QSBR Study on the Anaerobic Biodegradation of Chlorophenols

18 Physicochemical and quantum chemical parameters of 12 kinds of chlorophenols are calculated in this paper. QSBR （quantitative structure-biodegradability relationship） study is performed using simca statistical software by PLS regression analysis method on anaerobic biodegradation data （logKb）, and the QSBR model is developed with favorable prediction. The model shows that the size and energy of the molecule are the dominant factors affecting the anaerobic biodegradation of chlorophenols. And the degradation rate constants （logKb） increase with the increase of core-core repulsion （CCR）, average molecular polarizability （α）, total surface area （TSA）, heat of formation （HOF） and total energy （TE）. while decrease with the increase of molecular connectivity index （^1X^V）, relative molecular mass （Mw） and electronic energy （EE）.

Chlorophenols in marine organisms from the southern coast of Hangzhou Bay,China,and an assessment of risks posed to human health

The composition of chlorophenols in marine organisms from the southern coast of Hangzhou Bay, China, was analyzed and the health risks posed to humans assessed. A total of 19 chlorophenols from 16 types of marine organism were analyzed across nine survey sections in Hangzhou Bay. The chlorophenols were analyzed by gas chromatography-mass spectrometry using a DB-5MS quartz capillary column. The concentrations of monochlorophenol, dichlorophenol, trichlorophenol, tetrachlorophenol, and pentachlorophenol ranged from below the detection limit(ND) to 132 μg/kg, ND–51.0 μg/kg, ND–42.5 μg/kg, ND–69.0 μg/kg, and ND–9.06 μg/kg, respectively. Additionally, concentration differences between each type of chlorophenol were not significant( P >0.05). However, significant differences were found between monochlorophenol( F =8.13, P <0.01) and total chlorophenol(F =5.19, P <0.01) concentrations. As the noncarcinogenic risk indices were <0.1(10-5 –10-2) for all of the organisms, no high risk was posed by 2-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, 2,4,5-trichlorophenol, 2,3,4,6-tetrachlorophenol, and pentachlorophenol to humans consuming marine organisms from the study area. Furthermore, the carcinogenic risks posed by 2,4,6-trichlorophenol and pentachlorophenol were lower than limits set by the International Commission on Radiological Protection and the US Environmental Protection Agency. However, the noncarcinogenic and carcinogenic risks posed by chlorophenols in marine organisms from four of the survey sections(Sizaopu, Niluoshan, Longshan Town and Xinhong zha) were higher than the other survey sections.

Catalytic Decomposition of Chlorophenols Using Fiber-supported Cobalt Phthalocyanine

A novel heterogeneous catalyst, viscose fiber- supported cobalt phthalocyanine （Co - TDTAPc - F）, was prepared by immobilizing cobalt tetra（2.4 - dichloro- 1,3, 5 -triazine）aminophtbalocyanine （Co- TDTAPc） on viscose fibers covalcntly. The oxidative removal of chlorophenols such as 2 - chlorophenoi, 4 - chlorophenol, 2, 4 - dichlorophenol, and 2, 4, 6 - trichlorophenol was investigated in the catalytic oxidative system of Co - TDTAPc- F/H2O2. Furthermore, more than 98% of these chloropbenols were decomposed in 4 h. Phenol, oxalic acid, maleic acid, and succinic acid, etc., were detected by high performance liquid chromatography （HPLC） and gas chromatography-mass spectrophotometer （GC - MS）, and these short-chain organic acids could be further oxidized easily. The results indicated that the catalytic oxidation in the Co- TDTAPc - F/H2O2 system leaded to a deeper oxidation. In addition, a degradation pathway for chlorophenols was proposed on the basis of detection of intermediate compounds.

Flow Injection Amperometric Determination of Phenol and Chlorophenols at Single Wall Carbon Nanotube Modified Glassy Carbon Electrode

Single wall carbon nanotube modified glassy carbon electrode (SWCNT/GCE) was used for flow-injection analysis (FIA) for phenolic compounds (phenol (P), 4-chlorophenol (CP), 2,4-dichlorophenol (DCP), 2,4,6-trichlorphenol (TCP) and pentachlorophenol (PCP)). Experimental variables such as the detection potential, flow rate and pH of the carrier solution, 0.1 M sodium acetate, were optimized. Under these conditions, the designed electrode showed a very good performance for the amperometric measurements, with no need to apply a cleaning or pre-treatment procedure. The operational stability was tested with 20 repetitive injections of each analyte and was found to be good. The analytical performance of the SWCNT/GCE electrode under flow through conditions was tested and was found to be impressive. When it is compared with other enzymatic and non-enzymatic sensors, it shows wider dynamic range for the detection of phenolic compounds with low limits of detection. These results suggest that the method is quite useful for monitoring and analyzing phenols and chlorophenols.

Electrochemical treatment of wastewater containing chlorophenols using boron-doped diamond film electrodes

The electrochemical treatment of wastewater containing chlorophenols （2-monochlorophenol, 4-monochlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol） was carried out experimentally with synthetic boron-d0ped diamond （BDD） thin film electrodes. Current vs time curves under different cell voltages were measured. Removal rate of COD, instant current efficiency （ICE） and energy consumption were investigated under different current densities. The influence of supporting media is reported, which plays an important role in determining the global oxidation rate. The oxidative chloride is stronger than peroxodisulphate. The electrochemical characteristics of boron-doped diamond electrodes were investigated in comparison with active coating Ti substrate anode （ACT）. The experimental results show that BDD is markedly superior to ACT due to its different absorption properties.

ADSORPTION CHARACTERISTICS OF CHLOROPHENOLS FROM AQUATIC SYSTEMS BY HYPERCROSSLINKED RESINS MODIFIED WITH BENZOYL GROUP

A hypercrosslinked polymeric adsorbent （ZH-03） for adsorbing and removing chlorophenolic compounds from their aqueous solutions was studied, including the static adsorption. The equilibrium adsorption data were fit to Freundlich adsorption isothermic models to evaluate the model parameters. Thermodynamic studies on the adsorption of chlorophenolic compounds on ZH-03 indicated that there were chemisorption transitions for 2,4,6-trichlorophenol and physical adsorption processes for 2-chlorophenol and 2,6-chlorophenol, and ZH-03 showed the homogeneous nature of the adsorbent surface. Column adsorption for chlorophenols wastewater shows the advantages of the ZH-03 adsorbent for adsorbing the following chlorophenolic compounds as 2-chlorophenol, 2,6-dichlorophenol and 2,4,6-trichlorophenol. Sodium hydroxide was used for desorpting chlorophenols from ZH-03 and showed excellent performance.

Development of Simultaneous HPLC-Fluorescence Assay of Phenol and Chlorophenols in Tap Water after Pre-Column Derivatization with 3-Chlorocarbonyl-6,7-dimethoxy-1- methyl-2(1H)-quinoxalinone

Chlorophenols (2-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, 2,6-dichlorophenol and 2,4, 6-trichlorophenol) may be presented in natural waters or drinking water as a result of disinfection processes involving chlorination, or as contaminants derived from domestic products, industrial operations and agricultural chemicals. A previous HPLC-UV method for determination of phenol and five chlorophenols in tap water using 4-fluoro-7-nitro-2,1,3-benzoxadiaole as a UV labeling reagent shows limited sensitivity. Here, we present an improved HPLC-fluorescence detection method for simultaneous determination of phenol and the above chlorophenols in tap water after pre-column derivatization with 3-chlorocarbonyl-6,7-dimethoxy-1-methyl-2(1H)-quino- xalinone (DMEQ-COCl), using a short, narrow column (50 × 2.1 mm i.d., packed with 5 μm particles of C18 material) to improve the sensitivity. Standard samples containing the compounds are derivatized with DMEQ-COCl in borate buffer (pH 9.0) at room temperature for 3 mins. The response is linear in the concentration range of 0.01 - 0.05 to 0.5 mg/L with r2 values ≥0.9967 for all compounds. The lower limits of detection are 0.001 to 0.008 mg/L, and the coefficients of variation are less than 8.8%. The recovery values from tap water spiked with standard samples are satisfactory. The present method is suitable for examining whether or not tap water samples are contaminated with phenol and chlorophenols in excess of regulatory values.

Extraction and Determination of Three Chlorophenols by Hollow Fiber Liquid Phase Microextraction - Spectrophotometric Analysis, and Evaluation Procedures Using Mean Centering of Ratio Spectra Method

A method termed hollow fiber liquid phase microextraction (HF-LPME) was utilized to extract three chlo- rophenols, 2-chlorophenol (2-CP), 2,4-dichlorophenol (2,4-DCP) and 2,4,6- trichlorophenol (2,4,6-TCP), separately from water. The extracted chlorophenols were then separated, identified, and quantified by UV-Vis spectrophotometry with photodiode array detection (UV-Vis/DAD). In the study, experimental con-ditions such as organic phase identity, acceptor phase volume, sample agitation, extraction time, acceptor phase NaOH concentration, donor phase HCl concentration, salt addition, and UV absorption wavelength were optimized. The statistical parameters of the proposed method were investigated under the selected con-ditions. The analytical characteristics of the method such as detection limit, accuracy, precision, relative standard deviation (R.S.D.) and relative standard error (R.S.E.) was calculated. The results showed that the proposed method is simple, rapid, accurate and precise for the analysis of ternary mixtures.

Dechlorination of chlorophenols by zero valent iron impregnated silica

Laboratory studies were conducted to find out the efficacy of uniquely prepared zero valent iron impregnated silica in transforming xenobiotic chlorophenols namely 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol. Continuous mode column experiments were performed to investigate the transformation of chlorophenols by varying pH, column height, flow rate and initial chlorophenol concentration. Reusability study of the zero valent iron impregnated silica was studied as well as the morphological changes and the chemical composition of the catalyst medium were also investigated. Dechlorination kinetic studies were conducted and the order of dechlorination of chlorophenols was found to be 2,4,6-trichlorophenol 〉 2,4-dichlorophenol 〉 4-chlorophenol. The optimum pH, column height and flow rate were found to be 7, 20 cm and 0.75 L/hr respectively for all chlorophenols in the reaction duration of 4 hr. Intermediates formed during dechlorination study were identified by gas chromatography-mass spectroscopy analysis. This method was applied to real pulp and paper wastewater and was found satisfactory.

Probabilistic ecological risk assessment for three chlorophenols in surface waters of China

Individual and combined assessment of risks of adverse effects to aquatic ecosystems of three chlorophenols（CPs）,including 2,4dichlorophenol（2,4-DCP）,2,4,6-trichlorophenol（2,4,6-TCP） and pentachlorophenol（PCP）,were conducted.A probabilistic approach based on the concentrations of CPs in surface waters of China was used to determine the likelihood of adverse effects.The potential risk of CPs in surface waters of China was determined to be of concern,especially PCP and mixtures of CPs.The risks of adverse effects were examined as the joint probabilities of exposure and response.The joint probability for PCP was 0.271 in the worst case and 0.111 in the median case,respectively.Based on the cumulative probability,5% of aquatic organisms included in the assessment would be affected 21.36% of the time in the worst case and 5.99% of the time in median case,respectively.For the mixtures of CPs,the joint probability were 0.171 in the worst case and 0.503 in median case,respectively and 5% of species would be affected 49.83% of the time for the worst case and 12.72% in the median case,respectively.Risks of effects of the individual CPs,2,4-DCP and 2,4,6-TCP were deemed to be acceptable with a overlapping probability of 0.1 with 5% of species being affected less than 4% of the time.

Preconcentration of chlorophenols in water samples using threedimensional graphene-based magnetic nanocomposite as absorbent

In this paper, a novel magnetic solid-phase extraction method using three-dimensional graphene-based magnetic nanocomposite as adsorbent for the preconcentration of several chlorophenols from water samples prior to high-performance liquid chromatography analysis was developed. Various experimental parameters were investigated. Under the optimum conditions, the enrichment factors of the method were in the range of 186–312, and the limit of detection（S/N = 3） was 0.10 ng/mL. The recoveries of the method were in the range between 85.1% and 101.2%. The developed method has been successfully applied to the determination of chlorophenols in environmental water samples.

Effect of chlorine content of chlorophenols on their adsorption by mesoporous SBA-15

Studies on the effect of the chlorine content of chlorophenols （CPs） on their adsorption from aqueous solution by mesoporous SBA-15 are important in understanding the mechanisms of CP adsorption. In this study, three CPs with different degrees of chlorine content （i.e., 2-chlorophenol, 2,6-dichlorophenol and 2,4,6-trichlorophenol） were investigated. The effects of parameters such as temperature and solution pH were studied. The results showed that CP adsorption by SBA- 15 increased with increasing number of chlorine substituents and depended strongly on the temperature and solution pH. Thermodynamic parameters such as Gibbs free energy change （AGO）, enthalpy change （△H^0） and entropy change （△S^0） were also calculated. By comparison of the adsorption coefficient of CPs with varying physical-chemical properties （size, hydrophobicity and electron density）, we propose that hydrophobic interactions between CPs and the SBA-15 surface, as well as electron donor-acceptor （EDA） complexes between oxygen of the siloxane surface of SBA-15 （e--donor） and the n-system of the CPs （e--acceptor）, were dominant adsorption mechanisms.

Metal-organic framework derived magnetic nanoporous carbon as an adsorbent for the magnetic solid-phase extraction of chlorophenols from mushroom sample

In this work, a metal-organic framework derived nanoporous carbon （MOF-5-C） was fabricated and modified with Fe3O4 magnetic nanoparticles. The resulting magnetic MOF-5-derived porous carbon （Fe304@MOF-5-C） was then used for the magnetic solid-phase extraction of chlorophenols （CPs） from mushroom samples prior to high performance liquid chromatography-ultraviolet detection. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and N2 adsorption were used to characterize the adsorbent. After experimental optimization, the amount of the adsorbent was chosen as 8.0 mg, extraction time as 10 min, sample volume as 50 mL, desorption solvent as 0.4 mL （0.2 mL × 2） of alkaline methanol, and sample pH as 6. Under the above optimized conditions, good linearity for the analytes was obtained in the range of 0.8-100.0 ng g 1 with the correlation coefficients between 0.9923 and 0.9963. The limits of detection （SIN= 3） were in the range of 0.25-0.30 ng g-1, and the relative standard deviations were below 6.8%. The result showed that the Fe304@MOF-5-C has an excellent adsorption capacity for the analytes.

Adsorption of chlorophenols from aqueous solutions by pristine and surface functionalized single-walled carbon nanotubes

The adsorption of six kinds of chlorophenols on pristine, hydroxylated and carboxylated single-walled carbon nanotubes（SWCNTs） has been investigated. Pseudo-first order and pseudo-second order models were used to describe the kinetic data. All adsorption isotherms were well fitted with Langmuir, Freundlich and Polanyi–Manes models, due to surface adsorption dominating the adsorption process. The close linear relationship between log Kowand log Kdsuggested that hydrophobicity played an important role in the adsorption. The SWCNTs＇ adsorption capacity for chlorophenols was weakened by addition of oxygen-containing functional groups on the surface, due to the loss of specific surface area, the increase of hydrophilicity and the reduction of π–π interaction. The best adsorption capacity of pristine SWCNTs, SWCNT-OH and SWCNT-COOH for six chlorophenols varied from 19 to 84 mg/g, from 19 to 65 mg/g and from 17 to 65 mg/g,respectively. The effect of pH on the adsorption of 2,6-dichlorophenol（2,6-DCP）, was also studied. When p H is over the pK aof 2,6-dichlorophenol（2,6-DCP）, its removal dropped sharply. When ionic strength increased（Na Cl or KCl concentration from 0 to 0.02 mmol/L）,the adsorption capacity of 2,6-DCP on pristine SWCNTs decreased slightly. The comparison of chlorophenols adsorption by SWCNTs, MWCNTs and PAC was made, indicating that the adsorption rate of CNTs was much faster than that of PAC. The results provide useful information about the feasibility of SWCNTs as an adsorbent to remove chlorophenols from aqueous solutions.

Sorption of chlorophenols onto fruit cuticles and potato periderm

To better understand the interaction mechanisms of plant surfaces with polar organic compounds, sorption of 4-chlorophenol, 2,4- dichlorophenol, and 2,4,6-trichlorophenol by fruit cuticles （i.e., tomato, apple, and pepper）, and potato tuber periderm were investigated. The roles of cuticular components （waxes, cutin, cutan and sugar） on sorption of chlorophenols are quantitatively compared. Cutin and waxes govern the sorption capacity of bulk apple cuticle by hydrophobic interactions. Potato periderm with highest sugar content exhibits the lowest sorption capability for the chlorophenols. With the increase of hydrophobicity （i.e., Kow ） of sorbate, the relative contribution of lipophilic components （wax, cutin and cutan） on total sorption increases, however, the ratios of Koc to Kow decreases due to increasing ionization degree of sorbates.

Efficient removal of chlorophenols from water with a magnetic reduced graphene oxide composite

A magnetic reduced graphene oxide composite(MRGO) was successfully prepared by a simple and green method. MRGO was then used as an adsorbent and found to exhibit enhanced removal efficiency for various chlorophenols(CPs) from water compared with its precursors, graphene oxide(GO) and reduced graphene oxide. The CPs were o-chlorophenol, p-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol. Among them, 2,4,6-trichlorophenol, which exhibited the lowest water solubility and highest molecular weight, most easily bound to MRGO. The preferential interactions between MRGO and CPs were hydrophobic interactions(?-? stacking and hydrophobic effect). This result was confirmed by the equilibrium adsorption behavior in which isotherms were all well described by Freudlich model, indicating heterogeneous and multilayer adsorption. Therefore, CP adsorption was more favored under neutral and acidic conditions, and the decreased removal efficiency of MRGO at higher p H levels was due to the improved hydrophilicity of CPs for deprotonation effect. Moreover, MRGO showed fast removal of each CP, achieving adsorption equilibrium within 10.0 min, presented efficient separation from water under an external magnetic field, and was easily regenerated using dilute Na OH aqueous solution after reaching saturated adsorption. Adsorption capacity of the regenerated MRGO had almost no loss until after five cycles. In summary, MRGO was an efficient adsorbent for the removal of various CPs and had considerable application potential in water treatment.

分散液液微萃取-反相液液微萃取-扫集-胶束电动色谱法测定红酒中的3种氯酚类物质

建立了分散液液微萃取（DLLME）-反相液液微萃取（RP-LLME）-扫集-胶束电动色谱富集模型，并用于红酒中五氯酚（PCP）、2，4，6-三氯酚（TCP）和2，4-二氯酚（DCP）3种氯酚的测定。实验考察了两步微萃取的萃取参数对氯酚萃取率的影响和样品分离富集的电泳条件。最佳萃取条件 DLLME 为：3.5 mL 红酒（ pH 3.0，120 g / L NaCl），300μL 正己烷（萃取剂）；RP-LLME 为：25μL 0.16 mol / L NaOH（萃取剂）。最佳电泳条件：25 mmol / L NaH2 PO4，100 mmol / L 十二烷基硫酸钠（ SDS），30％（ v / v）乙腈，pH 2.3；分离电压-15 kV；样品基质为80 mmol / L NaH2 PO4；压力进样20 s×20.67 kPa（3 psi）。PCP 和 TCP 的线性范围为0.5～100μg / L（ r≥0.9910）， DCP 的线性范围为1.5～80μg / L（r =0.9851）。3种分析物的检出限（ S / N =3）为0.035～0.114μg / L，加标回收率为75.2％～104.7％，相对标准偏差≤6.17％。该方法富集倍数高、灵敏度高、重现性好、分析速度快，可为不同样品基质中痕量氯酚污染物及某些弱酸性有机污染物测定提供参考。

Electrochemical Removal of Chlorophenol Pollutants by Reactive Electrode Membranes: Scale-Up Strategy for Engineered Applications

Chlorophenols(CPs)are significant refractory pollutants that are highly toxic to humans and other organ-isms.Reactive electrode membranes(REMs)show considerable potential in the electrochemical removal of refractory pollutants by allowing flow-through operations with convection-enhanced mass transfer.However,relevant studies are commonly performed on the laboratory scale,and there is no straightfor-ward method that guarantees success in scaling up engineered REM reactors.In this study,we demon-strated that a tubular concentric electrode(TCE)configuration with a titanium suboxide ceramic anode and a stainless-steel cathode is suitable for large-scale CPs removal.Both theoretical and experi-mental results showed that the TCE configuration not only allows the electrode surface to be orthogonal to electric field lines everywhere,but also has an ohmic resistance that is inversely proportional to the length of the electrode.In addition,the TCE configuration can be operated in either the anode-to-cathode(AC)or the cathode-to-anode(CA)mode based on the flow direction,creating adjustable condi-tions for selective degradation of CPs.This was confirmed by 98%removal of 2,4-dichlorophenol(2,4-DCP)and 72.5%removal of chemical oxygen demand(COD)in the CA mode,in which the kinetic constant was one order of magnitude higher than that for the AC mode under flow-through single-pass operations.This can be explained by the lower activation energy and free energy in the CA mode,as revealed by the-oretical calculations and experimental measurements.The TCE configuration is also suitable for a numbering-up strategy to scale up the electrochemical reactor without increasing the ohmic resistance or decreasing the specific electrode area,achieving 99.4%removal of 2,4-DCP with an energy consump-tion of 1.5 kW·h·m^(-3) when three TCE modules were employed.This study presents a suitable electrode design configuration for the REM reactor,offering effective strategies to bridge the“Valley of Death”encountered when scaling up the electrochemical removal of CP pollutants.

Phenoxyacid Herbicides in Stormwater Retention Ponds: Urban Inputs

Surface water runoff from urban centers is a major source of environmental pollution which impacts water quality in downstream aquatic habitats. Phenoxyacid herbicides are some of the most widely globally used herbicides in agriculture and urban environments for weed control. Their transformation products which in- clude chlorophenols can be more toxic than the active ingredients. We used LC/MS/MS to analyzed simul- taneously these acid herbicides and their transformation products in stormwater retention ponds taken from an urban environment to examine the occurrence and potential release of these herbicides from urban inputs into downstream waters. 2,4-dichlorophenoxyacetic acid and mecoprop were detected in all samples col- lected from the ponds and at the highest concentrations, while 2-methyl-4-chlorophenoxyacetic acid was de- tected only in spring and summer. Two transformation products, 4-chloro-2-methylphenol and 2,4-di- chlorophenol were detected in samples primarily at inlet locations on the ponds indicating that degradation had occurred in surface soils prior to surface water runoff.

Studies on the Quantitative Structure-activity Relationship of Toxicity of Chlorophenol Serial Compounds in the ab initio Methods and Substitutive Position of Chlorine Atom (N_(PCS))

20 Quantum chemical parameters of chlorophenol compounds were fully optimized by using B3LYP method on both 6-31G^＊ and 6-311G^＊ basis sets. These structural parameters are taken as theoretical descriptors, and the experimental data of 20 compounds＇ aquatic photogen toxicity（-lgEC50） are used to perform stepwise regression in order to obtain two predicted -lgEC50 correlation models whose correlation coefficients R^2 are respectively 0.9186 and 0.9567. In addition, parameters of chlorine atom＇s substitutive positions and their correlations （NPCs） are taken as descriptors to obtain another predicted -lgEC50 model with the correlation coefficient R2 of 0.9444. Correlation degree of each independent variable in the three models is verified by using variance inflation factors （VIF） and t value. In the cross-validation method, cross-validation coefficients q^2 of 3 models are respectively 0.8748, 0.9119 and 0.8993, which indicates that the relativity and prediction ability of this model are superior to those of the model obtained by topological and BLYP methods.