Effects of activated carbon types and service life on removal of endocrine disrupting chemicals: amitrol, nonylphenol, and bisphenol-A

Removal performances of endocrine disrupting chemicals (EDC) such as amitrol, nonylphenol, and bisphenol-A were evaluated in this study using granular activated carbon (GAC) adsorption. This study found that GAC adsorption was effective in removal of EDCs with high K_ow value. Nonylphenol and bisphenol-A were effectively adsorbed onto all carbons (including the used carbons) tested in this study. As indicated by K_ow value, nonylphenol was more effectively adsorbed than bisphenol-A. The coal-based carbon was found more effective than other carbons in the adsorption of nonylphenol and bisphenol-A due to its larger pore volume. The adsorption capacity reduced with the operation year, and the extent of the reduction was different depending upon the carbon type and the operation year. Amitrol was effectively removed by biological degradation, but was poorly adsorbed. Since the microbes residing at the used carbons already accustomed to amitrol, the used carbons removed amitrol better than the virgin carbons. Although the coal-based carbon showed the best removal performance of amitrol, GAC adsorption could not be recommended for amitrol removal because considerable portion of incoming amitrol (9–87%) passed through GAC adsorption column. According to this study, pore volume mainly influenced the adsorption capacity, but the surface charge was also important due to electrical interaction. The adsorption parameters for nonylphenol and bisphenol-A provided by this study could be valuable when GAC adsorption was considered to handle an accidental spill of nonylphenol and bisphenol-A.     

微波辐射回用活性炭对水中亚甲基蓝和Cd~(2+)去除效果的研究

考察了微波-活性炭联合处理技术对模拟染料废水中亚甲基蓝和Cd2+的去除效果。对于100 mL浓度为1 000 mg/L的亚甲基蓝溶液、活性炭用量为10 g时,新活性炭对亚甲基蓝的去除率为99.99%;采用700 W微波对吸附亚甲基蓝的活性炭辐射10 min进行再生并回用,经微波辐射再生10次后活性炭对亚甲基蓝的去除率为99.68%,未经微波作用反复使用10次的活性炭对亚甲基蓝的去除率为85.41%。结果表明:微波处理有效地减缓了活性炭吸附能力的下降速率,实现了活性炭再生和反复使用。在吸附过程中,Cd2+使活性炭对亚甲基蓝的吸附能力略有下降,而共存的亚甲基蓝则促进了活性炭对Cd2+的吸附,对新炭和再生后活性炭物理化学特性的表征证明了活性炭对亚甲基蓝的吸附为物理吸附,对Cd2+的吸附为化学吸附。     

海绵铁还原耦合活性炭吸附-微波再生技术降解甲基橙

采用海绵铁(s-Fe0)还原耦合活性炭(GAC)吸附-微波(MW)再生技术降解甲基橙(MO)溶液,重点考察了s-Fe0投加量、粒径、微波功率等因素对MO去除效果的影响。结果表明,s-Fe0投加剂量为15.0 g/L、粒径为3～5 mm、超声波功率为200 W,反应1 h,MO的去除率为94.2%。其次,采用GAC吸附-MW再生技术(800 W,照射1 min)循环处理上述脱色后的MO废水。结果表明,GAC吸附可有效降低废水的生物毒性及残留的染料、TOC和总铁离子浓度,且MW辐射可有效再生吸附饱和的GAC颗粒。因此,s-Fe0还原耦合GAC吸附-MW再生技术可以有效降解MO染料,具有处理效果好、实现资源循环利用等优点。     

Impact of water saturation level on arsenic and metal mobility in the Fe-amended soil

The impact of water saturation level (oxidizing-reducing environment) on As and metal solubility in chromium, copper, arsenic (CCA)-contaminated soil amended with Fe-containing materials was studied. The soil was mixed with 0.1 and 1 wt% of iron grit (Fe(0)) and 1, 7 and 15 wt% of oxygen scarfing granulate (OSG, a by-product of steel processing). Solubility of As and metals was evaluated by a batch leaching test and analysis of soil pore water. Soil saturation with water greatly increased As solubility in the untreated as well as in the Fe-amended soil. This was related to the reductive dissolution of Fe oxides and increased concentration of As(III) species. Fe amendments showed As reducing capacity under both oxic and anoxic conditions. The cytotoxicity of the soil pore water correlated with the concentration of As(III). The Fe-treatments as well as water saturation of soil were less significant for the solubility of Cu, Cr and Zn than for As. The batch leaching test used for waste characterization substantially underestimated As solubility that could occur under water-saturated (anaerobic) conditions. In the case of soil landfilling, other techniques than Fe-stabilization of As containing soil should be considered.     

Prediction of the adsorption capacity for volatile organic compounds onto activated carbons by the Dubinin-Radushkevich-Langmuir model

Prediction of the adsorption capacity for volatile organic compounds (VOCs) onto activated carbons is elucidated in this study. The Dubinin-Radushkevich (D-R) equation was first used to predict the adsorption capacity of nine aromatic and chlorinated VOCs onto two different activated carbons. The two key parameters of the D-R equation were estimated simply from the properties of the VOCs using quantitative structure-activity relationship and from the pore size distribution of the adsorbent. The approach based on the D-R equation predicted well the adsorption capacity at high relative pressures. However, at the relative pressures lower than -1.5 x 10(-3), the D-R approach may significantly overestimate adsorption capacity. To extrapolate the approach to lower relative pressures, the integration of the D-R equation and the Langmuir isotherm, called the D-R-L model, was proposed to predict adsorption capacity over a wide range of relative pressures of VOCs. In this model, the Langmuir isotherm parameters were extracted from the predicted D-R isotherm at high relative pressures. Therefore, no experimental effort was needed to obtain the parameters of the D-R-L model. The model successfully predicted the adsorption capacity of aromatic and chlorinated hydrocarbons tested onto BPL and Sorbonorit B carbons over relative pressures ranging from 7.4 x 10(-5) to 0.03, suggesting that the model is applicable at the low relative pressures of VOCs often observed in many environmental systems. In addition, the molecular size of organic compounds may be an important factor affecting the adsorption capacity of activated carbons. For BPL carbon, an ultramicroporous adsorbent, the limiting pore volume Wo of the D-R equation decreased when the kinetic diameter of the adsorbate was larger than 6 angstroms. However, for Sorbonorit B carbon, no reduction of Wo was found, suggesting that the Wo may be related to the pore size distribution of the adsorbents, as well as to their molecular size. This size exclusion effect may play an important role in predicting the adsorption capacity of VOCs onto microporous adsorbents in the D-R-L model and in the corresponding D-R equation.     

微波辐射回用活性炭对水中亚甲基蓝和Cd2＋去除效果的研究

考察了微波-活性炭联合处理技术对模拟染料废水中亚甲基蓝和Cd2＋的去除效果。对于100 mL浓度为1 000 mg/L的亚甲基蓝溶液、活性炭用量为10 g时,新活性炭对亚甲基蓝的去除率为99.99%;采用700 W微波对吸附亚甲基蓝的活性炭辐射10 min进行再生并回用,经微波辐射再生10次后活性炭对亚甲基蓝的去除率为99.68%,未经微波作用反复使用10次的活性炭对亚甲基蓝的去除率为85.41%。结果表明：微波处理有效地减缓了活性炭吸附能力的下降速率,实现了活性炭再生和反复使用。在吸附过程中,Cd2＋使活性炭对亚甲基蓝的吸附能力略有下降,而共存的亚甲基蓝则促进了活性炭对Cd2＋的吸附,对新炭和再生后活性炭物理化学特性的表征证明了活性炭对亚甲基蓝的吸附为物理吸附,对Cd2＋的吸附为化学吸附。     

Fixed bed adsorption of acid dyes onto activated carbon

The context of the study here is the adsorption of acid dyes from wastewater arising from a nylon carpet printing plant which currently receives no treatment. Since nylon is a particularly difficult fibre to dye, acid dyes are required for successful coloration. However, their presence, in high concentrations, in aqueous effluent arising from the plant can create major problems with respect to disposal. A treatment method based on adsorption onto granular activated carbon (GAC F400) in a fixed column configuration is described and breakthrough data of the dyes determined. The breakthrough data were correlated using a model based on liquid and pore diffusion with a good fit of experimental results obtained. Trends in the effective diffusivity used in the model correlated with other authors. A slight decrease in effective diffusivity was found with decrease in particle size and was attributed to interactions between the relatively large molecular sized dye and the microspore structure found in granular activated carbon.     

Aerobic and anaerobic abiotic oxidation of squalene in the presence of hydroperoxides

Abiotic oxidation of squalene in the presence of hydroperoxysterols was studied in seawater under aerobic and anaerobic conditions. This ubiquitous isoprenoid alkene is quickly degraded in the presence of oxygen and its oxidation results mainly in the production of tertiary alcohols and to a lesser extent of epoxides and secondary alcohols. Although the degradation of squalene logically slows down under anaerobic conditions, a significant oxidation affording similar products than in the case of aerobic degradation has been observed. These results show that hydroperoxysterols, which seem to be well preserved in Recent sediments, could contribute to the oxidation of unsaturated lipids (such as squalene) in sedimentary environments under oxic and anoxic conditions.     

三氯乙酸与其他有机物在活性炭上的竞争吸附

通过等温吸附实验,考察了三氯乙酸(TCAA)与十二烷基苯磺酸钠(DBS)、腐殖酸(HA)在活性炭(GAC)上的竞争吸附现象。结果表明,GAC对TCAA的吸附符合Langmuir模型,对DBS和HA的吸附均符合Freudlich模型;在GAC上,DBS和HA对TCAA构成竞争吸附,大分子HA阻塞GAC的微孔,使得TCAA与DBS难以进入微孔;GAC对3种物质的吸附能力由大到小依次为DBS、TCAA和HA;离子型表面活性剂DBS憎水性一端与TCAA竞争吸附位,亲水性一端与TCAA形成吸附,使GAC总饱和吸附量有所加大。     

Adsorption behavior of alpha -cypermethrin on cork and activated carbon

Studies were undertaken to determine the adsorption behavior of alpha -cypermethrin [R)-alpha -cyano-3-phenoxybenzyl(1S)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, and (S)-alpha-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate] in solutions on granules of cork and activated carbon (GAC). The adsorption studies were carried out using a batch equilibrium technique. A gas chromatograph with an electron capture detector (GC-ECD) was used to analyze alpha -cypermethrin after solid phase extraction with C18 disks. Physical properties including real density, pore volume, surface area and pore diameter of cork were evaluated by mercury porosimetry. Characterization of cork particles showed variations thereby indicating the highly heterogeneous structure of the material. The average surface area of cork particles was lower than that of GAC. Kinetics adsorption studies allowed the determination of the equilibrium time - 24 hours for both cork (1-2 mm and 3-4 mm) and GAC. For the studied alpha -cypermethrin concentration range, GAC revealed to be a better sorbent. However, adsorption parameters for equilibrium concentrations, obtained through the Langmuir and Freundlich models, showed that granulated cork 1-2 mm have the maximum amount of adsorbed alpha-cypermethrin (q(m)) (303 microg/g); followed by GAC (186 microg/g) and cork 3-4 mm (136 microg/g). The standard deviation (SD) values, demonstrate that Freundlich model better describes the alpha -cypermethrin adsorption phenomena on GAC, while alpha -cypermethrin adsorption on cork (1-2 mm and 3-4 mm) is better described by the Langmuir. In view of the adsorption results obtained in this study it appears that granulated cork may be a better and a cheaper alternative to GAC for removing alpha -cypermethrin from water.     

Assessment of the abiotic transformation of 17β-estradiol in the presence of vegetable matter--II: the role of molecular oxygen

This study characterizes the effect of oxygen in the abiotic transformation of estrogens when they are contacted with a surrogate of the vegetable wastes found in sewage. 17β-Estradiol (E2) and 17β-¹⁴C₄-estradiol (¹⁴C-E2) were utilized as model compounds. Batch experiments were run under both oxic and anoxic conditions. In order to accomplish an accurate mass balance of the target estrogen, two analyses were performed simultaneously: first, radioactivity counting, and second, quantitation of E2 and ¹⁴C-E2, as well as their transformation product estrone and ¹⁴C₄-estrone, by Liquid Chromatography tandem Mass Spectrometry. Under oxic conditions, the total concentration of ¹⁴C-E2 was found to decrease by 78% in 72 h (15% and 7% remained in the liquid and solid phases, respectively). Conversely, when the estrogens were contacted with the synthetic influent under anoxic conditions, E2 was quantitatively recovered after 72 h (70% and 22% in aqueous and solid matrices, correspondingly). These results suggest that when the concentration of dissolved oxygen is null or limited, catalysis through an oxidative coupling mechanism is halted. Moreover, it was confirmed that the catalytic reaction occurred solely in the presence of the solid phase of the model vegetable matter.     

Adsorption behavior of α -cypermethrin on cork and activated carbon

Studies were undertaken to determine the adsorption behavior of α -cypermethrin [R)-α -cyano-3-phenoxybenzyl(1S)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, and (S)-α-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate] in solutions on granules of cork and activated carbon (GAC). The adsorption studies were carried out using a batch equilibrium technique. A gas chromatograph with an electron capture detector (GC-ECD) was used to analyze α -cypermethrin after solid phase extraction with C18 disks. Physical properties including real density, pore volume, surface area and pore diameter of cork were evaluated by mercury porosimetry. Characterization of cork particles showed variations thereby indicating the highly heterogeneous structure of the material. The average surface area of cork particles was lower than that of GAC. Kinetics adsorption studies allowed the determination of the equilibrium time—24 hours for both cork (1–2 mm and 3–4 mm) and GAC. For the studied α -cypermethrin concentration range, GAC revealed to be a better sorbent. However, adsorption parameters for equilibrium concentrations, obtained through the Langmuir and Freundlich models, showed that granulated cork 1–2 mm have the maximum amount of adsorbed α-cypermethrin (q_m) (303 μg/g); followed by GAC (186 μ g/g) and cork 3-4 mm (136 μg/g). The standard deviation (SD) values, demonstrate that Freundlich model better describes the α -cypermethrin adsorption phenomena on GAC, while α -cypermethrin adsorption on cork (1-2 mm and 3-4 mm) is better described by the Langmuir. In view of the adsorption results obtained in this study it appears that granulated cork may be a better and a cheaper alternative to GAC for removing α -cypermethrin from water.     

颗粒活性炭去除水中甲基叔丁基醚的可行性研究

随着甲基叔丁基醚（MTBE）作为汽油添加剂被持续大量使用，其已成为一种地下水中常见的有机污染物。本文通过纯净水、自来水和地下水中MTBE的平衡吸附容量和微型快速穿透实验（MCRB），比较了5种不同种类活性炭对MTBE的吸附性能。结果显示，苯酚值可准确预测活性炭样品对MTBE的平衡吸附容量大小次序，而丹宁酸值则可大致估计活性炭在实际处理应用时的吸附速度和吸附容量利用率。水样中共存的有机成分降低了活性炭对纯净水中MTBE的吸附容量，在背景TOC较低的去离子水中，活性炭对于MTBE的吸附性能反而比在地下水中降低得更多。穿透实验数据显示双柱串联的处理方式是高效应用活性炭吸附水中MTBE的优选工艺。使用环境友好的竹质活性炭去除地下水中MTBE具有良好的可行性和较高的性价比。     

Effects of humic substances on the decomposition of 2,4-dichlorophenol by ozone after extraction from water into acetic acid through activated carbon

The objectives of this study are to clarify the behavior of humic substances throughout the processes of 2,4-dichlorophenol (2,4-DCP) adsorption on granular activated carbon (GAC) from water and extraction into acetic acid, and the influence of the extracted humic substances on the decomposition of 2,4-DCP by ozone in the acetic acid. The adsorption capacity of GAC for 2,4-DCP was not influenced by the humic substances preloaded to have equilibrium concentration of 24.9mg Cl(-1) (14.5mg Cg(-1)). The adsorption capacity of GAC for 2,4-DCP decreased to one tenth of new GAC after the first adsorption-extraction step because of only 16% desorption in the first step. However, 2,4-DCP adsorbed on GAC was completely extracted after the second step suggesting that GAC can be used as adsorbent to transfer 2,4-DCP from water to acetic acid. The concentration ratio of 2,4-DCP from water into acetic acid was around 2x10(5), whereas the concentration ratio of humic substances was about 3.5, indicating that 2,4-DCP was selectively adsorbed and extracted by this system. The first order degradation rate constant for 2,4-DCP by ozone in acetic acid increased with the addition of humic substances. The rate constant with 16mg Cl(-1) of humic substances was 2.6 times as high as that without humic substances. Humic substances behaved as a promoter for the degradation of 2,4-DCP by ozone.     

颗粒活性炭深度处理抗生素废水

通过静态吸附实验,比较了13种不同材质、粒径的颗粒活性炭(granular activated carbon,GAC)对抗生素废水生化出水的吸附效果,选择KC16活性炭作为处理该废水的活性炭。KC16活性炭的进一步静态实验结果表明,当KC16活性炭投加量为30 g/L,吸附时间为6 h时,处理效果较好,TOC、COD、UV254、色度的去除率分别达到了86.99%、88.43%、89.69%和94.08%,并且污染物质(COD、TOC)的吸附符合Langmuir吸附等温式,吸附动力学符合准二级吸附动力学模型(R2>0.99)。动态吸附结果表明,在滤速为1.0 m/h,柱高为1 200 mm时,出水可以达到GB21903-2008《发酵类工业废水污染物排放标准》,处理每吨抗生素废水的活性炭用量为2.45 kg。     

Performance of three-phase three-dimensional electrode reactor for the reduction of COD in simulated wastewater-containing phenol

The removal of chemical oxygen demand (COD) from wastewater-containing phenol was investigated using three-phase three-dimensional electrode reactor. Special attention was paid to experimentally probe the performance of the reactor in COD removal in the process of repeated batch runs. The experimental results showed that the reactor could remove COD from phenol-containing wastewater much more efficiently than both granulated activated carbon (GAC) adsorption bed and conventional three-dimensional electrode. For 200th batch run, the three-phase three-dimensional electrode reactor with an airflow of 5 l min(-1) and a cell voltage of 30 V could remove 1350 ppm COD from the wastewater in 30 min while conventional three-dimensional electrode reactor with a same cell voltage and GAC adsorption bed with a same airflow only could remove 610 and 1000 ppm, respectively, at the same reaction duration. Although it was found that COD removal decreased with increasing repeated batch runs in our experimental range, due to adsorption saturation of GAC and electrode passivation, the extent of decrease for the three-phase three-dimensional electrode is much less than those for conventional three-dimensional electrodes and GAC adsorption beds. The passivated reactor could be partly re-activated by electrolysis in the presence of MnO2.     

活性炭纤维对染料的吸附性能研究

研究了聚丙烯腈活性炭纤维（P－ACF）、粘胶活性炭纤维（R－ACF）和颗粒活性炭（GAC）对5种红色染料的吸附能力,通过简单的模型,算出5种染料在两种活性炭纤维上的吸附速率常数。结果表明,尽管吸附能力随染料种类不同而有一定的差别,但总体上,聚丙烯腈活性炭纤维的吸附能力略低于颗粒活性炭,而粘胶活性炭纤维的吸附能力则远远优于前两种,对染料有着较大的吸附容量和较快的吸附速率。     

多孔镁铝复合氧化物对水溶液中Cr（VI）的吸附性能

摘要以镁盐、铝盐、纯碱和烧碱为原料制备了一种多孔镁铝复合氧化物（P—Mg3.1AlO4.6），其比表面积、平均孔径和总孔容分别为206．3m2／g、8．961nm和0．4208cm3／g。研究了这种多孑L材料对水溶液中cr（VI）的吸附性能，在25～45qC时，静态吸附量为82．32～141．7mg／g；当初始浓度100mg／L、流速5mL／min、床层高度10cm和pH=6时，半穿透时间、半穿透吸附量和饱和吸附量分别为406rain、49．28ing／g和51．30Ing／g；拟合参数及误差分析表明，cr（Ⅵ）在P—M敬。AIO4.6上的静态吸附过程符合Freundlich等温方程式和伪二级动力学方程，Yoon·Nelson模型能很好地预测cr（Ⅵ）在P—Mg3.1A104.6上的动态穿透曲线。     

Microwave Process for Volatile Organic Compound Abatement

ABSTRACT

The CHA Corporation has completed the U.S. Air Force Phase II Small Business Innovation Research program to investigate the feasibility of using a novel microwave-based process for the removal and destruction of volatile organic compounds (VOCs) in effluents from noncombustion sources, such as paint booth ventilation streams. Removal of solvents by adsorption, followed by the regeneration of saturated granular activated carbon (GAC) by microwave energy, was achieved in a single fixed-bed reactor. Microwave regeneration of the fixed-bed-saturated carbon restored the original GAC adsorption capacity. After 20 adsorption/regeneration cycles, the adsorption capacity dropped from 13.5 g methyl ethyl ketone (MEK)/100 g GAC to 12.5 g MEK/100 g GAC. During microwave regeneration of the GAC fixed bed, the concentrated desorbed paint solvent was oxidized by passing the solvent mixture through a fixed bed of an oxidation catalyst mixed with silicon carbide in a microwave reactor. A 98% oxidation efficiency was consistently achieved from the oxidation of VOCs in the microwave catalytic reactor.