Chemosphere最新文献

Harmful cyanobacterial blooms (HCB_s) have become a common issue in freshwater worldwide. Biological methods for controlling HCB_s are relatively cost effective and environmentally friendly. The strain of ascomycete GF6 was isolated from a water sample collected from the estuarine zone of the eastern part of the Gulf of Finland. Based on cultural and morphological features and data of phylogenetic analysis, the strain was identified as Aspergillus welwitschiae GF6. The isolated GF6 strain has algicidal activity against both cyanobacteria and green algae. The highest sensitivity to the algicidal action of strain GF6 was found in cyanobacteria (98.5-100%). The algicidal effect on green algae did not exceed 63-70%. It was shown that GF6 strain exhibited an indirect attack mode by releasing metabolites that inhibit and/or degrade algal cells. In this study, significantly increased malondialdehyde content in Microcystis aeruginosa cells indicated that GF6 strain caused oxidative damage to the algal cell membrane. Enhanced production of phytosynthetic pigments, increase in lifetime chlorophyll a fluorescence and in the levels of antioxidants were noted in Microcystis aeruginosa cells. Besides this, GF6 strain could reduce the microcystins content in the medium under inhibiting the growth of M. aeruginosa. Apart from the growth inhibition and cell degradation of M. aeruginosa, GF6 strain is able to remove microcystin-LR (MC-LR). The content of MC-LR at an initial concentration of 0.51 μg/mL decreased by 61% after 72 h of A.welwitschiae GF6 strain cultivation. In the process of MC-LR biodestruction, transformation products were identified - the conjugate of microcystin with glutathione and the linearized form of MC-LR. The isolated strain with algicidal activity and the ability to degrade microcystin is of interest for further research in order to be able to use it for convergent technology to prevent the mass development of cyanobacteria and detoxification of cyanotoxins in water bodies.

The aim of this study was to estimate the 18-74 years old Portuguese population's baseline exposure to inorganic arsenic, cadmium and lead and the risk of exceeding the respective Health Based Guidance Value, using a harmonised Total Diet Study (TDS) methodology. TDS food samples representative of the whole diet were prepared as consumed and analysed for total arsenic, cadmium and lead. European Food Safety Authority's conservative approach was used to estimate inorganic arsenic. Exposure was assessed using the Monte Carlo Risk Assessment software. At upper bound approach, the mean baseline exposure was estimated at 0.28 and 0.35 μg kg^-1 body weight day^-1 for inorganic arsenic and lead, respectively, and 1.36 μg kg^-1 body weight week^-1 for cadmium. Margins of exposure of below or close to one were found for inorganic arsenic and lead, whereas 5.4 % of individuals exceeded the Tolerable Weekly Intake for cadmium. These results indicate that adverse health effects cannot be ruled out. Bread was the common main contributor for the exposure to all three elements.

Perfluorocarboxylic acids and perfluorosulfonic acids accumulate in food webs, thus posing a serious threat to food safety. The European Food Safety Authority (EFSA) derived a tolerable weekly intake (TWI) of 4.4 ng/kg body weight for the sum of the four so-called EFSA-PFAS in 2020. More sensitive analytical methods are urgently needed, not only to monitor maximum levels, but also for future toxicological assessments of these substances. Therefore, in the present study a dual SPE approach for the purification of the extracts was chosen to attain high and valid sensitivity for the matrices egg, liver, milk and dairy products using liquid chromatography coupled with tandem mass spectrometry. This method achieved limits of quantification of 2.60 (PFOS) - 6.80 ng/kg (PFHxS) for egg, 9.80 (PFOS) - 46.0 ng/kg (PFHxS) for liver and 0.165 (PFNA) - 0.455 ng/kg (PFOS) for milk for the 4 EFSA-PFAS. Summed medians for the 4 EFSA-PFAS of 396 ng/kg in bovine liver and 54.0 ng/kg in pork liver, as well as 8.46 ng/kg in cheese and 4.57 ng/kg in milk were detected. The results were subjected to correlation analysis. Statistically significant strong correlations were identified between bovine and porcine liver for PFNA, PFDA, PFUnDA and PFOS. To summarize the PFAS content and the PFAS spectrum detected depend on the animal species examined. Furthermore, an estimation of the exhaustion of the TWI for children, women and men was conducted. In our model, a TWI exhaustion of more than 27.0% (children) was calculated for liver, milk and cheese.

Cyanobacteria harmful algal blooms in lakes are primarily driven by nutrient and temperature conditions, yet the interplay of these abiotic factors with microbial community dynamics during bloom events is complex and challenging to unravel. Despite advances through deep sequencing approaches, the underlying transcriptomic changes occurring within blooming and non-blooming taxa remains an actively expanding area of study. In this work, we examined a spring-summer bloom event in Anderson Lake, WA, which has experienced recurring annual blooms dominated by the filamentous, anatoxin-a producing, diazotroph: Dolichospermum sp. WA102. Our data reveal the overall transcriptional dominance by Dolichospermum sp. WA102 during the bloom, initiated with increasing temperature and light intensity under high available phosphorus but low nitrogen conditions. We find that heterocyst differentiation was already transcriptionally initiated prior to the bloom, facilitating downstream gene cascades necessary for rapid nitrogen fixation and metabolism. As the bloom progresses, phosphorus becomes depleted, necessitating the expression of Pho regulon components in Dolichospermum sp. WA102 and possibly curtailing the bloom itself. We dissect toxin production and the transcriptional subtleties of the anatoxin-a synthesis locus. Additionally, co-occurring taxa exhibited distinct gene expression profiles, with competition for nutrients, light, and potential allelopathic interactions acting as drivers. Overall, our data provide a unique transcriptomic perspective on a single-taxa-driven, anatoxin-producing bloom, highlighting its competitive adaptation to nutrient acquisition and favorable conditions. This deeper understanding of the genetic mechanisms underlying algal bloom events may aid in predicting and preventing future blooms.

Anaerobic digestion (AD) offers great potential for pollutant removal and bioenergy recovery. However, it faces challenges when using livestock manure (LSM) as a feedstock given its high content of refractory materials (e.g., lignocellulose, long-chain carbohydrates, lipids, and crude protein). This would significantly inhibit AD-microbial activities, reduce organic transformation efficiency and limit gas production. To overcome this, multifunctional metal-doped hydrochars (HCs) were introduced here as AD supplements/accelerators, given that LSM degradation under AD results in complex dissolved organic matter (DOM). To assess this, the current study investigates the molecular interactions/transformations within DOM during LSM-AD coupled with metal-doped HCs, via batch-mode experiments. Expansive data mining techniques were employed to analyze DOM using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Substantial increments in peptide-like along with decrements in highly unsaturated-like molecules were observed in HC@MnCl₂ containing-system. This indicates an increased capability for substrate hydrolysis and potential utilization of soluble microbial products (SMPs) (i.e., highly unsaturated-like molecules), leading to enhanced methane recovery (223.23 mL/g-VS_added, 1.77 times more than the control). However, accumulation of DOM-highly unsaturated molecules (i.e., a lack of SMPs' degradation) accompanied with low methane production (39.68 mL/g-VS_added) was noticed for HC@NiFe₂O₄. DOM reactivity during LSM-AD was validated via paired mass difference molecular network, indicating predominance of CHO and N-containing groups' transformations for HC@MnCl₂ and HC@NiFe₂O₄, respectively. Potential metabolites and abundant pathways were verified via KEGG database. This study improves our understanding of LSM-AD-DOM complex transformation matrix, the fate of bioavailable/recalcitrant compounds, and identification of potential DOM regulators from thousands of molecules.

Tyre and road wear particles (TRWPs) are estimated to be the largest source of microplastics in the environment and due to the intrinsic use of tyres in our society this will continue to grow. Understanding their degradation mechanisms and subsequent accumulation over time is important to gain insights into the fate and impact of these particles in the environment. Accelerated UV-ageing was performed on cryomilled tyre tread particles and TRWPs from a road simulator to investigate the abiotic degradation of rubber. Degradation was followed with thermogravimetric analysis (TGA) that led to an average abiotic degradation rate of 0.025 day^-1 when corrected for the acceleration factor. Static light scattering (SLS) showed that during degradation, the average particle size reduced by 0.03 μm day^-1 and smaller particles <10 μm were formed. Further characterisation with scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDX) confirmed these findings and showed that the sulphur content is reduced through UV-ageing suggesting that crosslinking breakage may be a mechanism of degradation. Analysis with gas chromatography and mass spectrometry (GC-MS) showed a substantial decrease in chemical additives by UV-induced oxidation and breakdown. Finally, with measurements in the field TRWP particle sizes and accumulation times were studied, confirming the experimentally determined degradation mechanisms.

Laccases are of particular interest in addressing environmental challenges, such as the degradation of triphenylmethane (TPM) dyes, including crystal violet (CV) and Coomassie Brilliant Blue (CBB), which are commonly used in SDS-PAGE for protein visualization. However, these dyes present significant environmental concerns due to their resistance to degradation, which makes their removal from industrial wastewater a major challenge. To address this, the current study investigates the potential of a novel CotA laccase derived from Bacillus sp. PAMC28748, an Antarctic bacterial isolate, for decolorizing these stubborn dyes. The CotA gene was successfully cloned and expressed, and the enzyme demonstrated optimal activity at pH 3 and 50 °C, which favors its maximum catalytic performance. The recombinant Bacillus sp. PAMC28748 rBCLac effectively decolorized CBB without additional mediators, whereas the degradation of CV required the use of the redox mediator ABTS. With ABTS, over 90 % decolorization was achieved at a 0.35 % concentration of CV after 240 min of incubation. Further investigation through molecular docking studies revealed that hydrogen bonding and hydrophobic interactions between the enzyme and the dye molecules are critical for effective degradation, highlighting the enzyme's specific interaction mechanisms. In addition to its catalytic effectiveness, the study also demonstrated the practical potential of the rBCLac system by recovering and reusing both ABTS and rBCLac through ultracentrifugation and acetone precipitation. The process maintained over 75 % efficiency across three cycles, despite a slight decline in enzyme activity, thus showcasing the system's sustainability and reusability. These findings collectively suggest that rBCLac, isolated from an extreme Antarctic environment, holds considerable promise as a candidate for the removal of industrial wastewater containing persistent dyes, with the added potential for cost-effective and sustainable water treatment through the reuse of both the enzyme and its mediator.

Global concern regarding transformation products (TPs) derived from contaminants, including pesticides, in the environment and during water treatment has been growing markedly. In the present study, we investigated the anti-acetylcholinesterase (AChE) activity of an aqueous solution of the organophosphorus insecticide disulfoton, a toxicological endpoint for determining the acceptable daily intake of disulfoton, both in the presence and the absence of metabolism during chlorination. Disulfoton rapidly reacted with free chlorine and completely disappeared within 0.25 h. Although the aqueous disulfoton solution did not induce anti-AChE activity before chlorination, the chlorinated samples did induce anti-AChE activity, both with (indirect toxicity) and without (direct toxicity) metabolism. These observations clearly indicated that disulfoton was converted into toxic TPs through reactions with free chlorine. Liquid chromatographic fractionation followed by an anti-AChE activity assay revealed that three TPs were responsible for the observed direct toxicity. Further mass spectrometric analyses showed that these TPs were disulfoton-oxon-sulfone, and mono- and dichloro-substituted derivatives of disulfoton-oxon-sulfoxide (O-(1-chloroethyl) S-[2-(ethanesulfinyl)ethyl] O-ethyl phosphorothioate and O-(1,2-dichloroethyl) S-[2-(ethanesulfinyl)ethyl] O-ethyl phosphorothioate, respectively), none of which were simply oxon. Results of the anti-AChE activity assay on the chemical standard of disulfoton-oxon-sulfone after metabolism and quantification of the disulfoton-oxon-sulfone in the chlorinated samples revealed that the observed indirect toxicity was solely induced by this TP. It is recommend that drinking water treatment plants that use free chlorine as a disinfectant monitor the concentrations of at least disulfoton-oxon-sulfone, which is commercially available, in finished water in addition to disulfoton itself, to ensure the safety of tap water.

Excess biological sludge processing and disposal have a significant impact on the energy balance and economics of wastewater treatment operations, and on receiving environments. Anaerobic digestion is probably the most widespread in-plant sludge processing method globally, since it stabilizes and converts biosolids organic matter into biogas, allowing partial recovery of their embedded chemical energy. A considerable number of studies concerning applicable techniques to improve biogas production, both in quantity and quality, include pre-treatment strategies to promote biosolids disintegration aimed at the release and solubilization of intracellular energy compounds, inorganic/biological amendments aimed at improving process performance, and sludge thermal pre-treatment. As for in-process amendments, iron, micro and macro-nutrients, ashes from waste incineration and nanoparticles addition have been studied for the improvement of enzymatic reactions. Recently, use of electrically conductive materials has been credited with the possibility to accelerate and stabilize the conversion of organic substrates to methane. The possibility of increasing both biogas generation and its relative biomethane content by interfacing anaerobic digestion with bioelectrochemical systems was also postulated. This review addresses the research gap surrounding the integration of anaerobic digestion with novel technologies, particularly bioelectrochemical systems, to enhance biogas production and methane enrichment. While existing studies focus on pre-treatment and in-process amendments, the feasibility, mechanisms, and benefits of such integration remain underexplored. By critically evaluating the current state of the art, this review identifies the potential of bioelectrochemical integration to improve energy recovery and process stability, while highlighting key challenges and research needs for advancing these technologies toward practical implementation.

This research aims to design a novel selective and multifunctional adsorbent based on Al/Cu modified hemp fibres as a novel and multifunctional adsorbent for removing different classes of pollutants. The adsorbent, which was widely characterized, was shown to be more effective in removing anionic dyes compared to cationic ones. Among the tested dyes, methyl orange (MO) was selected to understand how different parameters, such as temperature (20-80 °C), contact time, pH (2-12), initial dye concentration (50-300 ppm), salinity and adsorbent dosage (1-10 g/L) affect the removal capacity. The Langmuir model greatly describes the adsorption data with a q_m = 338.98 mg/g. Thermodynamic calculation proved that the adsorption process is spontaneous (negative ΔG) and endothermic (positive enthalpy) while the adsorption process is governed by either film or pore diffusion. The Design of Experiment algorithm was adopted to predict the recovery of MO through a response surface model by varying simultaneously the pH, temperature and initial dye concentration, in accordance with the experimental data. It was demonstrated the multifunctional properties of the produced adsorbent since it showed a great selectivity in removing two anti-inflammatory drugs (91% for piroxicam and 34% for diclofenc sodium salt). Finally, the selective removal of different anionic dyes in a mixed solution was proved, following the order methyl orange>congo red>acid yellow 17. The reported approach presents a sustainable, low-cost option for the preparation of novel and effective adsorbents with interesting properties to achieve remarkable adsorption of anionic dyes and anti-inflammatory drugs with a great reusability.