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.     

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.     

Nano-MnO<Subscript>2</Subscript>-mediated transformation of triclosan with humic molecules present: kinetics,products, and pathways

It has been shown that manganese dioxide (MnO₂) can mediate transformation of phenolic contaminants to form phenoxyl radical intermediates, and subsequently, these intermediates intercouple to form oligomers via covalent binding. However, the reaction kinetics and transformation mechanisms of phenolic contaminants with humic molecules present in nano-MnO₂-mediated systems were still unclear. In this study, it was proven that nano-MnO₂ were effective in transforming triclosan under acidic conditions (pH 3.5–5.0) during manganese reduction, and the apparent pseudo first-order kinetics rate constants (k?=?0.0599–1.5314 h^?1) increased as the pH decreased. In particular, the transformation of triclosan by nano-MnO₂ was enhanced in the presence of low-concentration humic acid (1–10 mg L^?1). The variation in the absorption of humic molecules at 275 nm supported possible covalent binding between humic molecules and triclosan in the nano-MnO₂-mediated systems. A total of four main intermediate products were identified by high-resolution mass spectrometry (HRMS), regardless of humic molecules present in the systems or not. These products correspond to a suite of radical intercoupling reactions (dimers and trimers), ether cleavage (2,4-dichlorophenol), and oxidation to quinone-like products, triggered by electron transfer from triclosan molecules to nano-MnO₂. A possible reaction pathway in humic acid solutions, including homo-coupling, decomposition, oxidation, and cross-coupling, was proposed. Our findings provide valuable information regarding the environmental fate and transformation mechanism of triclosan by nano-MnO₂ in complex water matrices.     

Formation of indoor nitrous acid (HONO) by light-induced NO<Subscript>2</Subscript> heterogeneous reactions with white wall paint

Gaseous nitrogen dioxide (NO₂) represents an oxidant that is present in relatively high concentrations in various indoor settings. Remarkably increased NO₂ levels up to 1.5 ppm are associated with homes using gas stoves. The heterogeneous reactions of NO₂ with adsorbed water on surfaces lead to the generation of nitrous acid (HONO). Here, we present a HONO source induced by heterogeneous reactions of NO₂ with selected indoor paint surfaces in the presence of light (300 nm?<?λ?<?400 nm). We demonstrate that the formation of HONO is much more pronounced at elevated relative humidity. In the presence of light (5.5 W m^?2), an increase of HONO production rate of up to 8.6?·?10⁹ molecules cm^?2 s^?1 was observed at [NO₂]?=?60 ppb and 50 % relative humidity (RH). At higher light intensity of 10.6 (W m^?2), the HONO production rate increased to 2.1?·?10¹⁰ molecules cm^?2 s^?1. A high NO₂ to HONO conversion yield of up to 84 % was observed. This result strongly suggests that a light-driven process of indoor HONO production is operational. This work highlights the potential of paint surfaces to generate HONO within indoor environments by light-induced NO₂ heterogeneous reactions.     

Behaviour and dynamics of di-ammonium phosphate in bauxite processing residue sand in Western Australia—I. NH<Subscript>3</Subscript> volatilisation and residual nitrogen availability

Background, aim and scope

Australia is the largest producer of bauxite in the world, with an annual output of approximately 62 million metric dry tons in 2007. For every tonne of alumina, about 2 tonnes of highly alkaline and highly saline bauxite-processing residue are produced. In Western Australia, Alcoa World Alumina, Australia (Alcoa) produces approximately 15 MT of residue annually from its refineries (Kwinana, Pinjarra and Wagerup). The bauxite-processing residue sand (BRS) fraction represents the primary material for rehabilitating Alcoa’s residue disposal areas (RDAs). However, the inherently hostile characteristics (high alkalinity, high salinity and poor nutrient availability) of BRS pose severe limitations for establishing sustainable plant cover systems. Alcoa currently applies 2.7 t ha^?1 of di-ammonium phosphate ((NH₄)₂HPO₄; DAP)-based fertiliser as a part of rehabilitation of the outer residue sand embankments of its RDAs. Limited information on the behaviour of the dominant components of this inorganic fertiliser in highly alkaline BRS is currently available, despite the known effects of pH on ammonium (NH₄) and phosphorus (P) behaviour. The aim of this study was to quantify the effects of pH on NH₃ volatilisation and residual nitrogen (N) in BRS following DAP applications.

Methods

The sponge-trapping and KCl-extraction method was used for determining NH₃ volatilisation from surface-applied DAP in samples of BRS collected from each of Alcoa’s three Western Australia Refineries (Kwinana, Pinjarra, Wagerup) under various pH conditions (pH 4, 7, 9 and 11). Following cessation of volatilisation, the residual N was extracted from BRS using 2 M KCl and concentrations of NH ₄ ⁺ –N and NO ₃ ^? –N were determined by flow injection analysis.

Results

The quantities of NH₃ volatilised increased dramatically as the pH increased from 4 to 11. Much of the N lost as NH₃ (up to 95.2%) occurred within a short period (24 h to 7 days), particularly for the pH 9 and 11 treatments. Concentrations of residual NH ₄ ⁺ –N recovered in DAP-treated BRS at the end of the experiment decreased with increasing pH. This finding was consistent with increasing loss of N via volatilisation as pH increased. The concentration of NO ₃ ^? –N was very low due to no nitrification in BRS.

Discussion

The pH was a key driver for NH₃ volatilisation from DAP-treated BRS and primarily controlled N dynamics in BRS. Results indicate that NH₄ not adsorbed by BRS was highly susceptible to volatilisation. The likely lack of nitrifying bacteria did not allow conversion of ammonium to nitrate, thereby further exacerbating the potential for loss via volatilisation

Conclusions

It was demonstrated that the pH is the key factor controlling the loss of inorganic N from BRS. Although volatilisation was considerably lower at pH 4, achieving this pH reduction in the field is not possible at present. Findings from this study highlight the need to better understand which forms of N fertiliser are most suitable for use in highly alkaline BRS.

Recommendation and perspectives

Although pH reduction is the most likely means of stopping NH₃ volatilisation in BRS, it is economically and operationally unfeasible to add sufficient acidity for adequately lowering pH in the BRS for revegetation. More attention on forms of fertilisers more suitable to highly alkaline, microbially inert soil conditions appears to be warranted.

     

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 the Multi-Year Carbon Balance of a Subarctic Palsa Mire with Micrometeorological Techniques

This article reports a dataset on 8 years of monitoring carbon fluxes in a subarctic palsa mire based on micrometeorological eddy covariance measurements. The mire is a complex with wet minerotrophic areas and elevated dry palsa as well as intermediate sub-ecosystems. The measurements document primarily the emission originating from the wet parts of the mire dominated by a rather homogenous cover of Eriophorum angustifolium. The CO₂/CH₄ flux measurements performed during the years 2001–2008 showed that the areas represented in the measurements were a relatively stable sink of carbon with an average annual rate of uptake amounting to on average ?46 g C m^?2 y^?1 including an equally stable loss through CH₄ emissions (18–22 g CH₄–C m^?2 y^?1). This consistent carbon sink combined with substantial CH₄ emissions is most likely what is to be expected as the permafrost under palsa mires degrades in response to climate warming.     

Study on the removal of elemental mercury from simulated flue gas by Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-CeO<Subscript>2</Subscript>/AC at low temperature

Fe₂O₃ and CeO₂ modified activated coke (AC) synthesized by the equivalent-volume impregnation were employed to remove elemental mercury (Hg⁰) from simulated flue gas at a low temperature. Effects of the mass ratio of Fe₂O₃ and CeO₂, reaction temperature, and individual flue gas components including O₂, NO, SO₂, and H₂O (g) on Hg⁰ removal efficiency of impregnated AC were investigated. The samples were characterized by Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Results showed that with optimal mass percentage of 3 % Fe₂O₃ and 3 % CeO₂ on Fe3Ce3/AC, the Hg⁰ removal efficiency could reach an average of 88.29 % at 110 °C. Besides, it was observed that O₂ and NO exhibited a promotional effect on Hg⁰ removal, H₂O (g) exerted a suppressive effect, and SO₂ showed an insignificant inhibition without O₂ to some extent. The analysis of XPS indicated that the main species of mercury on used Fe3Ce3/AC was HgO, which implied that adsorption and catalytic oxidation were both included in Hg⁰ removal. Furthermore, the lattice oxygen, chemisorbed oxygen, and/or weakly bonded oxygen species made a contribution to Hg⁰ oxidation.     

Climate change stimulates the growth of the intertidal macroalgae <Emphasis Type="Italic">Ascophyllum nodosum</Emphasis> near the northern distribution limit

Ascophyllum nodosum is a foundation macroalgae of the intertidal zone that distributes across latitude 41.3–69.7°N. We tested the hypothesis that growth of A. nodosum near the northern distribution edge increases with warming. We retrospectively quantified the growth of eight A. nodosum populations at West Greenland and North Norway (from 64°N to 69°N). For seven populations, we measured growth rates since 1997–2002 and for one of them we extended the time series back to 1956 using published estimates. Individuals at northern populations elongated between 2.0 and 9.1 cm year^?1 and this variability correlated with temperature and annual ice-free days. A spatial comparison of A. nodosum growth across the species distribution range showed that Northern (and coldest) populations grew at the slowest rates. Our results demonstrate that arctic climate change enhances the growth of A. nodosum populations and suggest that their productivity may increase in response to projected global warming.     

Physiological characteristics of <Emphasis Type="Italic">Plantago major</Emphasis> under SO<Subscript>2</Subscript> exposure as affected by foliar iron spray

Sulfur dioxide (SO₂) is considered as a main air pollutant in industrialized areas that can damage vegetation. In the present study, we investigated how exposure to SO₂ and foliar application of iron (Fe) would affect certain physiological characteristics of Plantago major. The plant seedlings exposed or unexposed to SO₂ (3900 μg m^?3) were non-supplemented or supplemented with Fe (3 g L^?1) as foliar spray. Plants were exposed to SO₂ for 6 weeks in 100 × 70 × 70 cm chambers. Fumigation of plants with SO₂ was performed for 3 h daily for 3 days per week (alternate day). Lower leaf Fe concentration in the plants exposed to SO₂ at no added Fe treatment was accompanied with incidence of chlorosis symptoms and reduced chlorophyll concentration. No visible chlorotic symptoms were observed on the SO₂-exposed plants supplied with Fe that accumulated higher Fe in their leaves. Both at with and without added Fe treatments, catalase (CAT) and peroxidase (POD) activity was higher in the plants fumigated with SO₂ in comparison with those non-fumigated with SO₂. Foliar application of Fe was also effective in increasing activity of antioxidant enzymes CAT and POD. Exposure to SO₂ led to reduced cellulose but enhanced lignin content of plant leaf cell wall. The results obtained showed that foliar application of Fe was effective in reducing the effects of exposure to SO₂ on cell wall composition. In contrast to SO₂, application of Fe increased cellulose while decreased lignin content of the leaf cell wall. This might be due to reduced oxidative stress induced by SO₂ in plants supplied with Fe compared with those unsupplied with Fe.     

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.     

Inactivation of <Emphasis Type="Italic">Escherichia coli</Emphasis> in fresh water with advanced oxidation processes based on the combination of O<Subscript>3</Subscript>, H<Subscript>2</Subscript>O<Subscript>2</Subscript>, and TiO<Subscript>2</Subscript>. Kinetic modeling

The purpose of this work was to study the efficiency of different treatments, based on the combination of O₃, H₂O₂, and TiO₂, on fresh surface water samples fortified with wild strains of Escherichia coli. Moreover, an exhaustive assessment of the influence of the different agents involved in the treatment has been carried out by kinetic modeling of E. coli inactivation results. The treatments studied were (i) ozonation (O₃), (ii) the peroxone system (O₃/0.04 mM H₂O₂), (iii) catalytic ozonation (O₃/1 g/L TiO₂), and (iv) a combined treatment of O₃/1 g/L TiO₂/0.04 mM H₂O₂. It was observed that the peroxone system achieved the highest levels of inactivation of E. coli, around 6.80 log after 10 min of contact time. Catalytic ozonation also obtained high levels of inactivation in a short period of time, reaching 6.22 log in 10 min. Both treatments, the peroxone system (O₃/H₂O₂) and catalytic ozonation (O₃/TiO₂), produced a higher inactivation rate of E. coli than ozonation (4.97 log after 10 min). While the combination of ozone with hydrogen peroxide or titanium dioxide thus produces an increase in the inactivation yield of E. coli regarding ozonation, the O₃/TiO₂/H₂O₂ combination did not enhance the inactivation results. The fitting of experimental values to the corresponding equations through non-linear regression techniques was carried out with Microsoft® Excel GInaFiT software. The inactivation results of E. coli did not respond to linear functions, and it was necessary to use mathematical models able to describe certain deviations in the bacterial inactivation processes. In this case, the inactivation results fit with mathematical models based on the hypothesis that the bacteria population is divided into two different subgroups with different degrees of resistance to treatments, for instance biphasic and biphasic with shoulder models.

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Graphical abstract ?

     

Synthesis and thermoluminescence properties of rare earth-doped NaMgBO<Subscript>3</Subscript> phosphor

Rare earth (Dy³⁺ and Sm³⁺)-doped sodium magnesium borate (NaMgBO₃) is synthesized by solution combustion synthesis method keeping their thermoluminescence properties in mind. The reaction produced very stable crystalline NaMgBO₃:RE (RE?=?Dy³⁺, Sm³⁺) phosphors. The phosphors are exposed to ⁶⁰Co gamma-ray radiations dose of varying rate from 5 to 25 Gy, and their TL characteristics with kinetic parameters are studied. NaMgBO₃:Dy³⁺ phosphor shows two peaks for lower doping concentration of Dy³⁺ while it reduced to single peak for the higher concentrations of activator Dy³⁺. NaMgBO₃:Dy³⁺ shows the major glow peak around 200 °C while NaMgBO₃:Sm³⁺ phosphors show two well-separated glow peaks at 200 and 332 °C respectively. The thermoluminescence intensity of these phosphors was compare with the commercially available TLD-100 (Harshaw) phosphor. The TL responses for gamma-ray radiations dose were found to be linear from 5 to 25 Gy for both phosphors while the fading in each case is calculated for the tenure of 45 days.     

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.     

Recycling of iron and silicon from drinking water treatment sludge for synthesis of magnetic iron oxide@SiO<Subscript>2</Subscript> composites

More attention has been paid to the deterioration of water bodies polluted by drinking water treatment sludge (DWTS) in recent years. It is important to develop methods to effectively treat DWTS by avoiding secondary pollution. We report herein a novel investigation for recovery of Si and Fe from DWTS, which are used for the synthesis of two iron oxide@SiO₂ composites for adsorption of reactive red X-3B (RRX-3B) and NaNO₂. The results show that Fe³⁺ (acid-leaching) and Si⁴⁺ (basic-leaching) can be successfully recovered from roasted DWTS. Whether to dissolve Fe(OH)₃ precipitation is the key point for obtaining Fe₃O₄ or γ-Fe₂O₃ particles using the solvothermal method. The magnetic characteristics of Fe₃O₄@SiO₂ (390.0 m² g^?1) or Fe₂O₃@SiO₂ (220.9 m² g^?1) are slightly influenced by the coated porous SiO₂ layer. Peaks of Fe–O stretching vibration (580 cm^?1) and asymmetric Si–O–Si stretching vibrations (1080 cm^?1) of Fe₃O₄@SiO₂ indicate the successful coating of a thin silica layer (20–150 nm). The adsorption capacity of RRX-3B and NaNO₂ by Fe₃O₄@SiO₂ is better than that of Fe₂O₃@SiO₂, and both composites can be recycled through an external magnetic field. This method is an efficient and environmentally friendly method for recycling DWTS.     

Start-up of sequencing batch reactor with <Emphasis Type="Italic">Thiosphaera pantotropha</Emphasis> for treatment of high-strength nitrogenous wastewater and sludge characterization

Biological treatment of high-strength nitrogenous wastewater is challenging due to low growth rate of autotrophic nitrifiers. This study reports bioaugmentation of Thiosphaera pantotropha capable of simultaneously performing heterotrophic nitrification and aerobic denitrification (SND) in sequencing batch reactors (SBRs). SBRs fed with 1:1 organic-nitrogen (N) and NH₄ ⁺-N were started up with activated sludge and T. pantotropha by gradual increase in N concentration. Sludge bulking problems initially observed could be overcome through improved aeration and mixing and change in carbon source. N removal decreased with increase in initial nitrogen concentration, and only 50–60 % removal could be achieved at the highest N concentration of 1000 mg L^?1 at 12-h cycle time. SND accounted for 28 % nitrogen loss. Reducing the settling time to 5–10 min and addition of divalent metal ions gradually improved the settling characteristics of sludge. Sludge aggregates of 0.05–0.2 mm diameter, much smaller than typical aerobic granules, were formed and progressive increase in settling velocity, specific gravity, Ca²⁺, Mg²⁺, protein, and polysaccharides was observed over time. Granulation facilitated total nitrogen (TN) removal at a constant rate over the entire 12-h cycle and thus increased TN removal up to 70 %. Concentrations of NO₂ ^?-N and NO₃ ^?-N were consistently low indicating effective denitrification. Nitrogen removal was possibly limited by urea hydrolysis/nitrification. Presence of T. pantotropha in the SBRs was confirmed through biochemical tests and 16S rDNA analysis.     

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.     

The effects and the toxicity increases caused by bicarbonate,chloride, and other water components during the UV/TiO<Subscript>2</Subscript> degradation of oxazaphosphorine drugs

The influences of HCO₃ ^?, Cl^?, and other components on the UV/TiO₂ degradation of the antineoplastic agents ifosfamide (IFO) and cyclophosphamide (CP) were studied in this work. The results indicated that the presence of HCO₃ ^?, Cl^?, NO₃ ^?, and SO₄ ^2? in water bodies resulted in lower degradation efficiencies. The half-lives of IFO and CP were 1.2 and 1.1 min and increased 2.3–7.3 and 3.2–6.3 times, respectively, in the presence of the four anions (initial compound concentration = 100 μg/L, TiO₂ loading =100 mg/L, anion concentration = 1000 mg/L, and pH = 8). Although the presence of HCO₃ ^? in the UV/TiO₂/HCO₃ ^? system resulted in a lower degradation rate and less byproduct formation for IFO and CP, two newly identified byproducts, P11 (M.W. = 197) and P12 (M.W. = 101), were formed and detected, suggesting that additional pathways occurred during the reaction of ?CO₃ ^? in the system. The results also showed that ?CO₃ ^? likely induces a preferred ketonization pathway. Besides the inorganic anions HCO₃ ^?, Cl^?, NO₃ ^?, and SO₄ ^2?, the existence of dissolved organic matter in the water has a significant effect and inhibits CP degradation. Toxicity tests showed that higher toxicity occurred in the presence of HCO₃ ^? or Cl^? during UV/TiO₂ treatment and within 6 h of reaction time, implying that the effects of these two anions should not be ignored when photocatalytic treatment is applied to treat real wastewater.     

Biosorption and degradation of decabromodiphenyl ether by <Emphasis Type="Italic">Brevibacillus brevis</Emphasis> and the influence of decabromodiphenyl ether on cellular metabolic responses

There is global concern about the effects of decabromodiphenyl ether (BDE209) on environmental and public health. The molecular properties, biosorption, degradation, accumulation, and cellular metabolic effects of BDE209 were investigated in this study to identify the mechanisms involved in the aerobic biodegradation of BDE209. BDE209 is initially absorbed by wall teichoic acid and N-acetylglucosamine side chains in peptidoglycan, and then, BDE209 is transported and debrominated through three pathways, giving tri-, hepta-, octa-, and nona-bromodiphenyl ethers. The C–C bond energies decrease as the number of bromine atoms on the diphenyl decreases. Polybrominated diphenyl ethers (PBDEs) inhibit protein expression or accelerate protein degradation and increase membrane permeability and the release of Cl^?, Na⁺, NH₄ ⁺, arabinose, proteins, acetic acid, and oxalic acid. However, PBDEs increase the amounts of K⁺, Mg²⁺, PO₄ ^3?, SO₄ ^2?, and NO₃ ^? assimilated. The biosorption, degradation, accumulation, and removal efficiencies when Brevibacillus brevis (1 g L^?1) was exposed to BDE209 (0.5 mg L^?1) for 7 days were 7.4, 69.5, 16.3, and 94.6 %, respectively.     

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.