Community Refinery Wastewater Photodegradation by Fe-Doped TiO<Subscript>2</Subscript> Films

Photocatalytic treatment of real community wastewater using Fe-doped TiO₂ nanofilm was prepared by modified sol-gel method together with a simple dip-coating technique. The process was investigated in a home-made batch photoreactor. The as-prepared nanocomposite film was characterized by UV-Vis diffuse, XRD, BET, and Fe-SEM analysis. The poultry processing wastewater was collected from Nakhonsawan Municipality. Subsequently, the photocatalytic treatment of the wastewater was performed using a home-made photoreactor operated in batch mode to demonstrate the effects of Fe-dopant concentration with various layer numbers. The catalysts were irradiated using four lamps of 15 W power that emitted visible light and performed at room temperature. The samples were collected every 15 min and analyzed for biochemical oxygen demand (BOD) and chemical oxygen demand (COD) removal efficiency compared to pure TiO₂ nanofilm and direct photolysis. From the results, the mixture of rutile and anatase was obtained with the maximum specific surface area of 150.12 mg²/g and the average particle size of 39.95 nm for 3 layers of 0.15% wt/v Fe-doped TiO₂. The BOD and COD value at 90 min time treatment was presented to be 8.87 and 32 mg L^?1, respectively, in the presence of 0.15% wt/v Fe-doped TiO₂ film photocatalysts. Moreover, atomic absorption spectrometric result ensured that no Ti contamination was detected in all parts of plants after watering by the treated water. Hence, the photocatalytic treatment markedly improved the quality of the community wastewater.     

Efficient Photocatalytic Reduction of CO<Subscript>2</Subscript> Present in Seawater into Methanol over Cu/C-Co-Doped TiO<Subscript>2</Subscript> Nanocatalyst Under UV and Natural Sunlight

Photocatalytic reduction of CO₂ in seawater into chemical fuel, methanol (CH₃OH), was achieved over Cu/C-co-doped TiO₂ nanoparticles under UV and natural sunlight. Photocatalysts with different Cu loadings (0, 0.5, 1, 3, 5, and 7 wt%) were synthesized by the sol–gel method and were characterized by XRD, SEM, UV–Vis, FTIR, and XPS. Co-doping with C and Cu into TiO₂ remarkably promoted the photocatalytic production of CH₃OH. This improvement was attributed to lowering of bandgap energy, specific catalytic effect of Cu for CH₃OH formation, and the minimization of photo-generated carrier recombination. Co-doped TiO₂ with 3.0 wt% Cu was found to be the most active catalyst, giving a maximum methanol yield rate of 577 μmol g-cat^?1 h^?1 under illumination of UV light, which is 5.3-fold higher than the production rate over C-TiO₂ and 7.4 times the amount produced using Degussa P25 TiO₂. Under natural sunlight, the maximum rate of the photocatalytic production of CH₃OH using 3.0 wt% Cu/C-TiO₂ was found to be 188 μmol g-cat^?1 h^?1, which is 2.24 times higher than that of C-TiO₂, whereas, no CH₃OH was observed for P25.     

Visible-Light-Driven Photocatalytic N-Doped TiO<Subscript>2</Subscript> for Degradation of Bisphenol A (BPA) and Reactive Black 5 (RB5) Dye

Bisphenol A (BPA) and reactive black 5 (RB5) dye are among the most persistent and non-biodegradable contaminants in water which require an urgent need for the development of effective removal method. The ubiquitous existence of both contaminants could interfere with the human health and aquatic environmental balance. Photocatalytic process as one of advanced oxidation processes (AOPs) has shown high performance for degradation of organic compounds to the harmless materials under sensible condition. Therefore, this study aims to develop a visible-light-driven photocatalyst that can efficiently degrade BPA and RB5 present in household water. N-doped TiO₂ were successfully synthesized via simple and direct sol–gel method. The prepared TiO₂ nanoparticles were characterized by field emission scanning microscope (FE-SEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR), and Brunauere Emmette Teller (BET) analysis. The incorporation of nitrogen in TiO₂ lattice exhibited excellent optical responses to visible region as revealed by UV–Vis–NIR spectroscopy absorption capability at 400–600 nm. The photocatalytic activity of the N-doped TiO₂ nanoparticles was measured by photocatalytic degradation of BPA and RB5 in an aqueous solution under visible-light irradiations. Degradation of BPA and RB5 was 91.3% and 89.1%, respectively after 360 min illumination. The degradation of BPA and RB5 by N-doped TiO₂ was increased up to 89.8% and 88.4%, respectively under visible-light irradiation as compared to commercial TiO₂ P25. This finding clearly shows that N-doped TiO₂ exhibits excellent photocatalytic degradation of BPA and RB5 under visible irradiation, hence have a promising potential in removing various recalcitrant contaminants for water treatment to fulfill the public need to consume clean water.

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Graphical Abstract ?

     

Photocatalytic Removal of the Antibiotic Cefotaxime on TiO<Subscript>2</Subscript> and ZnO Suspensions Under Simulated Sunlight Radiation

This study presents the main results about the removal of the antibiotic cefotaxime (CTX) under simulated sunlight radiation using heterogeneous photocatalysis with titanium dioxide (TiO₂) and zinc oxide (ZnO) in aqueous solutions. The effects of pH and catalyst initial load on pollutant removal were assessed considering the response surface methodology and a central composite circumscribed experimental design, which allowed to determine the optimized conditions that lead to a higher substrate elimination. Experimental results indicated that evaluated parameters have a significant effect on antibiotic removal in both TiO₂ and ZnO suspensions. In addition, the role of photogenerated holes, hydroxyl, and superoxide anion radicals on CTX degradation was evaluated to clarify the reaction mechanism. Finally, analysis of the dissolved organic carbon content in solutions and the antibacterial activity of treated samples showed that photocatalytic treatments were able to reduce a considerable portion of the organic matter present in the systems and its antimicrobial activity.     

Photocatalytic Efficiency of TiO<Subscript>2</Subscript> Supported on Raw Red Clay Disks to Discolour Reactive Red 141

In this work, disks containing different amount of the TiO₂ precursor impregnated on the raw red clay were produced. The disks were obtained by pressing in metal template and subsequently calcined at 500 °C. The raw clay was used as rigid support to fix the TiO₂. The materials were characterized by X-ray diffraction, diffuse reflectance spectroscopy, N₂ adsorption-desorption (BET and BJH), scanning electron microscopy, and Fourier transform infrared (FTIR) spectroscopy. The ability of disks to produce superoxide and hydroxyl radicals after photoexcitation with UV irradiation was monitored by EPR. The catalytic efficiency was evaluated by the Reactive Red 141 dye discoloration under artificial UV light and sunlight. The reaction parameters such as concentration of RR-141 and irradiation source were evaluated. The results showed that the disks were able to decolorize 97.5% under sunlight at 60 min. The disks were also efficient in the discoloration until the tenth cycle, resulting in discoloration values near the initial cycles. Additionally, the dye fragments produced in cleavage of molecule during the reaction were evaluated by LC/MS-MS.

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Graphical Abstract

     

TiO<Subscript>2</Subscript> photocatalytic degradation of 4-chlorobiphenyl as affected by solvents and surfactants

Purpose  

TiO₂ photocatalytic degradation of 4-chlorobiphenyl (PCB3) in aqueous solution under UV irradiation was investigated as affected by different environmental factors, including initial PCB3 concentration, TiO₂ content, UV intensity, H₂O₂ concentration, cosolvents, and surfactants.     

Soil N<Subscript>2</Subscript>O emissions and N<Subscript>2</Subscript>O/(N<Subscript>2</Subscript>O+N<Subscript>2</Subscript>) ratio as affected by different fertilization practices and soil moisture

The objective of this work was to evaluate the effect of the chemical nature and application frequency of N fertilizers at different moisture contents on soil N₂O emissions and N₂O/(N₂O+N₂) ratio. The research was based on five fertilization treatments: unfertilized control, a single application of 80 kg ha⁻¹ N-urea, five split applications of 16 kg ha⁻¹ N-urea, a single application of 80 kg ha⁻¹ N–KNO₃, five split applications of 16 kg ha⁻¹ N–KNO₃. Cumulative N₂O emissions for 22 days were unaffected by fertilization treatments at 32% water-filled pore space (WFPS). At 100% and 120% WFPS, cumulative N₂O emissions were highest from soil fertilized with KNO₃. The split application of N fertilizers decreased N₂O emissions compared to a single initial application only when KNO₃ was applied to a saturated soil, at 100% WFPS. Emissions of N₂O were very low after the application of urea, similar to those found at unfertilized soil. Average N₂O/(N₂O+N₂) ratio values were significantly affected by moisture levels (p = 0.015), being the lowest at 120% WFPS. The N₂O/(N₂O+N₂) ratio averaged 0.2 in unfertilized soil and 0.5 in fertilized soil, although these differences were not statistically significant.     

Preparation of Highly Efficient CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript> Composite Photocatalyst for the Degradation of Rhodamine B Dye from Aqueous Solution

CoFe₂O₄/Zn₂SnO₄ composite was synthesized using a simple two-step process and applied as a novel-efficient photocatalyst for the rhodamine B degradation from aqueous solution. Characterization techniques such as X-ray diffraction (XRD), N₂ adsorption-desorption isotherms, scanning electron microscopy (SEM), EDS analysis, and diffuse reflectance spectroscopy were employed in order to investigate the physical and chemical properties of composite. Higher values of the specific surface area, pore volume and diameter, and a smaller band-gap energy promoted a greater catalytic activity of CoFe₂O₄/Zn₂SnO₄ composite when compared to Zn₂SnO₄. A rapid decolorization of dye solution was observed at 40 min of reaction using the CoFe₂O₄/Zn₂SnO₄ catalyst, being 2.5 times faster than the Zn₂SnO₄ alone. Therefore, the CoFe₂O₄/Zn₂SnO₄ composite shows extraordinarily high photocatalytic activity toward the degradation of rhodamine B dye from aqueous solution.     

Seasonal Dynamics of Soil CO<Subscript>2</Subscript> Concentration and CO<Subscript>2</Subscript> Fluxes from the Soil of the Former Lake Texcoco,Mexico

Seasonal changes of the soil CO₂ concentration and the rate of CO₂ fluxes emission from the soil formed on the sediments of the former Lake Texcoco, which occupied a significant part of the Mexico Valley until the mid-17th century, were studied. The soils (Fluvic Endogleyic Phaeozems) were characterized by a low CO₂ fluxes rate, which is related to their high alkalinity. The mean values of soil respiration were 6.0–14.1 mg C/(m² h) depending on vegetation type, which corresponds to 60–157 g C/(m² yr). The contribution of plants to the CO₂ fluxes insignificantly varied by seasons and depended on the species composition of vegetation. The soil CO₂ concentration and soil respiration in eucalypt (Eucalyptus globulus Labill.) plantation were two times higher than those in the grass–subshrub area, the ground cover of which consisted of Distichlis spicata (L.) Greene and Suaeda nigra (Raf.) J.F. Macbr. species. This can be related to the significant volumes of gas production during the respiration of eucalypt roots and associated rhizosphere community. The contribution of the root systems of grass cover to the soil CO₂ fluxes in eucalypt plantation slightly varied within the year and was equal to 24% on the average. In the grass–subshrub area, its value varied from 41% in the cold season to 60% in the warm season. The spatial variability of soil CO₂ concentration and its flux rate to the atmosphere was due to the differences in plant species composition and hydrothermal conditions, and their temporal trend was closely related to the seasonal accumulation of plant biomass and soil temperature.     

Improved Photodegradation Efficiency of 2,4-DCP Through a Combined Q<Subscript>3</Subscript>Fe(III)-Decorated Porous g-C<Subscript>3</Subscript>N<Subscript>4</Subscript>/H<Subscript>2</Subscript>O<Subscript>2</Subscript> System

Graphitic carbon nitride (g-C₃N₄) is a photocatalyst with wide application in removal of organic pollutants. In this study, we designed a porous g-C₃N₄ (p-g-C₃N₄)/8-quinolinolato iron(III) (Q₃Fe)/H₂O₂ system to enhance the organic pollutant removal efficiency by combining photocatalysis and Fenton interaction under neutral condition. The p-g-C₃N₄ was prepared through a two-step thermal oxidation reaction. Afterwards, Q₃Fe-coupled p-g-C₃N₄ was prepared by an impregnating method. The 2,4-dichlorophenol (2,4-DCP) photodegradation ratio and decomposition rate of the p-g-C₃N₄/Q₃Fe/H₂O₂ system are approximately 5 and 18 times as high as those of individual p-g-C₃N₄ system, respectively. Besides, its degradation rate is 4.3 times as high as that in the p-g-C₃N₄/H₂O₂ system. Meanwhile, Q₃Fe/g-C₃N₄ also exhibits higher activity than individual p-g-C₃N₄ in 2,4-DCP photo-decomposing. On the basis of the results of the radical trapping experiments and the Fe(II) concentration in different systems, the synergistic effect between photocatalysis and Fenton reaction is vital for the efficient pollutant degradation. The coupled system combining p-g-C₃N₄ with Q₃Fe and H₂O₂ shows potential for efficient treatment of recalcitrant organic pollutants. The combined system in this work indicated a new idea for the decomposition of organic pollutants.     

Solar Decolorization of Methylene Blue by Magnetic MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript>-MWCNT/Ag<Subscript>3</Subscript>VO<Subscript>4</Subscript> Visible Active Photocatalyst

MgFe₂O₄-MWCNT/Ag₃VO₄ photocatalyst was prepared for benefiting the visible region of solar spectrum. Prepared catalyst was characterized by using scanning electron microscope (SEM), X-ray diffraction (XRD), and energy-dispersive X-ray spectroscopy (EDX). Photocatalytic activity was measured by methylene blue (MB) decolorization under visible light obtained from a 105-W tungsten light bulb. Dye decolorization and its kinetics were followed up by means of a UV-vis spectrophotometer. Kinetic model of decolorization was found to be compatible with first-order kinetics. The effects of pH and concentration of MB solution on the decolorization efficiency were determined. Low and high pH conditions were found to be more effective in increasing the MB decolorization yield and rate. On the other hand, due to the low transparency of concentrated MB solutions, an increase on decolorization time and a lowering in decolorization yield were encountered. Thanks to the magnetic MgFe₂O₃ nanoparticles, 96% of the catalyst could be recovered by a simple magnetic bar. It was observed that simulated wastewater containing MB was also successfully decolorized showing that visible region-sensitive MgFe₂O₄-MWCNT/Ag₃VO₄ photocatalyst can be benefited as a potential, efficient, and reusable material for the removal organic pollutants in aquatic environment.     

Soil nitrogen mineralization and fate of (<Superscript>15</Superscript>NH<Subscript>4</Subscript>)<Subscript>2</Subscript>SO<Subscript>4</Subscript> in field-incubated soil in a hardwood plantation of subtropical Australia: the effect of mulching

Background, aim, and scope  

Mulching is frequently used to overcome the drought problem in hardwood plantations that are increasingly being established in lower rainfall areas of Queensland, Australia because of increasing land values. In addition to soil water content, soil nitrogen (N) availability is another critical determinant of plantation productivity in these areas. The purpose of this study was to understand how soil mineral N dynamics, in situ N mineralization, and the fate of fertilized N would be affected by mulching during the early establishment of hardwood plantations.     

Effects of TiO<Subscript>2</Subscript> Nanoparticles on the Neotropical Cladoceran <Emphasis Type="Italic">Ceriodaphnia silvestrii</Emphasis> by Waterborne and Dietary Routes

The impact of nanoparticles (NPs) in zooplankton is poorly studied, particularly when organisms are exposed through diet. Food, constituted mainly by unicellular algae, can act as an important route of contamination for zooplankton. Since unicellular algae have a high surface area in relation to their volume, NPs can interact with their cell membranes and walls, as well as with exopolysaccharides secreted by them. In the present research, we investigated both the acute effects of waterborne titanium dioxide nanoparticles (TiO₂ NPs), and its chronic effects via dietary exposure on the Neotropical freshwater zooplankton Ceriodaphnia silvestrii Daday, 1902 (Crustacea: Cladocera). The observed acute effects served as support for chronic tests, in which we investigated the effects of TiO₂ NPs on survival and life history parameters (body length, numbers of eggs, and neonates produced) of cladoceran adult females, using the freshwater cosmopolitan chlorophycean Raphidocelis subcapitata as source of contamination of TiO₂ NPs for zooplankton. R. subcapitata cells were exposed to concentrations of 0, 0.01, 1, and 10 mg L^?1 of TiO₂ NPs for 96 h, and then provided as food for females of C. silvestrii until the third brood was released. Significant toxic effects were observed in body length and total number of neonates and eggs produced by females of C. silvestrii at concentrations of 1 and 10 mg L^?1 of TiO₂ NPs. Survival was the most sensitive parameter when exposure was given via food. From the concentration of 0.01 mg L^?1 of TiO₂ NPs, there was a decrease in the survival of C. silvestrii females. The quantification of TiO₂ NPs in algae evidenced that they have retained NPs in their cells, being, therefore, an important route of exposure and toxicity of TiO₂ NPs to the studied microcrustacean.     

Photodegradation of Bisphenol A with ZnO and TiO<Subscript>2</Subscript>: Influence of Metal Ions and Fenton Process

In this study, photocatalytic degradation of bisphenol A (BPA) was investigated using two types of catalysts (TiO₂ and ZnO) with various metal ion concentrations and amounts of added H₂O_2. A kinetic test was performed to observe the changes of BPA over time under UV irradiation in a photocatalytic reactor. Experimental results demonstrated that degradation efficiency of ZnO was higher than that of TiO₂. The degradation rate increased as catalyst dosage increased until reaching optimum dosage, after which degradation rate decreased. The addition of H₂O₂ improved the degradation efficiency of BPA, with the degradation efficiency increasing with the amount of H₂O₂. All metal ions, including Fe²⁺, Ni²⁺, and Cu²⁺, inhibited the degradation of BPA by ZnO at natural pH, whereas Fe²⁺ and Ni²⁺ enhanced degradation efficiency of BPA at acidic pH. Comparison of BPA degradation with H₂O₂ only, ZnO/H₂O₂, Fe²⁺/H₂O₂, and ZnO/Fe²⁺/H₂O₂ revealed that Fe²⁺/H₂O₂ was more efficient than other processes at lower pH (pH?=?3.44), whereas ZnO/H₂O₂ the most efficient at higher pH (pH?=?6.44). These results indicate that ZnO/H₂O₂ process was observed to be the most efficient of all processes. Degradation efficiency of BPA by ZnO was also influenced by additional parameters, including H₂O₂ concentration, metal ions, and solution pH.     

Effect of CO<Subscript>2</Subscript> on nitrification and immobilization of NH<Subscript>4</Subscript><Superscript>+</Superscript>-N

A laboratory incubation experiment was conducted to demonstrate that reduced availability of CO₂ may be an important factor limiting nitrification. Soil samples amended with wheat straw (0%, 0.1% and 0.2%) and (¹⁵NH₄)₂SO₄ (200 mg N kg^–1 soil, 2.213 atom% ¹⁵N excess) were incubated at 30±2°C for 20 days with or without the arrangement for trapping CO₂ resulting from the decomposition of organic matter. Nitrification (as determined by the disappearance of NH₄⁺ and accumulation of NO₃^–) was found to be highly sensitive to available CO₂ decreasing significantly when CO₂ was trapped in alkali solution and increasing substantially when the amount of CO₂ in the soil atmosphere increased due to the decomposition of added wheat straw. The co-efficient of correlation between NH₄⁺-N and NO₃^–-N content of soil was highly significant (r =0.99). During incubation, 0.1–78% of the applied NH₄⁺ was recovered as NO₃^– at different incubation intervals. Amendment of soil with wheat straw significantly increased NH₄⁺ immobilization. From 1.6% to 4.5% of the applied N was unaccounted for and was due to N losses. The results of the study suggest that decreased availability of CO₂ will limit the process of nitrification during soil incubations involving trapping of CO₂ (in closed vessels) or its removal from the stream of air passing over the incubated soil (in open-ended systems).     

Suppression of NH<Subscript>3</Subscript> and N<Subscript>2</Subscript>O emissions by massive urea intercalation in montmorillonite

Purpose  

A large amount of nitrogen (N) fertilizers has been broadcasted over soil surface for reliable crop production. Unfortunately, the broadcasted N vulnerable to volatilization and leaching can lead to serious environmental problems. As a new approach to mitigate N loss of broadcasted fertilizers, massive intercalation of urea into montmorillonite (MMT) was recently proposed to innovatively enhance the urea use efficiency. This study focuses on demonstrating the behaviors of the urea intercalated into MMT in soils.     

Solar Photocatalysis Using Fixed-Film TiO<Subscript>2</Subscript> for Microcystins from Colonial <Emphasis Type="Italic">Microcystis aeruginosa</Emphasis>

Microcystins (MCs) are endotoxins produced by cyanobacteria in freshwaters globally. With known potential for human health risks, rapid and effective treatment methods are needed for MCs. Previous studies have shown photocatalysis can achieve rapid half-lives with UV lamps and slurries of TiO₂. In this experiment, rates and extents of solar photocatalysis of MCs were measured using bench-scale reactors with fixed films of TiO₂ for solutions with a range of cellular:aqueous MC ratios. Since cellular MCs can be removed physically, photocatalysis rates were measured following sand filtration to discern the extent of MC removal post-filtration. Since UV energy drives photocatalysis using TiO₂, rates of removal were calculated as a function of cumulative UV insolation and time. For water containing < 10% aqueous MC, filtration removed 90% of total MC, and the subsequent photocatalysis half-life was 0.37 MJ/m² (or 111 min). For water with ~?50% aqueous MCs, filtration removed 52% of the total MCs, and the average half-life for photocatalysis was 0.38 MJ/m² (or 138 min). For the >?90% aqueous MC treatment, filtration removed 0% MCs, and the photocatalysis half-life for MCs was 0.37 MJ/m² (or 135 min). Previous studies have used clarified waters; however, results from this study are likely representative of scenarios with waters containing confounding water characteristics and use of solar light for UV, as anticipated in developing countries with less advanced water treatment methods. Photocatalysis is a rapid and effective process for decreasing concentrations of MCs and could be useful for mitigating risks from MC exposures in drinking water.     

A Stable Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/Expanded Perlite Composite Catalyst for Degradation of Rhodamine B in Heterogeneous Photo-Fenton System

A stable and efficient Fe₂O₃/expanded perlite (Fe₂O₃-Ep) composite catalyst was synthesized by a simple hydrothermal method for degradation of refractory contaminants in heterogeneous photo-Fenton system. X-ray diffraction and FT-IR analyses confirmed the presence of the Fe₂O₃ in the synthesized catalyst. The catalytic activity of the Fe₂O₃-Ep catalyst was evaluated by the degradation of rhodamine B (RhB, 5 mg/L) and metronidazole (MET, 5 mg/L) in the presence of H₂O₂ under visible light irradiation. The Fe₂O₃-Ep catalyst exhibited high efficiency for degradation of RhB at a wide pH range from 2 to 10 and showed excellent catalytic property for decomposition of MET as well. The degradation ratio of RhB was achieved 99%, and the removal ratio of COD was 62% within 90 min at the best experimental conditions (0.5 g/L of Fe₂O₃-Ep catalyst, 2 mL/L of H₂O₂). Furthermore, iron leaching of the Fe₂O₃-Ep catalyst during the catalytic degradation reaction was negligible and the catalyst still exhibited high catalytic activity and stability after five cycles. These results show that the catalyst can be used as a highly efficient heterogeneous photo-Fenton catalyst for the degradation of non-biodegradable refractory pollutants in water.     

pH-Based Strategies for an Efficient Addition of H<Subscript>2</Subscript>O<Subscript>2</Subscript> During Ozonation to Improve the Mineralisation of Two Contaminants with Different Degradation Resistances

Ozonation is an efficient process for the primary degradation of most substrates but not for their mineralisation. In this work, the ozonation enhanced with the addition of H₂O₂ was studied for two substrates with very different oxidation resistances: the dye rhodamine 6G (R6G) and the surfactant linear alkylbenzene sulfonate (LAS). With O₃ only, the primary degradation of R6G was completed in less than 10 min but its TOC removal only reached 45% in 1 h. By adding H₂O₂, TOC removal was increased to 70% with a molar ratio (mol H₂O₂/mol substrate) of 10. The analysis of pH decrease served to define the specific basicity loss (SBL). The optimum conditions for the R6G mineralisation were found to be associated with a SBL value between 1 and 10 ((min/g)/L)^?1, through an adequate addition of H₂O₂. Moreover, in the case of LAS, the addition of H₂O₂ for a greater efficiency should occur after the foaming period, above all formed at acid pH. LAS degradation was also considerably improved, and the optimum for primary degradation achieved in 10 min with a TOC removal of over 65% with a molar ratio (mol H₂O₂/mol substrate) of 20.

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? Graphical Abstract

     

Effect of Stover Management and Nitrogen Fertilization on N<Subscript>2</Subscript>O and CO<Subscript>2</Subscript> Emissions from Irrigated Maize in a High Nitrate Mediterranean Soil

A high soil nitrogen (N) content in irrigated areas quite often results in environmental problems. Improving the management practices of intensive agriculture can mitigate greenhouse gas (GHG) emissions. This study compared the effect of maize stover incorporation or removal together with different mineral N fertilizer rates (0, 200 and 300 kg N ha^?1) on the emission of nitrous oxide (N₂O) and carbon dioxide (CO₂) on a sprinkler-irrigated maize (Zea mays L.). The trail was conducted in the Ebro Valley (NE Spain) in a high nitrate-N soil (i.e. 200 g NO₃–N kg^?1). Nitrous oxide and CO₂ emissions were sampled weekly using a semi-static closed chamber and quantified using the photoacoustic technique in 2011 and 2012. Applying sidedress N fertilizer tended to increase N₂O emissions whereas stover incorporation did not have any clear effect. Nitrification was probably the main process leading to N₂O. Denitrification was limited by the low soil moisture content (WFPS <?54%), due to an adequate irrigation management. Emissions ranged from ??0.11 to 0.36% of the N applied, below the IPCC (2007) values. Nitrogen fertilization tended to reduce CO₂ emission, but only in 2011. Stover incorporation increased CO₂ emission. Nitrogen use efficiency decreased with increasing mineral fertilizer supply. The application of N in high N soils of the Ebro Valley is not necessary until the soil restores a normal mineral N content, regardless of stover management. This will combine productivity with keeping N₂O and CO₂ emissions under control provided irrigation is adequately managed. Testing soil NO₃ ^?–N contents before fertilizing would improve N fertilizer recommendations.