Ozonation of aniline promoted by activated carbon

The removal of aniline from aqueous solutions by simultaneous use of ozone and activated carbon was investigated at different solution pH. For comparative purposes, single ozonation and adsorption on activated carbon were carried out in the same experimental set-up. In order to evaluate the role of the activated carbon surface chemistry during ozonation, a commercial activated carbon, Norit GAC 1240 PLUS, was submitted to oxidation in the liquid phase with HNO(3). The texture and surface chemistry of the activated carbon samples were characterized. During ozonation, complete conversion of aniline was achieved after approximately 20 min, regardless of the presence of activated carbon. In all cases, several by-products were formed during ozonation. Nitrobenzene, o- and p-aminophenol were the primary aromatic oxidation by-products identified. In terms of TOC removal, best results were achieved by the simultaneous use of ozone and activated carbon. Though there is a strong contribution of adsorption, a considerable synergetic effect between ozone and activated carbon is observed. In general, activated carbon promotes the reaction of ozonation enhancing the efficiency of this treatment process. The basic activated carbon presented greater activity in this process leading to higher mineralization rates.     

Characteristics of biotic and abiotic removals of dissolved organic carbon in wastewater effluents using soil batch reactors.

Biodegradable dissolved organic carbon (BDOC) analyses and abiotic adsorption of dissolved organic carbon (DOC) from different wastewater effluent were conducted to evaluate biotic and abiotic removal mechanisms as a function of the initial DOC concentration and source of DOC using soil batch reactors. To obtain high DOC concentrations, a laboratory-scale reverse osmosis unit was used. It was found that BDOC fraction was independent of the initial DOC concentration and was dependent on the source of wastewater and/or the types of wastewater treatment. The BDOC fractions varied from 9 to 73%. Trickling filter effluent (Tucson, Arizona) showed the highest BDOC, ranging from 65 to 73% biodegradable, while wastewater treated by the soil aquifer treatment (SAT) (NW-4) was found to be most refractory, with DOC removals of 9 to 14%. For nitrified/denitrified tertiary effluent (Mesa, Arizona) and secondary effluent (Scottsdale, Arizona), 36 to 42% removal of DOC was observed during the BDOC test. The amount of BDOC in the wastewater depended not on the concentration of DOC, but on the effectiveness of pretreatment. Abiotic adsorption capacity of wastewater effluent varied from 6 to 18%. Molecular weight distribution analyses showed that more than 50% of DOC in the Scottsdale concentrate had a molecular weight of less than 1000 Da, and no significant change in distribution profiles occurred after approximately 12% abiotic adsorption with both soils with acclimated microorganisms (SAT soil) and soils without acclimated microorganisms (non-SAT soils). Hence, preferential adsorption was not observed and the presence of acclimated microbes did not influence adsorption.     

高效生物活性炭吸附工艺去除水体中甲基叔丁基醚的初步研究

通过对来自美国加州拉玛达(La Mirada)市污染点的原始菌源炭进行甲基叔丁基醚(MTBE)降解菌生物强化,试图建立具有更有效MTBE降解效果的生物活性炭(BAC)功能,尝试利用新形成的菌源炭覆盖新鲜椰壳活性炭(GAC)而达到新BAC功能的快速有效启动,并考察不同空床停留时间(EBCT)、GAC吸附饱和状态对BAC功能启动的影响。同时,对具有成熟BAC功能的炭柱中的混合菌落进行基于16SrDNA的聚合酶链反应(PCR)—变性梯度凝胶电泳(DGGE)分析,以确定混合菌落中的主要功能菌种属。结果表明,针对模拟的低MTBE浓度进水,新鲜GAC和菌源炭A添加体积分数分别为40%和60%的NAS柱出水MTBE质量浓度最终稳定低于0.005mg/L,平均去除率接近99%,出水MTBE完全达到美国环境保护署(EPA)的饮用水建议阈值(<20μg/L),建立了成熟的BAC功能;成熟的菌源炭可在30d左右通过覆盖法迅速实现新BAC功能的启动;EBCT的延长有利于新BAC功能的启动和维持,接种初期应尽量采用较长EBCT以保证取得足够和稳定的生物量;MTBE吸附饱和前后的GAC在启动新BAC功能时存在差异,鉴于吸附饱和GAC在接种初期会因MTBE解吸而造成出水MTBE浓度较高,建议采用新鲜活性炭覆盖需接种炭柱;BAC功能成熟炭柱中包括的5种主要菌种里有4种为未培养微生物,1种为未分类菌种,其理化性质和具体属性尚不明确。     

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。     

活性炭多维电极法去除水中腐殖酸过程与宏观动力学研究

采用活性炭多维电极法去除水中溶解态腐殖酸。实验结果表明 ,与活性炭单纯吸附法相比 ,活性炭多维电极法可显著提高对溶解态腐殖酸的去除率 ;在连续运行条件下 ,延长水力停留时间、升高槽电压、溶液偏碱性有利于腐殖酸的去除 ;高效液相色谱分析结果表明 ,电极的氧化还原作用可使有机物分子量变小或矿化 ,因而处理系统有可能延长活性炭的使用寿命     

Removal of organic polyelectrolytes and their metal complexes by adsorption onto xonotlite

Natural organic polyelectrolytes (humic and fulvic acids) and their metal complexes were removed by adsorption onto xonotlite. The removal percentages of humic and fulvic acids by xonotlite were approximately 80% and 30%, respectively. Humic acid removal from solution by adsorption onto xonotlite took place more readily than fulvic acid removal. The molecular weight distributions of the humic substances remaining in solution after adsorption with the xonotlite were measured with size exclusion chromatography. A comparison of molecular weight distributions demonstrated conclusively that large molecular weight components were adsorbed preferentially, indicating that adsorption efficiency depends on the number of functional groups of humic substances. Furthermore, the surface topography of the adsorbent was observed before and after adsorption by scanning electron microscopy. The calculated heat of adsorption was of 330 kJ mol(-1) which was evaluated from the Clapeyron-Clausius equation. Therefore, the adsorption type can be considered chemical. Since xonotlite can be easily synthesized and obtained at low cost, the adsorption method of humic and fulvic acids is superior to their precipitation.     

Organic compounds adsorption onto activated carbon: the effect of association between dissolved humic substances and pesticides

The quantitative determination of pesticide binding to dissolved humic substances is relevant to both water treatment operation using activated carbon adsorption process and the application of transport models that predict the environmental distribution patterns of a given hydrophobic contaminant. In this study and in a first set of experiments, the extent of binding between (i) three pesticides of environmental concern, aldicarb, lindane and pentachlorophenol, and (ii) dissolved commercial humic acid and soil extracted fulvic acid, was determined using dialysis experiments and water solubility enhancement tests. In a second set of experiments, the influence of dissolved humic substances or pesticide on the retention of the other co-adsorbate onto activated carbon was investigated in binary systems. It was found that association was negligible for aldicarb and that the pesticide sorption onto activated carbon was not affected by humic acid (8.5 mg liter(-1) DOC). The association constants K for lindane and pentachlorophenol were identical in the presence of fulvic acid (logK=4.1) but lower than that observed with humic acid. In the presence of humic acid, binding affinity for pentachlorophenol (logK=4.6) was higher than the one observed for lindane (logK=4.4), despite its much higher water solubility. This observation suggests that the aromatic character of the pentachlorophenol molecule contributes to association interactions with humic acid. From co-adsorption experiments onto activated carbon it was found that fulvic acid (7.7 mg litre(-1) DOC) slightly enhances sorption kinetics of pentachlorophenol. Lindane (1 mg litre(-1)) does not affect sorption kinetics for fulvic acid but markedly enhances both the sorption kinetics and adsorptive capacity for humic acid. Activated carbon retention of dissolved humic substances or pesticide appears to be enhanced by the association potential that exists between these co-adsorbates in some binary systems.     

Effect of advanced oxidants generated via ultraviolet light on a sequentially loaded and regenerated granular activated carbon biofilter

The objective of this research was to investigate a sequentially loaded and regenerated granular activated carbon (GAC) biofilter system and to determine whether regenerative ozonation/advanced oxidation could improve the removal and biodegradation of a volatile organic compound from a contaminated airstream. Bench-scale reactors were constructed to operate in a manner analogous to a commercially available system manufactured by Terr-Aqua Environmental Systems (only with longer contact time). The GAC system consisted of two GAC biofilter beds that operated in a cyclical manner. On a given day, the first GAC bed adsorbed methyl isobutyl ketone from a simulated waste airstream, while the second bed underwent regeneration; then on the next day, the second bed was in the adsorption mode while the first was regenerated. Three bench-scale systems were used to compare the performance under three operating conditions: (1) ozone/ associated oxidant regeneration of a GAC biofilter system that was seeded with microorganisms from a field site, (2) a humid air regeneration of a seeded GAC biofilter, and (3) a humid air regeneration of an unseeded GAC biofilter. For the advanced oxidant regenerated GAC biofilter, a maximum removal efficiency of >95% was achieved with an empty bed contact time of 148 sec and an influent concentration of 125 ppm methyl isobutyl ketone, and 90-95% was achieved at 148-sec empty bed contact time and a 1150-ppm influent.     

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.     

Mutagenicity and identification of products formed by aqueous ozonation of humic acids of different origins

Ozonated soil-humic acid induced direct mutagenicity on TA98, TA100 and TA104, while not the ozonated reagent- and wastewater-humic acids. Oxygen radicals generated from mutagens such as glyoxal and hydrogen peroxide identified as the ozonation products might, in part, contribute to the mutagenicity of ozonated soil-humic acid.     

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.     

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.     

四种净水工艺对水源水微量有机物去除的研究

以UV254和CODMn代表饮用水源水中有机物替代指标.对常规处理、生物陶粒预处理、生物滤池、生物活性炭(BAC)、颗粒活性炭(GAC)、纳滤和光催化氧化进行组合,形成不同的处理流程,研究各流程对UV254和CODMn的去除效果.结果表明,各工艺流程都有一定的处理效率,其中以生物滤池和纳滤为主的组合流程处理效果最佳.此流程对UV254的去除率接近100%,CODMn的去除率达到78.6%,大大提高了饮用水的安全性.     

FIA/MS analysis of temporally ozonated benzo[a]pyrene and pyrene and their reaction products: inhibition of gap junction-mediated intercellular communication

In this study, the polycyclic aromatic hydrocarbons, benzo[a]pyrene (BaP) and pyrene, were subjected to temporal ozonation. The products from ozonation of 5 mg l(-1) BaP and 5 mg l(-1) pyrene, for varying time intervals (0, 1, 2, 3, 4, 5, 6, 8, 10, 20, and 30 min) were tested for their effects on gap junction-mediated intercellular communication (GJIC) in Clone 9 rat liver cells. Additionally, the ozonation products were also analyzed by flow injection analysis/mass spectrometry (FIA/MS) and the results were compared with the toxicity observed in the GJIC assay. Treatment of the Clone 9 cells with 5 mg l(-1) of ozonated BaP products resulted in a decrease in GJIC that was inversely proportional to the length of ozonation. The products from 1 min of ozonation resulted in a 92% decrease in the rate of GJIC, but with >5 min ozonation, the products did not suppress GJIC. In contrast, pyrene (0.5 mg l(-1)) required >10 min of ozonation to alleviate its effects on GJIC. FIA/MS, using atmospheric pressure chemical ionization (APCI), demonstrated products with higher molecular weights (MW) than their corresponding parent compounds, BaP (MW 252) and pyrene (MW 202). Ozonation of pyrene formed significantly fewer products than BaP. More importantly, pyrene ozonation products were constant from 1 to 10 min, while BaP ozonation products seemed to vary between time intervals. With the longer ozonation times (20 and 30 min), BaP and pyrene formed similar products (m/z peaks 157, 111, and 96). The suppression of GJIC by ozonated products seemed to correlate with oxidation of the aromatic ring framework. Further oxidation (longer ozonation times) to lower MW products correlated with restoration of normal GJIC.     

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.     

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。     

天然溶解性有机质对黑炭吸附萘和菲的抑制作用

研究了土壤天然溶解性有机质(富里酸或腐殖酸)对黑炭吸附萘和菲的影响.结果表明:增加天然溶解性有机质的负载量能够减弱黑炭对萘和菲的吸附能力;而同在100mg的负载量条件下,不同分子量的富里酸或腐殖酸的负载对黑炭吸附萘和菲的抑制作用没有明显差别;相对于富里酸或腐殖酸单独负载,金属离子(Al3+或Fe3+)和富里酸或腐殖酸联...     

Effect of ozonation on the biodegradability of atrazine in GAC columns

Abstract

The biodegradation of atrazine as influenced by preozonation was studied in biological GAC columns. Metabolism of isopropyl‐¹⁴C atrazine produced more ¹⁴CO₂ than ring‐UL‐¹⁴C atrazine, indicating dealkylation was more rapid than ring cleavage. Preozonation increased mineralization of ring‐UL‐¹⁴C atrazine and, consequently, enhanced the performance of the GAC columns. Sixty‐two percent of the influent atrazine was converted to ¹⁴CO₂ in columns that received ozonated atrazine and ozonated surface water, while 50% of the influent atrazine was converted to ¹⁴CO₂ in columns that received untreated atrazine and ozonated surface water, and only 38% of the influent atrazine was converted to ¹⁴CO₂ in columns with untreated influent.     

生物活性炭法深度处理纺织废水二级出水中生物活性的研究

采用上流式曝气生物活性炭法处理碱减量印染废水二级生物处理出水,利用TTC-脱氢酶活性(DHA)法监测反应器内DHA生物活性分布.研究发现反应器内生物炭表面附着生物膜活性较高,特别是反应器上部生物碳粒同样具有较高的DHA活性,这与反应器运行一年多能够保持对COD、色度和UV等较高去除率有一定关系.还研究了活性炭吸附、反应器反冲洗对DHA活性的影响.本研究为曝气生物活性炭法有效去除印染碱减量废水中难降解有机物提供了一定的理论依据.     

Ozonation of aqueous solution of alpha endosulfan

Ozonation of alpha endosulfan and the effects of some parameters such as pH, temperature and partial pressure on ozonation were investigated and the kinetic constants were calculated in this study. Alpha endosulfan solutions were ozonated in a lab-scale semi-batch reactor under variable experimental conditions. Increase in dissolved ozone concentration had a positive effect on oxidation rate. Alpha endosulfan could be removed up to 94% at pH 4 for an ozonation time of 60 minutes. The oxidation reaction was found to be of second order and of first order with respect to both ozone and alpha endosulfan. The temperature dependent reaction expression of alpha endosulfan was obtained as kd = (1.889 exp(- 2.21 x 10(-3)/T). It was concluded that, although the rate of reaction was lower than the rate of other pesticide oxidation reported in the literature. alpha endosulfan presented an obvious reaction to ozonation.