Chlorinated Aromatic Compounds Research Articles

Augmented degradation performance of dielectric barrier discharge plasma via optimized hydroxyl radical generation

Dielectric barrier discharge (DBD) plasma demonstrates significant potential for eliminating chlorinated aromatic compounds (CACs), while its commercial application has been hampered by inadequate generation and diffusion of active species. In response, this work introduced iron-biochar composites (Fe/BC) into DBD system to enhance the generation of highly oxidative hydroxyl radicals (OH) from underutilized O3 and H2O2, thereby reducing the diffusion of OH and accelerating the degradation of CACs. The results indicated that, in just 15 min, the combined system achieved remarkable degradation rates exceeding 95% for six diverse CACs, with the degradation rate constant increasing up to 4.27 times when compared to DBD alone. Moreover, the varied response of pollutants implied that the enhanced degradation efficiency was primarily facilitated by the reduced mass transfer distance between pollutants and formed OH. The activation of O3 on Lewis acidic sites not only directly promoted the generation of OH through free radical chain reactions but also indirectly induced more conversion of H2O2 into OH by facilitating the Fe3+/Fe2+ cycle. The identification of intermediates and toxicity analysis substantiated its environmental sustainability. This study offers a viable technical pathway and theoretical foundation for enhancing the efficiency of plasma-based treatment of organic wastewater.

Oxygen-mediated dielectric barrier discharge plasma for enhanced degradation of chlorinated aromatic compounds

Chlorinated aromatic compounds (CACs), a kind of refractory pollutants, pose a potential risk to the environment and human health. Herein, dielectric barrier discharge (DBD) plasma is employed to enhance the degradation of 2,4-dichlorophenol (2,4-DCP) from water, and O2 is the most efficient working atmosphere with totally 2,4-DCP degradation in 40 min. O3, ·OH, ·O2– and 1O2 are the main active species responsible for the degradation, while the contribution of hydrated electrons and reactive nitrogen species is almost negligible. Moreover, highly efficient o-Nitrochlorobenzene (o-NCB) and chlorobenzene (CB) degradation and mineralization are also achieved in DBD/O2 process. All the CACs are completely degraded in 60 min following the degradation rate order of CB > 2,4-DCP > o-NCB, which almost follows the order of ionization potential values. The mineralization efficiencies of CB, 2,4-DCP and o-NCB reach 61.14 %, 70.50 % and 92.77 % in DBD/O2 process, respectively, which are 1.74,1.15 and 1.28 times higher than that in DBD process alone. Based on theoretical calculation and intermediates analysis, three common degradation pathways are proposed including hydroxylation, dechlorination and ring-opening. Soil remediation experiments further indicate the high efficiency and promising perspective of DBD/O2 process in CACs contaminated soil treatment. This work is instructive to elucidate the importance of O2 atmosphere in the degradation of CACs by DBD plasma system and provides an alternative way for removing CACs from water and soil.

Enhanced adsorption of aqueous chlorinated aromatic compounds by nitrogen auto-doped biochar produced through pyrolysis of rubber-seed shell

ABSTRACT The adsorption of chlorinated aromatic compounds (CACs) on pristine biochar was often limited. Surface modification can greatly improve the adsorption capacity of biochar. In this work, by pyrolysis activation of rubber-seed shell wastes, nitrogen auto-doped biochar (RSS-NBC) was synthesized and used for purifying CACs-containing wastewater. Systematic characterization results showed that after proper treatment, the as-prepared RSS-NBC had high specific surface area, abundant surface oxygen- and nitrogen-containing functional groups, and nano-scale pore structure. Batch adsorption experiments were conducted with using three typical CACs probing pollutants, i.e. 1,2-dichlorobenzene (1,2-DCB), 2,4-dichlorophenol (2,4-DCP) and 2,4-dichlorobenzoic acid (2,4-DCBA). The adsorption experiments results showed that the maximum adsorption amounts of 1, 2-DCB, 2,4-DCP, and 2,4-DCBA could reach 2284, 1921, and 1142 mg/g at 298.15 K. Moreover, 90% of the equilibrium adsorption amount can be reached within 0.5 h. The adsorption kinetic results showed that the adsorption processes of the three CACs followed the pseudo-second-order rate model and were dominated by chemisorption. Also, the adsorption isotherms of 1, 2-DCB and 2, 4-DCP belonged to the Freundlich model and were valid for multilayer adsorption, while the adsorption of 2,4-DCBA followed Langmuir model and single-layer adsorption. The thermodynamics data indicated that the spontaneous adsorption process of 1, 2-DCB and 2, 4-DCP was endothermic while that of 2,4-DCBA was exothermic. After 5 cycles of adsorption-regeneration, the removal efficiency of RSS-NBC particles still remained more than 80% for the three typical CACs, indicating that it could be reused as an effective and retrievable adsorbent in the treatment of CACs-containing effluents.

Hydrodechlorination of Different Chloroaromatic Compounds at Room Temperature and Ambient Pressure—Differences in Reactivity of Cu- and Ni-Based Al Alloys in an Alkaline Aqueous Solution

It is well known that the hydrodechlorination (HDC) of chlorinated aromatic contaminants in aqueous effluents enables a significant increase in biodegradability. HDC consumes a low quantity of reactants producing corresponding non-chlorinated and much more biodegradable organic compounds. Two commonly used precious metals free Al alloys (Raney Al-Ni and Devarda’s Al-Cu-Zn) were compared in reductive action in an alkaline aqueous solution. Raney Al-Ni alloy was examined as a universal and extremely effective HDC agent in a diluted aqueous NaOH solution. The robustness of Raney Al-Ni activity is illustrated in the case of HDC of polychlorinated aromatic compounds mixture in actual waste water. In contrast, Devarda’s Al-Cu-Zn alloy was approved as much less active for HDC of the tested chlorinated aromatic compounds, but with a surprisingly high selectivity on cleavage of C-Cl bonds in the meta and sometimes the ortho position in chlorinated aniline and sometimes chlorinated phenol structures. The reaction of both tested alloys with chlorinated aromatic compounds in the aqueous NaOH solution is accompanied by dissolution of aluminum. Dissolved Al in the alkaline HDC reaction mixture is very useful for subsequent treatment of HDC products by coagulation and flocculation of Al(OH)3 caused by simple neutralization of the alkaline aqueous phase after the HDC reaction.

Preparation of Pd/GO/Cu Electrode and Its Electrochemical Degradation for 2,4-Dichlorophenol.

Chlorinated aromatic compounds (CACs) are a class of persistent organic pollutants, which have serious damage to water environment due to their own stable structure. But a good many of CACs were abandoned because of their tremendous yields and wide applications, so it is urgent to find the effective degradation methods for CACs. The electrochemical method is supposed to be a simple, environmentally friendly and effective pathway to degrade CACs. In this paper, a Pd/GO/Cu composite electrode was prepared by a combination of impregnation method and constant current electrodeposition method, which showed good electrochemical degradation efficiency for the 2,4-dichlorophenol. Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to characterize the surface structure, functional group composition, crystal structure and surface element valence of the electrode. Moreover, the stability of the electrode was investigated, and the preparation conditions of the electrode were optimized.

Diversity of the bphA1 Genes in a Microbial Community from Anthropogenically Contaminated Soil and Isolation of New Pseudomonads Degrading Biphenyl/Chlorinated Biphenyls

Molecular biological and cultivation-based approaches were used to investigate the microbial community of tehnogenic soil contaminated with poorly degradable toxic (chlorinated) aromatic compounds. Diversity of the bphA1 genes, the key genes for the degradation of biphenyl/polychlorinated biphenyls (PCB) was assessed, and new bacterial degraders of biphemyl/PCB were isolated. Cloning of the PCR product obtained using the DNA isolated from soil as a template and the primers to the biphenyl 2,3-dioxygenase α-subunit gene (bphA1) revealed two types of the genes of aromatic dioxygenases (DO) with the highest similarity (97.8‒99.5%) to the genes encoding the Rieske cluster of DO α-subunits (bphA1) from uncultured bacteria. Two biphenyl-degrading isolates obtained from an enrichment culture of a soil sample incubated with biphenyl were identified as Pseudomonas (VRP2-6 and VRP2-2). According to their 16S rRNA gene sequences, they exhibited the highest similarity to the type strain of P. taiwanensis (99%) and P. alcaligenes (100%), respectively. Analysis of the bphA1 sequences of strains VRP2-6 and VRP2-2 revealed the similarity to those of the known biphenyl-degrading pseudomonads not exceeding 97.3%. The isolate VRP2-6 efficiently utilized ortho- and para-monochlorinated biphenyls and degraded dichlorinated biphenyl oxidizing both the ortho- and para-chlorinated rings of the biphenyl molecule. New pseudomonad strains may be of interest for development of biotechnologies aimed at monitoring and remediation of biphenyl/PCB-contaminated soils.

Optimization of nucleophilic dechlorination of polychlorinated biphenyls: calculation and experiment

The nucleophilic substitution of aromatic chlorine atoms in polychlorinated biphenyls structures for non-toxic substituents was investigated. The reaction of industrial polychlorobiphenyls mixture Sovol with sodium methoxide in bipolar aprotic solvent was studied. Thermodynamic modeling and the HSC software were used to evaluate the reactivity of polychlorobiphenyls congeners from mixture Sovol toward sodium methoxide in dimethyl sulfoxide, and the calculation results were compared with experimental data. The reactivity of polychlorinated biphenyls was evaluated using gas chromatography and gas chromatography/mass spectrometry. Experimental and computational studies confirm that under the reaction conditions, the most reactive congeners are hepta-, hexa- and pentachlorobiphenyls, and the trichlorinated congeners represent the lowest reactivity. The tetrachlorobiphenyls possess an intermediate position. The optimal thermodynamic and chemical conditions at which occurs complete dechlorination of toxic chlorinated aromatic compounds under the conditions of nucleophilic substitution were proposed. The optimal conditions for the complete replacement of chlorine atoms in polychlorinated biphenyls congeners with methoxy groups were detected: temperature = 170 °C, ratio of polychlorinated biphenyls/sodium methoxide was 1:6 and reaction time was 4 h.

Porostereum sp., Associated with Saffron (Crocus sativus L.), is a Latent Pathogen Capable of Producing Phytotoxic Chlorinated Aromatic Compounds.

Saffron (Crocus sativus L.) is one of the most expensive spices in the world due to its medicinal and aromatic value. However, saffron production is severely affected by the corm rot disease throughout the saffron producing countries. In this study, we report a basidiomycetous latent pathogen of saffron, designated as CSE26, capable of producing phytotoxic compounds. CSE26 is a highly odorous basidiomycete with monomitic hyphal system. Molecular phylogeny of ITS and 28S ribosomal gene sequence of CSE26 assigned it as Porostereum spadiceum. It was found to produce corm rot in C. sativus under in vivo and field conditions, with a disease severity index of 0.7 and 0.5, respectively. CSE26 was found to produce chlorinated aromatic compounds (CAMs) having phytotoxic activity against Arabidopsis plants. Therefore, these compounds may be acting as pathogenic determinants of CSE26. However, there is a need to study the level of production of these CAMs by this fungus in the natural environment and their effects on plant health.

Bioremediation of PCB-contaminated shallow river sediments: The efficacy of biodegradation using individual bacterial strains and their consortia

Elimination of dangerous toxic and hydrophobic chlorinated aromatic compounds, mainly PCBs from the environment, is one of the most important aims of the environmental biotechnologies. In this work, biodegradation of an industrial mixture of PCBs (Delor 103, equivalent to Aroclor 1242) was performed using bacterial consortia composed of four bacterial strains isolated from the historically PCB-contaminated sediments and characterized as Achromobacter xylosoxidans, Stenotrophomonas maltophilia, Ochrobactrum anthropi and Rhodococcus ruber. The objective of this research was to determine the biodegradation ability of the individual strains and artificially prepared consortia composed of two or three bacterial strains mentioned above. Based on the growth parameters, six consortia were constructed and inoculated into the historically contaminated sediment samples collected in the efflux canal of Chemko Strážske plant – the former producer of the industrial mixtures of PCBs. The efficacy of the biotreatment, namely bioaugmentation, was evaluated by determination of ecotoxicity of treated and non-treated sediments. The most effective consortia were those containing the strain R. ruber. In the combination with A. xylosoxidans, the biodegradation of the sum of the indicator congeners was 85% and in the combination with S. maltophilia nearly 80%, with inocula applied in the ratio 1:1 in both cases. Consortium containing the strain R. ruber and S. maltophilia showed pronounced degradation of the highly chlorinated PCB congeners. Among the consortia composed of three bacterial strains, only that consisting of O. anthropi, R. ruber and A. xylosoxidans showed higher biodegradation (73%). All created consortia significally reduced the toxicity of the contaminated sediment.

Aromatic Halogenation by Using Bifunctional Flavin Reductase-Halogenase Fusion Enzymes.

The remarkable site selectivity and broad substrate scope of flavin-dependent halogenases (FDHs) has led to much interest in their potential as biocatalysts. Multiple engineering efforts have demonstrated that FDHs can be tuned for non-native substrate scope and site selectivity. FDHs have also proven useful as in vivo biocatalysts and have been successfully incorporated into biosynthetic pathways to build new chlorinated aromatic compounds in several heterologous organisms. In both cases, reduced flavin cofactor, usually supplied by a separate flavin reductase (FR), is required. Herein, we report functional synthetic, fused FDH-FR proteins containing various FDHs and FRs joined by different linkers. We show that FDH-FR fusion proteins can increase product titers compared to the individual components for in vivo biocatalysis in Escherichia coli.

A simple and effective approach for catalytic reductive dechlorination of aromatic compounds

An efficient process for the preparation of 2(3),9(10),16(17),23(24)-octa(n-hexyl)cobalt(II)phthalocyanine, ((n-hexyl)8CoPc) (2) was described. The novel cobalt(II)phthalocyanine was characterized by spectroscopic methods. It was employed as a catalyst for the room temperature reductive dechlorination of chlorinated aromatic compounds (CACs). The results were showed that the CACs were completely dechlorinated within 110–120 min.

Formation of persistent chlorinated aromatic compounds in simulated and real fly ash from iron ore sintering

Effects of carbon concentration and Cu additive in simulated fly ash (SFA) and real fly ash (RFA) on the formation of polychlorinated dibenzofurans (PCDFs), polychlorinated dibenzo-p-dioxins (PCDDs), chlorobenzenes, and polychlorinated biphenyls which were all regarded as persistent chlorinated aromatics in iron ore sintering were investigated. In the annealing process of SFA with various carbon contents, the yield of chlorinated aromatics and the I-TEQ obtained their maximum at 10 wt% carbon content. Active carbon in SFA acted as the carbon source as well as an adsorbent which led to higher production of PCDD/F in solid phase at 10 wt% carbon content. The increase of carbon content will be beneficial on the formation of 2,3,7,8-Chloro-substituted PCDF compared with 2,3,7,8-Chloro-substituted PCDD. In addition, the CuCl2·2H2O was a much more powerful catalyst in the formation of chlorinated aromatic compounds compared with elementary Cu, since it served as both a catalyst and a chlorine donor. However, the RFA behaved similarly with SFA with elementary Cu in the formation of chlorinated aromatic compounds. The effect of carbon content and copper additives on formation of 2,3,7,8-chloro-substituted congeners displayed similar characteristics with the tetra- to octa-PCDD/F isomers and even the total PCDD/Fs.

Formation of persistent chlorinated aromatic compounds in simulated and real fly ash from iron ore sintering

Formation of persistent chlorinated aromatic compounds in simulated and real fly ash from iron ore sintering

Halogenase-Inspired Oxidative Chlorination Using Flavin Photocatalysis.

Chlorine gas or electropositive chlorine reagents are used to prepare chlorinated aromatic compounds, which are found in pharmaceuticals, agrochemicals, and polymers, and serve as synthetic precursors for metal‐catalyzed cross‐couplings. Nature chlorinates with chloride anions, FAD‐dependent halogenases, and O2 as the oxidant. A photocatalytic oxidative chlorination is described based on the organic dye riboflavin tetraacetate mimicking the enzymatic process. The chemical process allows within the suitable arene redox potential window a broader substrate scope compared to the specific activation in the enzymatic binding pocket.

Unintentional formed PCDDs, PCDFs, and DL-PCBs as impurities in Chinese pentachloronitrobenzene products.

Pentachloronitrobenzene (PCNB) products have been reported to contain relatively high levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) as impurities. No data was available for Chinese PCNB products which are still produced and used in China. Therefore, we analysed Chinese PCNB products, including two raw pesticides and three formulations available on the market. In all samples, PCDDs, PCDFs, and dioxin-like polychlorinated biphenyls (DL-PCBs) were detected at levels exceeding Japanese regulation limits. The concentrations of PCDDs and PCDFs (0.16 to 0.93 ng TEQ g(-1)) were lower than the PCNB formulations measured from the Australian market (3.9 ng TEQ g(-1)). However, the Toxic Equivalent (TEQ) contribution from DL-PCBs (0.7 to 2.5 ng TEQ g(-1)) to total TEQ was higher compared to PCDDs and PCDFs. This discovery demonstrated that it is necessary to consider the DL-PCBs impurity in organochlorine pesticides and other organochlorine chemicals in particular chlorinated aromatic compounds for adequate risk assessment. In addition to DL-PCBs, other unintentionally POPs-hexachlorobenzene (HCB) (3.7 to 52 ng g(-1)) and pentachlorobenzene (PeCBz) (0.04 to 0.3 ng g(-1)) which are listed in the Stockholm Convention-were detected in the PCNB samples. The PCNB production steps were assessed for their unintentional POPs formation potential. Thermolysis of the aromatic compounds using iron chloride (FeCl3) as catalyst is suggested as relevant production step for (DL-)PCBs formation. Since the levels in the formulated PCNB recalculated to active ingredient were higher compared to the raw pesticide, the formulation process (e.g., milling) may also have had an influence on additional PCDD/Fs and PCBs formation.

Influence of the Properties of Macromolecular Carbon on de Novo Synthesis of PCDDs, PCDFs, PCBs, and Chlorobenzenes

We examined the influence of the properties of macromolecular carbon on thermochemical de novo synthesis of toxic chlorinated aromatic compounds (aromatic-Cls), such as polychlorinated dibenzo-p-dioxins (PCDDs), furans (PCDFs), biphenyls (PCBs), and chlorobenzenes (CBzs). Six types of macromolecular carbons were prepared. Some activated carbon samples were modified by chemical solvents, such as nitric acid, hydrogen peroxide, sulfuric acid, and urea solutions, to change the properties of the activated carbon. We characterized six macromolecular carbons by surface area (8.8–1540 m2/g), free radicals (Ns = not analyzed to 67.0 × 1019 g–1, g = 2.0011–2.0098), and functional groups (O–H, C–H, C=O, C=C, C–O, and C–OH). Concentrations of aromatic-Cls at 300–400°C, such as PCDDs, PCDFs, PCBs, and CBzs, were clearly influenced by the type of macromolecular carbon. Their distribution between the ash/gas phases implied that increasing the surface area mainly enhanced the adsorption capacity of macromolecular carbon, while increasing the number of free radicals mainly enhance the reaction activity of macromolecular carbon. The PCDD/PCDF ratio suggested that various modifications of macromolecular carbon contributed to the generation of PCDDs in addition to the catalytic behavior of copper. Under most conditions, the surface area of macromolecular carbon did not have a strong correlation with the generation of PCDDs, PCBs, and CBzs, but it did show have a correlation with the generation of PCDFs. One of the destructive effects of aromatic-Cls resulted from the free radicals in macromolecular carbon. The C=O bond (ca. 1720 cm–1) functional group in macromolecular carbon had no strong correlation with the generation of aromatic-Cls, because free radicals had a destructive effect. The functionalities of ether (C–O) or phenolic OH (C–OH) in macromolecular carbon were causative factors in the generation of oxygen-containing aromatic-Cls, such as PCDDs and PCDFs.

Organochlorines in surface soil at electronic-waste wire burning sites and metal contribution evaluated using quantitative X-ray speciation

Heavy metals and toxic chlorinated aromatic compounds (aromatic-Cls) such as dioxins and polychlorinated biphenyls (PCBs) are found at high concentrations and persist in surface soil at wire burning sites (WBSs) in developing countries in which various wire cables are recycled to yield pure metals. Chlorine K-edge near-edge X-ray absorption fine structure (NEXAFS) is used to detect the specific chemical form of Cl and estimate its amount using a spectrum jump in the solid phase. Quantitative X-ray speciation of Cl was applied to study the mechanisms of aromatic-Cls formation in surface soil at WBSs in Southeast Asia. Relationships between aromatic-Cls and chlorides of heavy metals were evaluated because heavy metals are promoters of the thermochemical solid-phase formation of aromatic-Cls.

Chlorine disinfection of dye wastewater: Implications for a commercial azo dye mixture

Azo dyes, the most widely used family of synthetic dyes, are often employed as colorants in areas such as textiles, plastics, foods/drugs/cosmetics, and electronics. Following their use in industrial applications, azo dyes have been found in effluents and various receiving waters. Chemical treatment of effluents containing azo dyes includes disinfection using chlorine, which can generate compounds of varying eco/genotoxicity. Among the widely known commercial azo dyes for synthetic fibers is C.I. Disperse Red 1. While this dye is known to exist as a complex mixture, reports of eco/genotoxicity involve the purified form. Bearing in mind the potential for adverse synergistic effects arising from exposures to chemical mixtures, the aim of the present study was to characterize the components of commercial Disperse Red 1 and its chlorine-mediated decoloration products and to evaluate their ecotoxicity and mutagenicity. In conducting the present study, Disperse Red 1 was treated with chlorine gas, and the solution obtained was analyzed with the aid of LC–ESI-MS/MS to identify the components present, and then evaluated for ecotoxicity and mutagenicity, using Daphnia similis and Salmonella/microsome assays, respectively. The results of this study indicated that chlorination of Disperse Red 1 produced four chlorinated aromatic compounds as the main products and that the degradation products were more ecotoxic than the parent dye. These results suggest that a disinfection process using chlorine should be avoided for effluents containing hydrophobic azo dyes such commercial Disperse Red 1.

Convenient Chlorination of Some Special Aromatic Compounds Using N-Chlorosuccinimide

Some chlorinated aromatic compounds, including indole, benzofuran,carbazole, pyridine and aniline derivatives, are difficult to obtainthrough convenient chlorination. We herein report their efficientsynthesis through chlorination with N-chlorosuccinimide(NCS). Optimization of the reaction conditions, including the temperatureand the choice of solvent, was also investigated. This approach,which is characterized by a facile procedure, comparatively highyields and environmentally friendly features, provides a straightforwardand inexpensive route to several chlorinated aromatic compounds.

Photocatalytic degradation kinetics and mechanism of pentachlorophenol based on Superoxide radicals

The micron grade multi-metal oxide bismuth silicate (Bii 2SiO 20, BSO) was prepared by the chemical solution decomposition technique. Photocatalytic degradation of pentachlorophenol (PCP) was investigated in the presence of BSO under xenon lamp irradiation. The reaction kinetics followed pseudo first-order and the degradation ratio achieved 99.1% after 120 min at an initial PCP concentration of 2.0 mg/L. The pH decreased from 6.2 to 4.6 and the dechlorination ratio was 68.4% after 120 min at an initial PCP concentration of 8.0 mg/L. The results of electron spin resonance showed that Superoxide radical (O 2 ·−) was largely responsible for the photocatalytic degradation of PCP. Interestingly, this result was different from that of previous photocatalytic reactions where valence band holes or hydroxyl radicals played the role of major oxidants. Some aromatic compounds and aliphatic carboxylic acids were determined by GC/MS as the reaction intermediates, which indicated that O 2 ·− can attack the bond between the carbon and chlorine atoms to form less chlorinated aromatic compounds. The aromatic compounds were further oxidized by O 2 ·− to generate aliphatic carboxylic acids which can be finally mineralized to CO 2 and H 2O.