Co-polymerization of penta-halogenated phenols in humic substances by catalytic oxidation using biomimetic catalysis

Introduction

A synthetic water-soluble meso-tetra(2,6-dichloro-3-sulfonatophenyl)porphyrinate of iron(III) chloride, Fe-(TDCPPS)Cl, was employed to catalyze the oxidative co-polymerization of penta-halogenated phenols in two humic materials of different origin.

Materials and methods

Co-polymerization of pentachlorophenol (PCP) was followed by high-performance size-exclusion chromatography (HPSEC), the unbound PCP recovered from reacting humic solutions was evaluated by gas-chromatography/electron capture detector, and the oxidative catalyzed coupling of pentafluorophenol (PFP) into humic matter was assessed by liquid-state ¹⁹F-NMR spectroscopy. HPSEC showed that the catalyzed oxidative coupling between PCP and humic molecules increased the apparent weight-average molecular weight (M _w) values in both humic substances.

Results and discussion

HPSEC further indicated that the co-polymerization reaction turned the loosely bound humic supramolecular structures into more stable conformations, which could no longer be disrupted by the disaggregating effect of acetic acid. The occurrence of covalent linkages established between PCP and humic molecules was also suggested by the very little amount of PCP found free in solution after the catalyzed co-polymerization. ¹⁹F-NMR spectroscopy suggested that also PFP could be oxidatively coupled to humic materials. PFP-humic co-polymerization reaction produced ¹⁹F-spectra with many more ¹⁹F signals and wider chemical shifts spread than for PFP alone or PFP subjected to catalyzed coupling without humic matter.

Conclusions

These findings show that biomimetic iron-porphyrin is an efficient catalyst for the covalent binding of polyhalogenated phenols to humic molecules, thereby suggesting that the co-polymerization reaction may become a useful technology to remediate soils and waters contaminated by polyhalogenated phenols and their analogues.     

Effects of humic substances on the decomposition of 2,4-dichlorophenol by ozone after extraction from water into acetic acid through activated carbon

The objectives of this study are to clarify the behavior of humic substances throughout the processes of 2,4-dichlorophenol (2,4-DCP) adsorption on granular activated carbon (GAC) from water and extraction into acetic acid, and the influence of the extracted humic substances on the decomposition of 2,4-DCP by ozone in the acetic acid. The adsorption capacity of GAC for 2,4-DCP was not influenced by the humic substances preloaded to have equilibrium concentration of 24.9mg Cl(-1) (14.5mg Cg(-1)). The adsorption capacity of GAC for 2,4-DCP decreased to one tenth of new GAC after the first adsorption-extraction step because of only 16% desorption in the first step. However, 2,4-DCP adsorbed on GAC was completely extracted after the second step suggesting that GAC can be used as adsorbent to transfer 2,4-DCP from water to acetic acid. The concentration ratio of 2,4-DCP from water into acetic acid was around 2x10(5), whereas the concentration ratio of humic substances was about 3.5, indicating that 2,4-DCP was selectively adsorbed and extracted by this system. The first order degradation rate constant for 2,4-DCP by ozone in acetic acid increased with the addition of humic substances. The rate constant with 16mg Cl(-1) of humic substances was 2.6 times as high as that without humic substances. Humic substances behaved as a promoter for the degradation of 2,4-DCP by ozone.     

Nano-MnO<Subscript>2</Subscript>-mediated transformation of triclosan with humic molecules present: kinetics,products, and pathways

It has been shown that manganese dioxide (MnO₂) can mediate transformation of phenolic contaminants to form phenoxyl radical intermediates, and subsequently, these intermediates intercouple to form oligomers via covalent binding. However, the reaction kinetics and transformation mechanisms of phenolic contaminants with humic molecules present in nano-MnO₂-mediated systems were still unclear. In this study, it was proven that nano-MnO₂ were effective in transforming triclosan under acidic conditions (pH 3.5–5.0) during manganese reduction, and the apparent pseudo first-order kinetics rate constants (k?=?0.0599–1.5314 h^?1) increased as the pH decreased. In particular, the transformation of triclosan by nano-MnO₂ was enhanced in the presence of low-concentration humic acid (1–10 mg L^?1). The variation in the absorption of humic molecules at 275 nm supported possible covalent binding between humic molecules and triclosan in the nano-MnO₂-mediated systems. A total of four main intermediate products were identified by high-resolution mass spectrometry (HRMS), regardless of humic molecules present in the systems or not. These products correspond to a suite of radical intercoupling reactions (dimers and trimers), ether cleavage (2,4-dichlorophenol), and oxidation to quinone-like products, triggered by electron transfer from triclosan molecules to nano-MnO₂. A possible reaction pathway in humic acid solutions, including homo-coupling, decomposition, oxidation, and cross-coupling, was proposed. Our findings provide valuable information regarding the environmental fate and transformation mechanism of triclosan by nano-MnO₂ in complex water matrices.     

Electrogeneration of H(2) for Pd-catalytic hydrodechlorination of 2,4-dichlorophenol in groundwater

A novel electrolytic groundwater remediation process, which used the H₂ continuously generated at cathode to achieve in situ catalytic hydrodechlorination, was developed for the treatment of 2,4-dichlorophenol (2,4-DCP) in groundwater. Catalytic hydrodechlorination using Pd supported on bamboo charcoal and external H₂ showed that 2,4-DCP was completely dechlorinated to phenol within 30 min at pH ? 5.5. In a divided electrolytic system, the catalytic hydrodechlorination of 2,4-DCP in cathodic compartment by H₂ generated at the cathode under 20 and 50 mA reached 100% at 120 and 60 min, respectively. Two column experiments with influent pHs of 5.5 (unconditioned) and 2 were conducted to evaluate the feasibility of this process. The 2,4-DCP removal efficiencies were about 63% and nearly 100% at influent pHs of 5.5 and 2, respectively. Phenol was solely produced by 2,4-DCP hydrodechlorination, and was subsequently degraded at the anode. A low pH could enhance the hydrodechlorination, but was not necessarily required. This study provides the preliminary results of a novel effective electrolytic process for the remediation of groundwater contaminated by chlorinated aromatics.     

溶液中阴离子和腐殖酸对UV/H2O2降解2,4-二氯酚的影响

研究了UV/H2O2工艺对2,4-二氯酚(2,4-DCP)的去除效果和水中阴离子、腐殖酸对该工艺降解2,4-DCP的影响.结果表明:UV/H2O2工艺可以有效地去除水中2,4-DCP,光降解过程符合一级反应动力学模型;在H2O2投加量为8 mg/L、1个30 W低压汞灯照射下,2,4-DCP在蒸馏水和自来水中反应速率常数分别为0.023 2、0.016 2 min-1;NO-3、Cl-、HCO-3对2,4-DCP光降解有抑制作用,当3种阴离子摩尔浓度为0.5、10.0、20.0 mmol/L时,对2,4-DCP光降解的抑制程度为HCO-3＞NO-3＞Cl-;腐殖酸在低浓度时,促进光降解反应进行,在高浓度时,2,4-DCP的光降解受到抑制.自来水中的反应速率常数低于蒸馏水中的反应速率常数是由于水中多种阴离子和腐殖酸影响的结果.     

Use of hairy roots extracts for 2,4-DCP removal and toxicity evaluation by Lactuca sativa test

2,4-Dichlorophenol (2,4-DCP) is widely distributed in wastewaters discharged from several industries, and it is considered as a priority pollutant due to its high toxicity. In this study, the use of different peroxidase extracts for 2,4-DCP removal from aqueous solutions was investigated. Tobacco hairy roots (HRs), wild-type (WT), and double-transgenic (DT) for tomato basic peroxidases (TPX1 and TPX2) were used to obtain different peroxidase extracts: total peroxidases (TPx), soluble peroxidases (SPx), and peroxidases ionically bound to the cell wall (IBPx). All extracts derived from DT HRs exhibited higher peroxidase activity than those obtained from WT HRs. TPx and IBPx DT extracts showed the highest catalytic efficiency values. The optimal conditions for 2,4-DCP oxidation were pH 6.5, H₂O₂ 0.5 mM, and 200 U mL^?1 of enzyme, for all extracts analyzed. Although both TPx extracts were able to oxidize different 2,4-DCP concentrations, the removal efficiency was higher for TPx DT. Polyethylene glycol addition slightly improved 2,4-DCP removal efficiency, and it showed some protective effect on TPx WT after 2,4-DCP oxidation. In addition, using Lactuca sativa test, a reduction of the toxicity of post removal solutions was observed, for both TPx extracts. The results demonstrate that TPx extracts from both tobacco HRs appear to be promising candidate for future applications in removing 2,4-DCP from wastewaters. This is particularly true considering that these peroxidase sources are associated with low costs and are readily available. However, TPx DT has increased peroxidase activity, catalytic efficiency, and higher removal efficiency than TPx WT, probably due to the expression of TPX1 and TPX2 isoenzymes.     

纳米Pd／Fe双金属颗粒对单氯酚及二氯酚的还原脱氯

采用改进液相化学还原法制备纳米Pd／Fe双金属颗粒,研究其钯化率为0．045％和0．135％的条件下分别对3种单氯酚（2-CP、3-CP和4-CP）和3种二氯酚（2,3-DCP、2,4-DCP和2,6-DCP）的脱氯反应。结果表明,合成的纳米Pd／Fe颗粒分散性良好,粒径分布介于25～40nm。纳米Pd／Fe双金属颗粒对单氯酚及二氯酚具有良好的去除效果,3种单氯酚和3种二氯酚的脱氯难易程度分别为2-CP〉4-CP〉3-CP和2,6-DCP〉2,4-DCP〉2,3-DCP,脱氯反应均符合拟一级反应动力学方程。通过还原脱氯实验揭示了分子中氯原子的化学环境对还原脱氯过程具有明显影响。     

Role of dissolved humic acids in the biodegradation of a single isomer of nonylphenol by Sphingomonas sp

This study shows the important role of humic acids in the degradation of ¹⁴C and ¹³C labeled isomer of NP by Sphingomonas sp. strain TTNP3 and the detoxification of the resulting metabolites. Due to the association of NP with humic acids, its solubility in the medium was enhanced and the extent of mineralization of nonylphenol increased from 20% to above 35%. This was accompanied by the formation of significant amounts of NP residues bound to the humic acids, which also occurred via abiotic reactions of the major NP metabolite hydroquinone with the humic acids. Gel permeation chromatography showed a non-homogenous distribution of NP residues with humic acids molecules, with preference towards molecules with high-molecular-weight. Solid state ¹³C nuclear magnetic resonance spectroscopy indicated that the nonextractable residues resulted exclusively from the metabolites. The chemical shifts of the labeled carbon indicated the possible covalent binding of hydroquinone to the humic acids via ester and possibly ether bonds, and the incorporation of degradation products of hydroquinone into the humic acids. This study provided evidences for the mediatory role of humic acids in the fate of NP as a sink for bacterial degradation intermediates of this compound.     

Decomposition of trichloroethylene and 2,4-dichlorophenol by ozonation in several organic solvents

The effects of chemical characteristics of organic solvents on the decomposition rate constants of undissociative trichloroethylene (TCE) and dissociative 2,4-dichlorophenol (2,4-DCP) by ozonation were studied. The TCE and 2,4-DCP decomposition by ozonation in organic solvents followed to the first-order reaction kinetics with respect to TCE or 2,4-DCP concentration. The orders of the rate constants among organic solvents for undissociative TCE and dissociative 2,4-DCP were different indicating that the ozonation rates for undissociative and dissociative compounds were dependent on the chemical property of organic solvent. The decomposition of undissociative TCE by ozonation was a simple electrophilic reaction, which was dependent on acceptor number (AN) of the solvent. On the other hand, the decomposition of dissociative 2,4-DCP was dependent on by the dissociation of the compounds and would be dependent on donor number (DN) of the solvent. Finally, TCE in acetic acid was transformed to chlorinated intermediates and chloride ion and then these intermediates were continuously oxidized to chlorine gas.     

V2O5-TiO2-AlF3/Al2O3催化臭氧化2,4-滴丙酸的氧化效能

为了提高有机物的臭氧化降解效率,工作中利用浸渍法制备了一种新型的三组分催化剂(记为V2O5-TiO2-AlF3/Al2O3)。催化臭氧化降解2,4-滴丙酸的实验结果表明,该催化剂能有效提高臭氧化的效率,体系可能遵循羟基自由基的作用机理。利用相对法计算结果表明,与单独臭氧化相比,V2O5-TiO2-AlF3/Al2O3催化臭氧化体系具有更大的Rct值。重复实验结果表明,该催化剂具有相对较好的稳定性。以上研究结果对推广催化臭氧化技术在实际废水处理中的应用具有重要的实际意义。     

Biogenic volatile organic compounds as a potential stimulator for organic contaminant degradation by soil microorganisms

The effects of monoterpenes on the degradation of ¹⁴C-2,4-dichlorophenol (DCP) were investigated in soils collected from areas surrounding monoterpene and non-monoterpene-emitting vegetation. Indigenous microorganisms degraded ¹⁴C-2,4-DCP to ¹⁴CO₂, after 1 d contact time. Degradation was enhanced by prior exposure of the soils to 2,4-DCP for 32 d, increasing extents of mineralisation up to 60%. Monoterpene amendments further enhanced 2,4-DCP degradation, but only following pre-exposure to both 2,4-DCP and monoterpene, with total 2,4-DCP mineralisation extents of up to 71%. Degradation was greatest at the higher monoterpene concentrations (≥1 μg kg⁻¹). Total mineralisation extents were similar between concentrations, but higher than the control and the 0.1 μg kg⁻¹ amendment, indicating that increases in monoterpene concentration has a diminishing enhancing effect. We suggest that monoterpenes can stimulate the biodegradation of 2,4-DCP by indigenous soil microorganisms and that monoterpene amendment in soils is an effective strategy for removing organic contaminants.     

Fungal bioconversion of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (2,4-DCP)

Ninety strains of fungi from the collection of our mycology laboratory were tested in Galzy and Slonimski (GS) synthetic liquid medium for their ability to degrade the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) and its by-product, 2,4-dichlorophenol (2,4-DCP) at 100 mg l(-1), each. Evolution of the amounts of each chemical in the culture media was monitored by HPLC. After 5 days of cultivation, the best results were obtained with Aspergillus penicilloides and Mortierella isabellina for 2,4-D and with Chrysosporium pannorum and Mucor genevensis for 2,4-DCP. The data collected seemed to prove, on one hand, that the strains responses varied with the taxonomic groups and the chemicals tested, and, on the other hand, that 2,4-D was less accessible to fungal degradation than 2,4-DCP. In each case, kinetics studies with the two most efficient strains revealed that there was a lag phase of 1 day before the onset of 2,4-D degradation, whereas there was none during 2,4-DCP degradation. Moreover, 2,4-DCP was detected transiently during 2,4-D degradation. Finally, M. isabellina improved its degradation potential in Tartaric Acid (TA) medium relative to GS and Malt Extract (ME) media.     

Catalytic ozonation of 2,4-Dichlorophenoxyacetic acid using alumina in the presence of a radical scavenger

Using a laboratory-scale mixed reactor, the performance of alumina in degrading 2,4-Dichlorophenoxyacetic acid with ozone in the presence of tert-butyl alcohol radical scavenger was studied. The operating variables investigated were the dose of alumina catalyst and solution pH. Results showed that using ozone and alumina leads to a significant increase in 2,4-D removal in comparison to non-catalytic ozonation and adsorption processes. The observed reaction rate constants (k_obs ) for 2,4-D during ozonation were found to increase linearly with increasing catalyst dose. At pH 5, the k_obs value increased from 19.3 to 26 M^?1 s^?1 and 67 M^?1 s^?1 when varying the alumina dose from 1 to 2 and 4 g L^?1, respectively. As pH was increased, higher reaction rates were observed for both non-catalytic ozonation and catalytic ozonation processes. Thus, at pH 3 and using a catalyst dose of 8 g L^?1, the k_obs values for non-catalytic ozonation and catalytic ozonation processes were 3.4 and 58.9 M^?1 s^?1, respectively, whereas at pH 5 reaction rate constants of 6.5 and 128.5 M^?1 s^?1 were observed, respectively. Analysis of total organic carbon suggested that catalytic ozonation with alumina achieved a considerable level of mineralization of 2,4-D. Adsorption of 2,4-D on alumina was found to play an important role in the catalytic ozonation process.     

Removal of Alachlor from Water by Catalyzed Ozonation in the Presence of Fe2+, Mn2+, and Humic Substances

Abstract

The effects of Fe(II), Mn(II) and humic substances on the catalyzed ozonation of alachlor, an endocrine disruptor were investigated. Results revealed that small amounts of Fe(II), Mn(II), and humic substances could enhance the ozonation of alachlor, but larger amounts of them would retard the oxidation. These results were successfully identified by an electron paramagnetic resonance (EPR) spectroscopy/spin-trapping method that could quantify hydroxyl radicals. The production of hydroxyl radicals was obviously increased with the increasing of Fe(II) concentration, which contributed to enhance ozonation at low concentrations. But the excess Fe(II) consumed some of the radicals when it was added at a higher concentration (1.5 mg/L). However, no obvious radicals were observed when a different amount of Mn(II) was used, and the catalytic ozonation of alachlor by Mn(II) mainly followed the mechanism of “active sites created on the surface of MnO₂.” The radical pathway was followed when alachlor was ozonated with different concentrations of humic substances because of its radical initiating, promoting, and inhibiting effects.     

Reductive transformation of 2,4-dichlorophenoxyacetic acid by nanoscale and microscale Fe3O4 particles

Reductive transformation of 2,4-dichlorophenoxyacetic acid (2,4-D) by nanoscale and microscale Fe₃O₄ was investigated and compared. Disappearance of the parent species and formation of reaction intermediates and products were kinetically analyzed. Results suggest that the transformation of 2,4-D followed a primary pathway of its complete reduction to phenol and a secondary pathway of sequential reductive hydrogenolysis to 2,4-dichlorophenol (2,4-DCP), chlorophenol (2-CP, 4-CP) and phenol. About 65% of 2,4-D with initial concentration of 50 μ M was transformed within 48 h in the presence of 300 mg L^?1 nanoscale Fe₃O₄, and the reaction rates increased with increasing dosage of nanoscale Fe₃O₄. The decomposition of 2,4-D proceeded rapidly at optimum pH 3.0. Chloride was identified as a reduction product for 2,4-D in the magnetite–water system. Reductive transformation of 2,4-D by microscale Fe₃O₄ was slower than that by nanoscale Fe₃O₄. The reactions apparently followed pseudo-first-order kinetics with respect to the 2,4-D transformation. The degradation rate of 2,4-D decreased with the increase of initial 2,4-D concentration. In addition, anions had a significant adverse impact on the degradation efficiency of 2,4-D.     

Adsorption of phenols by papermill sludges

In this paper we studied the sorption capacity of paper mill sludges for phenols. Phenol, 2-chlorophenol (2-CP), 3-chlorophenol 3-CP). 4-chlorophenol (4-CP), 2-nitrophenol (2-NP), 4-nitrophenol (4-NP), 2.4-dichlorophenol (2,4-DCP), 3,4-dichlorophenol (3,4-DCP) 3,5-dichlorophenol (3,5-DCP) and 2,4,5-trichlorophenol (2,4,5-TCP) were chosen for the sorption tests. Kinetic experiments showed that substituted-phenol sorption on papermill sludge was rapid (equilibrium was reached after 3 h); conversely, the time taken by the phenol to reach equilibrium conditions was 260 h. Experimental data showed that particle diffusion was involved in the sorption process but was not the only rate-limiting mechanism; several other mechanisms were involved. The adsorption isotherms showed the following order of retention capacity of papermill sludge: 2-NP = 4-NP < < 2-CP < phenol < 4-CP < or = 3-CP < 2,4 DCP<3,4 DCP=2,4,5 TCP<3,5 DCP. In all cases the experimental data showed a good fit with the Hill equation. which is mathemratically equivalent to the Langmuir-Freundlich model obtained by assuming that the surface is homogeneous, and that the adsorption is a cooperative process influenced by adsorbate-adsorbate interactions.     

Remediation of a chlorinated aromatic hydrocarbon in water by photoelectrocatalysis

Photoelectrocatalysis driven by visible light offers a new and potentially powerful technology for the remediation of water contaminated by organo-xenobiotics. In this study, the performance of a visible light-driven photoelectrocatalytic (PEC) batch reactor, applying a tungsten trioxide (WO₃) photoelectrode, to degrade the model pollutant 2,4-dichlorophenol (2,4-DCP) was monitored both by toxicological assessment (biosensing) and chemical analysis. The bacterial biosensor used to assess the presence of toxicity of the parent molecule and its breakdown products was a multicopy plasmid lux-marked E. coli HB101 pUCD607. The bacterial biosensor traced the removal of 2,4-DCP, and in some case, its toxicity response suggests the identification of transient toxic intermediates. The loss of the parent molecule, 2,4-DCP determined by HPLC, corresponded to the recorded photocurrents. Photoelectrocatalysis offers considerable potential for the remediation of chlorinated hydrocarbons, and that the biosensor based toxicity results identified likely compatibility of this technology with conventional, biological wastewater treatment.     

Modelling 2,4-dichlorophenol bioavailability and bioaccumulation by the freshwater fingernail clam Sphaerium corneum using artificial particles and humic acids

The complex and variable composition of natural sediments makes it very difficult to predict the bioavailability and bioaccumulation of sediment-bound contaminants. Several approaches have been proposed to overcome this problem, including an experimental model using artificial particles with or without humic acids as a source of organic matter. For this work, we have applied this experimental model, and also a sample of a natural sediment, to investigate the uptake and bioaccumulation of 2,4-dichlorophenol (2,4-DCP) by Sphaerium corneum. Additionally, the particle-water partition coefficients (K(d)) were calculated. The results showed that the bioaccumulation of 2,4-DCP by clams did not depend solely on the levels of chemical dissolved, but also on the amount sorbed onto the particles and the characteristics and the strength of that binding. This study confirms the value of using artificial particles as a suitable experimental model for assessing the fate of sediment-bound contaminants.     

Aerobic granulation for 2,4-dichlorophenol biodegradation in a sequencing batch reactor

Development of aerobic granules for the biological degradation of 2,4-dichlorophenol (2,4-DCP) in a sequencing batch reactor was reported. A key strategy was involving the addition of glucose as a co-substrate and step increase in influent 2,4-DCP concentration. After operation of 39d, stable granules with a diameter range of 1-2mm and a clearly defined shape and appearance were obtained. After granulation, the effluent 2,4-DCP and chemical oxygen demand concentrations were 4.8mgl(-1) and 41mgl(-1), with high removal efficiencies of 94% and 95%, respectively. Specific 2,4-DCP biodegradation rates in the granules followed the Haldane model for substrate inhibition, and peaked at 39.6mg2,4-DCPg(-1)VSS(-1)h(-1) at a 2,4-DCP concentration of 105mgl(-1). Efficient degradation of 2,4-DCP by the aerobic granules suggests their potential application in the treatment of industrial wastewater containing chlorophenols and other inhibitory chemicals.     

Effects of chronic exposure of 2,4-dichlorophenol on the antioxidant system in liver of freshwater fish Carassius auratus

There were few reports on the antioxidant response of aquatic organisms exposed to 2,4-dichlorophenol (2,4-DCP). This research explored the hepatic antioxidant responses of fish to long-term exposure of 2,4-DCP for the first time. Freshwater fish Carassius auratus were chosen as experimental animals. The fish were exposed to six different concentrations of 2,4-DCP (0.005-1.0 mg/l) for 40 days and then liver tissues were separated for determination. As shown from the results, 40 days afterwards, the activities of catalase (CAT) and selenium-dependent glutathione peroxidase (Se-GPx) and the content of oxidized glutathione (GSSG) were induced significantly on the whole compared to control group; superoxide dismutase (SOD) responded to 2,4-DCP exposure at only 0.005 mg/l; the content of reduced glutathione (GSH) was suppressed continuously except Group 7; the activity of glutathione reductase was inhibited initially and then restored to control level from Group 4 on; glutathione S-transferase had only slight responses in Groups 3 and 4. Total glutathione (tGSH) and GSH/GSSG ratio were also calculated to analyze the occurrence of oxidative stress. Besides, good dose-effect relations, which cover most of the exposure concentration range, were found between 2,4-DCP level and CAT activity, GSSG content, Se-GPx activity, respectively. In conclusion, SOD and Se-GPx may be potential early biomarkers of 2,4-DCP contamination in aquatic ecosystems, and further studies will be necessary.