Hexachlorobenzene Removal Research Articles

Fe2O3 micron particles are critical for electron transfer and the distribution of electrochemically active bacteria in soil MFCs

Fe2O3 plays a complex role in soil electron transfer. A microbial fuel cell (MFC) was constructed to drive the directional transfer of electrons in soil, and the results revealed that Fe2O3 acts first as a capacitor, intercepting and reserving the electrons produced by electrochemically active bacteria (EAB) in the soil, which leads to a decrease in hexachlorobenzene (HCB) removal efficiency with increasing proportions of Fe2O3 dosing (R2 = 0.85). The Fe2O3 then exerted its semiconductor properties in synergy with dissolved Fe2+ as an electron mediator to promote the flow of electrons in the soil. Power generation by the MFC was significantly and positively correlated with the concentration of dissolved Fe2+ (r = 0.51) and the Fe2O3 dosing proportion (r = 0.97). The higher HCB removal efficiency, spatial distribution of intercepted electrons, and abundance of electron transfer metabolic pathways confirmed that Fe2O3 promoted electron-flow fluxes in soil. Additionally, Geobacter sp., (direct electron transfer) and Pseudomonas sp., (indirect electron transfer) were the dominant electrochemically active bacteria in the anode and soil of MFC, respectively. In this study, both dissolved (Fe2+) and solid state (Fe2O3) electron mediators functioned as electron transporters in soil, we propose an internal “electron internet” of soil consisting of points and lines.

Photochemical transformation of hexachlorobenzene (HCB) in solid-water system: Kinetics, mechanism and toxicity evaluation

As one of the first batch of persistent organic pollutants (POPs) included in Stockholm Convention, hexachlorobenzene (HCB) has attracted great attention because of its wide occurrence and great environmental risks. Considering the easy adsorption of HCB on solids and the complexity of natural particles, we systematically investigated the photodegradation of HCB on the surface of silica gel (SG) in aqueous solution in this work to reveal its fate in natural waters. Under mercury lamp irradiation, more than 90% of HCB loaded on SG could be removed after 240 min. Moreover, the effects of solution pH and water constituents were examined, and results showed that the presence of NO2−, NO3−, Fe3+ and humic acid (HA) significantly inhibited the reaction due to the scavenging of ROS and/or competitive absorption of light. According to radical quenching experiments and electron paramagnetic resonance (EPR) spectra, hydroxyl radicals and singlet oxygen generated on the surface of SG could participate in the transformation of HCB, but •OH played a dominant role. Based on products identified by high performance liquid chromatography-mass spectrometry (HPLC-MS) and gas chromatography-mass spectrometry (GC-MS), two main pathways were proposed for the removal of HCB, including dechlorination and hydroxylation which represent direct and indirect photodegradation, respectively, and the occurrence of these two reactions was further supported by density functional theory (DFT) calculations. From the quantitative analysis of penta-chlorobenzene, it was estimated that dechlorination and hydroxylation contributed to approximately 44.4% and 55.6% of initial HCB degradation, respectively. Furthermore, toxicity predictions by the ecological structure–activity relationship model (ECOSAR) suggested that the toxicity of HCB was decreased in the photodegradation process. This study would provide important information for understanding the photochemical transformation mechanism of HCB at the solid/water interface.

A new photocatalytic reactor for hexachlorobenzene removal in water

A new photocatalytic reactor for hexachlorobenzene removal in water

Enhanced HCB removal using bacteria from mangrove as post-treatment after electrochemical oxidation using a laser-prepared Ti/RuO2–IrO2–TiO2 anode

The environmental persistence of hexachlorobenzene (HCB) is a challenge that promotes studies for efficient treatment alternatives to minimize its environmental impact. Here, we evaluated the HCB removal by electrochemical, biological, and combined approaches. The electrochemical treatment of 4 μM HCB solutions was performed using a synthesized Ti/RuO2–IrO2–TiO2 anode, while the biological treatment using mangrove-isolated bacteria was at 24, 48, and 72 h. The HCB degradability was assessed by analyzing chemical oxygen demand (COD), microbial growth capacity in media supplemented with HCB as the only carbon source, gas chromatography, and ecotoxicity assay after treatments. The synthesized anode showed a high voltammetric charge and catalytic activity, favoring the HCB biodegradability. All bacterial isolates exhibited the ability to metabolize HCB, especially Bacillus sp. and Micrococcus luteus. The HCB degradation efficiency of the combined electrochemical-biological treatment was evidenced by a high COD removal percentage, the non-HCB detection by gas chromatography, and a decrease in ecotoxicity tested with lettuce seeds. The combination of electrochemical pretreatment with microorganism degradation was efficient to remove HCB, thereby opening up prospects for in situ studies of areas contaminated by this recalcitrant compound.

Atmospheric deposition of semivolatile organic pollutants in European high mountains: Sources, settling and chemical degradation

Bulk atmospheric deposition samples, including wet and dry deposition, were collected during 2004–2006 in four high mountain European lakes: Skalnate Pleso (Tatra mountains, Slovakia), Gossenköllesee (Alps, Austria), Redon (Pyrenees, Spain), and Lochnagar (Grampian Mountains, Scotland). Samples were analysed for polycyclic aromatic hydrocarbons (PAHs), polychlorobiphenyls (PCBs), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs), endosulfans, and polybromodiphenyl ethers (PBDEs).The deposition of PCBs, HCHs, and low brominated BDEs reflected baseline contributions from long range atmospheric transport. This was also the case for PAHs in Redon and Gossenköllesee, endosulfans in Lochnagar and Gossenköllesee and HCB in these three lakes. However, Skalnate received PAHs, endosulfans, and HCB from regional sources as it was the case for endosulfans in Redon. The distinct origin of these pollutants was reflected in the relative composition of some metabolites such as the proportion of endosulfan sulfate vs α- and β-endosulfans or the relative composition of BDE47 and BDE99.Wet deposition was the main process for atmospheric removal of PAHs, HCHs, and HCB. In addition, warm season revolatilization from soils and melting snow with subsequent condensation at low temperature were significant for volatile PAHs, HCB, low chlorinated PCBs, and endosulfans.Reaction with OH radicals was not a significant loss process of HCHs and HCB in remote areas, dominated by wet deposition, whereas PCBs and PAHs were significantly removed by both wet deposition and OH radical oxidation, the latter dominating in the highest altitude sites. Photolysis was the main atmospheric removal process of PBDEs, dominating over atmospheric deposition and OH depletion in all sites.

Alumina-mediated photocatalytic degradation of hexachlorobenzene in aqueous system: Kinetics and mechanism

Five kinds of Al2O3 were characterized by SEM, TEM, FT-IR and BET surface area, and then used as carriers to investigate the photochemical removal of hexachlorobenzene (HCB) in aqueous system. The results showed that HCB coated on the surfaces of all Al2O3 could be photodegraded rapidly, and Neutral-Al2O3 presented the best performance. Meanwhile, the efficient removal of HCB in real water matrices, including tap water, river water and secondary clarifier effluent showed the potential practical application of Al2O3. EPR and theoretical calculation revealed the generation of hydroxyl radicals on Al2O3 surface under 500 W Xe lamp irradiation. Nine intermediates and a small amount of Cl− were identified by GC/MS, LC/MS and IC analysis, which was further verified by transition state calculations. These results can provide a new technique for HCB removal in water and wastewaters, and give more insights into the environmental ecological risk assessment of this pollutant.

Remediation of hexachlorobenzene-contaminated soils with alkyl glycoside-enhanced desorption and zero-valent iron-EDTA-air treatment.

In this work, the use of a coupled process, alkyl glycoside (APG) enhanced soil desorption followed by the zero-valent iron-ethylenediaminetetraacetic acid (EDTA)-air (ZEA) Fenton-like system, was investigated for the remediation of a simulated hexachlorobenzene (HCB)-contaminated diatomite soil and a real HCB-contaminated soil. Three surfactants with different concentrations were studied to obtain the suitable soil desorption agent. Compared with APG0810 and Triton x-100, APG0814 showed a better solubilization effect due to its lower critical micelle concentration. With addition of 3000mg L-1 APG0814, 35% of HCB was removed from contaminated diatomite soil, and a small amount of residual APG in diatomite soil was found to be beneficial for the soil dispersion. After treatment with the ZEA system, the removal efficiency of HCB in the diatomite soil desorption solution reached 76% in 2 h; we observed that a small amount of APG retained in the desorption solution accelerated the HCB removal. A real HCB-contaminated soil was used to verify the remediation effects. This study demonstrates that our approach is a feasible alternative for remediating soil contaminated with hydrophobic organic compounds.

Structure and function of the bacterial communities during rhizoremediation of hexachlorobenzene in constructed wetlands.

Vertical flow constructed wetlands (VF CWs) are considered to be effective for treating organic pollutants. The rhizosphere of macrophytes such as Phragmites sp., Typha sp. serves as an active and dynamic zone for the microbial degradation of organic pollutants. However, it is still not clear how soil bacterial communities respond to macrophytes and pollutants during the process. For this purpose, the seedlings of Phragmites australis and Typha angustifolia were planted respectively in the VF CWs added with HCB at a dose of 2mg/kg. During 96days of cultivation, we monitored hexachlorobenzene (HCB) removal efficiency by GC/MS and the structure of the rhizosphere bacterial communities in the different VF CWs by denaturing gradient gel electrophoresis (DGGE), and constructed bacterial clone library based on PCR-amplified 16S rRNA gene. As expected, the rhizosphere bacterial communities also remained insensitive to HCB exposure in the wetland soil. The diversity of these microbes presented two stages, from the varied up and down to equilibrium in the entire experimental period. Molecular analysis revealed that the phylum Firmicutes dominated over the bacterial communities. The genera that increased under HCB stress included the well-known HCB-degrading bacteria (Pseudomonas sp. and Alcaligenes sp.) and other common bacteria found in contaminated soil but with lesser known practical functions (Burkholderia sp., Lysinibacillus fusiformis, and Bacillus cereus). Furthermore, there was a certain variance in the relative abundances of the bacterial phyla and HCB removal efficiency among different VF CW treatments. The degradation of HCB in T. angustifolia microcosms was faster than that in P. australis and unvegetated wetlands, and the highest bacterial diversity and richness was found in the VF CWs comprising T. angustifolia.

Reductive dechlorination of hexachlorobenzene subjected to several conditions in a bioelectrochemical system

A microbial fuel cell (MFC) is a very promising way to remove organic pollutants. Hexachlorobenzene (HCB) is a widely used agricultural pesticide. In this study, single-chamber and membrane-less soil MFCs were constructed. The HCB was degraded to pentachlorobenzene (PeCB), tetrachlorobenzene (TeCB), and trichlorobenzene (TCB) in sequence by a reductive dechlorination process in soil MFCs. The influences of the external resistance, concentration of phosphate buffer, and electrode spacing in soil MFCs on the degradation rate and removal efficiency of HCB were analyzed. The results showed that the degradation rate and removal efficiency of HCB were increased when the external resistance decreased from 2000 to 20Ω, and also when the concentration of phosphate buffer increased. The anode area played a significant role in dechlorination of HCB. Altering the spacing of the reducing electrode resulted in a lower ohmic resistance in the soil MFCs. The ohmic resistance was negatively correlated with the removal efficiency and degradation rate (P<0.05). In conclusion, HCB removal efficiency could be enhanced by soil MFCs, the performance of which was improved by a decrease in external resistance and internal resistance, and an increase in phosphate buffer concentration, rather than just by shortening the electrode spacing.

Ordered Mesoporous Carbonaceous Materials with Tunable Surface Property for Enrichment of Hexachlorobenzene.

A gradient pyrolysis approach has been adopted for synthesis of ordered mesoporous carbonaceous materials with different surface and textural properties for removal of hexachlorobenzene. The resultant ordered mesoporous carbonaceous materials possess high surface areas (364-888 m2/g), large pore volumes (0.23-0.47 cm3/g), uniform pore sizes (2.6-3.8 nm), and tunable hydrophobic properties. They show high-efficiency removal performances for hexachlorobenzene with high adsorption capacity of 594.2-992.1 μg/g. An enhanced removal rate (>99%) can be obtained with the increasing pyrolysis temperature (900 °C) as a result of the strong hydrophobic-hydrophobic interaction between the carbon framework and hexachlorobenzene molecules. Furthermore, the adsorption behaviors follow the Sips isotherm model and obey the pseudo-first-order kinetic model.

Simultaneous degradation of refractory organic pesticide and bioelectricity generation in a soil microbial fuel cell with different conditions

ABSTRACTIn this study, the soil microbial fuel cells (MFCs) were constructed based on sandy soil to remove the refractory organic pesticide hexachlorobenzene (HCB) in topsoil by a simple method. The construction of membraneless single-chamber soil MFCs by setting up the cathode- and the anode-activated carbon, inoculating the sludge and adding the co-substrates can promote HCB removal significantly. The results showed that HCB removal efficiencies in the soils contaminated with 40, 80 and 200 mg/kg were 71.14%, 62.15% and 50.06%, respectively, which were 18.65%, 18.46% and 19.17% higher than the control, respectively. The electricity generation of soil MFCs in different HCB concentrations was analyzed. The highest power density reached was 70.8 mW/m2, and an internal resistance of approximately 960 Ω was obtained when an external resistance loading of 1000 Ω was connected. Meanwhile, the influences of temperature, substrate species and substrate concentrations on soil MFCs initial electricity production were investigated. The addition of the anionic surfactant sodium dodecyl sulfate (SDS) into the soil MFCs system contributed to the improvement in HCB removal efficiency.

Ferrite as an effective catalyst for HCB removal in soil: Characterization and catalytic performance

A novel nano-scale ferrite (MgFe2O4) was employed for hexachlorobenzene (HCB) removal in soil with microwave (MW) treatment. MW-generated hole (h+)/electron pair could activate water and oxygen adsorbed on the surface of MgFe2O4 to produce OH and O2−. Radical scavenging tests confirmed it was OH but not h+ and O2− that directly oxidized HCB. O2− was a responsible oxidant of intermediates decomposition. Thus the co-existing of water and molecular oxygen had significant enhancement on HCB catalytic oxidation, showing high degradation (80%) and dechloriantion (93%) after 20min of MW radiation. Electron spin resonance analysis demonstrated that O2− and OH radicals were aroused from MW-induced h+/electron activation of molecule oxygen and water, but not from the lattice oxygen and –OH groups in the structure of ferrites. Thermal desorption of HCB occurred at the wide temperature of the surface soil at the range of 90–500°C, and obviously catalytic oxidation happed at a temperature range of 90–620°C in the water/oxygen-contained system. Complicated pyrolytic reactions happed at 90–670°C in the absence of water and oxygen. The addition of MgFe2O4 with MW radiation elevated soil temperature, leading to HCB pyrolysis that fitted well with the first order kinetics model. When soil was vitrified at >670°C, with the process of thermal fixation, changes of the soil structure took place.

Effects of co-present cations and anions on hexachlorobenzene removal by activated carbon, nano zerovalent iron and nano zerovalent/activated carbon composite

Activated carbon, nano zerovalent iron (nZVI), and nano zerovalent iron/activated carbon (nZVI/AC) have all been found to be effective for hexachlorobenzene (HCB) removal either through adsorption, dechlorination, or both. Detailed investigations on the effects of several anions and cations normally present in aqueous streams on the removal of HCB were carried out to evaluate the potential performance of these materials in field treatment. Effects of ions were analyzed from the perspectives of changes in pH, ionic strength, and redox conditions. Results showed that ions that facilitate zerovalent iron corrosion, i.e. bicarbonate, chloride, chloride, ferrous, and copper, could greatly enhance HCB removal by nZVI, while HCB adsorption by activated carbon was more a factor of solution pH and ionic strength. The effects of ions on nZVI/AC were more complicated since both nZVI and activated carbon played a role in HCB removal. The results lead to a better understanding of HCB removal by these materials and could be employed in the consideration of choosing materials and prediction of treatment efficiency.

Rapid mechanochemical synthesis of VOx/TiO2 as highly active catalyst for HCB removal

A rapid (1.5h) one-step ball milling (BM) method was developed to synthesize VOx/TiO2 (VTi-BM) and WOx or MoOx doped VOx/TiO2 (VWTi-BM or VMoTi-BM). Catalytic activity on gaseous POPs removal was tested using hexachlorobenzene (HCB) as surrogate. Catalytic performance decreased in the order of VWTi-BM (T50%=230°C)>VMoTi-BM (260°C)>VTi-BM (270°C)>VTi-WI (300°C; VOx/TiO2 synthesized by wetness impregnation method). The intermediates from oxidation of HCB were analyzed by off gas analysis, from which 2,2,4,5-tetrachloro-4-cyclopentene-1,3-dione (TCCD), dichloromaleic anhydride (DCMA) and tetrachloro-1,4-bezoquinone (TCBQ) were identified. Furthermore, a possible mechanism for the oxidation of HCB over VOx/TiO2 catalysts was proposed. Mechanism studies showed that BM samples possess better dispersion of the VOx species and more surface chemisorbed oxygen. Doping WOx or MoOx into VOx/TiO2 by ball milling can further enhance catalytic performance by increasing surface acid sites.

Removal of PCBs and HCB from contaminated solids using a novel successive self-propagated sintering process.

Thermal treatments are the primary technologies used to remove persistent organic pollutants from contaminated solids. The high energy consumption during continuous heating, required cost for treating the exhaust gas, and potential formation of secondary pollutants during combustion have prevented their implementation. A novel successive self-propagated sintering process was proposed for removing polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) from contaminated solids in a low-cost and environmentally friendly way. Nine laboratory-scale experiments involving different initial concentrations of pollutants and solid compositions were performed. Almost all PCBs (>99%) and HCB (>97%) were removed from solids under constant experimental conditions. Varying initial concentrations of PCBs and HCB in the contaminated solids did not influence the removal efficiency of the pollutants; however, the degradation efficiency of pollutants increased as their initial concentrations increased. Although varying levels of PCDD/Fs were detected in the effluent gas, they were all within the emission standard limit.

Simultaneous degradation of toxic refractory organic pesticide and bioelectricity generation using a soil microbial fuel cell

In this study, the soil microbial fuel cells (MFCs) were constructed in the topsoil contaminated with toxic refractory organic pesticide, hexachlorobenzene (HCB). The performance of electricity generation and HCB degradation in the soil-MFCs were investigated. The HCB degradation pathway was analyzed based on the determination of degradation products and intermediates. Experimental results showed that the HCB removal efficiencies in the three groups (soil MFCs group, open circuit control group and no adding anaerobic sludge blank group) were 71.15%, 52.49% and 38.92%, respectively. The highest detected power density was 77.5mW/m2 at the external resistance of 1000Ω. HCB was degraded via the reductive dechlorination pathway in the soil MFC under anaerobic condition. The existence of the anode promoted electrogenic bacteria to provide more electrons to increase the metabolic reactions rates of anaerobic bacteria was the main way which could promote the removal efficiencies of HCB in soil MFC.

Irreversible thyroid disruption induced after subchronic exposure to hexachlorobenzene in male rats

Thyroid hormones play a complex role in the toxicity of hexachlorobenzene (HCB) and related compounds. Time-course and dose-response experiments for free- and total thyroxine (T4) and triiodothyronine (T3) plasma levels for thyroid-stimulating hormone (TSH) and thyroid gland histomorphology were determined in male Wistar rats. Also, we examined the possible reversibility of changes noted after removal of HCB. Rats treated with this organochlorine compound resulted in a hypertrophy of the thyroid gland and altered thyroid function by decreasing significantly the levels of total- and free T4 in a dose-dependent manner (total T4: 28 and 51%; free T4: 21 and 37%), and this decrease was seen as early as 21 days and thereafter. Free T3 was also decreased by 21% with the highest dose starting from day 21. No significant changes were observed in the circulating levels of total T3 In response to the decrease of thyroid hormones, a dose-dependent increase of TSH levels (27 and 31%, respectively, for 4 mg and 16 mg/kg of HCB body weight) was observed after 21 days of HCB treatment. We have observed a hypertrophy and hyperplasia of follicular cells and a decrease in colloid volume in histological picture. When HCB was removed and changed by vehicle, the thyroid relative weight and plasma TSH continued to rise and serum thyroid hormones remained suppressed. These findings suggest that subchronic exposure of rats to HCB induced an irreversible hypothyroidism state.

Effect of Polarity Reversal on Hexachlorobenzene Removal during Electrokinetic Fenton Process

AbstractExperimental evidence shows that the electrokinetic Fenton process is very effective for cleaning soil contaminated with organic compounds, especially hydrophobic and persistent organic pollutants. Despite the technological progress in recent years, there are still several performance-related issues to be addressed, such as its implication on the final soil quality and different oxidant delivery schemes. This paper reports the results of a series of experiments carried out to explore the possibilities of using polarity reversal as an enhancement during electrokinetic Fenton treatment of soil contaminated with persistent organic pollutants. Laboratory-scale experiments were conducted with kaolin and hexachlorobenzene (HCB) as the model soil and contaminant, respectively. Experiments were performed both with and without added iron (Fe). Reversing the polarity of electrodes after a period during the experiments was found to be effective in aiding the reachability of the oxidant to the soil specimen i...

Dechlorination of hexachlorobenzene in treatment microcosm wetlands

There is little understanding of the pathways of hexachlorobenzene (HCB) removal in treatment wetlands. The aim of this research was to evaluate HCB dechlorination as affected by common reed (Phragmites australis) and broad-leaved cattail (Typha latifolia) applications in neutralized and enriched with nutrients peat with high, low and nil HCB concentration (300, 15, and 0μg/g, respectively). After 10 weeks of the experiment, HCB removal was 49.4–67.2% in High-HCB peat, and 57.6–74.8% in Low-HCB peat. The mean removal of HCB was 53.5% in the unvegetated and 68.7% in the vegetated microcosm wetlands. The amount of HCB metabolites showed that dechlorination rates in Low-HCB microcosms were higher than in High-HCB microcosms, which were mainly attributed to the lower phytotoxicity and higher dissolved organic carbon (DOC) content than that of Low-HCB. Although HCB uptake by plants was <0.1% of the initial concentration, in both High-HCB and Low-HCB peats vegetated with Typha and Phragmites, enhanced HCB dechlorination rate was found. This was probably because the roots and its exudates enhanced dechlorination process. Microbial degradation was the predominating process in HCB removal. The following dechlorinated metabolites of HCB were detectable from the water, macrophytes and peat samples: PeCB, 1,2,3,4-, 1,2,3,5- and 1,2,4,5-TeCB, 1,2,3-, 1,2,4- and 1,3,5-TCB.

Remediation of hexachlorobenzene contaminated soils by rhamnolipid enhanced soil washing coupled with activated carbon selective adsorption

The present study investigates the selective adsorption of hexachlorobenzene (HCB) from rhamnolipid solution by a powdered activated carbon (PAC). A combined soil washing-PAC adsorption technique is further evaluated on the removal of HCB from two soils, a spiked kaolin and a contaminated real soil. PAC at a dosage of 10 g L −1 could achieve a HCB removal of 80–99% with initial HCB and rhamnolipid concentrations of 1 mg L −1 and 3.3–25 g L −1, respectively. The corresponding adsorptive loss of rhamnolipid was 8–19%. Successive soil washing-PAC adsorption tests (new soil sample was subjected to washing for each cycle) showed encouraging leaching and adsorption performances for HCB. When 25 g L −1 rhamnolipid solution was applied, HCB leaching from soils was 55–71% for three cycles of washing, and HCB removal by PAC was nearly 90%. An overall 86% and 88% removal of HCB were obtained for kaolin and real soil, respectively, by using the combined process to wash one soil sample for twice. Our investigation suggests that coupling AC adsorption with biosurfactant-enhanced soil washing is a promising alternative to remove hydrophobic organic compounds from soils.