Advanced oxidation processes in the treatment of trifluraline effluent

The treatment of an effluent from the production of trifluraline was studied using a 1-L, semi-batch, tank-stirred glass reactor for performing three different advanced oxidation processes (photoperoxidation, Fenton, photo-Fenton). A commercial, medium-pressure mercury lamp was used for sample irradiation. The degradation was monitored by measurements of absorptiometric color reduction, UV-visible absorption spectra, and chemical oxygen demand (COD). The obtained results showed that the photo-Fenton process was the most effective treatment for the trifluraline effluent.     

Kinetic degradation of the pollutant guaiacol by dark Fenton and solar photo-Fenton processes

This work is first intended to optimize the experimental conditions for the maximum degradation of guaiacol (2-methoxyphenol) by Fenton’s reagent, and second, to improve the process efficiency through the use of solar radiation. Guaiacol is considered as a model compound of pulp and paper mill effluent. The experiments were carried out in a laboratory-scale reactor subjected or not to solar radiation. Hydrogen peroxide solution was continuously introduced into the reactor at a constant flow rate. The kinetics of organic matter decay was evaluated by means of the chemical oxygen demand (COD) and the absorbance measurements. The experimental results showed that the Fenton and solar photo-Fenton systems lead successfully to 90% elimination of COD and absorbance at 604 nm from a guaiacol solution under particular experimental conditions. The COD removal always obeyed a pseudo-first-order kinetics. The effect of pH, temperature, H₂O₂ dosing rate, initial concentration of Fe²⁺, and initial COD was investigated using the Fenton process. The solar photo-Fenton system needed less time and consequently less quantity of H₂O₂. Under the optimum experimental conditions, the solar photo-Fenton process needs a dose of H₂O₂ 40% lower than that used in the Fenton process to remove 90% of COD.     

A comparative study of photo-Fenton process assisted by natural sunlight,UV-A,or visible LED light irradiation for degradation of real textile wastewater: factorial designs,kinetics, cost assessment,and phytotoxicity studies

Environmental Science and Pollution Research - The present work aims to evaluate the treatment of the effluent from the textile industry via advanced oxidative processes of photo-Fenton assisted by...     

Hydroxyl radical concentration profile in photo-Fenton oxidation process: generation and consumption of hydroxyl radicals during the discoloration of azo-dye Orange II

Dynamic behaviors of hydroxyl (OH) radical generation and consumption in photo-Fenton oxidation process were investigated by measuring OH radical concentration during the discoloration of azo-dye Orange II. The effects of operating parameters for photo-Fenton discoloration, i.e. dosages of H₂O₂ and Fe, initial dye concentration, solution pH and UV irradiation, on the generation and consumption of OH radicals playing the main role in advanced oxidation processes were extensively studied. The scavenger probe or trapping technique in which coumarin is scavenger of OH radical was applied to estimate OH radical concentration in the photoreactor during the photo-Fenton discoloration process. The OH radical generation was enhanced with increasing the dosages of Fenton regents, H₂O₂ and Fe. At the initial stage of photo-Fenton discoloration of Orange II, the OH radical concentration rapidly increased (Phase-I) and the OH radical concentration decreased after reaching of OH radical concentration at maximum value (Phase-II). The decrease in OH radical concentration started when the complete discoloration of Orange II was nearly achieved and the H₂O₂ concentration became rather low. The dynamic behavior of OH radical concentration during the discoloration of Orange II was found to be strongly linked with the change in H₂O₂ concentration. The generation of OH radical was maximum at solution pH of 3.0 and decreased with an increase of solution pH. The OH radical generation rate in the Fenton Process was rather slower than that in the photo-Fenton process.     

Iron-impregnated zeolite catalyst for efficient removal of micropollutants at very low concentration from Meurthe river

In this paper, for the first time, faujasite Y zeolite impregnated with iron (III) was employed as a catalyst to remove a real cocktail of micropollutants inside real water samples from the Meurthe river by the means of the heterogeneous photo-Fenton process. The catalyst was prepared by the wet impregnation method using iron (III) nitrate nonahydrate as iron precursor. First, an optimization of the process parameters was conducted using phenol as model macro-pollutant. The hydrogen peroxide concentration, the light wavelength (UV and visible) and intensity, the iron loading immobilized, as well as the pH of the solution were investigated. Complete photo-Fenton degradation of the contaminant was achieved using faujasite containing 20 wt.% of iron, under UV light, and in the presence of 0.007 mol/L of H₂O₂ at pH 5.5. In a second step, the optimized process was used with real water samples from the Meurthe river. Twenty-one micropollutants (endocrine disruptors, pharmaceuticals, personal care products, and perfluorinated compounds) including 17 pharmaceutical compounds were specifically targeted, detected, and quantified. All the initial concentrations remained in the range of nanogram per liter (0.8–88 ng/L). The majority of the micropollutants had a large affinity for the surface of the iron-impregnated faujasite. Our results emphasized the very good efficiency of the photo-Fenton process with a cocktail of a minimum of 21 micropollutants. Except for sulfamethoxazole and PFOA, the concentrations of all the other microcontaminants (bisphenol A, carbamazepine, carbamazepine-10,11-epoxide, clarithromycin, diclofenac, estrone, ibuprofen, ketoprofen, lidocaine, naproxen, PFOS, triclosan, etc.) became lower than the limit of quantification of the LC-MS/MS after 30 min or 6 h of photo-Fenton treatment depending on their initial concentrations. The photo-Fenton degradation of PFOA can be neglected. The photo-Fenton degradation of sulfamethoxazole obeys first-order kinetics in the presence of the cocktail of the other micropollutants.     

Design and Performance Characterization Strategy Using Modeling for Biofiltration Control of Odorous Hydrogen Sulfide

Abstract

Biofilter, dynamic modeling software characterizing contaminant removal via biofiltration, was used in the preliminary design of a biofilter to treat odorous hydrogen sulfide (H₂S). Steady-state model simulations were run to generate performance plots for various influent concentrations, loadings, residence times, media sizes, and temperatures. Although elimination capacity and removal efficiency frequently are used to characterize biofilter performance, effluent concentration can be used to characterize performance when treating to a target effluent concentration. Model simulations illustrate that, at a given temperature, a biofilter cannot reduce H₂S emissions below a minimum value, no matter how large the biofilter or how long the residence time. However, a higher biofilter temperature results in lower effluent H₂S concentrations. Because dynamic model simulations show that shock loading can significantly increase the effluent concentration above values predicted by the steady-state model simulations, it is recommended that, to consistently meet treatment objectives, dynamic feed conditions should be considered. This study illustrates that modeling can serve as a valuable tool in the design and performance optimization of biofilters.     

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.     

Antibiotic Resistance of Enterococcus spp. Isolated from Wastewater and Sludge of Poultry Slaughterhouses

Antibiotimicrobial resistance was investigated in 537 Enterococcus spp. isolates recovered from 22 samples of crude inflow, treated effluent and sludge collected in wastewater treatment plants of eight poultry slaughterhouses of Portugal. No significant differences (P > 0.05) were found in the resistance to each antimicrobial agent with regards to the origin of the sample (inflow, sludge and effluent). Many of the isolates displayed resistance to tetracycline (85.7%), erythromycin (45.7%), nitrofurantoin (34.0%) and rifampicin (17.8%). Resistance was also observed, but to a lesser extent, to ciprofloxacin (10.2%), ampicillin (8.0%), chloramphenicol (4.6%), vancomycin (0.9%) and gentamicin (0.4%). Resistance to three or more antimicrobial classes was present in 37.1% of the isolates. Wastewater treatment resulted in viable enterococci decrease between less than 1 log and 4 log; nevertheless, more than 4.4 × 10⁵ colony forming units (CFU)/100 mL were present in the outflow of the plants and thus resistant enterococci are not prevented from reaching the general environment.     

Dynamic modelling for cork boiling wastewater treatment at pilot plant scale

Solar photo-Fenton process has been extensively reported to be highly efficient in the remediation of complex industrial wastewater containing several families of pollutants such as pharmaceuticals, dyes, pesticides, derivatives of wine, etc. Moreover, solar photo-Fenton mathematical modelling regarded as a powerful tool for scaling-up and process control purposes is hindered by the complexity and variability of its reaction mechanism which depends on the particular wastewater under study. In this work, non-biodegradable cork boiling wastewater has been selected as a case study for solar photo-Fenton dynamic modelling by using MATLAB® software. First of all physic-chemical pretreatment was applied attaining chemical oxygen demand (COD) reductions between 43 and 70 % and total suspended solid (TSS) reductions between 23 % and 59 %. After solar photo-Fenton treatment, COD decreased between 45 and 90 % after consumptions of H₂O₂ varying around 1.9 and 2.4 g/L. Individual calibration of the semi-empirical model by using experimental results made it possible to perfectly predict hydrogen peroxide variations throughout the treatment. It must be highlighted that slight deviations between predictions and experimental data must be attributed to important changes in wastewater characteristics.     

Fe(III)–EDDS complex in Fenton and photo-Fenton processes: from the radical formation to the degradation of a target compound

The present work compares the efficiency of homogenous Fenton and photo-Fenton processes in the presence of Fe(III)–EDDS complex under different experimental conditions. 4-tert-Butylphenol (4-t-BP), which is one of the endocrine disrupting chemicals, was used as a model pollutant to investigate the Fenton and photo-Fenton application. The efficiency of homogenous photo-Fenton process was significantly much higher than homogenous Fenton process, which is due to the rapid formation of Fe²⁺ under UV irradiation of the iron complex and the photochemical formation of HO^? from the photolysis of the complex Fe(III)–EDDS. Through the degradation of 4-t-BP, the effect of Fe(III)–EDDS concentration, H₂O₂ concentration, pH, and oxygen was investigated in both processes. Such trend was also correlated with pH calculating the polychromatic Fe²⁺ quantum yield formation at pH 4.0, 6.0, and 8.6. The results showed that at high Fe(III)–EDDS and H₂O₂ concentrations, a negative effect was found. By the way, the Fenton process was found to be enhanced at basic pH. These results can be very useful for the use and optimization of such iron complex in water treatment process as function of different physico-chemical conditions.     

Leaching and degradation of corn and soybean pesticides in an Oxisol of the Brazilian Cerrados

Pesticide pollution of ground and surface water is of growing concern in tropical countries. The objective of this pilot study was to evaluate the leaching potential of eight pesticides in a Brazilian Oxisol. In a field experiment near Cuiabá, Mato Grosso, atrazine, chlorpyrifos, lambda-cyhalothrin, endosulfane alpha, metolachlor, monocrotofos, simazine, and trifluraline were applied onto a Typic Haplustox. Dissipation in the topsoil, mobility within the soil profile and leaching of pesticides were studied for a period of 28 days after application. The dissipation half-life of pesticides in the topsoil ranged from 0.9 to 14 d for trifluraline and metolachlor, respectively. Dissipation curves were described by exponential functions for polar pesticides (atrazine, metolachlor, monocrotofos, simazine) and bi-exponential ones for apolar substances (chlorpyrifos, lambda-cyhalothrin, endosulfane alpha, trifluraline). Atrazine, simazine and metolachlor were moderately leached beyond 15 cm soil depth, whereas all other compounds remained within the top 15 cm of the soil. In lysimeter percolates (at 35 cm soil depth), 0.8-2.0% of the applied amounts of atrazine, simazine, and metolachlor were measured within 28 days after application. Of the other compounds less than 0.03% of the applied amounts was detected in the soil water percolates. The relative contamination potentials of pesticides, according to the lysimeter study, were ranked as follows: metolachlor > atrazine = simazine > monocrotofos > endsulfane alpha > chlorpyrifos > trifluraline > lambda-cyhalothrin. This order of the pesticides was also achieved by ranking them according to their effective sorption coefficient Ke, which is the ratio of Koc to field-dissipation half-life.     

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.     

Lysimeter Test of Coke Plant Effluent Disposal to Land in India

ABSTRACT

From the Indian national point of view, the importance of coal carbonizing industries is great and growing. These industries produce huge quantities of highly polluted effluents and discharge them into rivers without proper treatment. A large coke plant of Bharat Coking Coal Ltd. has been surveyed, and the impact of its effluent on surface water quality is discussed. Approximately 175-200 m³ of effluents are discharged from the plant every day. Land application has been considered as a low-cost means of disposal of coke oven effluents. Column lysimeters were prepared by collecting soil from a nearby agricultural field, putting it layerwise into a column, and compacting it carefully to simulate the original in situ conditions. Raw effluents, diluted effluent, and water (as a blank) were applied to the three lysimeters twice a week with a 5 cm flooding. Upon application of diluted effluent (1:1) into lysimeter No. 2, the leachate collected at 190 cm depth was within the tolerance limit of drinking water standard (IS 10,500). The impact of raw and diluted effluent on groundwater quality and soil are discussed. The renovation efficiency of living filter (lysimeter No. 2) was 99.37% for oil and grease, 86.92% for COD, and 53.22% for TDS, and it is estimated that 2.73 hectares of land can be irrigated with the effluents of the coke plant without deteriorating groundwater and soil quality.     

Aerobic Treatment of a Nitrogen-Limited Chemical Process Waste water

Abstract

Nitrogen transformations and their effect on aerobic suspended growth treatment of an industrial wastewater were studied in three parallel bench-scale reactors operated at 5 "C at mean cell residence times (MCRT) of 15, 30, and 60 days. In normal process wastewater, the bulk of influent nitrogen was in organic form, and the fraction transformed was almost totally incorporated into synthesized biomass. Assimilative control by heterotrophs maintained ammonianitrogen levels below permitted effluent levels, and nitrification was not significant. Although volatile suspended solids had a nitrogen content of only 5% to 8%, effective organics removal was maintained, and total organic carbon and filtered daily average five-day biochemical oxygen demand (BODS) were below permitted effluent levels. A marked improvement in settleability and lower effluent total suspended solids was achieved by adding ammonia-nitrogen to the wastewater in excess of stoichiometric growth requirements.

During a batch production cycle of a cationic chemical, the ratio of nitrogen to chemical oxygen demand and the fraction of the total influent nitrogen in soluble form increased in the wastewater. Reactor effluent ammonia levels increased to above permit levels at all three MCRTs during treatment of wastewater containing cationic production effluents. The magnitude of ammonia increase was greater for longer MCRTs, suggesting that synthesis of cell mass was not capable of assimilating the increased ammonia supply under these non-steady conditions. The experimental results suggest several potential strategies for operating the aerobic process at the treatment facility, including adding nitrogen to improve settleability and discontinuing these additions when wastewater contains a high ratio of nitrogen to chemical oxygen demand and an elevated soluble nitrogen fraction     

Determination of Commonly Used Herbicides in Surface Water Using Solid-Phase Extraction and Dual-Column HPLC-DAD

The present study describes the application of different solid-phase extraction techniques for the extraction, separation, and quantitative determination of 10 commonly used herbicides with different chemical structures (chlorsulfuron, diuron, bentazone, linuron, chlorpropham, fenoxoprop-ethyl, MCPA, diclofop-methyl, fluazifop-butyl, trifluraline) in water. Octadecyl (C₁₈) Empore extraction disks, octadecyl (C₁₈), and stryene divinylbenzene (SDB) Bond Elut Env cartridges were compared for solid-phase extraction efficiency. Herbicides were separated and quantified by reversed-phase high performance liquid chromatography with diode-array detection (HPLC-DAD) with simultaneous separation on two columns of differing polarity (C₁₈ and CN) to confirm identification. Analytical separation was performed simultaneously on C₁₈ and CN columns. Reanalysis of the sample extracts on a (cyano) CN column were used to confirm the identity of these compounds. Method optimization and validation parameters were presented in this work. Recoveries varied from 76.0% to 99.0% for C₁₈ disks, from 75.1% to 100.0% for C₁₈ cartridges, and from 54.0% to 98.0% for SDB cartridges over concentrations at 0.025–0.4 μg L^?1. The limits of detection were 0.012–0.035 μg L^?1.     

Improvement of solar photo-Fenton by extracts of amazonian fruits for the degradation of pharmaceuticals in municipal wastewater

Extracts of copoazu (Theobroma gramdiflorum), canangucha (Maurita Flexuosa), and coffee (Coffea arabica) were explored as enhancers of the solar photo-Fenton process to eliminate acetaminophen, sulfamethoxazole, carbamazepine, and diclofenac in raw municipal wastewater. The process, at pH 6.2 and 5 mg L^?1 of iron without the presence of extracts, had a very limited action (~35% of the pollutants degradation at 90 min of treatment) due to the iron precipitation. Interestingly, the extract addition increased the soluble iron forms, but only copoazu extract improved the pollutant degradation (~95% of elimination at 20 min of the process action). The copoazu extract components acted as natural complexing agents, maintaining the soluble iron up to 2 mg L^?1 even after 90 min and, consequently, enhancing the pollutant degradation. The effect of copoazu extract dose on the process performance was also assessed, finding that an iron:polyphenols (from the copoazu extract) at a molar ratio equal to 1:0.16 was the most favorable condition. Then, the process improved by copoazu extract was applied to raw municipal wastewater. Remarkably, the process led to ~90% of total pharmaceuticals degradation at 20 min of treatment. This work evidenced the feasibility of amazonian fruit extracts to improve the solar photo-Fenton process to degrade pharmaceuticals in aqueous matrices at near-neutral pH.

     

Comparative analysis of trace contaminants in leachates before and after a pre-oxidation using a solar photo-Fenton reaction

Sanitary landfill leachates are a complex mixture of high-strength organic and inorganic persistent contaminants, which constitute a serious environmental problem. In this study, trace contaminants present in leachates were investigated by gas chromatography-mass spectrometry and gas chromatography-flame ionization detector before and after a pre-oxidation step using a solar photo-Fenton process. More than 40 organic compounds were detected and identified as benzene (0.09?±?0.07 mg?L^-1), trichlorophenol (TCP) (0.18?±?0.12 mg?L^-1), phthalate esters (Di-n-butyl phthalate (DBP), Butyl benzyl phthalate (BBP), Di(2-ethylhexyl) phthalate (DEHP)) (DBP: 0.47?±?0.01 mg?L^-1; BBP: 0.36?±?0.02 mg?L^-1; DEHP: 0.18?±?0.01 mg?L^-1), among others. Toluene, pentachlorophenol, dimethyl phthalate, diethyl phthalate, and Di-n-octyl phthalate were never detected in any of the samples. After the photo-Fenton treatment process, TCP decreased to levels below its detection limit, benzene concentration increased approximately three times, and DBP concentration decreased about 77 % comparatively to the raw leachate sample. The solar photo-Fenton process was considered to be very efficient for the treatment of sanitary landfill leachates, leading to the complete elimination of 24 of the detected micropollutants to levels below their respective detection limits and low to significant abatement of seven other organic compounds, thus resulting in an increase of the leachate biodegradability.     

The efficiency of electrocoagulation in treating wastewater from a dairy industry,Part I: Iron electrodes

Iron electrodes were used for electrocoagulation (EC) treatment of wastewater from a dairy plant. Electrolysis time, pH, current density and distance between electrodes were considered to assess the removal efficiency of chemical oxygen demand (COD), total solids (TS) and their fractions and turbidity. Samples were collected from the effluent of a dairy plant using a sampling methodology proportional to the flow. The treatments were applied according to design factorial of half fraction with two levels of treatments and three repetitions at the central point. The optimization of parameters for treating dairy industry effluent by electrocoagulation using iron electrodes showed that electric current application for 15 minutes, an initial sample pH close to neutral (pH 7.0) and a current density of 50 A ^{. m?2} resulted in a significant reduction in COD by 58 %; removal of turbidity, suspended solids and volatile suspended solids by 95 %; and a final treated effluent pH of approximately 9.5. Negative consequences of the type of electrode used were the emergence of an undesirable color and an increase in the proportion of dissolved solids in the treated effluent.     

Diagnosis of dissolved organic matter removal by GAC treatment in biologically treated papermill effluents using advanced organic characterisation techniques

Granular activated carbon (GAC) exhaustion rates on pulp and paper effluent from South East Australia were found to be a factor of three higher (3.62 cf. 1.47 kg m⁻³) on Kraft mills compared to mills using Thermomechanical pulping supplemented by Recycled Fibre (TMP/RCF). Biological waste treatment at both mills resulted in a final effluent COD of 240 mg L⁻¹. The dissolved organic carbon (DOC) was only 1.2 times higher in the Kraft effluent (70 vs. 58 mg L⁻¹), however, GAC treatment of Kraft and TMP/RCF effluent was largely different on the DOC persisted after biological treatment. The molecular mass (636 vs. 534 g mol⁻¹) and aromaticity (5.35 vs. 4.67 L mg⁻¹ m⁻¹) of humic substances (HS) were slightly higher in the Kraft effluent. The HS aromaticity was decreased by a factor of 1.0 L mg⁻¹ m⁻¹ in both Kraft and TMP/RCF effluent. The molecular mass of the Kraft effluent increased by 50 g mol⁻¹ while the molecular mass of the TMP/RCF effluent was essentially unchanged after GAC treatment; the DOC removal efficiency of the GAC on Kraft effluent was biased towards the low molecular weight humic compounds. The rapid adsorption of this fraction, coupled with the slightly higher aromaticity of the humic components resulted in early breakthrough on the Kraft effluent. Fluorescence excitation-emission matrix analysis of the each GAC treated effluent indicated that the refractory components were higher molecular weight humics on the Kraft effluent and protein-like compounds on the TMP/RCF effluent. Although the GAC exhaustion rates are too high for an effective DOC removal option for biologically treated pulp and paper mill effluents, the study indicates that advanced organic characterisation techniques can be used to diagnose GAC performance on complex effluents with comparable bulk DOC and COD loads.