Visible light photocatalytic antibacterial activity of Ni-doped and N-doped TiO<Subscript>2</Subscript> on <Emphasis Type="Italic">Staphylococcus aureus</Emphasis> and <Emphasis Type="Italic">Escherichia coli</Emphasis> bacteria

The Ni-doped and N-doped TiO₂ nanoparticles were investigated for their antibacterial activities on Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) bacteria. Their morphological features and characteristics such as particle size, surface area, and visible light absorbing capacity were compared and discussed. Scanning electron microscopy, X-ray diffraction, and UV–visible spectrophotometry were used to characterize both materials. The inactivation of E. coli (as an example of Gram-negative bacteria) and S. aureus (as an example of Gram-positive bacteria) with Ni-doped and N-doped TiO₂ was investigated in the absence and presence of visible light. Antibacterial activity tests were conducted using undoped, Ni-doped, and N-doped TiO₂. The N-doped TiO₂ nanoparticles show higher antibacterial activity than Ni-doped TiO₂. The band gap narrowing of N-doped TiO₂ can induce more visible light absorption and leads to the superb antibacterial properties of this material. The complete inactivation time for E. coli at an initial cell concentration of 2.7?×?10⁴ CFU/mL was 420 min which is longer than the 360 min required for S. aureus inactivation. The rate of inactivation of S. aureus using the doped TiO₂ nanoparticles in the presence of visible light is greater than that of E. coli. The median lethal dose (LD50) values of S. aureus and E. coli by antibacterial activity under an 18-W visible light intensity were 80 and 350 mg/ml for N-doped TiO₂, respectively.     

Green synthesis and characterization of gold and silver nanoparticles using <Emphasis Type="Italic">Mussaenda glabrata</Emphasis> leaf extract and their environmental applications to dye degradation

Plant-derived nanomaterials opened a green approach in solving the current environment issues. Present study focused on rapid microwave-assisted synthesis and applications of gold and silver nanoparticles mediated by aqueous leaf extract of Mussaenda glabrata. The synthesized nanoparticles were characterized by UV-vis, FT-IR, powder XRD, energy-dispersive X-ray spectroscopy (EDX), transmission electron (TEM), and atomic force microscopic techniques (AFM). FCC crystal structure of both nanoparticles was confirmed by peaks corresponding to (111), (200), (220), and (311) planes in XRD spectra and bright circular spots in SAED pattern. IC₅₀ values shown by gold and silver nanoparticles (44.1 ± 0.82 and 57.92 ± 1.33 μg/mL) reflected their high free radical scavenging potential. The synthesized gold and silver nanoparticles revealed their potency to inhibit pathogenic microorganisms Bacillus pumilus, Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, Aspergillus niger, and Penicillium chrysogenum. Anthropogenic pollutants rhodamine B and methyl orange were effectively degraded from aquatic environment and waste water sewages of dye industries using the prepared nanocatalysts. The catalytic capacities of the synthesized nanoparticles were also exploited in the reduction of 4-nitrophenol.

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Graphical abstract

     

Physiological and biochemical responses of <Emphasis Type="Italic">Machilus ichangensis</Emphasis> Rehd. et Wils and <Emphasis Type="Italic">Taxus chinensis</Emphasis> (Pilger) Rehd. to elevated O<Subscript>3</Subscript> in subtropical China

Considerable researches have documented the negative effects of ozone on woody species in North America and Europe; however, little is known about how woody tree species respond to elevated O₃ in subtropical China, and most of the previous studies were conducted using pot experiment. In the present study, Machilus ichangensis Rehd. et Wils (M. ichangensis) and Taxus chinensis (Pilger) Rehd. (T. chinensis), evergreen tree species in subtropical China, were exposed to non-filtered air (NF), 100 nmol mol^?1 O₃ (E1) and 150 nmol mol^?1 O₃ (E2), in open-top chambers under field conditions from 21st March to 2nd November 2015. In this study, O₃ fumigation significantly reduced net photosynthesis rate (Pn) in M. ichangensis in the three measurements and in T. chinensis in the last measurement. Also, non-stomatal factors should be primarily responsible for the decreased Pn. O₃ fumigation-induced increase in malondialdehyde, superoxide dismutase, and reduced ascorbic acid levels indicated that antioxidant defense mechanism had been stimulated to prevent O₃ stress and repair the oxidative damage. Yet, the increase of antioxidant ability was not enough to counteract the harm of O₃ fumigation. Because of the decrease in CO₂ assimilation, the growth of the two tree species was restrained ultimately. The sensitivity of the two tree species to O₃ can be determined: M. ichangensis > T. chinensis. It suggests a close link between the rising O₃ concentrations and the health risk of some tree species in subtropics in the near future.     

Enhanced UV-B and Elevated CO<Subscript>2</Subscript> Impacts Sub-Arctic Shrub Berry Abundance,Quality and Seed Germination

This study investigated the effects of long-term-enhanced UV-B, and combined UV-B with elevated CO₂ on dwarf shrub berry characteristics in a sub-arctic heath community. Germination of Vaccinium myrtillus was enhanced in seeds produced at elevated UV-B, but seed numbers and berry size were unaffected. Elevated UV-B and CO₂ stimulated the abundance of V. myrtillus berries, whilst UV-B alone stimulated the berry abundance of V. vitis-idaea and Empetrum hermaphroditum. Enhanced UV-B reduced concentrations of several polyphenolics in V. myrtillus berries, whilst elevated CO₂ increased quercetin glycosides in V. myrtillus, and syringetin glycosides and anthocyanins in E. hermaphroditum berries. UV-B × CO₂ interactions were found for total anthocyanins, delphinidin-3-hexoside and peonidin-3-pentosidein in V. myrtillus berries but not E. hermaphroditum. Results suggest positive impacts of UV-B on the germination of V. myrtillus and species-specific impacts of UV-B × elevated CO₂ on berry abundance and quality. The findings have relevance and implications for human and animal consumers plus seed dispersal and seedling establishment.     

Single and combined effects of aluminum (Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) and zinc (ZnO) oxide nanoparticles in a freshwater fish, <Emphasis Type="Italic">Carassius auratus</Emphasis>

The increasing use of nanoparticles (NPs) worldwide has raised some concerns about their impact on the environment. The aim of the study was to assess the toxicity of metal oxide nanoparticles, singly or combined, in a freshwater fish (Carassius auratus). The fish were exposed for 7, 14, and 21 days to different concentrations of NPs (10 μg Al₂O₃.L^?1, 10 μg ZnO.L^?1, 10 μg Al₂O₃.L^?1 plus 10 μg ZnO.L^?1, 100 μg Al₂O₃.L^?1, 100 μg ZnO.L^?1, and 100 μg Al₂O₃.L^?1 plus 100 μg ZnO.L^?1). At the end of each exposure period, antioxidant enzyme activity (catalase, glutathione-S-transferase, and superoxide dismutase), lipid peroxidation, and histopathology were assessed in the gills and livers of C. auratus. The results show an increase in catalase (CAT) and superoxide dismutase (SOD) activity in the gills and livers of fish, especially after 14 days of exposure to single and combined NPs, followed by a reduction at 21 days. An increase in glutathione S-transferase (GST) was observed in gills after 7 days for all tested NP concentrations (single and combined); while in livers, a significant increase was determined after 14 days of exposure to 100 μg.L^?1 of both single ZnO and Al₂O₃ NPs. Lipid peroxidation (LPO) significantly increased in gills after 7 days of exposure to 100 μg.L^?1 Al₂O₃ NPs (single or combined). In livers, LPO increased significantly after 7 days of exposure to all tested concentrations of both single ZnO and Al₂O₃ (except for 10 μg Al₂O₃.L^?1), and after 14 days of exposure to ZnO (10 and 100 μg.L^?1) and Al₂O₃ (100 μg.L^?1)_. The results from histological observations suggest that exposure to metal oxide NPs affected both livers and gills, presenting alterations such as gill hyperplasia and liver degeneration. However, the most pronounced effects were found in gills. In general, this study shows that the tested NPs, single or combined, are capable of causing sub-lethal effects on C. auratus, but when combined, NPs seem to be slightly more toxic than when added alone.     

Synergetic effects of Sr-doped CuBi<Subscript>2</Subscript>O<Subscript>4</Subscript> catalyst with enhanced photoactivity under UVA– light irradiation

Sr-doped CuBi₂O₄ micro-particles were successively synthesized via a solid-state technique and were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), and UV–vis diffuse reflectance spectroscopy (UV–vis-DRS) techniques. Results show that Sr-doped CuBi₂O₄ was crystallized with a spinel-type structure and tetragonal crystal system, and the band gap energy was about 1.35 eV. The as-prepared Sr-doped CuBi₂O₄ treated at 573 °C for 12 h exhibited the highest efficiency, as a result of 97.22 % of CR degradation within 220 min, which is approximately 31 times greater than CR photodegradation when catalyzed by CuBi₂O₄ (3.13 %) and about 2.3 times superior than that catalyzed by the untreated Sr–doped CuBi₂O₄ sample (42.08 %). Pseudo-first-order kinetic model gave the best fit, with highest correlation coefficients (R ²?=?0.94–0.97). The Sr–doping and extending reaction time up to 12 h could be effective in producing Sr-doped CuBi₂O₄ materials that delay electron–hole recombination, thereby increasing the lifetime of the electron electron–hole separation and support the charge carrier transfer to the catalyst surface. On the basis of the calculated energy band positions, superoxide radical anions (O₂ ^?–) were the main oxidative species responsible for the photocatalytic degradation of CR dye solution.     

Effects of realistic concentrations of TiO<Subscript>2</Subscript> and ZnO nanoparticles in <Emphasis Type="Italic">Prochilodus lineatus</Emphasis> juvenile fish

The impact of nanoparticles on fish health is still a matter of debate, since nanotechnology is quite recent. In this study, freshwater benthonic juvenile fish Prochilodus lineatus were exposed through water to three concentrations of TiO₂ (0.1, 1, and 10 μg l^?1) and ZnO (7, 70, and 700 μg l^?1) nanoparticles, as well as to a mixture of both (TiO₂ 1 μg l^?1?+?ZnO 70 μg l^?1) for 5 and 30 days. Nanoparticle characterization revealed an increase of aggregate size in the function of concentration, but suspensions were generally stable. Fish mortality was high at subchronic exposure to 70 and 700 μg l^?1 of ZnO. Nanoparticle exposure led to decreased acetylcholinesterase activity either in the muscle or in the brain, depending on particle composition (muscle—TiO₂ 10 μg l^?1; brain—ZnO 7 and 700 μg l^?1), and protein oxidative damage increased in the brain (ZnO 70 μg l^?1) and gills (ZnO 70 μg l^?1 and mixture) but not in the liver. Exposed fish had more frequent alterations in the liver (necrosis, vascular congestion, leukocyte infiltration, and basophilic foci) and gills (hyperplasia and epithelial damages, e.g., epithelial disorganization and epithelial loss) than the control fish. Thus, predicted concentrations of TiO₂ and ZnO nanoparticles caused detectable effects on P. lineatus that may have important consequences to fish health. But, these effects are much more subtle than those usually reported in the scientific literature for high concentrations or doses of metal nanoparticles.     

Monitoring an outdoor smoking area by means of PM<Subscript>2.5</Subscript> measurement and vegetal biomonitoring

The extension of pollutant accumulation in plant leaves associated with its genotoxicity is a common approach to predict the quality of outdoor environments. However, this approach has not been used to evaluate the environmental quality of outdoor smoking areas. This study aims to evaluate the effects of environmental tobacco smoke (ETS) by assessing particulate matter 2.5 μm (PM_2.5) levels, the pollen abortion assay, and trace elements accumulated in plant leaves in an outdoor smoking area of a hospital. For this, PM_2.5 was measured by active monitoring with a real time aerosol monitor for 10 days. Eugenia uniflora trees were used for pollen abortion and accumulated element assays. Accumulated elements were also assessed in Tradescantia pallida leaves. The median concentration of PM_2.5 in the smoking area in all days of monitoring was 66 versus 34 μg/m³ in the control area (P?<?0.001). In addition, the elements Al, Cd, Cu, Ni, Pb, Rb, Sb, Se, and V in Tradescantia pallida and Al, Ba, Cr, Cu, Fe, Mg, Pb, and Zn in Eugenia uniflora were in higher concentration in the smoking area when compared to control area. Smoking area also showed higher rate of aborted grains (26.1?±?10.7 %) compared with control (17.6?±?4.5 %) (P?=?0.003). Under the study conditions, vegetal biomonitoring proved to be an effective tool for assessing ETS exposure in outdoor areas. Therefore, vegetal biomonitoring of ETS could be a complement to conventional analyses and also proved to be a cheap and easy-handling tool to assess the risk of ETS exposure in outdoor areas.     

Investigation of low-level <Superscript>242</Superscript>Pu contamination on nutrition disturbance and oxidative stress in <Emphasis Type="Italic">Solanum tuberosum</Emphasis> L.

Plutonium associated with higher molecular weight molecules is presumed to be poorly mobile and hardly plant available. In our present study, we investigate the uptake and effects of Pu treatments on Solanum tuberosum plants in amended Hoagland medium at concentrations of [²⁴²Pu] = 100 and 500 nm, respectively. We found a direct proof of oxidative stress in the plants caused by these rather low concentrations. For the confirmation of oxidative stress, we explored the production of nitric oxide (NO) and hydrogen peroxide (H₂O₂) by epifluorescence microscopy. Oxidative stress markers like lipid peroxidation and superoxide radicals (O₂ ^??) are monitored through histochemical analysis. The biochemical parameters i.e. chlorophyll and carotenoids are measured as an indicator of cellular damage in the tested plants including the enzymatic parameters such as catalase and glutathione reductase. From our work, we conclude that Pu in low concentration has no significant effects on the uptake of many trace and macroelements. In contrast, the content of O₂ ^?? , malondialdehyde (MDA), and H₂O₂ increases with increasing Pu concentration in the solution, while the opposite effects was found for NO, catalase, and glutathione reductase. These findings prove that even low concentration of Pu regulates ROS production and generate oxidative stress in S. tuberosum L.     

Triclocarban: UV photolysis,wastewater disinfection,and ecotoxicity assessment using molecular biomarkers

Triclocarban (TCC) is an antibacterial agent found in pharmaceuticals and personal care products (PPCP). It is potentially bioaccumulative and an endocrine disruptor, being classified as a contaminant of emerging concern (CEC). In normal uses, approximately 96% of the used TCC can be washed down the drain going into the sewer system and eventually enter in the aquatic environment. UV photolysis can be used to photodegrade TCC and ecotoxicity assays could indicate the photodegradation efficiency, since the enormous structural diversity of photoproducts and their low concentrations do not always allow to identify and quantify them. In this work, the TCC was efficiently degraded by UVC direct photolysis and the ecotoxicity of the UV-treated mixtures was investigated. Bioassays indicates that Daphnia similis (48 h EC₅₀ = 0.044 μM) was more sensitive to TCC than Pseudokirchneriella subcapitata (72 h IC₅₀ = 1.01 μM). TCC and its photoproducts caused significant effects on Eisenia andrei biochemical responses (catalase and glutathione-S-transferase); 48 h was a critical exposure time, since GST reached the highest activity values. UVC reduced the TCC toxic effect after 120 min. Furthermore, TCC was photodegraded in domestic wastewater which was simultaneously disinfected for total coliform bacterial (TCB) (360 min) and Escherichia coli (60 min).

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Graphical abstract TCC degradation and ecotoxicological assessment

     

Experimental investigation of performance and emissions of a VCR diesel engine fuelled with <Emphasis Type="Italic">n</Emphasis>-butanol diesel blends under varying engine parameters

The continuous rise in the cost of fossil fuels as well as in environmental pollution has attracted research in the area of clean alternative fuels for improving the performance and emissions of internal combustion (IC) engines. In the present work, n-butanol is treated as a bio-fuel and investigations have been made to evaluate the feasibility of replacing diesel with a suitable n-butanol-diesel blend. In the current research, an experimental investigation was carried out on a variable compression ratio CI engine with n-butanol-diesel blends (10–25% by volume) to determine the optimum blending ratio and optimum operating parameters of the engine for reduced emissions. The best results of performance and emissions were observed for 20% n-butanol-diesel blend (B20) at a higher compression ratio as compared to diesel while keeping the other parameters unchanged. The observed deterioration in engine performance was within tolerable limits. The reductions in smoke, nitrogen oxides (NO _x ), and carbon monoxide (CO) were observed up to 56.52, 17.19, and 30.43%, respectively, for B20 in comparison to diesel at rated power. However, carbon dioxide (CO₂) and hydrocarbons (HC) were found to be higher by 17.58 and 15.78%, respectively, for B20. It is concluded that n-butanol-diesel blend would be a potential fuel to control emissions from diesel engines.

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Graphical abstract ?

     

<Emphasis Type="Italic">Ailanthus Altissima</Emphasis> and <Emphasis Type="Italic">Phragmites Australis</Emphasis> for chromium removal from a contaminated soil

The comparative effectiveness for hexavalent chromium removal from irrigation water, using two selected plant species (Phragmites australis and Ailanthus altissima) planted in soil contaminated with hexavalent chromium, has been studied in the present work. Total chromium removal from water was ranging from 55 % (Phragmites) to 61 % (Ailanthus). After 360 days, the contaminated soil dropped from 70 (initial) to 36 and 41 mg Cr/kg (dry soil), for Phragmites and Ailanthus, respectively. Phragmites accumulated the highest amount of chromium in the roots (1910 mg Cr/kg_{(dry tissue)}), compared with 358 mg Cr/kg_{(dry tissue)} for Ailanthus roots. Most of chromium was found in trivalent form in all plant tissues. Ailanthus had the lowest affinity for Cr^VI reduction in the root tissues. Phragmites indicated the highest chromium translocation potential, from roots to stems. Both plant species showed good potentialities to be used in phytoremediation installations for chromium removal.     

Effects of sewage sludge fertilizer on heavy metal accumulation and consequent responses of sunflower (<Emphasis Type="Italic">Helianthus annuus</Emphasis>)

Use of sewage sludge, a biological residue produced from sewage treatment processes in agriculture, is an alternative disposal technique of waste. To study the usefulness of sewage sludge amendment for Helianthus annuus, a pot experiment was conducted by mixing sewage sludge at 2.5, 5, and 7.5 % (w/w) amendment ratios to the agricultural soil. Soil pH decreased whereas electrical conductivity, organic matter, total N, available P, and exchangeable Na, K, and Ca increased in soil amended with sewage sludge in comparison to unamended soil. Sewage sludge amendment led to significant increase in Pb, Ni, Cu, Cr, and Zn concentrations of soil. The increased concentration of heavy metals in soil due to sewage sludge amendment led to increases in shoot and root concentrations of Cr, Cu, Ni, and Zn in plant as compared to those grown on unamended soil. Accumulation was more in roots than shoots for most of the heavy metals. Moreover, high metal removal for the harvestable parts of the crops was recorded. Sewage sludge amendment increased root and shoot length, leaves number, biomass, and antioxidant activities of sunflower. Significant increases in the activities of antioxidant enzymes and in the glutathione, proline, and soluble sugar content in response to amendment with sewage sludge may be defense mechanisms induced in response to heavy metal stress.

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Graphical abstract Origin, fate and behavior of sewage sludge fertilizer

     

Evaluation of the giant reed (<Emphasis Type="Italic">Arundo donax</Emphasis>) in horizontal subsurface flow wetlands for the treatment of recirculating aquaculture system effluent

Introduction

Two emergent macrophytes, Arundo donax and Phragmites australis, were established in experimental subsurface flow, gravel-based constructed wetlands (CWs) receiving untreated recirculating aquaculture system wastewater.

Materials and methods

The hydraulic loading rate was 3.75 cm day^?1. Many of the monitored water quality parameters (biological oxygen demand [BOD], total suspended solids [TSS], total phosphorus [TP], total nitrogen [TN], total ammoniacal nitrogen [TAN], nitrate nitrogen [NO₃], and Escherichia coli) were removed efficiently by the CWs, to the extent that the CW effluent was suitable for use on human food crops grown for raw produce consumption under Victorian state regulations and also suitable for reuse within aquaculture systems.

Results and discussion

The BOD, TSS, TP, TN, TAN, and E. coli removal in the A. donax and P. australis beds was 94%, 67%, 96%, 97%, 99.6%, and effectively 100% and 95%, 87%, 95%, 98%, 99.7%, and effectively 100%, respectively, with no significant difference (p?>?0.007) in performance between the A. donax and P. australis CWs. In this study, as expected, the aboveground yield of A. donax top growth (stems + leaves) (15.0?±?3.4 kg wet weight) was considerably more than the P. australis beds (7.4?±?2.8 kg wet weight). The standing crop produced in this short (14-week) trial equates to an estimated 125 and 77 t ?ha^?1 year^?1 biomass (dry weight) for A. donax and P. australis, respectively (assuming that plant growth is similar across a 250-day (September–April) growing season and a single-cut, annual harvest).

Conclusion

The similarity of the performance of the A. donax- and P. australis-planted beds indicates that either may be used in horizontal subsurface flow wetlands treating aquaculture wastewater, although the planting of A. donax provides additional opportunities for secondary income streams through utilization of the energy-rich biomass produced.

     

Inhibition of residual <Emphasis Type="Italic">n</Emphasis>-hexane in anaerobic digestion of lipid-extracted microalgal wastes and microbial community shift

Converting lipid-extracted microalgal wastes to methane (CH₄) via anaerobic digestion (AD) has the potential to make microalgae-based biodiesel platform more sustainable. However, it is apparent that remaining n-hexane (C₆H₁₄) from lipid extraction could inhibit metabolic pathway of methanogens. To test an inhibitory influence of residual n-hexane, this study conducted a series of batch AD by mixing lipid-extracted Chlorella vulgaris with a wide range of n-hexane concentration (～10 g chemical oxygen demand (COD)/L). Experimental results show that the inhibition of n-hexane on CH₄ yield was negligible up to 2 g COD/L and inhibition to methanogenesis became significant when it was higher than 4 g COD/L based on quantitative mass balance. Inhibition threshold was about 4 g COD/L of n-hexane. Analytical result of microbial community profile revealed that dominance of alkane-degrading sulfate-reducing bacteria (SRB) and syntrophic bacteria increased, while that of methanogens sharply dropped as n-hexane concentration increased. These findings offer a useful guideline of threshold n-hexane concentration and microbial community shift for the AD of lipid-extracted microalgal wastes.     

Copper bioaccumulation,photosystem II functioning,and oxidative stress in the seagrass <Emphasis Type="Italic">Cymodocea nodosa</Emphasis> exposed to copper oxide nanoparticles

Photosynthetic activity, oxidative stress, and Cu bioaccumulation in the seagrass Cymodocea nodosa were assessed 4, 12, 24, 48, and 72 h after exposure to two copper oxide nanoparticle (CuO NP) concentrations (5 and 10 mg L^?1). CuO NPs were characterized by scanning electron microscopy (SEM) and dynamic light scattering measurements (DLS). Chlorophyll fluorescence analysis was applied to detect photosystem II (PSII) functionality, while the Cu accumulation kinetics into the leaf blades was fitted to the Michaelis-Menten equation. The uptake kinetics was rapid during the first 4 h of exposure and reached an equilibrium state after 10 h exposure to 10 mg L^?1 and after 27 h to 5 mg L^?1 CuO NPs. As a result, 4-h treatment with 5 mg L^?1 CuO NPs, decreased the quantum yield of PS II photochemistry (Φ _PSΙΙ ) with a parallel increase in the regulated non-photochemical energy loss in PSII (Φ _NPQ ). However, the photoprotective dissipation of excess absorbed light energy as heat, through the process of non-photochemical quenching (NPQ), did not maintain the same fraction of open reaction centers (q _p ) as in control plants. This reduced number of open reaction centers resulted in a significant increase of H₂O₂ production in the leaf veins serving possibly as an antioxidant defense signal. Twenty-four-hour treatment had no significant effect on Φ _PSΙΙ and q _p compared to controls. However, 24 h exposure to 5 mg L^?1 CuO NPs increased the quantum yield of non-regulated energy loss in PSII (Φ _NO ), and thus the formation of singlet oxygen (¹O₂) via the triplet state of chlorophyll, possible because the uptake kinetics had not yet reached the equilibrium state as did 10 mg L^?1. Longer-duration treatment (48 and 72 h) had less effect on the allocation of absorbed light energy at PSII and the fraction of open reaction centers, compared to 4-h treatment, suggesting the function of a stress defense mechanism. The response of C. nodosa leaves to CuO NPs fits the “Threshold for Tolerance Model” with a threshold time (more than 4 h) required for induction of a stress defense mechanism, through H₂O₂ production.     

Effect of alginate on the aggregation kinetics of copper oxide nanoparticles (CuO NPs): bridging interaction and hetero-aggregation induced by Ca<Superscript>2+</Superscript>

The stability of CuO nanoparticles (NPs) is expected to play a key role in the environmental risk assessment of nanotoxicity in aquatic systems. In this study, the effect of alginate (model polysaccharides) on the stability of CuO NPs in various environmentally relevant ionic strength conditions was investigated by using time-resolved dynamic light scattering. Significant aggregation of CuO NPs was observed in the presence of both monovalent and divalent cations. The critical coagulation concentrations (CCC) were 54.5 and 2.9 mM for NaNO₃ and Ca(NO₃)₂, respectively. The presence of alginate slowed nano-CuO aggregation rates over the entire NaNO₃ concentration range due to the combined electrostatic and steric effect. High concentrations of Ca²⁺ (>6 mM) resulted in stronger adsorption of alginate onto CuO NPs; however, enhanced aggregation of CuO NPs occurred simultaneously under the same conditions. Spectroscopic analysis revealed that the bridging interaction of alginate with Ca²⁺ might be an important mechanism for the enhanced aggregation. Furthermore, significant coagulation of the alginate molecules was observed in solutions of high Ca²⁺ concentrations, indicating a hetero-aggregation mechanism between the alginate-covered CuO NPs and the unabsorbed alginate. These results suggested a different aggregation mechanism of NPs might co-exist in aqueous systems enriched with natural organic matter, which should be taken into consideration in future studies.

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Graphical abstract Hetero-aggregation mechanism of CuO nanoparticles and alginate under high concentration of Ca²⁺

     

Measurements of β and α hexachlorocyclohexane in <Emphasis Type="Italic">Juglans regia</Emphasis> and <Emphasis Type="Italic">Prunus spinosa</Emphasis> trees in a contaminated area,central Italy

Vegetables play an important role in the human diet, and the transfer of toxic contaminants from the soil to plants has been little studied for most tree species and their edible portions. In an area affected by hexachlorocyclohexane (HCH) contamination, in the Sacco River Valley (central Italy), measurements of β- and α-HCH isomers were made on different parts of two tree species: Juglans regia and Prunus spinosa. Concentrations were analysed in roots, branches, leaves, fruits, and seeds. A spatial evaluation of the results highlighted an inverse association of contamination with distance from the river, which is the main route of transport in the environment. Results in J. regia showed decreasing values in this order: branches > leaves > husks > nutmeat. Results in P. spinosa showed decreasing values in the following order: branches > leaves > fruits. In J. regia, nutmeat values were all below limit of detection (LOD, 0.0005 mg/kg), except in one case in which a very low concentration of β-HCH was found (0.006 mg/Kg), compliant with maximum residue limits (MRLs). The ability of J. regia to store large quantities of β-HCH in wooden and leafy parts but not in edible kernels makes this plant a potential and precious tool in remediation and economical reconversion of polluted areas. It is also valuable for food and wood manufacturing.     

Toxicity,uptake, and accumulation of nano and bulk cerium oxide particles in <Emphasis Type="Italic">Artemia salina</Emphasis>

Although the toxicological impact of metal oxide nanoparticles has been studied for the last few decades on aquatic organisms, the exact mechanism of action is still unclear. The fate, behavior, and biological activity of nanoparticles are dependent on physicochemical factors like size, shape, surface area, and stability in the medium. This study deals with the effect of nano and bulk CeO₂ particles on marine microcrustacean, Artemia salina. The primary size was found to be 15 ± 3.5 and 582 ± 50 nm for nano and bulk CeO₂ (TEM), respectively. The colloidal stability and sedimentation assays showed rapid aggregation of bulk particles in seawater. Both the sizes of CeO₂ particles inhibited the hatching rate of brine shrimp cyst. Nano CeO₂ was found to be more toxic to A. salina (48 h LC₅₀ 38.0 mg/L) when compared to bulk CeO₂ (48 h LC₅₀ 92.2 mg/L). Nano CeO₂-treated A. salina showed higher oxidative stress (ROS) than those treated with the bulk form. The reduction in the antioxidant activity indicated an increase in oxidative stress in the cells. Higher acetylcholinesterase activity (AChE) was observed upon exposure to nano and bulk CeO₂ particles. The uptake and accumulation of CeO₂ particles were increased with respect to the concentration and particle size. Thus, the above results revealed that nano CeO₂ was more lethal to A. salina as compared to bulk particles.