water as it passes through the Mn deposit zone. Microbe-mediated oxidation of Mn(II) and formation of Mn(III/IV)-oxides can thus have considerable local environmental impact by removing metals from aquatic environments.

Metal contaminated soil leachates from an art glass factory elicit stress response, alter fatty acid metabolism and reduce lifespan in Caenorhabditis elegans.

The present study evaluated the toxicity of metal contamination in soils from an art glass factory in Småland Sweden using a Caenorhabditis elegans nematode model. The aim of the study was to chemically analyze the soil samples and study the biological effects of water-soluble leachates on the nematodes using different physiological endpoints. The total metal content showed that As, Cd and Pb were at levels above the guideline values for soils in areas around the factory. Less than 10% of the total metal content in the soil was found in the water-soluble leachates, however, Al, As, Fe and Pb remained higher than the guideline values for safe drinking water. Exposure of C. elegans to the water-soluble leachates, at both post-hatching larvae stage (L1-young adult) for 48 h and at the young adult stage (L4) for 6 h, showed significant gene alteration. Although the nematodes did not exhibit acute lethality, lifespan was significantly reduced upon exposure. C. elegans also showed altered gene expression associated with stress response and fat metabolism, as well as enhanced accumulation of body fat. The study highlighted the significance of assessing environmental samples using a combination of gene expression analysis, fatty acid metabolism and lifespan for providing valuable insight into the negative impact of metals. The altered fat metabolism and reduced lifespan on exposure to soil leachates motivates further studies to explore the mechanism of the toxicity associated with the metals present in the environment.

Comparison of MP AES and ICP-MS for analysis of principal and selected trace elements in nitric acid digests of sunflower (Helianthus annuus).

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.

Conditioning sulfidic mine waste for growth of Agrostis capillaris--impact on solution chemistry.

Contamination of the environment due to mining and mineral processing is an urgent problem worldwide. It is often desirable to establish a grass cover on old mine waste since it significantly decreases the production of leachates. To obtain sustainable growth, it is often necessary to improve several properties of the waste such as water-holding capacity, nutrient status, and toxicity. This can be done by addition of organic materials such as wood residues, e.g., compost. In this study, we focus on the solution chemistry of the leachates when a substrate containing historic sulfidic mine waste mixed with 30 % (volume) bark compost is overgrown by Agrostis capillaris. The pot experiments also included other growth-promoting additives (alkaline material, mycorrhiza, and metabolizable carbon) to examine whether a more sustainable growth could be obtained. Significant changes in the plant growth and in the leachates composition were observed during 8 weeks of growth. It was concluded that in this time span, the growth of A. capillaris did not affect the composition of the leachates from the pots. Instead, the composition of the leachates was determined by interactions between the bark compost and the mine waste. Best growth of A. capillaris was obtained when alkaline material and mycorrhiza or metabolizable carbon was added to the substrate.