Acetamiprid,carbendazim, diuron and thiamethoxam sorption in two Brazilian tropical soils

Sorption of acetamiprid ((E)-N1-[(6-chloro-3-pyridyl)methyl]-N2-cyano-N1-methylacetamidine), carbendazim (methyl benzimidazol-2-ylcarbamate), diuron (N-(3,4-dichlorophenyl)-N, N-dimethyl urea) and thiamethoxam (3-(2-chloro-thiazol-5-ylmethyl)-5-methyl-[1,3,5]oxadiazinan-4-ylidene-N-nitroamine) was evaluated in two Brazilian tropical soils, Oxisol and Entisol, from Primavera do Leste region, Mato Grosso State, Brazil. To describe the sorption process, batch experiments were carried out. Linear and Freundlich isotherm models were used to calculate the K _d and K _f coefficients from experimental data. The K _d values were utilized to calculate the partition coefficient normalized to soil organic carbon (K _oc ). For the pesticides acetamiprid, carbendazim, diuron and thiamenthoxan the K _oc (mL g^{? 1}) values ranged in both soils from 98 – 3235, 1024 – 2644, 145 – 2631 and 104 – 2877, respectively. From the studied pesticides, only carbendazim presented correlation (r² = 0.82 and p < 0.01) with soil organic carbon (OC) content. Acetamiprid and thiamethoxam showed low sorption coefficients, representing a high risk of surface and ground water contamination.     

Photolytic and photocatalytic degradation of 6-chloronicotinic acid

This work describes for the first time the photolytic and photocatalytic degradation of 6-chloronicotinic acid (6CNA) in double deionised water, which is a degradation product of neonicotinoid insecticides imidacloprid and acetamiprid, and it is known to appear in different environmental matrices. Photolytic experiments were performed with three UVA (ultraviolet A) polychromatic fluorescent lamps with broad maximum at 355 nm, while photocatalytic experiments were performed using immobilised titanium dioxide (TiO₂) on six glass slides in the spinning basket inside a photocatalytic quartz cell under similar irradiation conditions. Photolytic degradation revealed no change in concentration of 6CNA within 120 min of irradiation, while the photocatalytic degradation within 120 min, obeyed first-order kinetics. The observed disappearance rate constant was k = 0.011 ± 0.001 min⁻¹ and t_1/2 was 63.1 ± 5.5 min. Mineralisation rate was estimated through total organic carbon (TOC) and measurements revealed no carbon removal in case of photolysis after 120 min of exposure. However in photocatalytic experiments 46 ± 7% mineralisation was achieved within 120 min of irradiation. Nevertheless, the removal of total nitrogen (TN) was not observed across all experiments. Ion chromatographic analyses indicated transformation of chlorine atoms to chloride and increase of nitrate(V) ions only via photocatalytic experiments. Efficiency of selected advanced oxidation process (AOP) was investigated through toxicity assessment with Vibrio fischeri luminescent bacteria and revealed higher adverse effects of treated samples on bacteria following photocatalytic degradation in spite of the fact that higher mineralisation was achieved. New hydroxylated product generated in photocatalytic experiments with TiO₂, was confirmed with liquid chromatography-electro spray ionisation mass spectrometry (LC-ESI-MS/MS) analyses, gas chromatography-mass spectrometry (GC-MS) and nuclear magnetic resonance spectroscopy (¹H NMR).     

Comparative acute toxicity of two phytosanitary molecules,lambda-cyhalothrin and acetamiprid,on Nile Tilapia (Oreochromis Niloticus) juveniles

Abstract

This study aimed to compare the toxicity for fish of two active ingredients (lambda-cyhalothrin-20?g L^?1, a pyrethroid, and acetamiprid-15?g L^?1, a neonicotinoid) which are components of a commercial insecticide (Acer 35 EC) used in cotton crop in many West African countries. The juveniles of Oreochromis niloticus (4.01?±?0.34?g, mean body weight) were exposed for 96?h to increasing concentrations of active ingredients (lambda-cyhalothrin and acetamiprid) or a mixture similar to Acer 35 EC (composed by 20?g of chemical compound lambda-cyhalothrin and 15?g of acetamiprid dissolved in 1?L of acetone). The experiments were carried out under controlled conditions in aquaria according to OECD Guidelines. During the experiments, the behavioral responses (loss of balance, color change, hyperactivity, etc.) that usually precede death were observed in exposed fish. Mortalities were recorded in each aquarium and the LC₅₀-96h of each chemical was determined. The LC₅₀-96h obtained were respectively 0.1268, 0.0029, 182.9 and 0.5685?ppm for Acer 35 EC, lambda-cyhalothrin, acetamiprid and mixture. All insecticides used in this study had profound impact on Nile tilapia behavior which may confirm the neurotoxicity of each single active compound as well as of their mixture.     

Photocatalytic degradation of the herbicide pendimethalin using nanoparticles of BaTiO3/TiO2 prepared by gel to crystalline conversion method: A kinetic approach

Photocatalytic degradation of the herbicide, pendimethalin (PM) was investigated with BaTiO₃/TiO₂ UV light system in the presence of peroxide and persulphate species in aqueous medium. The nanoparticles of BaTiO₃ and TiO₂ were obtained by gel to crystallite conversion method. These photo catalysts are characterized by energy dispersive x-ray analysis (EDX), scanning electron microscope (SEM), x-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) adsorption isotherm and reflectance spectral studies. The quantum yields for TiO₂ and BaTiO₃ for the degradation reactions are 3.166 Einstein m^?2 s^?1 and 2.729 Einstein m^?2 s^?1 and catalytic efficiencies are 6.0444 × 10^?7 mg^?2h^?1L² and 5.403 × 10^?7 mg^?2h^?1L², respectively as calculated from experimental results. BaTiO₃ exhibited comparable photocatalytic efficiency in the degradation of pendimethalin as the most widely used TiO₂ photocatalyst. The persulphate played an important role in enhancing the rate of degradation of pendimethalin when compared to hydrogen peroxide. The degradation process of pendimethalin followed the first-order kinetics and it is in agreement with Langmuir-Hinshelwood model of surface mechanism. The reason for high stability of pendimethalin for UV-degradation even in the presence of catalyst and oxidizing agents were explored. The higher rate of degradation was observed in alkaline medium at pH 11. The degradation process was monitored by spectroscopic techniques such as ultra violet-visible (UV-Vis), infrared (IR) and gas chromatography mass spectroscopy (GC-MS). The major intermediate products identified were: N-propyl-2-nitro-6-amino-3, 4-xylidine, (2, 3-dimethyl-5-nitro-6-hydroxy amine) phenol and N-Propyl-3, 4-dimethyl-2, 6-dinitroaniline by GC-MS analysis and the probable reaction mechanism has been proposed based on these products.     

Solar CPC pilot plant photocatalytic degradation of bisphenol A in waters and wastewaters using suspended and supported-TiO2. Influence of photogenerated species

Photocatalytic degradation of bisphenol A (BPA) in waters and wastewaters in the presence of titanium dioxide (TiO₂) was performed under different conditions. Suspensions of the TiO₂ were used to compare the degradation efficiency of BPA (20 mg L^?1) in batch and compound parabolic collector (CPC) reactors. A TiO₂ catalyst supported on glass spheres was prepared (sol–gel method) and used in a CPC solar pilot plant for the photodegradation of BPA (100 μg L^?1). The influence of OH·, O₂ ^·?, and h ⁺ on the BPA degradation were evaluated. The radicals OH· and O₂ ^·? were proved to be the main species involved on BPA photodegradation. Total organic carbon (TOC) and carboxylic acids were determined to evaluate the BPA mineralization during the photodegradation process. Some toxicological effects of BPA and its photoproducts on Eisenia andrei earthworms were evaluated. The results show that the optimal concentration of suspended TiO₂ to degrade BPA in batch or CPC reactors was 0.1 g L^?1. According to biological tests, the BPA LC₅₀ in 24 h for E. andrei was of 1.7?×?10^?2 mg cm^?2. The photocatalytic degradation of BPA mediated by TiO₂ supported on glass spheres suffered strong influence of the water matrix. On real municipal wastewater treatment plant (MWWTP) secondary effluent, 30 % of BPA remains in solution; nevertheless, the method has the enormous advantage since it eliminates the need of catalyst removal step, reducing the cost of treatment.     

Enhanced removal of tetracycline via advanced oxidation of sodium persulfate and biochar adsorption

Advanced oxidation of antibiotic tetracycline (TC) is becoming an accessible and efficient technology. The removal of TC from the complex wastewater needs to be lucubrated. In this study, a TC removal system involving degradation and adsorption was established. TC degradation was accomplished by enhanced advanced oxidation via the addition of sodium persulfate (SP) and biochar into simulated wastewater containing Mn²⁺ and TC wastewater. The adsorption of TC and its derivatives was removed by biochar. The results indicate that the optimized reaction parameters were 3.0 g/L of biochar prepared at 600 °C (B600) and 400 mg/L of SP under acidic condition, and the removal percentage of TC was 87.48%, including 74.23% of degradation and 13.28% of adsorption; the anions Cl^?, NO₃^?, and H₂PO₄^? had negligible effects on the removal of TC in this Mn²⁺/B600/SP system. The system also functioned well with an aqueous solution with a high chemical oxygen demand (COD) concentration. Electron paramagnetic resonance (EPR) analysis indicated that ·OH and SO₄^? free radicals were present in the Mn²⁺/B600/SP system. Based on the testing and analysis results, a removal mechanism and potential TC degradation pathway for this system were proposed. TC can be degraded by ·OH and SO₄^? via three degradation pathways. Mn²⁺ can be precipitated as MnO₂, and a part of the TC and its derivatives can be adsorbed on the biochar surface. The Mn²⁺/B600/SP system also performed satisfactorily for a complex aqueous solution with various cations and antibiotics.

     

Photocatalytic degradation of contaminants of concern with composite NF-TiO2 films under visible and solar light

This study reports the synthesis and characterization of composite nitrogen and fluorine co-doped titanium dioxide (NF-TiO₂) for the removal of contaminants of concern in wastewater under visible and solar light. Monodisperse anatase TiO₂ nanoparticles of different sizes and Evonik P25 were assembled to immobilized NF-TiO₂ by direct incorporation into the sol–gel or by the layer-by-layer technique. The composite films were characterized with X-ray diffraction, high-resolution transmission electron microscopy, environmental scanning electron microscopy, and porosimetry analysis. The photocatalytic degradation of atrazine, carbamazepine, and caffeine was evaluated in a synthetic water solution and in an effluent from a hybrid biological concentrator reactor (BCR). Minor aggregation and improved distribution of monodisperse titania particles was obtained with NF-TiO₂-monodisperse (10 and 50 nm) from the layer-by-layer technique than with NF-TiO₂?+?monodisperse TiO₂ (300 nm) directly incorporated into the sol. The photocatalysts synthesized with the layer-by-layer method achieved significantly higher degradation rates in contrast with NF-TiO₂-monodisperse titania (300 nm) and slightly faster values when compared with NF-TiO₂-P25. Using NF-TiO₂ layer-by-layer with monodisperse TiO₂ (50 nm) under solar light irradiation, the respective degradation rates in synthetic water and BCR effluent were 14.6 and 9.5?×?10^?3?min^?1 for caffeine, 12.5 and 9.0?×?10^?3?min^?1 for carbamazepine, and 10.9 and 5.8?×?10^?3?min^?1 for atrazine. These results suggest that the layer-by-layer technique is a promising method for the synthesis of composite TiO₂-based films compared to the direct addition of nanoparticles into the sol.     

Stability of 6:2 fluorotelomer sulfonate in advanced oxidation processes: degradation kinetics and pathway

Perfluorooctane sulfonate (PFOS), a widely used mist suppressant in hard chrome electroplating industry, has been listed in the Stockholm Convention for global ban. 6:2 Fluorotelomer sulfonate (6:2 FTS) acid and salts have been adopted as alternative products in the market, but no data about their abiotic degradation has been reported. In the present study, the degradability of 6:2 FTS potassium salt (6:2 FTS-K) was evaluated under various advanced oxidation processes, including ultraviolet (UV) irradiation, UV with hydrogen peroxide (H₂O₂), alkaline ozonation (O₃, pH = 11), peroxone (O₃/H₂O₂), and Fenton reagent oxidation (Fe²⁺/H₂O₂). UV/H₂O₂ was found to be the most effective approach, where the degradation of 6:2 FTS-K followed the pseudo-first-order kinetics. The intermediates were mainly shorter chain perfluoroalkyl carboxylic acid (C₇ to C₂), while sulfate (SO₄ ^2?) and fluoride (F^?) were found to be the final products. The high yields of SO₄ ^2? and F^? indicate that 6:2 FTS-K can be nearly completely desulfonated and defluorinated under UV/H₂O₂ condition. The degradation should firstly begin with the substitution of hydrogen atom by hydroxyl radicals, followed by desulfonation, carboxylation, and sequential “flake off” of CF₂ unit. Compared with PFOS which is inert in most advanced oxidation processes, 6:2 FTS-K is more degradable as the alternative.     

Quantitative analysis of acetamiprid and imidacloprid residues in tomato fruits under greenhouse conditions

Abstract

A selective liquid chromatographic analytical method was studied for determination of two neonicotinoids, acetamiprid and imidacloprid, in tomato fruits under greenhouse conditions in Egypt. The fruits were extracted and cleaned up by QuEChERS method followed by HPLC determination. The method showed a good linearity with a determination coefficient (R²) of higher than 0.99 for the 0.0125–0.15 µg/mL concentration range. The method was validated using a blank tomato spiked at 5, 25 and 50 mg/kg and the recovery percentages were 83.71, 94.52 and 97.49% for acetamiprid and 88.59, 89.63 and 90.18% for imidacloprid, respectively. The rates of dissipation of both pesticides were studied and the preharvest intervals (PHIs) were calculated. Imidacloprid dissipated faster than acetamiprid and half-life periods were 1.30 and 2.07 days, respectively. Acetamiprid and imidacloprid residues were below the already established European maximum residue limits (EU MRLs) (0.5 mg/kg) 3 and 5 days after application, respectively.     

The effects and the toxicity increases caused by bicarbonate,chloride, and other water components during the UV/TiO<Subscript>2</Subscript> degradation of oxazaphosphorine drugs

The influences of HCO₃ ^?, Cl^?, and other components on the UV/TiO₂ degradation of the antineoplastic agents ifosfamide (IFO) and cyclophosphamide (CP) were studied in this work. The results indicated that the presence of HCO₃ ^?, Cl^?, NO₃ ^?, and SO₄ ^2? in water bodies resulted in lower degradation efficiencies. The half-lives of IFO and CP were 1.2 and 1.1 min and increased 2.3–7.3 and 3.2–6.3 times, respectively, in the presence of the four anions (initial compound concentration = 100 μg/L, TiO₂ loading =100 mg/L, anion concentration = 1000 mg/L, and pH = 8). Although the presence of HCO₃ ^? in the UV/TiO₂/HCO₃ ^? system resulted in a lower degradation rate and less byproduct formation for IFO and CP, two newly identified byproducts, P11 (M.W. = 197) and P12 (M.W. = 101), were formed and detected, suggesting that additional pathways occurred during the reaction of ?CO₃ ^? in the system. The results also showed that ?CO₃ ^? likely induces a preferred ketonization pathway. Besides the inorganic anions HCO₃ ^?, Cl^?, NO₃ ^?, and SO₄ ^2?, the existence of dissolved organic matter in the water has a significant effect and inhibits CP degradation. Toxicity tests showed that higher toxicity occurred in the presence of HCO₃ ^? or Cl^? during UV/TiO₂ treatment and within 6 h of reaction time, implying that the effects of these two anions should not be ignored when photocatalytic treatment is applied to treat real wastewater.     

Degradation of diethyl phthalate (DEP) by vacuum ultraviolet process: influencing factors,oxidation products,and toxicity assessment

The vacuum ultraviolet (VUV) process, which can directly produce hydroxyl radical from water, is considered to be a promising oxidation process in degrading contaminants of emerging concern, because of no need for extra reagents. In this study, the influencing factors and mechanism for degradation of diethyl phthalate (DEP) by the VUV process were investigated. The effects of irradiation intensity, inorganic anions, natural organic matter (NOM), and H₂O₂ dosage on the performance of VUV process were evaluated. The results showed that DEP could be more efficiently degraded by the VUV process compared with ultraviolet (UV)-254-nm irradiation. The presence of HCO₃^?, NO₃^? and NOM in the aqueous solutions inhibited the degradation of DEP to a different degree, mainly by competing hydroxyl radicals (HO^?) with DEP. Degradation rate and removal efficiency of DEP by VUV process significantly enhanced with the addition of H₂O₂, while excess H₂O₂ dosage could inhibit the DEP degradation. Moreover, based on the identified seven oxidation byproducts and their time-dependent evolution profiles, a possible pathway for DEP degradation during the VUV process was proposed. Finally, the ecotoxicity of DEP and its oxidation byproducts reduced overall according to the calculated results from Ecological Structure Activity Relationships (ECOSAR) program. The electrical energy per order (EE/O) was also assessed to analysis the energy cost of the DEP degradation in the VUV process. Our work showed the VUV process could be an alternative and environmental friendly technology for removing contaminants in water.

     

Photocatalytic degradation of p,p′-DDT under UV and visible light using interstitial N-doped TiO2

1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (or p,p′-DDT) is one of the most persistent pesticides. It is resistant to breakdown in nature and cause the water contamination problem. In this work, a major objective was to demonstrate the application of N-doped TiO₂ in degradation and mineralization of the p,p′-DDT under UV and visible light in aqueous solution. The N-doped TiO₂ nanopowders were prepared by a simple modified sol–gel procedure using diethanolamine (DEA) as a nitrogen source. The catalyst characteristics were investigated using XRD, SEM, TEM, and XPS. The adsorption and photocatalytic oxidation of p,p′-DDT using the synthesized N-doped TiO₂ under UV and visible light were conducted in a batch photocatalytic experiment. The kinetics and p,p′-DDT degradation performance of the N-doped TiO₂ were evaluated. Results show that the N-doped TiO₂ can degrade p,p′-DDT effectively under both UV and visible lights. The rate constant of the p,p′-DDT degradation under UV light was only 0.0121 min^?1, whereas the rate constant of the p,p′-DDT degradation under visible light was 0.1282 min^?1. Under visible light, the 100% degradation of p,p′-DDT were obtained from N-doped TiO₂ catalyst. The reaction rate of p,p′-DDT degradation using N-doped TiO₂ under visible light was sixfold higher than that under UV light. According to Langmuir-Hinshelwood model, the adsorption equilibrium constant (K) for the N-doped TiO₂ under visible light was 0.03078 L mg^?1, and the apparent reaction rate constant (k) was 1.3941 mg L^?1-min. Major intermediates detected during the p,p′-DDT degradation were p,p′-DDE, o,p′-DDE, p,p′-DDD and p,p′-DDD. Results from this work can be applied further for the breakdown of p,p′-DDT molecule in the real contaminated water using this technology.     

Pesticide dissipation curves in peach,pear and tomato crops in Uruguay*

Dissipation curves of azoxystrobin and of the neonicotinoids acetamiprid and thiacloprid in peach; azinphos-methyl and carbaryl in pear and azoxystrobin, chlorfenapyr and chlorpyrifos in high-tunnel tomato crops were studied in the Southern region of Uruguay. An analytical methodology based on solid phase extraction (SPE) and detection by High Performance Liquid Chromatography with Diode Array Detector (HPLC/DAD) was used for acetamiprid and thiacloprid. Coupled SPE and detection by Gas Chromatography with Mass Selective Detector (GC/MSD) was used for the detection of azinphos-methyl, azoxystrobin, carbaryl, chlorfenapyr and chlorpyrifos residues. Curves were modeled mathematically with Solver program of Microsoft Excel®. The best fit for acetamiprid and thiacloprid in peach was achieved with the exponential model (r²=0.961 and 0.944, respectively). In the case of peach fruits there is not a Maximum Residue Limit (MRL) for acetamiprid in the Codex Alimentarius, while 0.5 mg/kg is the value rated for thiacloprid. The MRLs accepted by the European Union (EU) are 0.1 mg/kg for acetamiprid and 0.3 mg/kg for thiacloprid. According to the curves determined in these experiments, thiacloprid residues 10 to 12 days after application (daa) were below the MRLs established by both sources. In the case of acetamiprid, 25 daa would be required, according to the exponential mathematical model, to get residues levels below the MRL values established by the EU. For azinphos methyl in pear, the residues detected were mathematically fitted to an exponential model (r²=0.999). According to it, residue levels under the MRL established by the EU (0.05 mg/kg) are gotten in our conditions in 20 daa. In plastic tunnel tomato chlorfenapyr residues were not detected from 16 daa, having the dissipation curve an exponential trend. In the same condition, there was not a decay of the azoxystrobin concentration during a 24-day trial, being it around 0.40 ± 0.05 mg/kg.     

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.     

银钛共负载型光催化材料降解甲基橙废水简

以膨胀珍珠岩为载体,采用溶胶凝胶法对其进行负载,制备出不同类型的光催化材料（TiO₂-EP、Ag⁺-TiO₂-EP）,并在模拟日光条件下,研究其对甲基橙溶液的降解效果。结果表明,浸渍3次且担载0.04% Ag⁺的负载型TiO₂光催化活性最高,在光催化剂用量为0.3 g,20 mL初始浓度为10 mg/L甲基橙溶液光照4 h后降解率可达81.6%,且甲基橙的光催化降解服从一级动力学方程。回收3次后仍有较强的活性,其2 h降解率为24.8%。     

4种高级氧化法处理高浓度正丙醇废水的动力学比较

研究了1%和10%(V/V)模拟正丙醇废水在UV/TiO2体系、UV/H2O2体系、Fe2+/H2O2体系和UV/TiO2/Fe2+/H2O2体系等4种工艺条件下的降解动力学过程,对比了降解动力学特点及工艺参数对动力学常数的影响,优化工艺参数。结果表明,UV/TiO2体系和Fe2+/H2O2体系的降解过程可分为零级反应阶段和一级反应阶段,转折点分别在反应开始后2 h和氧化剂浓度为6.7 g/L,UV/H2O2体系和UV/TiO2/Fe2+/H2O2体系分别符合零级反应和一级反应规律;相同工艺参数条件下,6 h反应后,组合工艺UV/TiO2/Fe2+/H2O2体系在处理效率达85%,比前3个体系分别高52.0%、8.3%和32.0%,与UV/TiO2体系和Fe2+/H2O2体系的处理效率之和持平,其协同效应提高了速率常数,在目标物浓度降低时依然可维持较高降解速率。而目标物浓度提高10倍后,UV能量利用率提高35.5倍,氧化剂用量是Fe2+/H2O2体系的1/7.1。     

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

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

Zero valent iron mediated degradation of the pharmaceutical diazepam

Parameters that influence the zero valent iron mediated degradation of the pharmaceutical diazepam (DZP) were evaluated including the iron concentration and its pre-treatment, the effect of complexation with EDTA and oxic versus anoxic condition. It was observed that acid pre-treatment of iron particles is important for degradation efficiency and that H₂SO₄ is a better choice than HCl, resulting in higher degradation of DZP. Under oxic conditions, the degradation of DZP achieved 96% after 60 min using Fe⁰ (25 g L⁻¹) pre-treated with H₂SO₄ in the presence of EDTA (119 mg L⁻¹), while mineralization achieved around 60% after the same time. Under anoxic conditions, degradation occurred, however at lower extent, achieving 67% after 120 min. The addition of EDTA improved the treatment efficiency in 20% leading to 99% DZP degradation after 120 min. The first intermediates formed during DZP degradation were identified using LC/MS analysis and revealed the formation of mono- and di-hydroxylated products from DZP during Fe⁰/EDTA/O₂ degradation, which evidences that OH was the main oxidizing species formed in this process.     

The reductive degradation of 1,1,1-trichloroethane by Fe(0) in a soil slurry system

Most studies on the treatment of chlorinated contaminants by Fe(0) focus on aqueous system tests. However, few is known about the effectiveness of these tests for degrading chlorinated contaminants such as 1,1,1-trichloroethane (TCA) in soil. In this work, the reductive degradation performance of 1,1,1-TCA by Fe(0) was thoroughly investigated in a soil slurry system. The effects of various factors including acid-washed iron, the initial 1,1,1-TCA concentration, Fe(0) dosage, slurry pH, and common constituents in groundwater and soil such as Cl^?, HCO₃ ^?, SO₄ ^2?, and NO₃ ^? anions and humic acid (HA) were evaluated. The experimental results showed that 1,1,1-TCA could be effectively degraded in 12 h for an initial Fe(0) dosage of 10 g L^?1 and a soil/water mass ratio of 1:5. The soil slurry experiments showed two-stage degradation kinetics: a slow reaction in the first stage and a fast reductive degradation of 1,1,1-TCA in the second stage. The reductive degradation of 1,1,1-TCA was expedited as the mass concentration of Fe(0) increased. In addition, high pHs adversely affected the degradation of 1,1,1-TCA over a pH range of 5.4–8.0 and the reductive degradation efficiency decreased with increasing slurry pH. The initial 1,1,1-TCA concentration and the presence of Cl^? and SO₄ ^2? anions had negligible effects. HCO₃ ^? anions had a accelerative effect on 1,1,1-TCA removal, and both NO₃ ^? and HA had inhibitory effects. A Cl^? mass balance showed that the amount of Cl^? ions released into the soil slurry system during the 1,1,1-TCA degradation increased with increasing reaction time, suggesting that the main degradation mechanism of 1,1,1-TCA by Fe(0) in a soil slurry system was reductive dechlorination with 1,1-DCA as the main intermediate. In conclusion, this study provides a theoretical basis for the practical application of the remediation of contaminated sites containing chlorinated solvent.     

Degradation of diuron in aqueous solution by ozonation

Degradation of diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] in aqueous solution and the proposed degradation mechanism of diuron by ozonation were investigated. The factors that affect the degradation efficiency of diuron were examined. The generated inorganic ions and organic acids during the ozonation process were detected. Total organic carbon removal rate and the amount of the released Cl^? increased with increasing ozonation time, but only 80.0% of the maximum theoretical concentration of Cl^? at total mineralization was detected when initial diuron concentration was 13.8 mg L^?1. For N species, the final concentrations of NO₃ ^? and NH₄ ⁺ after 60 min of reaction time were 0.28 and 0.19 mg L^?1, respectively. The generated acetic acid, formic acid and oxalic acid were detected during the reaction process. The main degradation pathway of diuron by ozonation involved a series of dechlorination-hydroxylation, dealkylation and oxidative opening of the aromatic ring processes, leading to small organic species and inorganic species. The degradation efficiency of diuron increased with decreasing initial diuron concentration. Higher pH value, more ozone dosage, additive Na₂CO₃, additive NaHCO₃ and additive H₂O₂ were all advantageous to improve the degradation efficiency of diuron.