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.     

Heterogeneous Fenton degradation of bisphenol A catalyzed by efficient adsorptive Fe3O4/GO nanocomposites

A new method for the degradation of bisphenol A (BPA) in aqueous solution was developed. The oxidative degradation characteristics of BPA in a heterogeneous Fenton reaction catalyzed by Fe₃O₄/graphite oxide (GO) were studied. Transmission electron microscopic images showed that the Fe₃O₄ nanoparticles were evenly distributed and were ～6 nm in diameter. Experimental results suggested that BPA conversion was affected by several factors, such as the loading amount of Fe₃O₄/GO, pH, and initial H₂O₂ concentration. In the system with 1.0 g L^?1 of Fe₃O₄/GO and 20 mmol L^?1 of H₂O₂, almost 90 % of BPA (20 mg L^?1) was degraded within 6 h at pH 6.0. Based on the degradation products identified by GC–MS, the degradation pathways of BPA were proposed. In addition, the reused catalyst Fe₃O₄/GO still retained its catalytic activity after three cycles, indicating that Fe₃O₄/GO had good stability and reusability. These results demonstrated that the heterogeneous Fenton reaction catalyzed by Fe₃O₄/GO is a promising advanced oxidation technology for the treatment of wastewater containing BPA.     

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.     

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.     

Effect of solution pH on aging dynamics and surface structural evolution of mZVI particles: H<Subscript>2</Subscript> production and spectroscopic/microscopic evidence

A microscale zero-valent iron (mZVI)-based in situ reactive zone is a promising technology for contaminated groundwater remediation. Estimation of mZVI aging behavior after its injection into the subsurface is essential for efficiency and longevity assessments. In this study, batch tests were conducted to investigate the effect of initial pH on mZVI aging dynamics, as well as the formation and evolution of aging products over 112 days. Results indicated that mZVI aging accelerated with decreasing initial pH. Corrosion rates of mZVI particles under pH 6.0 and 7.5 were approximately two orders of magnitude higher than those observed at pH 9.0. The morphological, structural, and compositional evolution of mZVI particles in three systems (pH = 6.0, 7.5, and 9.0) were investigated using scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. In acidic and neutral solutions, a thick passivation layer with loosely and unevenly distributed aging precipitates was observed, and Fe₃O₄ was the final aging precipitate. Nevertheless, in alkaline solutions, minute aging precipitates were detected on the mZVI surface at 112 day. Characterization results suggested that mZVI was oxidized via the Fe⁰–Fe(OH)₂–Fe₃O₄ route. These findings shed new light on mZVI aging mechanisms, particularly its physicochemical characteristics and the structural evolution of mZVI in field-scale groundwater remediation applications.     

Extraction of Sudan dyes from environmental water by hemimicelles-based magnetic titanium dioxide nanoparticles

A novel method for the extraction of Sudan dyes including Sudan I, II, III, and IV from environmental water by magnetic titanium dioxide nanoparticles (Fe₃O₄@TiO₂) coated with sodium dodecylsulfate (SDS) as adsorbent was reported. Fe₃O₄@TiO₂ was synthesized by a simple method and was characterized by transmission electron microscopy, Fourier-transform infrared spectrometry, and vibrating sample magnetometer. The magnetic separation was quite efficient for the adsorption and desorption of Sudan dyes. The effect of the amount of SDS, extraction time, pH, desorption condition, maximal extraction volume, and humic acid on the extraction process were investigated. This method was employed to analyze three environmental water samples. The results demonstrated that our proposed method had wide linear range (25–5,000 ng L^?1) with a good linearity (R ²?>?0.999) and low detection limits (2.9–7.3 ng L^?1). An enrichment factor of 1,000 was achieved. In all three spiked levels (25, 250, and 2,500 ng L^?1), the recoveries of Sudan dyes were in the range of 86.9–93.6 %. The relative standard deviations obtained were ranging from 2.5 to 9.3 %. That is to say, the new method was fast and effective for the extraction of Sudan dye from environmental water.     

Degradation of bisphenol A in aqueous solution by persulfate activated with ferrous ion

Degradation of bisphenol A (BPA) in aqueous solution was studied with high-efficiency sulfate radical (SO₄ ^?·), which was generated by the activation of persulfate (S₂O₈ ^2?) with ferrous ion (Fe²⁺). S₂O₈ ^2? was activated by Fe²⁺ to produce SO₄ ^?·, and iron powder (Fe⁰) was used as a slow-releasing source of dissolved Fe²⁺. The major oxidation products of BPA were determined by liquid chromatography-mass spectrometer. The mineralization efficiency of BPA was monitored by total organic carbon (TOC) analyzer. BPA removal efficiency was improved by the increase of initial S₂O₈ ^2? or Fe²⁺ concentrations and then decreased with excess Fe²⁺ concentration. The adding mode of Fe²⁺ had significant impact on BPA degradation and mineralization. BPA removal rates increased from 49 to 97 % with sequential addition of Fe²⁺, while complete degradation was observed with continuous diffusion of Fe²⁺, and the latter achieved higher TOC removal rate. When Fe⁰ was employed as a slow-releasing source of dissolved Fe²⁺, 100 % of BPA degradation efficiency was achieved, and the highest removal rate of TOC (85 %) was obtained within 2 h. In the Fe⁰–S₂O₈ ^2? system, Fe⁰ as the activator of S₂O₈ ^2? could offer sustainable oxidation for BPA, and higher TOC removal rate was achieved. It was proved that Fe⁰–S₂O₈ ^2? system has perspective for future works.     

Removal of PCBs in contaminated soils by means of chemical reduction and advanced oxidation processes

Although the chemical reduction and advanced oxidation processes have been widely used individually, very few studies have assessed the combined reduction/oxidation approach for soil remediation. In the present study, experiments were performed in spiked sand and historically contaminated soil by using four synthetic nanoparticles (Fe⁰, Fe/Ni, Fe₃O₄, Fe_3???x Ni _x O₄). These nanoparticles were tested firstly for reductive transformation of polychlorinated biphenyls (PCBs) and then employed as catalysts to promote chemical oxidation reactions (H₂O₂ or persulfate). Obtained results indicated that bimetallic nanoparticles Fe/Ni showed the highest efficiency in reduction of PCB28 and PCB118 in spiked sand (97 and 79 %, respectively), whereas magnetite (Fe₃O₄) exhibited a high catalytic stability during the combined reduction/oxidation approach. In chemical oxidation, persulfate showed higher PCB degradation extent than hydrogen peroxide. As expected, the degradation efficiency was found to be limited in historically contaminated soil, where only Fe⁰ and Fe/Ni particles exhibited reductive capability towards PCBs (13 and 18 %). In oxidation step, the highest degradation extents were obtained in presence of Fe⁰ and Fe/Ni (18–19 %). The increase in particle and oxidant doses improved the efficiency of treatment, but overall degradation extents did not exceed 30 %, suggesting that only a small part of PCBs in soil was available for reaction with catalyst and/or oxidant. The use of organic solvent or cyclodextrin to improve the PCB availability in soil did not enhance degradation efficiency, underscoring the strong impact of soil matrix. Moreover, a better PCB degradation was observed in sand spiked with extractable organic matter separated from contaminated soil. In contrast to fractions with higher particle size (250–500 and <500 μm), no PCB degradation was observed in the finest fraction (≤250 μm) having higher organic matter content. These findings may have important practical implications to promote successively reduction and oxidation reactions in soils and understand the impact of soil properties on remediation performance.     

Kinetics of imidazolium-based ionic liquids degradation in aqueous solution by Fenton oxidation

In the last few years, several works dealing with Fenton oxidation of ionic liquids (ILs) have proved the capability of this technology for their degradation, achieving complete ILs removal and non-toxic effluents. Nevertheless, very little is known about the kinetics of this process, crucial for its potential application. In this work, the effect of several operating conditions, including reaction temperature (50–90 °C), catalyst load (10–50 mg L^?1 Fe³⁺), initial IL concentration (100–2000 mg L^?1), and hydrogen peroxide dose (10–200% of the stoichiometric amount for the complete IL mineralization) on 1-butyl-3-methylimidazolium chloride ([C₄mim]Cl) oxidation has been investigated. Under the optimum operating conditions (T = 90 °C; [Fe³⁺]₀ = 50 mg L^?1; [H₂O₂]₀ = 100% of the stoichiometric amount), the complete removal of [C₄mim]Cl (1000 mg L^?1) was achieved at 1.5-min reaction time. From the experimental results, a potential kinetic model capable to describe the removal of imidazolium-based ILs by Fenton oxidation has been developed. By fitting the proposed model to the experimental data, the orders of the reaction with respect to IL initial concentration, Fe³⁺ amount and H₂O₂ dose were found to be close to 1, with an apparent activation energy of 43.3 kJ mol^?1. The model resulted in a reasonable fit within the wide range of operating conditions tested in this work.     

Application of Fenton, photo-Fenton, solar photo-Fenton, and UV/H2O2 to degradation of the antineoplastic agent mitoxantrone and toxicological evaluation

In the present study, selected advanced oxidation processes (AOPs)—namely, photo-Fenton (with Fe²⁺, Fe³⁺, and potassium ferrioxalate—FeOx—as iron sources), solar photo-Fenton, Fenton, and UV/H₂O₂—were investigated for degradation of the antineoplastic drug mitoxantrone (MTX), frequently used to treat metastatic breast cancer, skin cancer, and acute leukemia. The results showed that photo-Fenton processes employing Fe(III) and FeOx and the UV/H₂O₂ process were most efficient for mineralizing MTX, with 77, 82, and 90 % of total organic carbon removal, respectively. MTX probably forms a complex with Fe(III), as demonstrated by voltammetric and spectrophotometric measurements. Spectrophotometric titrations suggested that the complex has a 2:1 Fe³⁺:MTX stoichiometric ratio and a complexation constant (K) of 1.47 × 10⁴ M^–1, indicating high MTX affinity for Fe³⁺. Complexation partially inhibits the involvement of iron ions and hence the degradation of MTX during photo-Fenton. The UV/H₂O₂ process is usually slower than the photo-Fenton process, but, in this study, the UV/H₂O₂ process proved to be more efficient due to complexing of MTX with Fe(III). The drug exhibited no cytotoxicity against NIH/3T3 mouse embryonic fibroblast cells when oxidized by UV/H₂O₂ or by UV/H₂O₂/FeOx at the concentrations tested.     

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.     

Effects of hydromorphology and riparian vegetation on the sediment quality of agricultural low-order streams: consequences for stream restoration

Intensive agricultural land use imposes multiple pressures on streams. More specifically, the loading of streams with nutrient-enriched soil from surrounding crop fields may deteriorate the sediment quality. The current study aimed to find out whether stream restoration may be an effective tool to improve the sediment quality of agricultural headwater streams. We compared nine stream reaches representing different morphological types (forested meandering reaches vs. deforested channelized reaches) regarding sediment structure, sedimentary nutrient and organic matter concentrations, and benthic microbial respiration. Main differences among reach types were found in grain sizes. Meandering reaches featured larger mean grain sizes (50–70 μm) and a thicker oxygenated surface layer (8 cm) than channelized reaches (40 μm, 5 cm). Total phosphorous amounted for up to 1,500 μg?g^?1 DW at retentive channelized reaches and 850–1,050 μg?g^?1 DW at the others. While N-NH₄ accumulated in the sediments (60–180 μg?g^?1 DW), N-NO₃ concentrations were generally low (2–5 μg?g^?1 DW). Benthic respiration was high at all sites (10–20 g O₂ m^?2?day^?1). Our study shows that both hydromorphology and bank vegetation may influence the sediment quality of agricultural streams, though effects are often small and spatially restricted. To increase the efficiency of stream restoration in agricultural landscapes, nutrient and sediment delivery to stream channels need to be minimized by mitigating soil erosion in the catchment.     

Synthesis of Fe-doped Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocatalyst and its sonophotocatalytic activity on synthetic dye and real textile wastewater

The catalysts such as Fe, Bi₂O₃, and Fe-doped Bi₂O₃ were synthesized for the sonophotocatalytic treatment of synthetic dye and real textile wastewater. The resultant catalysts were characterized for its size and uniform shape using x-ray diffractogram (XRD) and scanning electron microscopy (SEM) which signified the nanorod shape formed Bi₂O₃. The higher ultraviolet light absorbance capacity of the catalysts was also evident using diffuse reflectance spectroscopy (DRS). Initially, the effect of conventional parameters such as initial pH, gas bubbling (argon, oxygen, air and nitrogen) and oxidant addition (H₂O₂ and peroxymonosulfate) in the presence of sonolysis (22 and 37 kHz frequency) and photolysis (UV-C light) on 10 ppm Basic Brown 1 dye was studied. The results showed that highest decolorization of 62 % was attained for 3 g/L peroxymonosulfate under 37 kHz frequency sonolysis treatment. Secondly, with the catalyst study, highest of 46 % dye color removal was obtained with 4 g/L Fe under 37 kHz frequency sonolysis treatment. The sonophotocatalytic treatment of dye with Fe-doped Bi₂O₃ catalyst in combination with peroxymonosulfate showed highest color removal of 99 %. Finally, the sonophotocatalytic treatment of real textile wastewater in the presence of 3 g/L Fe-doped Bi₂O₃ and 6 g/L peroxymonosulfate reduced the total organic carbon (TOC) and chemical oxygen demand (COD) level to 77 and 91 %, respectively, in 180 min. The reported treatment process was found to treat the synthetic dye and real textile wastewater effectively.     

Influence of operational key parameters on the photocatalytic decolorization of Rhodamine B dye using Fe2+/H2O2/Nb2O5/UV system

The present research deals with the development of a new heterogeneous photocatalysis and Fenton hybrid system for the removal of color from textile dyeing wastewater as Rhodamine B (RhB) solutions by using Fe²⁺/H₂O₂/Nb₂O₅ as a photocatalytic system. The application of this photocatalytic system for the decolorization of dye contaminants is not reported in the literature yet. Different parameters like dye concentration, Nb₂O₅/Fe²⁺ catalyst amount, pH, and H₂O₂ concentration have been studied. The optimum conditions for the decolorization of the dye were initial concentration of 10 mg L^?1 of dye, pH 4, and Nb₂O₅/Fe²⁺ catalyst concentration of 0.5 g L^?1/50 mg L^?1. The optimum value of H₂O₂ concentration for the conditions used in this study was 700 mg L^?1. Moreover, the efficiency of the Nb₂O₅/photo-Fenton hybrid process in comparison to photo-Fenton alone and a dark Fenton process as a control experiment to decolorize the RhB solution has been investigated. The combination of photo-Fenton and Nb₂O₅ catalysts has been proved to be the most effective for the treatment of such type of wastewaters. The results revealed that the RhB dye was decolorized in a higher percent (78 %) by the Nb₂O₅/photo-Fenton hybrid process (Fe²⁺/H₂O₂/Nb₂O₅/UV) than by the photo-Fenton process alone (37 %) and dark Fenton process (14 %) after 120 min of treatment. Moreover, the Nb₂O₅ catalyst as a heterogeneous part of the photocatalytic system was demonstrated to have good stability and reusability.     

Brain glutathione redox system significance for the control of silica-coated magnetite nanoparticles with or without mercury co-exposures mediated oxidative stress in European eel (Anguilla anguilla L.)

This in vitro study investigates the impact of silica-coated magnetite particles (Fe₃O₄@SiO₂/SiDTC, hereafter called IONP; 2.5 mg L^?1) and its interference with co-exposure to persistent contaminant (mercury, Hg; 50 μg L^?1) during 0, 2, 4, 8, 16, 24, 48, and 72 h on European eel (Anguilla anguilla) brain and evaluates the significance of the glutathione (GSH) redox system in this context. The extent of damage (membrane lipid peroxidation, measured as thiobarbituric acid reactive substances, TBARS; protein oxidation, measured as reactive carbonyls, RCs) decreased with increasing period of exposure to IONP or IONP + Hg which was accompanied with differential responses of glutathione redox system major components (glutathione reductase, GR; glutathione peroxidase, GPX; total GSH, TGSH). The occurrence of antagonism between IONP and Hg impacts was evident at late hour (72 h), where significantly decreased TBARS and RC levels and GR and glutathione sulfo-transferase (GST) activity imply the positive effect of IONP + Hg concomitant exposure against Hg-accrued negative impacts [vs. early (2 h) hour of exposure]. A period of exposure-dependent IONP alone and IONP + Hg joint exposure-accrued impact was perceptible. Additionally, increased susceptibility of the GSH redox system to increased period of exposure to Hg was depicted, where insufficiency of elevated GR for the maintenance of TGSH required for membrane lipid and cellular protein protection was displayed. Overall, a fine-tuning among brain glutathione redox system components was revealed controlling IONP + Hg interactive impacts successfully.     

Trace analysis of parabens preservatives in drinking water treatment sludge,treated, and mineral water samples

Parabens have been widely used as antimicrobial agents, mainly in food products, pharmaceuticals, and cosmetics. Although they are known as safe preservatives, they also cause some harm to human health, which has been discussed lately. Therefore, the aim of this study was to evaluate the occurrence of nine parabens (including isomers) in mineral and drinking waters, besides in drinking water treatment sludge (DWTS) samples with determination by liquid chromatography tandem mass spectrometry (LC-MS/MS). Both methods solid phase extraction (SPE) and QuEChERS were validated. Calibration curves showed a correlation coefficient of 0.99 for all compounds. LOQ values ranged from 0.04 to 4 μg L^?1 in aqueous matrices and from 5 to 500 ng g^?1 in DWTS. Recoveries between 70 and 115% were reached with RSD below 20% for all compounds in SPE whereas recoveries between 62 and 119% were found with RSD below 20% for almost all compounds in QuEChERS. Matrix effect had low values (<?20%); it was only above 20% for methylparaben in the SPE and for pentylparaben in the QuEChERS. Using a quick and simple extraction procedures with SPE, QuEChERS, and LC-MS/MS analyses, these methods proved to be selective and sensitive. They were successfully applied to real samples (treated water, mineral water, and sludge), and methylparaben was detected at concentration levels below 0.242 μg L^?1 in mineral and treated water samples and 10 ng g^?1 in DWTS samples.     

Application of chemical oxidation to remediate HCH-contaminated soil under batch and flow through conditions

This is the first study describing the chemical oxidation of hexachlorocyclohexanes (HCHs) in contaminated soil under water saturated and unsaturated flow through conditions. Soil contaminated with β-HCH (45 mg kg^?1) and γ-HCH (lindane, 25 mg kg^?1) was sampled from former lindane waste storage site. Efficiency of following treatments was tested at circumneutral pH: H₂O₂ alone, H₂O₂/Fe^II, Na₂S₂O₈ alone, Na₂S₂O₈/Fe^II, and KMnO₄. Experimental conditions (oxidant dose, liquid/solid ratio, and soil granulometry) were first optimized in batch experiments. Obtained results revealed that increasing dose of H₂O₂ improved the oxidation efficiency while in Na₂S₂O₈ system, maximum HCHs were removed at 300 mM. However, oxidation efficiency was slightly improved by Fe^II-activation. Increasing the solid/liquid ratio decreased HCH removal in soil samples crushed to 500 μm while an opposite trend was observed for 2-mm samples. Dynamic column experiments showed that oxidation efficiency followed the order KMnO₄ > Na₂S₂O₈/Fe^II > Na₂S₂O₈ whatever the flow condition, whereas the removal extent declined at higher flow rate (e.g., ~50% by KMnO₄ at 0.5 mL/min as compared to ~30% at 2 mL/min). Both HCH removal and oxidant decomposition extents were found higher in saturated columns than the unsaturated ones. While no significant change in relative abundance of soil mineral constituents was observed before and after chemical oxidation, more than 60% of extractable organic matter was lost after chemical oxidation, thereby underscoring the non-selective behavior of chemical oxidation in soil. Due to the complexity of soil system, chemical oxidation has rarely been reported under flow through conditions, and therefore our findings will have promising implications in developing remediation techniques under dynamic conditions closer to field applications.     

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.     

Remediation of acid mine drainage (AMD)-contaminated soil by Phragmites australis and rhizosphere bacteria

Experiments were conducted to assess the impact of citric acid (CA) and rhizosphere bacteria on metal uptake in Phragmites australis cultured in a spiked acid mine drainage (AMD) soil. Rhizosphere iron-oxidizing bacteria (Fe(II)OB) enhanced the formation of Fe plaque on roots, which decreased the uptake of Fe and Mn. CA inhibited the growth of Fe(II)OB, decreased the formation of metal plaque, raised the metal mobility in soil, and increased the accumulation of metals in all tissues of the reeds. The higher the CA dosage, the more metals accumulated into reeds. The total amount of metals in reeds increased from 7.8?±?0.5?×?10^?6 mol plant^?1 (Mn), 1.4?±?0.1?×?10^?3 mol plant^?1 (Fe), and 1.0?±?0.1?×?10^?4 mol plant^?1 (Al) in spiked soil without CA to 22.2?±?0.5?×?10^?6 mol plant^?1 (Mn), 3.5?±?0.06?×?10^?3 mol plant^?1 (Fe), and 5.0?±?0.2?×?10^?4 mol plant^?1 (Al) in soil added with 33.616 g C₆H₈O₇·H₂O for per kilogram soil. CA could be effective at enhancing the phytoremediation of metals from AMD-contaminated soil.     

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.