Fe-pillared bentonite,a stable Fenton catalyst for treatment of petroleum refinery wastewater

Fe-pillared bentonite (Fe-Bent) was prepared by ion exchange as heterogeneous catalyst for degradation of organic contaminants in petroleum refinery wastewater. X-ray diffraction analysis showed the existence of α-Fe₂O₃. The effects of pH, H₂O₂ concentration, and catalyst dosage on the rate of lowering the chemical oxygen demand (COD) were investigated in detail. Removal efficiency of COD can be up to 92% under the following conditions: dosage of Fe-Bent 7 g L^?1, pH value 3, and H₂O₂ concentration 10 mmol L^?1. Fe-Bent showed good stability for the degradation of organics in petroleum refinery wastewater for five cycles. The adsorption of organics in wastewater onto Fe-Bent could be well described by a pseudo-second-order kinetic model.     

Removal of carbamazepine from urban wastewater by sulfate radical oxidation

The occurrence of bioactive trace pollutants such as pharmaceuticals in natural waters is an emerging issue. Numerous pharmaceuticals are not completely removed in conventional wastewater treatment plants. Advanced oxidation processes may represent an interesting alternative to completely mineralize organic trace pollutants. In this article, we show that sulfate radicals generated from peroxymonosulfate/Co^II are more efficient than hydroxyl radicals generated from the Fenton’s reagent (H₂O₂/Fe^II) for the degradation of the pharmaceutical compound, carbamazepine. The second-order rate constant for the reaction of SO₄ ^·− with carbamazepine is 1.92·10⁹ M⁻¹ s⁻¹. In laboratory grade water and in real urban wastewater, SO₄ ^·− yielded a faster degradation of carbamazepine compared to HO^· . Under strongly oxidizing conditions, a nearly complete mineralization of carbamazepine was achieved, while under mildly oxidizing conditions, several intermediates were identified by LC–MS. These results show for the first time in real urban wastewater that sulfate radicals are more selective than hydroxyl radicals for the oxidation of an organic pollutant and may represent an interesting alternative in advanced oxidation processes.     

Microwave and Fenton's reagent oxidation of wastewater

We compared two H₂O₂ oxidation methods for the treatment of industrial wastewater: oxidation using Fenton's reagent [H₂O₂/Fe(II)] and microwave irradiation. Both methods were applied to the treatment of synthetic phenol solutions (100 mg L⁻¹) and of an industrial effluent containing a mixture of ionic and non-ionic surfactants at high load (20 g L⁻¹ of COD). The effects of initial pH, initial H₂O₂ concentration, Fenton catalyst amount and irradiation time were assessed. According to the oxidation of phenol, it has been found that the oxidation by Fenton's reagent is dependent on the pH, contrary to the microwave system, which is not influenced by this parameter. For both systems, a limiting amount of oxidant has been found; above this point the oxidation of phenol is not improved by a further addition of peroxide. The oxidation of the industrial surfactant effluent has only been successful with the Fenton's reagent. In this case, large amounts of ferrous ions are necessary for the precipitation of the ionic surfactants of the effluent, followed by the oxidation of the non-ionic constituents of the solution. Electronic Publication     

Treatment of organic pollutants by homogeneous and heterogeneous Fenton reaction processes

Nowadays, the water ecosystem is being polluted due to the rapid industrialization and massive use of antibiotics, fertilizers, cosmetics, paints, and other chemicals. Chemical oxidation is one of the most applied processes to degrade contaminants in water. However, chemicals are often unable to completely mineralize the pollutants. Enhanced pollutant degradation can be achieved by Fenton reaction and related processes. As a consequence, Fenton reactions have received great attention in the treatment of domestic and industrial wastewater effluents. Currently, homogeneous and heterogeneous Fenton processes are being investigated intensively and optimized for applications, either alone or in a combination of other processes. This review presents fundamental chemistry involved in various kinds of homogeneous Fenton reactions, which include classical Fenton, electro-Fenton, photo-Fenton, electro-Fenton, sono-electro-Fenton, and solar photoelectron-Fenton. In the homogeneous Fenton reaction process, the molar ratio of iron(II) and hydrogen peroxide, and the pH usually determine the effectiveness of removing target pollutants and subsequently their mineralization, monitored by a decrease in levels of total organic carbon or chemical oxygen demand. We present catalysts used in heterogeneous Fenton or Fenton-like reactions, such as H₂O₂–Fe³⁺(solid)/nano-zero-valent iron/immobilized iron and electro-Fenton-pyrite. Surface properties of heterogeneous catalysts generally control the efficiency to degrade pollutants. Examples of Fenton reactions are demonstrated to degrade and mineralize a wide range of water pollutants in real industrial wastewaters, such as dyes and phenols. Removal of various antibiotics by homogeneous and heterogeneous Fenton reactions is exemplified.     

Degradation of azo dyes in water by Electro-Fenton process

The degradation of the azo dyes azobenzene, p-methyl red and methyl orange in aqueous solution at room temperature has been studied by an advanced electrochemical oxidation process (AEOPs) under potential-controlled electrolysis conditions, using a Pt anode and a carbon felt cathode. The electrochemical production of Fenton's reagent (H₂O₂, Fe²⁺) allows a controlled in situ generation of hydroxyl radicals (^·OH) by simultaneous reduction of dioxygen and ferrous ions on the carbon felt electrode. In turn, hydroxyl radicals react with azo dyes, thus leading to their mineralization into CO₂ and H₂O. The chemical composition of the azo dyes and their degradation products during electrolysis were monitored by high performance liquid chromatography (HPLC). The following degradation products were identified: hydroquinone, 1,4-benzoquinone, pyrocatechol, 4-nitrocatechol, 1,3,5-trihydroxynitrobenzene and p-nitrophenol. Degradation of the initial azo dyes was assessed by the measurement of the chemical oxygen demand (COD). Kinetic analysis of these data showed a pseudo-first order degradation reaction for all azo dyes. A pathway of degradation of azo dyes is proposed. Specifically, the degradation of dyes and intermediates proceeds by oxidation of azo bonds and aromatic ring by hydroxyl radicals. The results display the efficiency of the Electro-Fenton process to degrade organic matter. Electronic Publication     

Coupled electrocoagulation–electro-Fenton for efficient domestic wastewater treatment

This article reports the first use of coupled electrocoagulation and electro-Fenton (EF-EC) to clean domestic wastewater. Domestic wastewater contains high amounts of organic, inorganic and microbial pollutants that cannot be usually treated in a single step. Here, to produce an effluent suitable for discharge in a single process step, a hybrid process combining electrocoagulation and electro-Fenton was simultaneously used to decrease chemical oxygen demand (COD), turbidity and total suspended solids (TSS) from domestic wastewater. The electrocoagulation–electro-Fenton process was firstly tested for the production of H₂O₂ using Ti–IrO₂ and vitreous carbon- or graphite electrodes arranged at the anode and the cathode, respectively. The concentration of H₂O₂ recorded at 1.5 A of current intensity during 60 min of electrolysis using vitreous carbon- and graphite electrodes at the cathode was 4.18 and 1.62 mg L^?1, respectively. By comparison, when the iron electrode was used at the anode, 2.05 and 1.06 mg L^?1 of H₂O₂ were recorded using vitreous carbon and graphite, respectively. The H₂O₂ concentration decrease was attributed to hydroxyl radical formation generated by the Fenton reaction. Electro-Fenton using iron electrode at the anode and vitreous carbon at the cathode with a current density imposed of 0.34 A dm^?2 ensures the removal efficiency of 50.1 % COD_T, 70.8 % TSS and 90.4 % turbidity. The electrocoagulation–electro-Fenton technique is therefore a promising secondary treatment to simultaneously remove organic, inorganic and microbial pollutants from domestic, municipal and industrial wastewaters.     

Removal of organophosphorus pesticides from water by electrogenerated Fenton's reagent

Aqueous solutions of organophosphorus pesticides were completely mineralized via in-situ generated hydroxyl radicals (HO^·) by the Electro-Fenton process. Formation of Fenton's reagent (H₂O₂, Fe²⁺) was carried out by simultaneous reduction of O₂ and Fe³⁺ on carbon cathode in acidic medium. The electrochemistry combined with Fenton's reagent provides an excellent way to continuously produce the hydroxyl radical, a powerful oxidant. We demonstrate the efficiency of the Electro-Fenton process to degrade three organophosphorus insecticides: malathion, parathion ethyl and tetra-ethyl-pyrophosphate (TEPP). Degradation kinetics and removals of chemical oxygen demand (COD) have been investigated. Here we show that the mineralization efficiency was over 80% for three organophosphorus pesticides.     

Photocatalytic oxidation of the textile dye basic red 18 with irradiated titanium dioxide

One of the major problems of textile wastewater is the presence of dye materials, because colour is visible to the public even if the dye concentration is lower than other pollutants, and needs therefore to be removed from the wastewater before it is discharged. Techniques based on “advanced oxidative processes” such as photocatalysed oxidation seem to be very promising for industrial wastewater treatment, especially for decolourization of textile effluents. In this work, we describe the photocatalytic degradation of the textile dye Basic Red 18 (BR 18) in aqueous solution using two different types of TiO₂ as photocatalyst: Degussa P25 (80% anatase) and Framitalia (100% anatase). Photooxidation of BR 18 was followed by HPLC analysis, and kinetic parameters were evaluated in order to optimise the treatment procedure. The results obtained in this work showed that the colour became virtually zero and the chemical oxygen demand (COD) is strongly reduced at the end of the treatment. The obtained results are compared with the efficiency of decolourization using the H₂O₂/UV System. Finally, marine mussel test was used to evaluate the efficiency of photocatalytic oxidation with TiO₂ in terms of ecotoxicity. A significant reduction of cumulative mortality was observed for the treated effluent.     

Enhancement on the ammonia oxidation capacity of ammonia-oxidizing archaeon originated from wastewater: Utilizing low-density static magnetic field

• AOA’s ammonia oxidizing capacity was enhanced under moderate magnetic field. • AOA possessed a certain magnetotaxis under uneven magnetic field. • Enhanced ammonia oxidizing capacity was lost once magnetic field was removed. Ammonia-oxidizing archaeon (AOA) could play important roles for nitrogen removal in the bioreactors under conditions such as low pH and low dissolved oxygen. Therefore, enhancing ammonia oxidation capability of AOA has great significance for water and wastewater treatment, especially under conditions like low dissolved oxygen concentration. Utilizing a novel AOA strain SAT1, which was enriched from a wastewater treatment plant by our group, the effect of magnetic field on AOA’s ammonia oxidation capability, its magnetotaxis and heredity were investigated in this study. Compared with control experiment, AOA’s maximum nitrite-N formation rate during the cultivation increased by 56.8% (0.65 mgN/(L·d)) with 20 mT magnetic field. Also, it was testified that AOA possessed a certain magnetotaxis. However, results manifested that the enhancement of AOA’s ammonia oxidation capability was not heritable, that is, lost once the magnetic field was removed. Additionally, the possible mechanism of improving AOA’s ammonia oxidation capability by magnetic field was owing to the promotion of AOA single cells’ growth and fission, rather than the enhancement of their ammonia oxidation rates. The results shed light on the application of AOA and methods to enhance AOA’s ammonia oxidation capability, especially in wastewater treatment processes under certain conditions.     

Wet oxidation of debarking water: changes in lignin content and biodegradability

The purpose of the research was to estimate optimal conditions for wet oxidation (WO) of debarking water from the paper industry. The WO experiments were performed at various temperatures, partial oxygen pressures and pHs. The experiments showed that lignin degradation and organics removal are affected remarkably by temperature and pH. At different WO conditions (pH 12, T 130–200°C), 78–97% of lignin reduction was detected. pH value of 12 caused faster removal of tannins/lignin content; pH value of five was more effective for removal of total organics, represented by chemical oxygen demand (COD) and total organic carbon. The highest biodegradability [biological oxygen demand (BOD)/COD] of 0.72 was obtained at a pH of ten and temperature of 200°C.     

Acidogenic sludge fermentation to recover soluble organics as the carbon source for denitrification in wastewater treatment: Comparison of sludge types

For biological nitrogen (N) removal from wastewater, a sufficient organic carbon source is requested for denitrification. However, the organic carbon/nitrogen ratio in municipal wastewater is becoming lower in recent years, which increases the demand for the addition of external organic carbon, e.g. methanol, in wastewater treatment. The volatile fatty acids (VFAs) produced by acidogenic fermentation of sewage sludge can be an attractive alternative for methanol. Chemically enhanced primary sedimentation (CEPS) is an effective process that applies chemical coagulants to enhance the removal of organic pollutants and phosphorus from wastewater by sedimentation. In terms of the chemical and biological characteristics, the CEPS sludge is considerably different from the conventional primary and secondary sludge. In the present study, FeCl₃ and PACl (polyaluminum chloride) were used as the coagulants for CEPS treatment of raw sewage. The derived CEPS sludge (Fe-sludge and Al-sludge) was then processed with mesophilic acidogenic fermentation to hydrolyse the solid organics and produce VFAs for organic carbon recovery, and the sludge acidogenesis efficiency was compared with that of the conventional primary sludge and secondary sludge. The results showed that the Fe-sludge exhibited the highest hydrolysis and acidogenesis efficiency, while the Al-sludge and secondary sludge had lower hydrolysis efficiency than that of primary sludge. Utilizing the Fe-sludge fermentation liquid as the carbon source for denitrification, more than 99% of nitrate removal was achieved in the main-stream wastewater treatment without any external carbon addition, instead of 35% obtained from the conventional process of primary sedimentation followed by the oxic/anoxic (O/A) treatment.

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Improving simulations of sulfate aerosols during winter haze over Northern China: the impacts of heterogeneous oxidation by NO<Subscript>2</Subscript>

We implemented the online coupled WRF-Chem model to reproduce the 2013 January haze event in North China, and evaluated simulated meteorological and chemical fields using multiple observations. The comparisons suggest that temperature and relative humidity (RH) were simulated well (mean biases are–0.2K and 2.7%, respectively), but wind speeds were overestimated (mean bias is 0.5 m?s^–1). At the Beijing station, sulfur dioxide (SO₂) concentrations were overpredicted and sulfate concentrations were largely underpredicted, which may result from uncertainties in SO₂ emissions and missing heterogeneous oxidation in current model. We conducted three parallel experiments to examine the impacts of doubling SO₂ emissions and incorporating heterogeneous oxidation of dissolved SO₂ by nitrogen dioxide (NO₂) on sulfate formation during winter haze. The results suggest that doubling SO₂ emissions do not significantly affect sulfate concentrations, but adding heterogeneous oxidation of dissolved SO₂ by NO₂ substantially improve simulations of sulfate and other inorganic aerosols. Although the enhanced SO₂ to sulfate conversion in the HetS (heterogeneous oxidation by NO₂) case reduces SO₂ concentrations, it is still largely overestimated by the model, indicating the overestimations of SO₂ concentrations in the North China Plain (NCP) are mostly due to errors in SO₂ emission inventory.

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Treatment of biologically treated effluents from baker's yeast industry by membrane and ozone technologies

This paper presents pilot‐scale membrane treatment results performed on biologically treated effluents from fermentation industry and ozone oxidation on concentrates from the same membrane treatment system. The results obtained from the ultrafiltration (UF) and/or the reverse osmosis (RO) systems indicate that membrane treatment are very effective for COD, Color, NH₃‐N and conductivity removal. Ozone oxidation of the membrane concentrates was tested to increase biodegradability of the wastes. The initial ratios of Biochemical oxygen demand (BOD₅) to Chemical oxygen demand (COD) were increased significantly by applying chemicaloxidation with O₃ and O₃ + H₂O₂.     

UV-C light-enhanced photo-Fenton oxidation of methyl parathion

The photodegradation of aqueous solutions containing 0.2 mM methyl parathion has been studied through the optimization of the [H₂O₂]/[Fe³⁺] ratio in a Fe³⁺/H₂O₂/UV-C flow system of 1.3 L capacity. The decay kinetics and TOC abatement have been analyzed for the experiments performed at pH 3.0 and room temperature. All experiments lead to the total methyl parathion destruction after a few minutes, following a pseudo-first-order decay kinetics. Total mineralization can be reached after 120 min at the optimum ratio found, due to the synergistic effect of the very oxidizing hydroxyl radical (^·OH) produced via the Fenton reagent and the effective photodecarboxylation at 253.7 nm.     

Wastewater treatment meets artificial photosynthesis: Solar to green fuel production,water remediation and carbon emission reduction

• Mitigating energy utilization and carbon emission is urgent for wastewater treatment. • MPEC integrates both solar energy storage and wastewater organics removal. • Energy self-sustaining MPEC allows to mitigate the fossil carbon emission. • MPEC is able to convert CO₂ into storable carbon fuel using renewable energy. • MPEC would inspire photoelectrochemistry by employing a novel oxidation reaction. Current wastewater treatment (WWT) is energy-intensive and leads to vast CO₂ emissions. Chinese pledge of “double carbon” target encourages a paradigm shift from fossil fuels use to renewable energy harvesting during WWT. In this context, hybrid microbial photoelectrochemical (MPEC) system integrating microbial electrochemical WWT with artificial photosynthesis (APS) emerges as a promising approach to tackle water-energy-carbon challenges simultaneously. Herein, we emphasized the significance to implement energy recovery during WWT for achieving the carbon neutrality goal. Then, we elucidated the working principle of MPEC and its advantages compared with conventional APS, and discussed its potential in fulfilling energy self-sustaining WWT, carbon capture and solar fuel production. Finally, we provided a strategy to judge the carbon profit by analysis of energy and carbon fluxes in a MPEC using several common organics in wastewater. Overall, MPEC provides an alternative of WWT approach to assist carbon-neutral goal, and simultaneously achieves solar harvesting, conversion and storage.     

Molecular transformation of dissolved organic matter in high-temperature hydrogen peroxide oxidation of a refinery wastewater

Environmental Chemistry Letters - Advanced oxidation processes have been extensively used in industrial wastewater treatment. However, the&nbsp;molecular transformation of dissolved organic...     

Total labile carbon in the euphotic zone of the Baltic Sea as measured by BOD

Total labile organic carbon was estimated in the euphotic zone of the Baltic Sea by a method based on the determination of the biological oxygen demand (BOD); the method is extremely simple, requires little sample water, and is quite precise (±4.5 μmol O₂/l or ±40.4 μgC_lab/l). The amount found was 1,150 μgC_lab/l, or about 29% of the total organic carbon. At 1 m, a relationship between biological activity, as measured by chlorophyll content, and the amount of labile carbon was found: ln C_lab (μg/l)=ln 6.87 (μg/l) +0.272 ln chlorophyll (μg/l), with a correlation coefficient of 0.86, which is significantly greater than zero at the 0.001 level.     

Removal of the herbicide amitrole from water by anodic oxidation and electro-Fenton

Here we demonstrate that an aqueous solution of the herbicide amitrole can be completely depolluted at pH 3.0 by anodic oxidation and electro-Fenton process. Anodic oxidation gives faster degradation with a boron-doped diamond anode than with a Pt anode. Electro-Fenton with a Pt anode and 1 mmol l ^–1 Fe²⁺ as catalyst yields the quickest depollution. Amitrole decay always follows a pseudo first-order reaction. NO₃^– and NH₄⁺ are accumulated in the medium during mineralization, although volatile N-products are also formed. These environmentally friendly electrochemical treatments could be applied to the remediation of wastewaters containing amitrole.     

Effect of algal bloom deposition on sediment respiration and fluxes

Using sediment cores collected in November 1989 from Aarhus Bight, Denmark, the fluxes of O₂, CO₂ (total CO₂), NH ₄ ⁺ , NO ₃ ^– +NO ₂ ^– and DON (dissolved organic nitrogen) across the sediment-water interface were followed for 20 d in an experimental continous flow system. On day 7, phytoplankton was added to the sediment surface, to see the result of simulated algal bloom sedimentation. Benthic O₂ consumption and CO₂ efflux, 38 to 41 mmol O₂ m^-2 d^-1 and 25 to 30 mmol CO₂ m^-2 d^-1, respectively, immediately increased by 39% and 100% after the algal addition, but gradually declined to the orginal level. Fluxes of NH ₄ ⁺ (1.0 to 1.2 mmol m^-2 d^-1) and DON (0.3 to 0.9 mmol m^-2 d^-1) increased due to the organic substrate addition. NH ₄ ⁺ and NO ₃ ^– flux changed direction, becoming an efflux and influx, respectively, for a few days and a large amount of DON (max. rate 4.0 mmol m^-2 d^-1) was immediately produced either by bacterial hydrolytic activity or from autolysis of the algae. DON was the most significant nitrogen component in pore water and in terms of N-flux from sediment. A temporary stimulation of anaerobic respiration processes (sulfate reduction and denitrification) and a decrease in nitrification were indicated. After the effect of the organic addition had declined, the fluxes gradually reverted to the original rates. The halflife of the added algal material, of which 20 to 30% was very labile, was estimated to be 2 to 3 wk.     

Rate and extent of decomposition of dissolved organic matter in surface seawater

An experiment on the decomposition of the dissolved organic matter (DOM) in surface seawater was carried out under controlled laboratory conditions during a cruise of the R.V. Hakuho-Maru in the North-Equatorial Pacific (August/November, 1969). Surface seawater was placed in 300 ml oxygen bottles and incubated in the dark at 25°C. After selected time intervals, the dissolved organic-carbon (DOC) and the dissolved oxygen (DO) were determined for each bottle. The DOM in the surface seawater was described in terms of two labile fractions and a refractory one. The DOC decreased from 0.96 to 0.74 mgC/l during the first 50 days of incubation. Approximately 20% of the initial DOC (Fraction F_I) was oxidized. The other labile fraction, F_II was assumed to be 30 to 40% of the total DOM. The remaining half of the total DOM (Fraction F_III) is probably refractory and resistant to biochemical oxidation. The rate constant for decomposition was 0.0052 day^–1 for the total DOM and 0.033 day^–1 for F _I.