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.     

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.     

Persistence,variance and toxic levels of organochlorine pesticides in fluvial sediments and the role of black carbon in their retention

The present study assesses the persistence and variation of organochlorine pesticides (OCPs) and their regulation by total organic carbon (TOC) and black carbon (BC) in freshwater sediment. Sediment samples from the Yamuna River, a major tributary of the Ganges (one of the most populated and intensively used rivers in Asia), had high levels of Σ₂₀OCPs (21.41 to 139.95 ng g^?1). β-Hexachlorocyclohexane (β-HCH) was the most predominant component. ΣHCH and Σdichloro-diphenyl-trichloroethane (DDT) constituted ~86 % of Σ₂₀OCPs. Isomer ratios indicated fresh usage of lindane, DDT and technical-grade HCH. Toxicological comparison with freshwater sediment quality guidelines showed γ-HCH and DDT at high levels of concern. β-HCH, α-HCH, endrin, heptachlor epoxide, dichloro-diphenyl-dichloroethane (DDD), dichloro-diphenyl-dichloroethylene and chlordane were above some of the guideline levels. TOC and BC had mean concentrations of 1.37?±?0.51 % and 0.46?±?0.23 mg g^?1, respectively. BC constituted 1.25 to 10.56 % of TOC. We observed low to moderate correlations of BC with isomers of HCH, p,p′-DDT and methoxychlor while of TOC with Σ₂₀OCPs, γ-HCH, endosulfan sulfate and methoxychlor. Principal component analysis enabled correlating and clustering of various OCPs, BC and TOC. OCP distribution was related with pH, electrical conductivity, soil moisture and finer fractions of sediment. OCPs with similarity in properties that determine their interactions with carbonaceous components of sediment clustered together. A number of factors may, thus, be involved in the regulation of interactive forces between BC and OCPs. BC in this study may be more important than TOC in the retention of some OCPs into fluvial sediments, thereby reducing their bioavailability. The finding is probably the first of its kind to report and emphasises the role of BC in the persistence of OCPs in fluvial sediments.     

Environmentally friendly system for the degradation of multipesticide residues in aqueous media by the Fenton’s reaction

A Fenton oxidation system employing zero-valent iron (whose source was swarf, a residue of metallurgical industries, in powder form) and hydrogen peroxide for the treatment of an aqueous solution with six pesticides was developed, and the effect of the iron metal content, pH, and hydrogen peroxide concentration was evaluated. The characterization of the aqueous solution resulted in: pH 5.6, 105 mg L^?1 of dissolved organic carbon, and 44.6 NTU turbidity. In addition, the characterization of the swarf by FAAS and ICP-MS showed 98.43?±?7.40 % of zero-valent iron. The removal was strongly affected by the content of iron metal, pH, and hydrogen peroxide concentration. The best degradation conditions were 2.0 g swarf, pH 2.0, and 5 mmol L^?1 H₂O₂. At the end of the treatment, the pesticide degradation ranged from 60 to 100 %, leading to 55 % mineralization. Besides, all hydrogen peroxide was consumed and the determination of total dissolved iron resulted in 2 mg L^?1. Thus, the advantages of this system are rapid degradation (up to 20 min), high-degradation rates, simple handling, and low cost.

微电解-Fenton深度处理制药废水影响因素与参数控制

采用铁炭微电解-Fenton联合工艺深度处理制药废水生化出水,探讨了初始pH、曝气量、反应时间等因素对微电解出水Fe2+和Fe3+变化规律、COD降解速率以及后续Fenton氧化效果的影响,为优化微电解-Fenton氧化联合工艺提出了微电解间歇加酸的理论。间歇加酸可提高微电解系统中COD降解速率和Fe2+含量,使后续Fenton氧化无需投加FeSO4·7H2O即可达到较好的COD去除效果。结果表明,当初始pH=2.5,曝气量为0.6 m3/h,间歇加酸30 min/次,微电解反应2 h,出水投加1 mL/L的H2O2进行Fenton氧化2 h,COD总去除率可达81.33%;间歇加酸30 min/次可将微电解反应2 h出水Fe2+浓度从50 mg/L提高至151 mg/L,COD降解速率从10.6 mg COD/(L·h)提高至22.2 mg COD/(L·h)。     

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.     

Deposition and regional distribution of HCHs and p,p′-DDX in the western and southern Tibetan Plateau: records from a lake sediment core and the surface soils

Tibetan Plateau is the world’s highest plateau, which provides a unique location for the investigation of global fractionation of organochlorine pesticides (OCPs). In this study, deposition and regional distribution of HCHs and p,p′-DDX in the western and southern Tibetan Plateau were investigated by the records from a sediment core of Lake Zige Tangco and 24 surface soils. Concentration of ΣHCHs in the surface soils of the western Tibetan Plateau was much higher than that of the southern part. Maximum fluxes of α-, β-, and δ-HCH in the sediment core were 9.0, 222, and 21 pg cm^?2 year^?1, respectively, which appeared in the mid-1960s. Significant correlations were observed between concentrations of α- and β-HCH in both the surface soils and the sediment core. Concentrations of both α- and β-HCH increased with the inverse of the average annual temperature of these sites. γ-HCH became the dominant isomer of HCHs after the late 1970s, and reached the maximum flux of 160 pg cm^?2 year^?1 in the early 1990s. There were no significant correlations between concentrations of γ-HCH and the other isomers in both the surface soils and the sediment core. The results suggested that there was input of Lindane at scattered sites in this area. In contrast to ΣHCHs, concentration of Σp,p′-DDX in the surface soils of the southern part was much higher than that of the western part. Maximum flux of Σp,p′-DDX was 44 pg cm^?2 year^?1, which appeared in the mid-1960s. Local emission of p,p′-DDT was found at scattered sites. This study provides novel data and knowledge for the OCPs in the western and southern Tibetan Plateau, which will help understand the global fractionation of OCPs in remote alpine regions.     

Nanoporous activated carbon fluidized bed catalytic oxidations of aqueous o, p and m-cresols: kinetic and thermodynamic studies

Nanoporous activated carbon prepared from rice husk through precarbonisation at 400 °C and phosphoric acid activation at 800 °C was used as fluidized bed in Fenton oxidation of the o, p and m-cresols in aqueous solution. The efficiencies of homogeneous Fenton oxidation, fluidized Fenton oxidation and aerobic biological oxidation systems for the removal of o, p and m-cresols in aqueous solution have been compared. The kinetic constants and the thermodynamic parameters for the homogeneous Fenton, heterogeneous Fenton and aerobic biological oxidations of o, p and m-cresols in synthetic wastewater were determined. The degradation of cresols in synthetic wastewater was confirmed using FT-IR, ¹H-NMR and UV–visible spectroscopy.     

Heterocatalytic Fenton oxidation process for the treatment of tannery effluent: kinetic and thermodynamic studies

Background, aim, scope

Treatment of wastewater has become significant with the declining water resources. The presence of recalcitrant organics is the major issue in meeting the pollution control board norms in India. The theme of the present investigation was on partial or complete removal of pollutants or their transformation into less toxic and more biodegradable products by heterogeneous Fenton oxidation process using mesoporous activated carbon (MAC) as the catalyst.

Materials and methods

Ferrous sulfate (FeSO₄·7H₂O), sulfuric acid (36?N, specific gravity 1.81, 98% purity), hydrogen peroxide (50% v/v) and all other chemicals used in this study were of analytical grade (Merck). Two reactors, each of height 50?cm and diameter 6?cm, were fabricated with PVC while one reactor was packed with MAC of mass 150?g and other without MAC served as control.

Results and discussion

The oxidation process was presented with kinetic and thermodynamic constants for the removal of COD, BOD, and TOC from the wastewater. The activation energy (Ea) for homogeneous and heterogeneous Fenton oxidation processes were 44.79 and 25.89?kJ/mol, respectively. The thermodynamic parameters ??G, ??H, and ??S were calculated for the oxidation processes using Van??t Hoff equation. Furthermore, the degradation of organics was confirmed through FTIR and UV?Cvisible spectroscopy, and cyclic voltammetry.

Conclusions

The heterocatalytic Fenton oxidation process efficiently increased the biodegradability index (BOD/COD) of the tannery effluent. The optimized conditions for the heterocatalytic Fenton oxidation of organics in tannery effluent were pH 3.5, reaction time?C4?h, and H₂O₂/FeSO₄·7H₂O in the molar ratio of 2:1.     

Electro-Fenton pretreatment for the improvement of tylosin biodegradability

The feasibility of an electro-Fenton process to treat tylosin (TYL), a non-biodegradable antibiotic, was examined in a discontinuous electrochemical cell with divided cathodic and anodic compartments. Only 15 min electrolysis was needed for total tylosin degradation using a carbon felt cathode and a platinum anode; while 6 h electrolysis was needed to achieve high oxidation and mineralization yields, 96 and 88 % respectively. Biodegradability improvement was shown since BOD₅/COD increased from 0 initially to 0.6 after 6 h electrolysis (for 100 mg L^?1 initial TYL). With the aim of combining electro-Fenton with a biological treatment, an oxidation time in the range 2 to 4 h has been however considered. Results of AOS (average oxidation state) and COD/TOC suggested that the pretreatment could be stopped after 2 h rather than 4 h; while in the same time, the increase of biodegradability between 2 and 4 h suggested that this latter duration seemed more appropriate. In order to conclude, biological cultures have been therefore carried out for various electrolysis times. TYL solutions electrolyzed during 2 and 4 h were then treated with activated sludge during 25 days, showing 57 and 67 % total organic carbon (TOC) removal, respectively, namely 77 and 88 % overall TOC removal if both processes were considered. Activated sludge cultures appeared, therefore, in agreement with the assessment made from the analysis of physico-chemical parameters (AOS and COD/TOC), since the gain in terms of mineralization expected from increasing electrolysis duration appeared too low to balance the additional energy consumption.     

Fenton氧化技术处理稠油污染土壤

利用Fenton氧化技术对稠油污染土壤进行氧化处理,分析对后续微生物修复的促进作用。向1 000 g石油类含量为8%的稠油污染土壤中加入10.0 mL 18 mmol/L Fe2+溶液与10.0 mL 30%H2O2,反应时间为2 h。氧化处理后土壤中石油烃的总去除率可达到31.38%,胶质去除率为45.22%,沥青质去除率为51.26%,胶质的分子量由1 841下降到1 472,沥青质的分子量由5 831下降到5 073。Fenton氧化可使土壤酶活、各类微生物的数量及呼吸强度有不同程度的下降,但在氧化后30 d内,土壤各类微生物数量都超过了原有水平,其中细菌数量最高达到9.84×105CFU/g,是氧化前的数量的1.57倍。以上实验结果表明,Fenton氧化可以有效去除土壤中胶质和沥青质,并且使土壤中微生物的生长速率加快。因此,Fenton氧化能够促进后续的微生物修复。     

Efficient removal of insecticide “imidacloprid” from water by electrochemical advanced oxidation processes

The oxidative degradation of imidacloprid (ICP) has been carried out by electrochemical advanced oxidation processes (EAOPs), anodic oxidation, and electro-Fenton, in which hydroxyl radicals are generated electrocatalytically. Carbon-felt cathode and platinum or boron-doped diamond (BDD) anodes were used in electrolysis cell. To determine optimum operating conditions, the effects of applied current and catalyst concentration were investigated. The decay of ICP during the oxidative degradation was well fitted to pseudo-first-order reaction kinetics and absolute rate constant of the oxidation of ICP by hydroxyl radicals was found to be k _abs(ICP)?=?1.23?×?10⁹ L mol^?1 s^?1. The results showed that both anodic oxidation and electro-Fenton process with BDD anode exhibited high mineralization efficiency reaching 91 and 94 % total organic carbon (TOC) removal at 2 h, respectively. For Pt-EF process, mineralization efficiency was also obtained as 71 %. The degradation products of ICP were identified and a plausible general oxidation mechanism was proposed. Some of the main reaction intermediates such as 6-chloronicotinic acid, 6-chloronicotinaldehyde, and 6-hydroxynicotinic acid were determined by GC-MS analysis. Before complete mineralization, formic, acetic, oxalic, and glyoxylic acids were identified as end-products. The initial chlorine and organic nitrogen present in ICP were found to be converted to inorganic anions Cl^?, NO₃ ^?, and NH₄ ⁺.     

Elimination of radiocontrast agent diatrizoic acid by photo-Fenton process and enhanced treatment by coupling with electro-Fenton process

The removal of radiocontrast agent diatrizoic acid (DIA) from water was performed using photo-Fenton (PF) process. First, the effect of H₂O₂ dosage on mineralization efficiency was determined using ultraviolet (UV) irradiation. The system reached a maximum mineralization degree of 60 % total organic carbon (TOC) removal at 4 h with 20 mM initial H₂O₂ concentration while further concentration values led to a decrease in TOC abatement efficiency. Then, the effect of different concentrations of Fenton’s reagents was studied for homogeneous Fenton process. Obtained results revealed that 0.25 mM Fe³⁺ and 20 mM H₂O₂ were the best conditions, achieving 80 % TOC removal efficiency at 4 h treatment. Furthermore, heterogeneous PF treatment was developed using iron-activated carbon as catalyst. It was demonstrated that this catalyst is a promising option, reaching 67 % of TOC removal within 4 h treatment without formation of iron leachate in the medium. In addition, two strategies of enhancement for process efficiency are proposed: coupling of PF with electro-Fenton (EF) process in two ways: photoelectro-Fenton (PEF) or PF followed by EF (PF-EF) treatments, achieving in both cases the complete mineralization of DIA solution within only 2 h. Finally, the Microtox tests revealed the formation of more toxic compounds than the initial DIA during PF process, while, it was possible to reach total mineralization by both proposed alternatives (PEF or PF-EF) and thus to remove the toxicity of DIA solution.     

Application of the Fenton’s process in a bubble column reactor for hydroquinone degradation

The aim of this study was to assess the degradation and mineralization of hydroquinone (HQ) by the Fenton’s process in a bubble column reactor (BCR). The effect of the main operating variables, namely, air flow rate, effluent volume, hydrogen peroxide (H₂O₂) concentration, catalyst (Fe²⁺) dose, initial pH, and temperature, were assessed. For all air flow rates tested, no concentration gradients along the column were noticed, evidencing that a good mixing was reached in the BCR. For the best conditions tested ([H₂O₂] = 500 mg/L, [Fe²⁺] = 45 mg/L, T = 24 °C, Q _air = 2.5 mL/min, pH = 3.0, and V = 5 L), complete HQ degradation was reached, with ~ 39% of total organic carbon (TOC) removal, and an efficiency of the oxidant use—η _H2O2—of 0.39 (ratio between TOC removed per H₂O₂ consumed normalized by the theoretical stoichiometric value); moreover, a non-toxic effluent was generated. Under these conditions, the intermediates and final oxidation compounds identified and quantified were a few carboxylic acids, namely, maleic, pyruvic, and oxalic. As a strategy to improve the TOC removal, a gradual dosage of the optimal H₂O₂ concentration was implemented, being obtained ~ 55% of mineralization (with complete HQ degradation). Finally, the matrix effect was evaluated, for which a real wastewater was spiked with 100 mg/L of HQ; no reduction in terms of HQ degradation and mineralization was observed compared to the solution in distilled water.     

Response surface modeling for optimization heterocatalytic Fenton oxidation of persistence organic pollution in high total dissolved solid containing wastewater

The rice-husk-based mesoporous activated carbon (MAC) used in this study was precarbonized and activated using phosphoric acid. N₂ adsorption/desorption isotherm, X-ray powder diffraction, electron spin resonance, X-ray photoelectron spectroscopy and scanning electron microscopy, transmission electron microscopy, ²⁹Si-NMR spectroscopy, and diffuse reflectance spectroscopy were used to characterize the MAC. The tannery wastewater carrying high total dissolved solids (TDS) discharged from leather industry lacks biodegradability despite the presence of dissolved protein. This paper demonstrates the application of free electron-rich MAC as heterogeneous catalyst along with Fenton reagent for the oxidation of persistence organic compounds in high TDS wastewater. The heterogeneous Fenton oxidation of the pretreated wastewater at optimum pH (3.5), H₂O₂ (4 mmol/L), FeSO₄?7H₂O (0.2 mmol/L), and time (4 h) removed chemical oxygen demand, biochemical oxygen demand, total organic carbon and dissolved protein by 86, 91, 83, and 90 %, respectively.     

Distributions, sources, and ecological risks of hexachlorocyclohexanes in the sediments from Haihe Plain, Northern China

The levels of hexachlorocyclohexanes (HCHs) in the sediments from Haihe Plain, China, were measured by a gas chromatograph with a ⁶³Ni microelectron capture detector. The spatial distributions, possible sources, and potential ecological risks of these compounds were analyzed. The residual level of total HCHs was 33.84?±?173.37 ng?g^?1 dry weight (d.w.) with ranges of 0.13?～?1,107.41 ng?g^?1 d.w. Much higher ΣHCH contents were found in the lower reaches of some rivers and in the mouth of the main stream receiving tributaries. The predominance of β-HCH (36 %) in the sediments was similar to that in the soils from Haihe Plain. The high percentages of γ-HCH (23–41 %) could be detected at 25 % of the sampling sites in the seven river systems. There were statistically significant positive relationships between the contents of HCHs and total organic carbon. Lindane was identified as the primary source of HCHs in the sediments, and it seemed that recent illegal lindane inputs still existed in some areas in Haihe Plain, as indicated by the α-/γ-HCH and β-/(α?+?γ)-HCH ratios. Severe potential ecological risks of γ-HCH to benthic organisms at some sampling sites were found based on the consensus-based sediment quality guidelines.     

Electro-oxidation of the dye azure B: kinetics,mechanism, and by-products

In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals (^?OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by ^?OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19?×?10⁹ M^?1 s^?1. It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.     

Photolysis of atrazine in aqueous solution: role of process variables and reactive oxygen species

Photochemical advanced oxidation processes have been considered for the treatment of water and wastewater containing the herbicide atrazine (ATZ), a possible human carcinogen and endocrine disruptor. In this study, we investigated the effects of the photon emission rate and initial concentration on ATZ photolysis at 254 nm, an issue not usually detailed in literature. Moreover, the role of reactive oxygen species (ROS) is discussed. Photon emission rates in the range 0.87?×?10¹⁸–3.6?×?10¹⁸ photons L^?1 s^?1 and [ATZ]₀?=?5 and 20 mg L^?1 were used. The results showed more than 65 % of ATZ removal after 30 min. ATZ photolysis followed apparent first-order kinetics with k values and percent removals decreasing with increasing herbicide initial concentration. A fivefold linear increase in specific degradation rate constants with photon emission rate was observed. Also, regardless the presence of persistent degradation products, toxicity was efficiently removed after 60-min exposure to UV radiation. Experiments confirmed a noticeable contribution of singlet oxygen and radical species to atrazine degradation during photolysis. These results may help understand the behavior of atrazine in different UV-driven photochemical degradation treatment processes.     

Determination of octanol-air partition coefficients and supercooled liquid vapor pressures of organochlorine pesticides

Octanol-air partition coefficients (K_OA) and supercooled liquid vapor pressures (P_L) of nine organochlorine pesticides (OCPs) including p,p′-DDE, p,p′-DDD, o,p′-DDT, o,p′-DDE, o,p′-DDD, α-HCH, β-HCH, γ-HCH, δ-HCH were determined as functions of temperature using a gas chromatographic retention time method. Among them, the K_OA of o,p′-DDE and o,p′-DDD and the P_L of o,p′-DDE, o,p′-DDD, β-HCH and δ-HCH were determined for the first time. The determined K_OA and P_L values of investigated compounds at 25°C ranged from 3.14 × 10⁷ (α-HCH) to 3.76×10⁹ (p,p′-DDD), and 8.95×10^{? 4} Pa (p,p′-DDD) to 1.08×10^{? 1} Pa (α-HCH), respectively. The K_OA and P_L data were compared with published data. The K_OA values of o,p′-DDT at 25°C were 3.23×10⁹, higher than o,p′-DDE (1.02×10⁹) and o,p′-DDD (2.01×10⁹), indicating o,p′-DDT were more preferred to partition in soil compared with the metabolites. The K_OA values were lower and P_L values were higher for o,p′-DDE and o,p′-DDD, compared with their p,p′-isomeric counterparts, leading to a potential difference in behavior and fate of these isomers. The discrepancies among chemicals are obvious, which reflected in the increasing K_OA and decreasing P_L values in order of α-HCH, γ-HCH, β-HCH, δ-HCH, o,p′-DDE, p,p′-DDE, o,p′-DDD, o,p′-DDT, p,p′-DDD. For each compound, the LogK_OA decreased linearly with reciprocal absolute temperature, while LogP_L had a significant positive correlation with the inverse absolute temperature. The present study suggested that the method of gas chromatographic retention time was appropriate to measure the K_OA and P_L of a number of OCPs.     

Synthetic olive mill wastewater treatment by Fenton’s process in batch and continuous reactors operation

Degradation of total phenol (TPh) and organic matter, (expressed as total organic carbon TOC), of a simulated olive mill wastewater was evaluated by the Fenton oxidation process under batch and continuous mode conditions. A mixture of six phenolic acids usually found in these agro-industrial wastewaters was used for this purpose. The study focused on the optimization of key operational parameters of the Fenton process in a batch reactor, namely Fe²⁺ dosage, hydrogen peroxide concentration, pH, and reaction temperature. On the assessment of the process efficiency, > 99% of TPh and > 56% of TOC removal were attained when [Fe²⁺] = 100 ppm, [H₂O₂] = 2.0 g/L, T = 30 °C, and initial pH = 5.0, after 300 min of reaction. Under those operational conditions, experiments on a continuous stirred-tank reactor (CSTR) were performed for different space-time values (τ). TOC and TPh removals of 47.5 and 96.9%, respectively, were reached at steady-state (for τ = 120 min). High removal of COD (> 75%) and BOD₅ (> 70%) was achieved for both batch and CSTR optimum conditions; analysis of the BOD₅/COD ratio also revealed an increase in the effluent’s biodegradability. Despite the high removal of lumped parameters, the treated effluent did not met the Portuguese legal limits for direct discharge of wastewaters into water bodies, which indicates that coupled chemical-biological process may be the best solution for real olive mill wastewater treatment.