Catalytic amination and dechlorination of para-nitrochlorobenzene (p-NCB) in water over palladium-iron bimetallic catalyst

Chemical treatment of para-nitrochlorobenzene (p-NCB) by palladium/iron (Pd/Fe) bimetallic particles represents one of the latest innovative technologies for the remediation of contaminated soil and groundwater. The amination and dechlorination reaction is believed to take place predominantly on the surface site of the Pd/Fe catalysts. The p-NCB was first transformed to p-chloroaniline (p-CAN) then quickly reduced to aniline. 100% of p-NCB was removed in 30 min when bimetallic Pd/Fe particles with 0.03% Pd at the Pd/Fe mass concentration of 3g 75 ml(-1) were used. The p-NCB removal efficiency and the subsequent dechlorination rate increased with the increase of bulk loading of palladium and Pd/Fe. As expected, p-NCB removal efficiency increased with temperature as well. In particular, the removal efficiency of p-NCB was measured to be 67%, 79%, 80%, 90% and 100% for reaction temperature 20, 25, 30, 35 and 40 degrees C, respectively. Our results show that no other intermediates were generated besides Cl(-), p-CAN and aniline during the catalytic amination and dechlorination of p-NCB.     

Analysis of chlorothalonil and degradation products in soil and water by GC/MS and LC/MS

We present a method using gas chromatography (GC) and liquid chromatography (LC) coupled to a mass selective detector to measure concentrations of the fungicide chlorothalonil and several of its metabolites in soil and water. The methods employed solid-phase extraction using a hydrophobic polymeric phase for the isolation of analytes. In lake water, average analyte recoveries ranged from 70% to 110%, with exception of pentachloronitrobenzene that gave low recoveries (23%). The method detection limits were determined to be in the range of 1 and 0.1microg l(-1) for the LC and GC methods, respectively. In soil samples, recoveries ranged from 80% to 95% for 4-hydroxy-2,5,6-trichloroisophthalonitrile (metabolite II) and 1,3-dicarbamoyl-2,4,5,6-tetrachlorobenzene (metabolite III). Limits of detection (LOD) were 0.05 and 0.02microg g(-1), respectively. Chlorothalonil and other metabolites were analyzed by GC giving recoveries ranging from 54% to 130% with LOD of 0.001-0.005microg g(-1).     

Catalytic degradation of Orange II by UV-Fenton with hydroxyl-Fe-pillared bentonite in water

Although homogeneous photo-Fenton system is a very efficient method for organic wastewater treatment, it suffers from costly pH adjustment as well as difficult separation of catalysts from aqueous in practical application. Through cation exchange reaction, hydroxyl-Fe-pillared bentonite (H-Fe-P-B) was successfully prepared as a solid catalyst for UV-Fenton to degrade non-biodegradable azo-dye Orange II. Compared with raw bentonite, the content of iron, interlamellar distance and external surface area of H-Fe-P-B increased remarkably. H-Fe-P-B had good photosensitivity and catalyst reactivity. And the catalytic activity of H-Fe-P-B for H(2)O(2) came from hydroxyl-Fe between sheets rather than Fe(3+) or Fe(2+) in tetrahedral or octahedral sheets of bentonite. In UVA-H(2)O(2) system, H(2)O(2) could destroy the azo bond of excited Orange II molecules but could not effectively mineralize it. After 120 min treatment, 83% discoloration was obtained while only 2% of TOC was removed. When H-Fe-P-B was used as catalyst, a significant degradation of Orange II was observed at the same condition as UVA-H(2)O(2) system. Almost 100% discoloration and more than 60% TOC removal of Orange II could be achieved after 120 min treatment. Because of the strong surface acidity and the electronegativity of H-Fe-P-B, the pH range of this catalyst in the Orange II discoloration could be extended up to 9.5. And this catalyst showed good stability during Orange II degradation in water in wide range of pH (3.0-9.5). These results indicated that the H-Fe-P-B was a promising catalyst for UV-Fenton system.     

Monitoring the sonochemical degradation of phthalate esters in water using solid-phase microextraction

The sonochemical degradation of aqueous solutions containing low concentrations of six phthalate esters at an ultrasonic frequency of 80 kHz has been investigated. Ultrasonic treatment was found capable of removing the four higher molecular mass phthalates (di-n-butyl phthalate, butylbenzyl phthalate, di-(2-ethylhexyl) phthalate and di-n-octyl phthalate) within 30-60 min of irradiation. The rest (dimethyl phthalate and diethyl phthalate) were more recalcitrant and nearly complete removal could be achieved only after prolonged irradiation times. The relative reactivity of phthalates was explained in terms of their hydrophobicity. Experiments were carried out at an overall initial phthalate concentration of 240 microg l(-1), values of electric power of 75 and 150 W, temperatures of 21 and 50 degrees C and in the presence of NaCl to study the effect of various operating conditions on degradation. Solid-phase microextraction (SPME) coupled with GC-MS proved to be a powerful analytical tool to monitor the sonochemical degradation of phthalate esters at low microg l(-1) concentration levels, minimising the risk of secondary contamination during sample preparation, a major parameter to consider during phthalates analysis. The advantages as well as disadvantages of using SPME are also highlighted.     

催化超临界水氧化对氨基苯酚

采用CuO／γ-Al2O3和MnO2/γ-Al2O3为催化剂、H2O2为氧化剂，在一连续流固定床反应器中进行了超临界水氧化对氨基苯酚实验。实验结果表明，CuO和MnO2催化剂对于对氨基苯酚的氧化降解具有显著的促进作用。对氨基苯酚的去除率随反应温度和压力的升高、停留时间的延长而提高，在24～26MPa和400～450℃条件下，数秒钟内COD去除率可达到99％以上，催化剂CuO／γ-Al2O3的催化效果优于MnO2／γ-Al2O3。证明了催化超临界水氧化技术的高效性。     

纳米钯?铝双金属对水中3-氯酚的脱氯降解研究

采用置换沉积法制备了纳米钯/铝双金属催化剂,氢解还原去除水相中难降解有毒有机物3-氯酚(3-CP),考察了溶液pH、钯负载量、纳米钯/铝双金属投加量、反应温度对脱氯效果的影响并解析相关反应机制。结果表明:(1)初始pH 3.0时,沉积液中93.25%(质量分数,下同)～96.67%的钯可有效负载于铝材上。(2)在pH为3.0、纳米钯/铝双金属投加量为2g/L、钯负载量为1.16%(质量分数)、反应温度为25℃下降解初始摩尔浓度为0.389mmol/L的3-CP,反应终了时脱氯率在99%以上。利用纳米钯/铝双金属降解氯代有机污染物具有高效低耗的优势,在实际应用上具有较好的前景。     

Preparation of a novel iron-based biochar composite for removal of hexavalent chromium in water

The chitosan-stabilized ferrous sulfide nanoparticles were loaded on biochar to prepare a composite material FeS-CS-BC for effective removal of hexavalent chromium in water. BC and FeS-CS-BC were characterized by Brunauer–Emmett–Teller (BET), scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) analyses. Batch experiments were employed to evaluate the Cr(VI) removal performance. The experimental results showed that the removal rate of Cr(VI) by FeS-CS-BC(FeS:CS:BC?=?2:2:1) reached 98.34%, which was significantly higher than that of BC (44.58%) and FeS (79.91%). In the pH range of 2–10, the removal of Cr(VI) by FeS-CS-BC was almost independent of pH. The limitation of coexisting anions (Cl^?、SO₄^2?、NO₃^?) on Cr(VI) removal was not too obvious. The removal of Cr(VI) by FeS-CS-BC was fitted with the pseudo-second-order dynamics, which was a hybrid chemical-adsorption reaction. The X-ray photoelectron spectroscopy (XPS) analysis result showed that Cr(VI) was reduced, and the reduced Cr(VI) was fixed on the surface of the material in the form of Cr(VI)–Fe(III).

Removal of hexavalent chromium from wastewater by FeS-CS-BC composite synthesized by impregnation.

     

Characterisation of the abiotic degradation pathways of oxytetracyclines in soil interstitial water using LC-MS-MS

The fate of oxytetracyclines (OTCs) in soil interstitial water was investigated and the structure of a number of degradation products elucidated in a time-related experiment. A previously developed separation method for LC–MS–MS able to base separate and quantify OTC and three of its epimers and degradation products was applied. Compounds detected were 4-epi-oxytetracycline (EOTC) (t_R=3.0 min), OTC (t_R=4.4 min), -apo-oxytetracycline (-apo-OTC) (t_R=11.4 min) and β-apo-oxytetracycline (β-apo-OTC) (t_R=18.4 min). Furthermore, we tentatively identified 4-epi-N-desmethyl-oxytetracycline (E-N-DM-OTC) (t_R=3.0 min), N-desmethyl-oxytetracycline (N-DM-OTC) (t_R=3.5), N-didesmethyl-oxytetracycline (N-DDM-OTC), 4-epi-N-didesmethyl-oxytetracycline (E-N-DDM-OTC) (t_R=3.7 and 4.7 min) and 2-acetyl-2-decarboxamido-oxytetracycline (t_R=8.7) in all samples. Most compounds were only present in trace concentrations (less than 2%) relative to the parent OTC. EOTC was on the other hand formed up to a ratio of 0.6 relative to parent OTC concentration. Only EOTC, E-N-DM-OTC, N-DM-OTC, N-DDM-OTC and E-N-DDM-OTC were formed during the time-related experiment. All other compounds were probably only present as impurities in the spiked OTC formulation as they declined in concentration from the start of the experiment. Half-lives (T_1/2, days) of the OTCs in soil interstitial water were in the order of 2 days (EOTC) to 270 days (β-apo-OTC).     

Light-induced degradation of metsulfuron-methyl in water

Photodegradation of metsulfuron-methyl, a sulfonylurea herbicide, has been investigated in aqueous solution at different pH and excitation wavelengths. The efficiency of the process has been evaluated through quantum yield determinations. The identification of the photoproducts indicates that the major photochemical pathway is initiated by C-S bond dissociation followed by involvement of water to yield the main final products; the behaviour in water is shown to differ markedly from that in an organic environment.     

Characterizing pesticide sorption and degradation in microscale biopurification systems using column displacement experiments

Biopurification systems treating pesticide contaminated water are very efficient, however they operate as a black box. Processes inside the system are not yet characterized. To optimize the performance, knowledge of degradation and retention processes needs to be generated. Therefore, displacement experiments were carried out for four pesticides (isoproturon, bentazone, metalaxyl, linuron) in columns containing different organic mixtures. Bromide, isoproturon and bentazone breakthrough curves (BTCs) were well described using the convection-dispersion equation (CDE) and a first-order degradation kinetic approach. Metalaxyl and linuron BTCs were well described using the CDE model expanded with Monod-type kinetics. Freundlich sorption, first-order degradation and Monod kinetics coefficients were fitted to the BTCs. Fitted values of the distribution coefficient K_f,column were much lower than those determined from batch experiments. Based on mobility, pesticides were ranked as: bentazone > metalaxyl - isoproturon > linuron. Based on degradability, pesticides were ranked as: linuron > metalaxyl - isoproturon > bentazone.     

Genotoxic assessment on river water using different biological systems

This paper reports genotoxicity and toxicity data in water samples collected in Sinos River, an important water course in the hydrographic region of Guaíba Lake, Rio Grande do Sul State, south of Brazil. This river is exposed to intense anthropic influence by numerous shoes, leather, petrochemical, and metallurgy industries. Water samples were collected at two moments (winter 2006 and spring 2006) at five sites of Sinos River and evaluated using in vitro V79 Chinese hamster lung fibroblasts (cytotoxicity, comet assay and micronucleus test) and Allium cepa test (toxicity and micronucleus test). Comet and micronucleus tests revealed that water samples collected exerted cytotoxic, toxic, genotoxic and mutagenic effects. The results showed the toxic action of organic and inorganic agents found in the water samples in all sites of Sinos River, for both data collections. The main causes behind pollution were the domestic and industrial toxic discharges. The V79 and A. cepa tests were proved efficient to detect toxicity and genotoxicity caused by complex mixtures. This study also showed the need for constant monitoring in sites with strong environmental degradation caused by industrial discharges and urban sewages.     

Modeling and optimization of reductive degradation of chloramphenicol in aqueous solution by zero-valent bimetallic nanoparticles

Purpose

The present study aims to investigate the individual and combined effects of temperature, pH, zero-valent bimetallic nanoparticles (ZVBMNPs) dose, and chloramphenicol (CP) concentration on the reductive degradation of CP using ZVBMNPs in aqueous medium.

Method

Iron?Csilver ZVBMNPs were synthesized. Batch experimental data were generated using a four-factor statistical experimental design. CP reduction by ZVBMNPs was optimized using the response surface modeling (RSM) and artificial neural network-genetic algorithm (ANN-GA) approaches. The RSM and ANN methodologies were also compared for their predictive and generalization abilities using the same training and validation data set. Reductive by-products of CP were identified using liquid chromatography-mass spectrometry technique.

Results

The optimized process variables (RSM and ANN-GA approaches) yielded CP reduction capacity of 57.37 and 57.10?mg?g^?1, respectively, as compared to the experimental value of 54.0?mg?g^?1 with un-optimized variables. The ANN-GA and RSM methodologies yielded comparable results and helped to achieve a higher reduction (>6%) of CP by the ZVBMNPs as compared to the experimental value. The root mean squared error, relative standard error of prediction and correlation coefficient between the measured and model-predicted values of response variable were 1.34, 3.79, and 0.964 for RSM and 0.03, 0.07, and 0.999 for ANN models for the training and 1.39, 3.47, and 0.996 for RSM and 1.25, 3.11, and 0.990 for ANN models for the validation set.

Conclusion

Predictive and generalization abilities of both the RSM and ANN models were comparable. The synthesized ZVBMNPs may be used for an efficient reductive removal of CP from the water.     

富氧条件下流化床内Ru基双贵金属催化去除碳颗粒

采用等体积浸渍法制备了系列Ru基双贵金属催化剂.利用程序升温技术研究了富氧条件下Ru基双贵金属催化剂催化氧化碳颗粒的反应,考察了双贵金属活性组分比例、载体以及双贵金属组合对催化活性的影响.还对固定床与流化床内碳颗粒氧化进行了比较,分析了流化床内碳颗粒低温氧化的原因.结果表明,双贵金属摩尔比为1∶1时具有较高的催化活性,复合载体TiO2/SiO2更易与双贵金属组分形成协同效应,不同贵金属取代形成的双贵金属催化剂中,Ru-X/TiO2/SiO2(X=Rh、Ag和Ir)的催化活性较高.与固定床相比,流化床因其良好的传热和传质特性,使得碳颗粒催化氧化温度最多可降低50℃左右.流化床是一种类似于尾气中气流流动状态的反应装置,具有潜在的应用前景.     

Nylon 6,6 modified screen printed carbon electrodes as electrochemical sensors for rapid chlorothalonil determination in water samples using differential pulse cathodic stripping voltammetry

A newly developed electrochemical sensor for chlorothalonil based on nylon 6,6 film deposited onto screen printed electrode (SPE) with electrochemical modulation of pH at the electrode/solution interface was studied for the first time. Differential pulse cathodic stripping voltammetry (DPCSV) was used to carry out the electrochemical and analytical studies. Experimental parameters such as accumulation potential, initial potential, accumulation time and pH of Britton-Robinson buffer have been optimized. Chlorothalonil gave optimum analytical signal in a medium of 0.04?M Britton-Robinson buffer at pH 6.0. A well-defined reduction peak was observed, at E_p= ?0.851 and ?0.938?V vs. Ag/AgCl (3.0?M KCl) for both bare SPE and modified SPE, respectively. The peak currents of modified SPE were significantly increased as compared to bare SPE. At the modified SPE, a linear relationship between the peak current and chlorothalonil concentration was obtained in the range from 0.1 to 2.8?×?10^?6?M with a detection limit of 1.53?×?10^?8?M (S/N=?3). The practical applicability of the newly developed method has been demonstrated on analyses of real water samples. The newly developed sensor shows good reproducibility with RSD of 3.92%. The nylon 6,6 modified SPE showed itself as promising sensor with good selectivity for chlorothalonil determination.     

Simultaneous determination of chlorothalonil and its metabolite 4-hydroxychlorothalonil in greenhouse air: dissipation process of chlorothalonil

An analytical method was developed and tested for the simultaneous determination of chlorothalonil and its main metabolite 4-hydroxychlorothalonil, in airborne samples. High performance liquid chromatography equipped with Ultra-violet detector was used to separate and quantify the analytes. Glass microfibre filters for the collection of the analytes' particles were tested. Solid sorbents, such as Tenax, Florisil, XAD-2 and silica gel, were studied to find out the most suitable material for the collection of the analytes in the gas phase. The results have shown that only chlorothalonil was trapped in the vapor phase with highest results obtained when silica gel was the sorbent of choice. Linearity was demonstrated in a wide concentration range 0.01-10.00 mg L(-1). Recoveries from spiked glass microfibre filters and silica gel cartridges for chlorothalonil and 4-hydroxychlorothalonil were almost quantitative. The quantification limits were calculated to be 8.4 and 19.6 ng m(-3) in air for chlorothalonil and 4-hydroxychlorothalonil, respectively. The two analytes spiked on the GF/A filters and silica gel cartridges were proven to be stable for more than 15 days, at 4degrees C and ambient temperature. The applicability of the present method was demonstrated by the analysis of the chlorothalonil and its metabolite in greenhouse air.     

Identification of degradation products of thiram in water, soil and plants using LC-MS technique

In order to evaluate the deleterious effects of exposure to pesticides on a target population, a comprehensive study on their degradation in the various segments of ecosystem under varying environmental conditions is needed. In view of this, a study has been carried out on the metabolic pathways of thiram, a dithiocarbamate fungicide, in a variety of matrices namely water and soil under controlled conditions and plants in field conditions. The identification of degradation products was carried out in samples collected at various time points using LC-MS. The degradation products identified can be rationalized as originating by a variety of processes like hydrolysis, oxidation, N-dealkylation and cyclization. As a result of these processes the presence of some metabolites like dimethyl dithiocarbamate, bis(dimethyl carbamoyl) disulphide, bis(dimethyl dithiocarbamoyl) trisulphide and N-methyl-amino-dithiocarbamoyl sulphide was observed in all the cases. However, some different metabolites were observed with the change in the matrix or its characteristics such as cyclised products 2(N, N-dimethyl amino)thiazoline carboxylic acid and 2-thioxo-4-thiazolidine were observed only in plants. The investigations reflect that degradation initiates with hydrolysis, subsequently oxidation/dealkylation, followed by different types of reactions. The pathways seem to be complex and dependent on the matrices. Dimethyl dithiocarbamate and oxon metabolites, which are more toxic than parent compound, seem to persist for a longer time. Results indicate persistence vis-a-vis toxicity of pesticide and its metabolites and also provide a data bank of metabolites for forensic and epidemiological investigations.     

Characterizing pesticide sorption and degradation in macro scale biopurification systems using column displacement experiments

The efficiency of biopurification systems to treat pesticide-contaminated water was previously studied in microcosms. To validate the obtained results, macrocosm systems were set-up. Four pesticides (linuron, isoproturon, bentazone, and metalaxyl) were continuously applied to ten different organic substrate mixes. Retention of the pesticides was similar and in some cases slightly lower in the macrocosms compared to the microcosms. Differences in retention between the different mixes were however minimal. Moreover, the classification of the retention strength of the pesticides was identical to that observed in microcosms: linuron > isoproturon > metalaxyl > bentazone. Monod kinetics were used to describe delayed degradation, which occurred for isoproturon, metalaxyl and bentazone. No breakthrough of linuron was observed, thus, this pesticide was appointed as the most retained and/or degraded pesticide, followed by isoproturon, metalaxyl and bentazone. Finally, most of the matrix mixes efficient in degrading or retaining pesticides were mixes containing dried cow manure.     

催化光度法测定水中痕量亚硝酸根

基于亚硝酸根对溴酸钾氧化结果紫而使其褪色的催化作用,建立了灵敏的催化光度测定痕量亚硝酸根的新方法,测定范围为０．０２－０．１６μｇ／ｍＬ,用于水样中亚硝酸根的测定,获得了满意结果。     

Photosensitized degradation of Irgarol 1051 in water

Irgarol 1051 (2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine) is a herbicide analogue that is added to antifouling agents used on ships. Our former study on its degradation in sunlight suggested that unknown photosensitizers in natural waters accelerated the photodegradation to the degradation product, M1. In this study, the photodegradation of Irgarol in water was investigated in the presence of some photosensitizers. Test water containing Irgarol or M1, with or without photosensitizers, was irradiated with light from a UV-A fluorescent lamp for 48h. The concentrations of Irgarol and M1 in the test water were determined by HPLC after solid-phase extraction. M1 was more stable than Irgarol when irradiated in the presence of photosensitizers such as acetone, benzophenone, tryptophan, and rose bengal. Hydrogen peroxide (HP) accelerated the photodegradation of Irgarol, and the product M1 was degraded in the presence of more than 100mgl(-1) HP after 10h. Natural humic substances (NHS) also accelerated the photodegradation of Irgarol, but in this case, the product M1 persisted even when Irgarol was completely degraded. Photosensitized degradation of Irgarol by NHS may result in the accumulation of M1 in aquatic environments.