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.     

Enhanced in situ bioremediation of phenol in bioestimulated unsaturated and saturated sand-bed columns.

Biodegradation of phenol was observed in unsaturated sandbed columns, in which phenol concentration declined from 298 mg phenol/kg sand to less than 1 mg/kg after 21 days. In saturated sand-bed columns, phenol concentration declined from 230 mg phenol/kg to less than 1 mg/kg after 37 days. Pseudo-first-order phenol biodegradation rates were in the range 0.25 days(-1) (R2 = 0.9) to 0.66 days(-1) (R2 = 0.85) and 0.08 days(-1) (R2 = 0.68) to 0.14 days(-1) (R2 = 0.84) in the unsaturated and saturated sand-bed columns, respectively. Unsaturated columns presented a higher biomass density (21.5 mg/g) in the sand-bed and lower biomass concentration in the aqueous phase (3.5 NTU) compared with the saturated columns (6.4 mg/g and 14.0 NTU). A high concentration of phenol releases in the sand-bed columns resulted in an initial inhibition of microbial activity and destabilization of the attached biomass.     

Implication of hydraulic properties of bioremediated diesel-contaminated soil

The hydraulic properties, such as hydraulic conductivity and water retention, of aged diesel-contaminated and bioremediated soils were examined and implications of the hydraulic properties for assessing bioremediation performance of soils were proposed. Bioremediation of diesel-contaminated soil was performed over 80 d using three treatments; (I) no nutrient added, column-packed soil, (II) nutrient added, column-packed soil, and (III) nutrient added, loosen soil. Diesel reduction in treatment I soil (control soil) was negligible while treatment III showed the greatest extent of diesel biodegradation. All treatments showed greatest rates of diesel biodegradation during the first 20 d, followed by a much retarded biodegradation rate in the remaining incubation period. Reduction of the degradation rate due to entrained diesel within inaccessible soil pores was hypothesized and tested by measuring the hydraulic properties of two column-packed soils (treatments I and II). The hydraulic conductivity of treatment II soil (nutrient added) was consistently above that of treatment I soil (no nutrient added) at pressure heads between 0 and 15 cm. In addition, the water retention of treatment II soil was greater at pressure heads <100 cm (equivalent to pore size of >30 microm), suggesting that biodegradative removal of hydrocarbons results in enhanced wettability of larger soil pores. However, water retention was not significantly different for control and biodegraded soils at pressure heads >100 cm, where smaller size soil pores were responsible for the water retention, indicating that diesel remained in smaller soil pores (e.g., <30 microm). Both incubation kinetics and hydraulic measurements suggest that hydrocarbons located in small pores with limited microbe accessibility may be recalcitrant to bioremediation.     

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.     

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.     

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.     

Dissipation and leaching of (14)C-monocrotophos in Soil Columns under subtropical climate

Dissipation and leaching behavior of 14C-monocrotophos was studied for 365 days under field conditions using PVC cylinders. The first set (24 cylinders) was spiked with 1.0 microCi 14C-labeled monocrotophos along with 1.06 mg unlabeled monocrotophos to give a concentration of 2 mg kg -1 in the soil up to 15 cm depth. The second set (24 cylinders) received 14C-labeled monocrotophos along with other non-labeled insecticides viz., dimethoate @ 300 g a.i ha-1, deltamethrin @ 12.5 g a.i ha-1, endosulfan @ 750 g a.i ha-1, cypermethrin @ 60 g a.i ha-1, and triazophos @ 600 g a.i ha-1 at an interval of 15 days each as recommended for the cotton crop. 14C-monocrotophos dissipated faster, up to 45% in first 90 days in columns treated with only monocrotophos compared to 25% in columns that received monocrotophos along with other insecticides. However, both the columns showed similar residues 180 days onward. After 180 days of treatment, 46% radiolabeled residues were observed, which reduced up to 39.6% after 365 days. Leaching of 14C-monocrotophos to 15-30 cm soil layer was observed in both the experimental setups. In the 15-30 cm soil layer of both soil columns, up to 0.19 mg 14C-monocrotophos kg-1d. wt. soil was detected after 270 days.     

Use of tracer tests to investigate changes in flow and transport properties due to bioclogging of porous media

Tracer tests were conducted in three laboratory columns to study changes in the hydraulic properties of a porous medium due to bioclogging. About 30 breakthrough curves (BTCs) for each column were obtained. The BTCs were analyzed using analytical equilibrium and dual-porosity models, and estimates of the hydrodynamic dispersion and mass transfer coefficients were obtained by curve fitting. The change in transport properties developed in three stages: an initial phase (I) with no significant changes in transport properties, phase II with growth of biomass near the inlet of the columns causing changes in dispersivity, and phase III with added growth of micro-colonies deeper in the columns causing mass transfer of solutes from the water phase to the biophase. Tracer transport changed from being uniform to more non-uniform with increase in mass transfer of the tracer between the mobile phase and the immobile biomass. An increase in the bulk dispersivity value of up to one order of magnitude was observed. Numerical simulations suggest that local dispersivity values may be as much as 40 times higher in the more severe clogged areas inside the column. The bulk hydraulic conductivities of the columns decreased by up to three orders of magnitude. The hydraulic conductivity and dispersivity parameters were almost recovered after disinfection of the columns. Different models relating the changes of the hydraulic conductivity to the changes in the mobile porosity due to bioclogging were reviewed, and the micro-colony relation of Thullner et al. [Thullner, M., Zeyer, J., Kinzelbach, W., 2002. Influence of microbial growth on hydraulic properties of pore networks, Transport in Porous Media, 49, 99-122.] was found to best describe the relation between the bulk hydraulic parameters.     

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.     

腐殖质含量对填料净化污水效能的影响

掺入与腐殖垃圾级配相同的砂配置腐殖质含量分别为1.09%、0.87%、0.65%、0.44%和0.01%的5种填料,装填0.5 m厚度的试验柱,构建人工快速渗滤系统处理生活污水,并测定饱和水力渗透系数,研究腐殖质含量对填料净化污水效能的影响。结果表明,在相同的水力负荷（1 m/d）和污染负荷下,5种腐殖质填料对COD和TP的平均去除率存在明显差异,腐殖质含量为1.09%、0.87%和0.65%的3种填料对COD的去除率较腐殖质含量为0.01%的填料均高出14%以上。腐殖质含量与TP去除率呈现正相关性。腐殖质含量最高的填料（1#）其初始K值最大达3.23×10^-2 cm/s,约为腐殖质含量最低的填料（5#）的5倍,其稳定运行时间最长。     

Impact of microbial activity on the hydraulic properties of fractured chalk

The impact of microbial activity on fractured chalk transmissivity was investigated on a laboratory scale. Long-term experiments were conducted on six fractured chalk cores (20 cm diameter, 23-44 cm long) containing a single natural fracture embedded in a porous matrix. Biodegradation experiments were conducted under various conditions, including several substrate and oxygen concentrations and flow rates. 2,4,6-Tribromophenol (TBP) was used as a model contaminant (substrate). TBP biodegradation efficiency depended mainly on the amount of oxygen. However, under constant oxygen concentration at the core inlet, elevating the flow rates increased the removal rate of TBP. Transmissivity reduction was clearly related to TBP removal rate, following an initial slow decline and a further sharp decrease with time. The fracture's transmissivity was reduced by as much as 97% relative to the initial value, with no leveling off of the clogging process. For the most extreme cases, reductions of 262 and 157 microm in the equivalent hydraulic apertures were recorded for fractures with initial apertures of 495 and 207 microm, respectively. The reductions in fracture transmissivity occurred primarily because of clogging by bacterial cells and extracellular polymeric substances (EPS) produced by the bacteria. Most of the biodegradation activity was concentrated near the fracture inlet, where the most suitable biodegradation conditions (nutrients and oxygen) prevailed, suggesting that the clogging had occurred in that vicinity. The clogging must have changed the structure of the fracture void, thereby reducing the active volume participating in flow and transport processes. This phenomenon caused accelerated transport of non-reactive tracers and doubled the fracture's dispersivity under constant flow rates.     

Use of tandem circulation wells to measure hydraulic conductivity without groundwater extraction

Conventional methods to measure the hydraulic conductivity of an aquifer on a relatively large scale (10-100 m) require extraction of significant quantities of groundwater. This can be expensive, and otherwise problematic, when investigating a contaminated aquifer. In this study, innovative approaches that make use of tandem circulation wells to measure hydraulic conductivity are proposed. These approaches measure conductivity on a relatively large scale, but do not require extraction of groundwater. Two basic approaches for using circulation wells to measure hydraulic conductivity are presented; one approach is based upon the dipole-flow test method, while the other approach relies on a tracer test to measure the flow of water between two recirculating wells. The approaches are tested in a relatively homogeneous and isotropic artificial aquifer, where the conductivities measured by both approaches are compared to each other and to the previously measured hydraulic conductivity of the aquifer. It was shown that both approaches have the potential to accurately measure horizontal and vertical hydraulic conductivity for a relatively large subsurface volume without the need to pump groundwater to the surface. Future work is recommended to evaluate the ability of these tandem circulation wells to accurately measure hydraulic conductivity when anisotropy and heterogeneity are greater than in the artificial aquifer used for these studies.     

A tiered ecological risk assessment of three chlorophenols in Chinese surface waters

Introduction

The ecological risks posed by three chlorophenols (CPs), 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), and pentachlorophenol (PCP) in Chinese surface waters were assessed.

Materials and methods

This was achieved by applying a tiered ecological risk assessment (ERA) approach ranging from deterministic methods to probabilistic options to measured concentrations of CPs in surface water of seven major watersheds and three drainage regions in China and the chronic toxicity data for indigenous Chinese species.

Results and discussion

The results show that the risks of three chlorophenols are ranked PCP>2,4-DCP??2,4,6-TCP. PCP posed little ecological risk while 2,4-DCP and 2,4,6-TCP posed negligible or de minimis risk in Chinese surface water. However, the risks varied with different river basins, for example, PCP posed some ecological risk in the Yangtze, Huaihe, and Pearl Rivers. The magnitude of 2,4-DCP and 2,4,6-TCP pollution in North China was more serious than that in South China.

Conclusion

The probabilistic risk assessment approach, which can provide more information for risk managers and decision makers, was favored over the screening-level single-value estimate method. However, the results from all tiers of the ERA methods in the framework were consistent with each other.     

Effects of 2,4,6-Trichlorophenol on Clarias batrachus: a biomarkers approach

Environmental Science and Pollution Research - 2,4,6-Trichlorophenol (2,4,6-TCP) is a common waste among the resulting chlorophenols generated in the production of common products classified as an...     

Irrigation of soil with synthetic landfill leachate--speciation and distribution of selected pollutants

The fates and toxicities of selected landfill leachate pollutants in a soil with a low attenuation potential were investigated. Soil columns consisting of a loamy sand which had been irrigated with synthetic landfill leachates were dissected and analysed for pH, electrical conductivity, copper and zinc species, iron and phenol concentrations and microbial activity. Copper was found to be least mobile and accumulated in the top 4 cm of the soil columns. Sequential extraction of the soil revealed that at least two-thirds of the total copper was in the EDTA-, NaOH-extractable and residual fractions. Approximately 2% of the copper was water soluble and between 1 and 22% was in the MgCl(2)-extractable fraction. Zinc and phenol were relatively mobile and were detected throughout the soil-column profile as well as in the column effluents. The greatest zinc fraction (55-71%) was MgCl(2)-extractable. Zinc solubility in water was again low (1-4%). Phenol was partially adsorbed by the soil but its main attenuation occurred by biodegradation. Microbial activity was affected by the availability of the carbon source as well as the presence of copper and zinc. Copper was more inhibitory to microbial activity than zinc. In the presence of phenol, the simultaneous application of zinc and copper distinctly reduced microbial activity. No inhibitory effect of copper and zinc was observed in the absence of phenol when the microorganisms were severely carbon limited.     

Derivation of predicted no effect concentrations (PNEC) for 2,4,6-trichlorophenol based on Chinese resident species

2,4,6-Trichlorophenol (2,4,6-TCP) is a common chemical intermediate and a by-product of water chlorination and combustion processes, and is a priority pollutant of the aquatic environment in many countries. Although information on the toxicity of 2,4,6-TCP is available, there is a lack of information on the predicted no-effect concentration (PNEC) of 2,4,6-TCP, mainly due to the shortage of chronic and site-specific toxicity data. In the present study, acute and sub-chronic toxicity of 2,4,6-TCP on six different resident Chinese aquatic species were determined. PNEC values were calculated and compared by use of two approaches: assessment factor (AF) and species sensitivity distribution (SSD). Values for acute toxicity ranged from 1.1 mg L⁻¹ (Plagiognathops microlepis) to 42 mg L⁻¹ (Corbicula fluminea) and the sub-chronic no observed effect concentrations (NOECs) ranged from 0.05 mg L⁻¹ (Mylopharyngodon piceus) to 2.0 mg L⁻¹ (C. fluminea). PNECs obtained by the assessment factor approach with acute (AF = 1000, 0.001 mg L⁻¹) or chronic (AF = 10, 0.005 mg L⁻¹) toxicity data were one order of magnitude less than those from SSD methods (0.057 mg L⁻¹). PNEC values calculated using SSD methods with a 50% certainty for 2,4,6-TCP was less than those obtained by use of the USEPA recommend final chronic value (FCV) method (0.097 mg L⁻¹) and the one obtained by use of the USEPA recommend acute-to-chronic (ACR) methods (0.073 mg L⁻¹). PNECs derived using AF methods were more protective and conservative than that derived using SSD methods.     

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.     

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

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.     

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。     

Bioretention column studies of phosphorus removal from urban stormwater runoff.

This study investigated the effectiveness of bioretention as a stormwater management practice using repetitive bioretention columns for phosphorus removal. Bioretention media, with a higher short-term phosphorus sorption capacity, retained more phosphorus from infiltrating runoff after 3 mg/L phosphorus loading. A surface mulch layer prevented clogging after repetitive total suspended solids input. Evidence suggests that long-term phosphorus reactions will regenerate active short-term phosphorus adsorption sites. A high hydraulic conductivity media overlaying one with low hydraulic conductivity resulted in a higher runoff infiltration rate, from 0.51 to 0.16 cm/min at a fixed 15-cm head, and was more efficient in phosphorus removal (85% mass removal) than a profile with low conductivity media over high (63% mass removal). Media extractions suggest that most of the retained phosphorus in the media layers is available for vegetative uptake and that environmental risk thresholds were not exceeded.