Gas chromatographic methods for monitoring of wastewater chlorophenol degradation in anaerobic reactors

Wastewater samples from an anaerobic reactor were extracted with hexane and derivatized with diazomethane (method 1) and with acetic anidride (method 2). Gas chromatography with electron-capture detection (ECD) was employed for separating the parent compound and intermediates trichlorophenols (TCP) and dichlorophenols (DCP) which originated from the penta chlorophenol (PCP) degradation process. The relations between concentrations of PCP, TCP and DCP areas were linear in the range of concentrations of 0.2 to 8 mg/L and 0.025 mg/L to 5 mg/L for methods 1 and 2, respectively. The repeatability of the extraction methods was satisfactory, with variation coefficients lower than 11%. For method 1, at the fortification level of 0.2 mg/L, recovery of PCP, TCP, and DCP was 112%, 74% and 45%, respectively. For method 2, the corresponding recovery values at the fortification level of 0.1 mg/L were 91%, 93% and 103%, respectively. Storage of the frozen samples did not alter their PCP determination properties. The chromatographic methods adapted for chlorophenol determination in wastewater were suitable with relatively simple manipulation techniques. The obtained results were reproducible and allowed identification of intermediates formed during the PCP degradation process.     

Sequential UV-biological degradation of chlorophenols

The sequential UV-biological degradation of a mixture of 4-chlorophenol (CP), 2,4-dichlorophenol (DCP), 2,4,6-trichlorophenol (TCP), and pentachlorophenol (PCP) was first tested with each pollutant supplied at an initial concentration of 50 mg l(-1). Under these conditions, the chlorophenols were photodegraded in the following order of removal rate: PCP>TCP>DCP>CP with only CP and DCP remaining after 40 h of irradiation. The remaining CP (41 mg l(-1)) and DCP (13 mg l(-1)) were then completely removed by biological treatment with an activated sludge mixed culture. Biodegradation did not occur in similar tests conducted with a non-irradiated mixture due to the high microbial toxicity of the solution. UV treatment lead to a significant reduction of the phytotoxicity to Lipedium sativum but no further reduction of phytotoxicity was observed after biological treatment. Evidence was found that the pollutants were partially photodegraded into toxic and non-biodegradable products. When the pollutants were tested individually (initial concentration of 50 mg l(-1)), PCP, TCP, DCP, 4-CP were photodegraded according to first order kinetic model (r2>99) with half-lives of 2.2, 3.3, 5.7, and 54 h, respectively. The photoproducts were subsequently biodegraded. This study illustrates the potential of UV as pre-treatment for biological treatment in order to remove toxicity and enhance the biodegradability of organic contaminants. However, it also shows that UV treatment must be carefully optimized to avoid the formation of toxic and/or recalcitrant photoproducts and results from studies conducted on single contaminants cannot be extrapolated to mixtures.     

Sequential photochemical-biological degradation of chlorophenols

UV/TiO₂/H₂O₂, UV/TiO₂ and UV/H₂O₂ were compared as pre-treatment processes for the detoxification of mixtures of 4-chlorophenol (4CP), 2,4-dichlorophenol (DCP), 2,4,6-trichlorophenol (TCP) and pentachlorophenol (PCP) prior to their biological treatment. When each chlorophenol was initially supplied at 50 mg l⁻¹, UV/TiO₂/H₂O₂ treatment supported the highest pollutant removal, COD removal, and dechlorination efficiencies followed by UV/TiO₂ and UV/H₂O₂. The remaining toxicity to Lipedium sativum was similar after all pre-treatments. Chlorophenol photodegradation was always well described by a first order model kinetic (r² > 0.94) and the shortest 4CP, DCP, TCP and PCP half-lives of 8.7, 7.1, 4.5 and 3.3 h, respectively, were achieved during UV/TiO₂/H₂O₂ treatment. No pollutant removal was observed in the controls conducted with H₂O₂ or TiO₂ only. Inoculation of all the photochemically pre-treated mixtures with activated sludge microflora was followed by complete removal of the remaining pollutants. Combined UV/TiO₂/H₂O₂-biological supported the highest detoxification, dechlorination (99%) and COD removal (88%) efficiencies. Similar results were achieved when each chlorophenol was supplied at 100 mg l⁻¹. COD and Cl mass balances indicated UV, UV/H₂O₂, and UV/TiO₂ treatments lead to the formation of recalcitrant photoproducts, some of which were chlorinated.     

Hydraulic residence time effects on performance of an activated sludge unit treating wastewater containing dichlorophenol.

Wastewaters containing chlorophenol compounds are difficult to treat by biological means because of the toxic effects of those compounds on microorganisms. To investigate the adverse effects of chlorophenols on microorganisms, synthetic wastewater containing 2,4 dichlorophenol (DCP) was biologically treated in an activated sludge unit at different hydraulic residence times (HRTs) between 5 and 40 hours, whereas the feed chemical oxygen demand (COD), DCP concentrations, and sludge age were kept constant at 2500 +/- 50 mg/L, 150 mg/L, and 20 days, respectively. The resazurin method based on dehydrogenase activity was used for assessment of the feed and effluent wastewater toxicity. Percent COD, DCP, and toxicity removals increased, and the effluent COD, DCP, and toxicity levels decreased with increasing HRT. Biomass concentration in the aeration tank increased with increasing HRT because of low levels of DCP at high HRT levels, resulting in high COD, DCP, and toxicity removals. The sludge volume index decreased with increasing HRT, yielding well-settling organisms as a result of low levels of toxicity and high concentrations of active cells. Percent DCP and COD removals decreased with increasing specific DCP loading rate. The rates of DCP and COD removals showed a maximum at a low DCP concentration of 6 mg/L in the aeration tank, corresponding to a 25-hour HRT.     

超声波和零价铁联用对氯代苯酚脱氯降解作用的研究

采用超声波和零价铁联用对氯代有机物3氯苯酚(CP)、2,4-二氯苯酚(DCP)和2,4,6-三氯苯酚(TCP)模拟废水进行了脱氯处理研究。以单因素法, 考察了铁粉初始投加量、溶液的初始浓度、超声波功率和溶液的pH值等因素对氯代酚降解的影响,并探讨了降解反应动力学。结果表明,超声波和零价铁联用对氯酚具有显著的降解效果,当水样初始浓度为25 mg/L,溶液pH呈弱酸性,超声波功率为200 W时,氯代酚的脱氯效率达到最大值。降解反应符合准一级反应,CP、DCP和TCP的反应速率常数分别0.0613 h^-1、0.374 h^-1和0.197 h^-1。     

Simultaneous removal of nitrate and pentachlorophenol from simulated groundwater using a biodenitrification reactor packed with corncob

Both nitrate and pentachlorophenol (PCP) are familiar pollutants in aqueous environment. This research is focused on the simultaneous removal of nitrate and PCP from simulated contaminated groundwater using a laboratory-scale denitrification reactor packed with corncob as both carbon source and biofilm support. The reactor could be started up readily, and the removal efficiencies of nitrate and PCP reached up to approximately 98 % and 40–45 % when their initial concentrations were 50 mg N/L and 5 mg/L, respectively, after 15-day continuous operation at 10 h of hydraulic retention time (HRT) and 25 °C. Approximately 91 % of PCP removal efficiency was achieved, with 2.47 mg/L of chloride ion release at 24 h of HRT. Eighty-two percent of chlorine in PCP removed was ionized. The productions of 3-chlorophenol and phenol and chloride ion release indicate that the reductive dechlorination reaction is a major degradation pathway of PCP under the experimental conditions.     

Determination of pentachlorophenol (PCP) in waste wood--method comparison by a collaborative trial

Two independently developed and validated procedures for the determination of pentachlorophenol (PCP) in waste wood were compared by means of a collaborative trial. Both methods foresee quantification of PCP by gas chromatography (GC-ECD) after acetylation and differ with regard to the use of methanol or toluene/sulphuric acid, respectively, as solvent in the sonication extraction step. Test samples with established analyte homogeneity were prepared from a ground "real life" starting material. A total of 23 participating laboratories with experience in wood preservative analysis were instructed to apply both methods to three levels of content in the range of 0.5-20 mg PCP/kg. In case of the toluene/sulphuric acid extraction, lower recoveries and higher interlaboratory dispersion of results at the higher PCP contents were observed. Seen against the background of the Horwitz equation a reproducibility standard deviation of approximately 19% for the methanol extraction at the 4.5 mg/kg level meets the requirement for a sound analytical method. Thus, the sonication extraction procedure with methanol has been annexed as a reference method to the German waste wood regulation.     

以两种酚类有机物为基质的微生物燃料电池产电特性

以城市污水处理厂的厌氧污泥为接种微生物,在外电阻为1900Ω下,采用双室微生物燃料电池(MFC)分别对以难降解的有毒有机物2,4-二氯苯酚(DCP),对硝基苯酚(PNP),对硝基苯酚和2,4-二氯苯酚为基质时进行有机物降解和产电性能的研究。实验结果表明以DCP(50 mg/L)为单一基质时,MFC的运行周期长达225 h左右,负载两端的最大电压值达393.7 mV,库仑效率为13.73%;而以PNP和DCP为混合基质时,PNP明显促进DCP的降解,使得DCP的去除率高达64.52%,同时PNP的去除率也达到94.47%。实验最终表明,MFC能够以2,4-二氯苯酚和对硝基苯酚为基质,在实现DCP和PNP降解的同时可稳定高效地向外输出电能。     

高效代谢解偶联剂的筛选及对SBR系统综合运行效能的影响

活性污泥法是最常用的污水处理技术,但它同时会产生大量的剩余污泥,需要进行额外的处理和处置.活性污泥的解偶联代谢能有效地减少剩余污泥的产量.比较了5种代谢解偶联剂,即2,4-二硝基苯酚(DNP)、邻氨基苯酚(AP)、2,4,6-三氯苯酚(TCP)、3,3',4,5-四氯水杨酰苯胺(TCS)、丙二酸的污泥减量效果和对COD去除能力的影响.结果表明,当它们在各自的最佳质量浓度20、1 5、4、1.2、15 mg/L时,污泥的表观增长系数分别降低了62.39%、63.75%、59.40%、34.58%和53.75%,而COD去除率仅有轻微下降.重点研究了15 mg/L的丙二酸和4 mg/L的TCP对SBR系统运行效能和污泥沉降性能的影响.发现在长期运行过程中,两者都能有效降低系统的污泥产量,而对COD去除率的影响较低,但使用丙二酸6 d后极大地影响了污泥的沉降性能,而TCP对污泥的沉降性能影响很小.     

Biodegradation of low aqueous concentration pentachlorophenol (PCP) contaminated groundwater

Bioremedial treatment to remove low level organic contamination to regulatory standards has met with limited success. In this study source water from a contaminated surficial aquifer at a former wood treatment facility was used to evaluate the potential for indigenous microorganisms to degrade low level (< 1.0 mg) pentachlorophenol (PCP) to a regulatory drinking water standard of 0.001 mg/L. PCP degradation was evaluated in series of batch reactors in a two phase study to (a) determine the rate and extent of PCP removal and (b) evaluate the impact of nutrient amendment (N and P) on removal rate. All reactors with the exception of the abiotic control demonstrated PCP removal to a level < 0.002 mg/L within a maximum period of 32 d with and without nutrient amendment. A regression analysis of reactive phosphate (ortho-P) concentration versus removal rate produced an R2 of 0.94 (p = 0.006) indicating a significant correlation between the level of available phosphate and PCP degradation rate. Selective bacterial enumeration (for PCP degrading bacteria) revealed PCP-degrading bacteria increased in abundance prior to and in conjunction with the degradation phase to a density of between 10(3) to 10(4) CFU/ml. Isolates were also analyzed for total fatty acids using Fatty Acid Methyl Ester (FAME) methodology and the results indicated that PCP degrading bacteria were present in the aquifer and consisted of predominately fluorescent, oxidase positive Pseudomonas species. Overall, data indicate that autochthonous microbes are capable of removing low level PCP (< 1.0 mg/L) to approach if not reach the regulatory standard of 0.001 mg/L with the addition of oxygen, with or without nutrient amendment. Results of this research can be applied to full-scale implementation of in-situ or ex-situ bioremediation of groundwater at former wood treatment facilities.     

Dechlorination and destruction of 2,4,6-trichlorophenol and pentachlorophenol using hydrogen peroxide as the oxidant catalyzed by molybdate ions under basic condition

The dechlorination and destruction of 2,4,6-trichlorophenol (TCP) and pentachlorophenol (PCP) under basic condition using hydrogen peroxide as the oxidant catalyzed by molybdate ions have been studied. Under ambient conditions of temperature and pressure, more than 95% of millimolar solutions of TCP and PCP can be converted to CO2 and CO, chlorinated and nonchlorinated carboxylic acid in 40 min. Up to 2.4 chloride ions per TCP and 3.5 chloride ions per PCP were released. TOC measurements indicated that 18% and 11% of the carbon was mineralized for TCP and PCP respectively after an hour of reaction. The results of ESR measurements suggested that the reaction possibly proceeded via the pathway with singlet oxygen.     

纳米TiO2/EP光催化降解罗丹明B废水的研究

通过溶胶-凝胶法制备出可漂浮于水面的膨胀珍珠岩(EP)负载型TiO2,研究其在水中对罗丹明B(RB)的去除效果、吸附降解动力学以及最佳工艺条件,并研究其多次回收再生后的降解效果。结果表明,浸渍3次的负载型TiO2光催化活性最高,回收5次后活性变化很小,降解率下降不到8%;光催化剂用量为0.2 g,20 mL初始浓度为10 mg/L和15mg/L RB溶液光照6 h后降解率分别达98%和74%。在实验浓度范围内,该光催化反应可用一级反应动力学方程描述。     

腐殖酸和铁对阿特拉津光降解影响的研究

为考察除草剂在水体中的自净性能,对模拟太阳光(λ> 290 nm)下腐殖酸和铁元素对阿特拉津的光化学降解进行了研究。结果表明,单独辐照阿特拉津几乎不降解。在分别加入3、5和10 mg/L的腐殖酸时,阿特拉津的降解率分别为34.36 %、40.74%和15.66 %;在Fe(Ⅲ)投加量从0.01 mmol/L增加到0.2 mmol/L时,阿特拉津的降解率从24.36 %增加到34.97 %。而在当腐殖酸与铁共存时,阿特拉津降解率则进一步提高。紫外可见光谱和荧光光谱均表明,腐殖酸-铁络合物的形成及其光化学作用,促进了阿特拉津的降解。     

微波辅助空气氧化水溶液中的PCP

采用活性炭为催化剂,对微波辅助空气氧化水溶液中的五氯酚进行了处理研究.考察了活性炭投加量、微波功率、辐射时间和通气量对溶液中五氯酚的去除率的影响.结果表明,在通气量为0.2 L/min,微波功率800 W和微波辐射60 min时,五氯酚的去除率可达到90%以上;对微波辐射前后的滤液进行紫外扫描和pH分析,可证实五氯酚被降解.     

Determination of tris(4-chlorophenyl)methanol and tris(4-chlorophenyl)methane in fish, marine mammals and sediment

Tris(4-chlorophenyl)methanol (TCP) and tris(4-chlorophenyl)methane (TCPMe) were determined in aquatic organisms and sediment by a method based on Soxhlet extraction, gel permeation chromatography, fractionation over silica and gas chromatography/mass spectrometry (GC/MS) analysis. TCPMe was identified as the 4-substituted isomer after synthesis of this compound. TCP could be determined by GC/MS with negative chemical ionistation (GC/NCI-MS) with a detection limit of 0.02 g kg(-1) and a recovery of 90%. TCP concentrations in marine mammals from the North Sea and Dutch Wadden Sea ranged from 0.2 to 2 mg kg(-1), and those in marine and freshwater fish samples from 0.005 to 0.4 mg kg(-1) on a lipid wt basis. TCP concentrations in two Rhine delta sediment samples were 1.2 and 3.0 microg kg(-1) dry wt, respectively. TCPMe concentrations, determined by GC/MS with electron impact (GC/EI-MS), were 10-50% of the TCP concentration in all samples analysed.     

Degradation of pentachlorophenol by pure and mixed cultures in two different soils

GOAL, SCOPE AND BACKGROUND: Pentachlorophenol (PCP) is the second highest volume pesticide used in the United States. It is a mutagenic compound whose exposure poses significant health effects, One of the most desirable, environmentally friendly treatment methods is bioremediation. For soil-based contamination, the effectiveness of bioremediation will also be affected by the presence of an active indigenous population, sorption of the contaminant onto the soil, and environmental parameters. METHODS: Two pure strains and their mixed culture were used to evaluate PCP biodegradation in two different field soils, Columbia (CO) and New Mexico (NM). Biostimulation of the indigenous microbes was evaluated by adding nutrients. The efficiency of adding bacteria strains (bioaugmentation) for degrading PCP was determined with Arthrobacter sp., Flavobacterium sp. and a 50:50 mixture of the two bacteria strains. RESULTS: In CO soil, only 24%, 12% and 25% of the initial PCP concentration were degraded by Flavobacterium sp., Arthrobacter sp. and mixed culture, respectively. Arthrobacter sp. was used in NM soil with two initial concentrations and achieved degradation efficiencies of 57% and 61% for 361 and 95 mg kg- concentrations, respectively. Discussion. Analysis via statistical methods showed that the bacteria had different efficiencies on PCP degradation in each soil. 2 CONCLUSIONS: All bacteria catalyzed a higher PCP degradation when present in NM soil. Second, Flavobacterium sp. degraded more PCP than Arthrobacter sp. in CO soil. The mixed culture achieved the highest degradation efficiency regardless of the initial concentration or soil origin. RECOMMENDATIONS AND PERSPECTIVES: The effect of the soil properties, such as the soil organic matter (SOM) on PCP biodegradation should be investigated. Future work can also investigate the effect of aging time on biodegradation.     

Trace level determination of selected organophosphorus pesticides and their degradation products in environmental air samples by liquid chromatography-positive ion electrospray tandem mass spectrometry

This paper describes a new analytical method for determination of organophosphorus pesticides (OPs) along with their degradation products involving liquid chromatography (LC) positive ion electrospray (ESI+) tandem mass spectrometry (MS-MS) with selective reaction monitoring (SRM). Chromatography was performed on a Gemini C6-Phenyl (150 mmx2.0 mm, 3 microm) with a gradient elution using water-methanol with 0.1% formic acid, 2 mM ammonium acetate mobile phase at a flow rate of 0.2 mL min(-1). The LC separation and MS/MS operating conditions were optimized with a total analysis time less than 40 minutes. Method detection limits of 0.1-5 microg L(-1) for selected organophosphorus pesticides (OP), OP oxon degradation products, and other degradation products: 3,5,6-trichloro-2-pyridinol (TCP); 2-isopropyl-6-methyl-4-pyrimidol (IMP); and diethyl phosphate (DEP). Some OPs such as fenchlorphos are less sensitive (MDL 30 microg L(-1)). Calibration curves were linear with coefficients of correlation better than 0.995. A three-point identification approach was adopted with area from first selective reaction monitoring (SRM) transition used for quantitative analysis, while a second SRM transition along with the ratio of areas obtained from the first to second transition are used for confirmation with sample tolerance established by the relative standard deviation of the ratio obtained from standards. This new method permitted the first known detection of OP oxon degradation products including chlorpyrifos oxon at Bratt's Lake, SK and diazinon oxon and malathion oxon at Abbotsford, BC in atmospheric samples. Atmospheric detection limits typically ranged from 0.2-10 pg m(-3).     

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.     

纳米TiO_2/EP光催化降解罗丹明B废水的研究

通过溶胶-凝胶法制备出可漂浮于水面的膨胀珍珠岩（EP）负载型TiO2,研究其在水中对罗丹明B（RB）的去除效果、吸附降解动力学以及最佳工艺条件,并研究其多次回收再生后的降解效果。结果表明,浸渍3次的负载型TiO2光催化活性最高,回收5次后活性变化很小,降解率下降不到8%;光催化剂用量为0.2 g,20 mL初始浓度为10 mg/L和15mg/L RB溶液光照6 h后降解率分别达98%和74%。在实验浓度范围内,该光催化反应可用一级反应动力学方程描述。     

臭氧与TiO2/UV协同降解对氯苯酚

利用O3／UV、TiO2／UV和O3／TiO2／UV降解对氯苯酚表明，臭氧与TiO2／UV具有明显的协同作用，如在本实验条件下降解5min后，上述3者对对氯苯酚的去除率分别为55％、10％和77%。O3／TiO2／UV协同作用的本质是由于臭氧能带走二氧化钛光致电子空穴对中的电子，从而产生了更多的羟基自由基，加速了有机物的降解。