Microbial dechlorination of 2,4,6‐trichlorophenol in anaerobic sewage sludge

Abstract

The dechlorination of 2,4,6‐trichlorophenol (TCP) in municipal sewage sludge with a chlorophenol (CP)‐adapted consortium was investigated. Results show that dechlorination rates differed according to the source of the sludge samples used in the batch experiments. No significant differences in 2,4,6‐TCP dechlorination were observed following treatment with inoculum at densities ranging from 10% to 50% (V/V), but a significant delay was noted at 5% (V/V) density. Overall, results show that the higher the 2,4,6‐TCP concentration, the slower the dechlorination rate. The addition of acetate, lactate, pyruvate, vitamin B₁₂ or manganese dioxide did not results in a significant change in 2,4,6‐TCP dechlorination. Data collected from a bioreactor experiment revealed that pH 7.0 and a total solid concentration of 10 g/L were optimal for dechlorination. Dechlorination rates decreased significantly at higher agitation speeds. 2,4,6‐TCP dechlorination was enhanced under methanogenic conditions, but it was inhibited under denitrifying and sulfate‐reducing conditions.     

Microbial dechlorination of polychlorinated biphenyls in anaerobic sewage sludge.

The potential of a chlorophenol (CP)-adapted consortium to dechlorinate polychlorinated biphenyls (PCBs) in sewage sludge was investigated. Results show that dechlorination rates differed significantly depending on sludge source and PCB congener. Higher total solid concentrations in sewage sludge and higher concentrations of chlorine in PCB resulted in slower dechlorination rates. No significant difference was found for 2,3,4,5-CB dechlorination from pH 6.0 to pH 8.0; however, dechlorination did not occur at pH 9.0 during a 41-day incubation period. Results show that at concentrations of 1 to 10 mg/L, the higher the PCB concentration, the faster the dechlorination rate. In addition, dechlorination rates were in the following order: methanogenic conditions > sulfate-reducing conditions > denitrifying conditions. The addition of acetate, lactate, pyruvate, and ferric chloride decreased lag times and enhanced dechlorination; however, the addition of manganese dioxide had an inhibitory effect. Dechlorination rates were also enhanced by the addition of PCB congeners, including 2,3,4-CB, 2,3,4,5-CB and 2,3,4,5,6-CB in mixture. Overall results show that the CP-adapted consortium has the potential to enhance PCB dechlorination. The optimal dechlorination conditions presented in this paper may be used as a reference for feasibility studies of PCB removal from sludge.     

改性Pd/GAC粒子电极吸附-电催化去除2,4,6-三氯苯酚

以6 mol·L⁻¹硝酸和450 ℃高温共同改性后的颗粒活性炭(granular activated carbon,GAC)为载体,采用硼氢化钠还原法制备了改性Pd/GAC粒子电极,研究了电极对2,4,6-三氯苯酚(2,4,6-trichlorophenol,2,4,6-TCP)的去除能力、动力学特征及脱氯机理。结果表明,通过改性,GAC的比表面积(560.791 m²·g⁻¹)提高了1.5倍,孔容提高了36.02%,对2,4,6-TCP的最大吸附容量为199.2 mg·g⁻¹。在优化条件下,改性粒子电极4 h内对30 mg·L⁻¹的2,4,6-TCP去除率达到94.7%,反应速率常数为0.014 min⁻¹,钯的催化活性为0.3 (min·mmol)⁻¹。通过对反应过程中有机氯和无机氯变化的分析,阐明了改性Pd/GAC粒子电极强化去除2,4,6-TCP的过程。从还原途径、直接和间接还原贡献等方面探究了改性粒子电极电催化脱氯机理。     

Reductive dechlorination and biodegradation of 2,4,6-trichlorophenol using sequential permeable reactive barriers: laboratory studies

The reductive dechlorination and biodegradation of 2,4,6-trichlorophenol (2,4,6-TCP) was investigated in a laboratory-scale sequential barrier system consisting of a chemical and biological reactive barrier. Palladium coated iron (Pd/Fe) was used as a reactive barrier medium for the chemical degradation of 2,4,6-TCP, and a sand column seeded with anaerobic microbes was used as a biobarrier following the chemical reactive barrier in this study. Only phenol was detected in the effluent from the Pd/Fe column reactor, indicating that the complete dechlorination of 2,4,6-TCP was achieved. The residence time of 30.2-21.2h was required for the complete dechlorination of 2,4,6-TCP of 100 mg l(-1) in the column reactor. The surface area-normalized rate constant (k(SA)) is 3.84 (+/-0.48)x10(-5)lm(-2)h(-1). The reaction rate in the column tests was one order of magnitude slower than that in the batch test. In the operation of the biobarrier, about 100 microM of phenol was completely removed with a residence time of 7-8d. Consequently, the dechlorination prior to biodegradation turns out to increase the overall treatability. Moreover, the sequential permeable reactive barriers, consisting of iron barrier and biobarrier, could be recommended for groundwater contaminated with toxic organic compounds such as chlorophenols.     

An integrated anaerobic/aerobic bioprocess for the remediation of chlorinated phenol-contaminated soil and groundwater.

An investigation of biodegradation of chlorinated phenol in an anaerobic/aerobic bioprocess environment was made. The reactor configuration used consisted of linked anaerobic and aerobic reactors, which served as a model for a proposed bioremediation strategy. The proposed strategy was studied in two reactors before linkage. In the anaerobic compartment, the transformation of the model contaminant, 2,4,6-trichlorophenol (2,4,6-TCP), to lesser-chlorinated metabolites was shown to occur during reductive dechlorination under sulfate-reducing conditions. The consortium was also shown to desorb and mobilize 2,4,6-TCP in soils. This was followed, in the aerobic compartment, by biodegradation of the pollutant and metabolites, 2,4-dichlorophenol, 4-chlorophenol, and phenol, by immobilized white-rot fungi. The integrated process achieved elimination of the compound by more than 99% through fungal degradation of metabolites produced in the dechlorination stage. pH correction to the anaerobic reactor was found to be necessary because acidic effluent from the fungal reactor inhibited sulfate reduction and dechlorination.     

pH值对"Fe0-厌氧微生物"体系去除2,4,6-三氯酚过程的影响

考察了pH值对"Fe0-厌氧微生物"体系降解2,4,6,-三氯酚(2,4,6-TCP)效果的影响,结果表明:pH值是影响"Fe0-厌氧微生物"体系降解2,4,6-TCP效果的重要参数,初始pH值直接影响微生物活性和铁腐蚀,进而影响过程pH值变化,反过来又影响铁腐蚀和微生物活性,pH 7.0～9.0的中性偏碱范围较适于厌氧微生物生长。Fe0与微生物对目标污染物的降解具有协同促进作用,其协同促进机制表现在3方面:Fe0与微生物对体系过程pH值具有互补调节作用,可将体系的pH值调节值适于微生物生长的中性范围;Fe0腐蚀产生的Fe2+和H2可为微生物代谢提供电子对和营养物质,从而促进生物还原脱氯的进行;Fe0的腐蚀过程直接对氯代有机物还原脱氯,而微生物又可促进Fe0腐蚀。     

pH值对“Fe^0．厌氧微生物”体系去除2，4，6-三氯酚过程的影响

考察了pH值对“Fe^0一厌氧微生物”体系降解2,4,6,一三氯酚（2,4,6．TCP）效果的影响,结果表明：pH值是影响“Fe^0-厌氧微生物”体系降解2,4,6-TCP效果的重要参数,初始pH值直接影响微生物活性和铁腐蚀,进而影响过程pH值变化,反过来又影响铁腐蚀和微生物活性,pH7．0～9．0的中性偏碱范围较适于厌氧微生物生长。Fe^0与微生物对目标污染物的降解具有协同促进作用,其协同促进机制表现在3方面：Fe^0与微生物对体系过程pH值具有互补调节作用,可将体系的pH值调节值适于微生物生长的中性范围;Fe^0腐蚀产生的Fe2＋和H2可为微生物代谢提供电子对和营养物质,从而促进生物还原脱氯的进行;Fe^0的腐蚀过程直接对氯代有机物还原脱氯,而微生物又可促进Fe^0腐蚀。     

Evaluation of TCDD biodegradability under different redox conditions

Polychlorinated dibenzo-p-dioxins have been generated as unwanted by-products in many industrial processes. Although their widespread distribution in different environmental compartments has been recognized, little is known about their fate in the ultimate environment sinks. The highly stable dioxin isomer 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) has been called the most toxic compound known to man. In this laboratory microcosm study, TCDD bioavailability was evaluated under five reduction/oxidation (redox) conditions including aerobic biodegradation, aerobic cometabolism, methanogenesis, iron reduction, and reductive dechlorination. Activated sludge and aquifer sediments from a TCDD and a pentachlorophenol (PCP) contaminated site were used as the inocula. Acetate, sludge cake, and cane molasses were used as the primary substrates (carbon sources) in cometabolism and reductive dechlorination microcosms. After a 90-day incubation period, microcosms constructed under reductive dechlorination conditions were the only treatment showing promising remediation results. The highest TCDD degradation rate [up to 86% of TCDD removal (with an initial concentration of 96 microg/kg of soil)] was observed in the microcosms with anaerobic activated sludge as the microbial inocula and sludge cakes as the primary substrates. Except for reductive dechlorination microcosms, no significant TCDD removal was observed in the microcosms prepared under other conditions. Thus, application of an effective primary substrate to enhance the reductive dechlorination process is a feasible method for TCDD bioremediation. Bioremediation expense can be significantly reduced by the supplement of some less expensive alternative substrates (e.g., sludge cakes, cane molasses). Results would be useful in designing a scale-up in situ or on-site bioremediation system such as bioslurry reactor for field application.     

2,4,6-三氯酚在盐城湿地土壤中的吸附行为

2,4,6-三氯酚(2,4,6-TCP)是造纸废水中的有机污染物之一,具有毒性强、难生物降解等特点。为了解盐城湿地土壤对2,4,6-TCP的吸附行为,采用批平衡实验研究了2,4,6-TCP在该土壤中的动力学和热力学吸附特征,并考察了不同溶液pH及离子强度对土壤吸附2,4,6-TCP的影响。结果表明,在水土比为10:1的条件下,当溶液pH为3~9时,吸附系数Kd随pH的升高由8.01 L/g降到1.57 L/g;当CaCl2溶液浓度为0、0.01和0.1 mol/L时,该土壤对10 mg/L 2,4,6-TCP的吸附量则分别为20.64、26.62和39.57 mg/kg。与拟一级动力学模型和拟二级动力学模型相比,双室一级动力学模型能较好地描述湿地土壤对2,4,6-TCP的动态吸附过程。在288、298和308 K温度下Freundlich方程能较好地拟合2,4,6-TCP的吸附等温线,吸附系数Kf随温度的升高依次为5.91、7.35和11.14 (mg/kg)/(mg/L)n,该吸附过程为自发的吸热反应。     

Urinary concentrations of trichlorophenols in the Korean adult population: results of the National Human Biomonitoring Survey 2009

Trichlorophenols such as 2,4,5-trichlorophenol (2,4,5-TCP) and 2,4,6-trichlorophenol (2,4,6-TCP) are organochlorine compounds to which the general public can be exposed via contaminated food, water, and air. This study assessed exposure to 2,4,5-TCP and 2,4,6-TCP in Koreans age 18–69 years based on the Korean National Human Biomonitoring Survey conducted in 2009. Using data from 1,865 representative Koreans, we found that the geometric mean urinary concentrations of 2,4,5-TCP and 2,4,6-TCP were 83.4 pg/mL [95 % confidence interval (CI)?=?78.6–88.6] and 0.39 ng/mL (95 % CI?=?0.35–0.42), respectively. The creatinine-adjusted geometric mean 2,4,5-TCP and 2,4,6-TCP levels were 78.8 ng/g creatinine (95 % CI?=?73.8–84.1) and 0.36 μg/g creatinine (95 % CI?=?0.33–0.40), respectively. Of the Korean adult population, about 67.5 and 87.5 % had respective urine 2,4,5-TCP and 2,4,6-TCP concentrations >0.05 ng/mL (the limit of detection, LOD). Urine 2,4,5-TCP concentrations were significantly associated with age and place of residence, whereas urine 2,4,6-TCP concentrations were higher in rural residents. These findings suggest that most Koreans had detectable levels of 2,4,5-TCP and 2,4,6-TCP in their urine and that the body burden of 2,4,5-TCP and 2,4,6-TCP varied according to demographic and geographic factors.     

Deriving freshwater quality criteria for 2,4,6-trichlorophenol for protection of aquatic life in China

Freshwater quality criteria of 2,4,6-trichlorophenol (2,4,6-TCP) were developed with particular reference to the aquatic biota in China, and based on USEPA's guidelines. Acute toxicity tests were performed on nine different domestic species indigenous to China to determine 48 h LC(50) and 96 h LC(50) values for 2,4,6-TCP. In addition, 21 d survival-reproduction test with Daphnia magna, 30 d embryo-larval test with Carassius auratus, 60 d fry-juvenile test with Ctenopharyngodon idellus, 30 d early life stage test with Bufo bufo gargarizans and 96 h growth inhibition test with Scenedesmus obliqaus were also conducted to estimate lower chronic limit and upper chronic limit values. The final acute value (FAV) was 2.01 mg/l 2,4,6-TCP. Acute-to-chronic ratios ranged from 5.01 to 12.2. The final chronic value (FCV) and the final plant value (FPV) of 2,4,6-TCP were 0.226 and 2.24 mg/l respectively. Based on FAV, FCV and FPV for 2,4,6-TCP, a criteria maximum concentration of 1.01 mg/l and a criterion continuous concentration of 0.226 mg/l were derived. The results of this study provide useful data for deriving national or local water quality criteria for 2,4,6-TCP based on aquatic biota in China.     

Fenton试剂和活化过硫酸钠氧化降解土壤中的二氯酚和三氯酚

氯酚类物质（chlorophenols, CPs）在环境介质中广泛存在且具有很强环境毒性。为探究化学氧化修复场地氯酚类污染的可行性,通过室内实验、模拟搅拌实验、现场中试,开展应用Fenton试剂和活化过硫酸钠氧化降解土壤CPs的研究。结果表明,化学氧化可有效降解土壤中的CPs,在氧化剂用量和CPs总量摩尔比为15:1时,CaO活化Na2S2O8能高效降解土壤中的二氯酚（2,4-DCP）和三氯酚（2,4,6-TCP）,室内实验和现场中试的去除率均达90%以上,处理后的2,4-DCP和2,4,6-TCP浓度均低于《展览会用地土壤环境质量评价标准》（HJ 350-2007）A类标准限值。Fenton试剂在室内实验中降解率达90%以上,但现场中试对2,4-DCP和2,4,6-TCP的降解率仅为66.1%、23.8%,处理后2,4-DCP浓度仍超过A类标准限值1倍以上。此外,在修复过程中,约70%的2,4-DCP、2,4,6-TCP会向液相转移,因此,需要关注修复系统引入水后污染物向液相中的转移可能造成的二次污染。研究结果可为氯酚类污染土壤的修复提供新思路,并为实际工程应用提供理论依据。     

Hydroxyl radical generation and oxidative stress in Carassius auratus liver as affected by 2,4,6-trichlorophenol

With Carassius auratus, one of the main economic fish species in Eastern China as test material, this paper studied the hydroxyl radical generation and oxidative stress in its liver under the effect of 2,4,6-trichlorophenol (2,4,6-TCP). Different doses of 2,4,6-TCP were injected intraperitoneally into the fishes, and the Electron paramagnetic resonance (EPR) spectra of hepatic free radicals, activities of superoxide dismutase (SOD), catalase (CAT) and glutathione-s-transferase (GST), levels of reduced glutathione (GSH) and oxidized glutathione (GSSG), and malondialdehyde (MDA) contents were determined 24h after injection. The results showed that under the effects of 2,4,6-TCP, the generation of free radical that was considered to be hydroxyl radical increased significantly, the activities of antioxidant enzymes decreased, with CAT most strongly affected and followed by SOD and GST, the GSH level decreased significantly while GSSG level had little difference, resulting in a decreased GSH/GSSG ratio, and the MDA content increased significantly. All the test parameters showed that C. auratus was subjected to oxidative stress and damage when exposed to 2,4,6-TCP.     

PCDD/DF formations by the heterogeneous thermal reactions of phenols and their TiO2 photocatalytic degradation by batch-recycle system

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/DFs) formation by the thermal reactions of phenols with CuCl2 under oxygen flux were carried out in relation to their formation mechanisms. To evaluate the effect of photocatalytic degradation of titanium dioxide (TiO2) thin film prepared by the sol-gel method, the photocatalysis of PCDD/DFs in acetonitrile/water solution by batch-recycle system was conducted. For the thermal reaction system of powder mixtures of 2,4,5-trichlorophenol (2,4,5-TCP) and CuCl2, the formation rates were 8.1 microg/g-2,4,5-TCP/min for total PCDD/DFs and 6.9 microg/g-2,4,5-TCP/min for PCDDs, and total PCDD/DF rate was higher by approximately 40 fold compared to phenol vapor/oxygen/CuCl2 powder system. For the system of 2,4,5-TCP, PCDDs were mainly formed via ortho-phenoxyphenols (POP) intermediate by the condensation of 2,4,5-trichlorophenate. For PCDD/DF photocatalytic degradations, most PCDD congeners photodecomposed rapidly and the rates presented more than 70% (as dechlorination rates of 76% for PCDDs) at 24 h after irradiation, using PCDD/DFs formed with 2,4,5-TCP. The rate constants were in the order of 4.8-6.1 x 10(-3) min(-1), assuming the pseudo-first-order reactions for their low levels.     

响应面法优化污泥电渗透脱水工艺参数

以泥饼含固率作为衡量污泥脱水效果的指标,采用响应面法进行污泥电渗透脱水工艺参数的优化研究。结果表明,最佳反应条件为初始污泥含固率为8.58%,初始电压梯度为20.88 V/cm,初始污泥厚度为2.25 cm,此条件下得到的污泥含固率为48.82%(预测值为48.45%)。方差分析结果表明,回归模型达到显著水平,在研究区域(初始污泥含固率:5%~10%、初始电压梯度12~30 V/cm、初始污泥厚度:1~2.5 cm)内拟合较好,与实验结果吻合度较高。     

Influence of chemical oxygen demand/total Kjeldahl nitrogen ratio and sludge age on nitrification of nitrogenous wastewater.

Four laboratory-scale biological nitrification units (influent total Kjeldahl nitrogen [TKN] = 1002 to 1062 mg/L) were operated at chemical oxygen demand (COD)/TKN ratios of approximately 0.5, 1.0,15, and 2.0 and at three different sludge ages of 30, 20, and 10 days to study the influence of COD/TKN, sludge age, COD loading, and TKN loading on nitrification and nitrifiers. Percent nitrification was found to increase with decreases in COD/TKN and increases in sludge age. The average nitrifier concentration increased from 460 mg/L at a COD/TKN of 2.22 and a sludge age of 10 days to 706 mg/L at a COD/TKN of 0.676 and a sludge age of 30 days. The nitrifier fraction was found to be higher at a lower COD/TKN and lower at a higher COD/TKN. The nitrifier fraction increased with the decrease in sludge age and COD loadings and the increase in TKN loadings. The effect of sludge age on the nitrifier fraction was amplified at a COD/ TKN of approximately 0.5 rather than at approximately 2.0. The nitrification rate (kilograms TKN oxidized per kilograms nitrifiers per day) was shown to be dependent on COD/TKN and sludge age. The activity performed by Nitrobacter was affected at all COD/TKN ratios studied as well as at a sludge age of 10 days. This was manifested by the accumulation of high levels of nitrite-nitrogen in the nitrified effluent. The presence of heterotrophs did not affect nitrification rates and the growth of nitrifiers, which were found to be beneficial. High sludge age and COD loadings resulted in a higher sludge volume index of more than 200 mL/g mixed liquor suspended solids. Microscopic examination showed filamentous structure of sludge under these conditions. It is concluded from the investigations that a sludge age of 30 days and a COD/TKN of approximately 1.0 are optimal to yield maximum nitrification and nitrifier growth rates for treating high-strength nitrogenous wastewater.     

Effect of lead on the sorption of 2,4,6-trichlorophenol on soil and peat

The effect of lead on the sorption of 2,4,6-trichlorophenol (2,4,6-TCP) on soil and peat was investigated using a batch equilibration method. Lead markedly diminished the sorption of 2,4,6-TCP, and 2,4,6-TCP had little effect on lead sorption. Peat was a more effective adsorbent for 2,4,6-TCP than soil. The desorption hysteresis of 2,4,6-TCP verified the presence of high-energy sorption sites. Mechanisms of lead suppression effect on the 2,4,6-TCP sorption included the following: Firstly, lead accelerated the aggregation of colloids, the aggregates covered the surface in part and shrunk the pore sizes of the adsorbents, hence decreased the sorption of 2,4,6-TCP. Secondly, X-ray absorption and Fourier transform infrared spectroscopy study suggested that lead competed with 2,4,6-TCP for carboxylic, phenolic and Si-OH groups of organic matter and clay minerals. Such competition was partly responsible for the overall suppression effect of lead on the sorption of 2,4,6-TCP.     

Biodegradation of 2,4,6-trichlorophenol and associated hydraulic conductivity reduction in sand-bed columns

The aim of this research was to investigate the long-term hydraulic conductivity changes in sand-bed columns exposed to 2,4,6-trichlorophenol (TCP). Continuous flow laboratory studies were conducted using sand-bed columns (15 cm i.d.; 200 cm length) at 20+/-1 degrees C during 365 d. The influence of (i) initial loads of 2,4,6-TCP (15, 30, 45 and 60 mg kg(-1) of 2,4,6-TCP), and (ii) recirculating water velocity (0.09, 0.56 and 1.18 cm min(-1)) on the biodegradation of 2,4,6-TCP and hydraulic conductivity changes in the sand-bed columns were investigated. The experimental results indicated that biodegradation of 2,4,6-TCP followed pseudo-first-order kinetics in the range of k(1)=0.01-1.64 d(-1), and it was influenced by initial load (p<0.01) and recirculating water velocity (p<0.01). Indigenous microbial biomass growth and changes resulted in a spatial (180 cm) and temporal (365 d) reduction of hydraulic conductivity in the sand-bed columns by up to two orders of magnitude during biodegradation of 2,4,6-TCP. The fastest hydraulic conductivity reductions were observed in the sand-bed column operated at the highest recirculating water velocity and highest cumulative load of 2,4,6-TCP following 365 d of continuous treatment (p<0.05).     

A disappearance model for the prediction of trichlorophenol ozonation

The disappearance and modeling of the ozonation of 2,4,6-trichlorophenol (TCP) was studied under different initial TCP concentrations and initial pH levels. The ozonation of TCP was found to follow a pseudo-first-order reaction. The degradation rates increased with the initial pH, and decreased with initial TCP concentration. 2,6-Dichlorohydroquinone was identified as the major intermediate, indicating that dechlorination and hydroxylation co-occurred during TCP ozonation. A model was proposed to quantitatively predict the pseudo-first-order rate constants under different initial TCP concentration and different initial pH levels. The proposed model can successfully describe the reaction; therefore another practical equation was proposed to predict the TCP removal rate at any detention time, which has high potential for practical applications and reactor design.     

Influences of pH and current on electrolytic dechlorination of trichloroethylene at a granular-graphite packed electrode

Electrolytic dechlorination using a granular-graphite packed cathode is an alternative method for the remediation of chlorinated organic compounds. Its effectiveness under various conditions needs experimental investigation. Dechlorination of trichloroethylene (TCE) was conducted under various conditions in an electrolytic reactor with a platinum-gauze anode and a granular-graphite packed cathode. The higher the applied current, the more TCE was eliminated and more hydrogen and oxygen gasses were generated. Current efficiency decreased with a decrease in TCE concentration during each dechlorination experiment. But, the current efficiency concentration coefficient (CECC), which was defined as current efficiency divided by concentration, was a better indicator of current efficiency. The CECC was not significantly affected by current, but it varied with pH value. The pH effects were results of the involvement of electrolytes in the proton reduction and the electron transfer at the cathode. A lower pH value favored TCE dechlorination in potassium chloride, which is an electrolyte that was not involved in cathode reactions with protons and electrons. In ammonium acetate and potassium nitrate, which involve proton reduction and/or electron transfer, the pH value affected TCE dechlorination through proton limitation and electron competition.