Loofa egyptiaca as a novel adsorbent for removal of direct blue dye from aqueous solution

In this paper, Loofa egyptiaca (LE), an agricultural plant cultivated in Egypt, was used to prepare low-cost activated carbon (LE_C1 and LE_C2) adsorbents. The adsorbents (LE, LE_C1 and LE_C2) were evaluated for their ability to remove direct blue 106 dye from aqueous solutions. Batch mode experiments were conducted using various parameters such as pH, contact time, dye concentration and adsorbent concentration. The surface chemistry of LE, LE_C1 and LE_C2 was analyzed by scanning electron microscopy (SEM). The experimental data were examined using Langmuir, Freundlich, Temkin and Harkins–Jura isotherms. The results showed that the adsorption of direct blue 106 was maximal at the lowest value of pH (pH = 2). Removal efficiency was increased with an increase in dye concentration and a decrease in amount of adsorbent. Maximum adsorption capacity was found to be 57.14, 63.3 and 73.53 mg/g for LE, LE_C1 and LE_C2 respectively. Kinetics were also investigated using pseudo-first-order, pseudo-second-order and intra-particle diffusion models. The experimental data fitted very well with the pseudo-first-order and pseudo-second-order kinetic models. The results indicate that LE, LE_C1 and LE_C2 could be employed as adsorbents for the removal of direct blue dye from aqueous solutions.     

Octanol–air partition coefficients of polybrominated biphenyls

The octanol–air partition coefficients (K_OA) for PBB15, PBB26, PBB31, PBB49, PBB103 and PBB153 were determined as a function of temperature using a gas chromatographic retention time technique with 1,1,1-trichloro-2,2-bis (4-chlorophenyl) ethane (p,p′-DDT) as a reference substance. The internal energies of phase change from octanol to air (Δ_OAU) were calculated for the six compounds and were in the range from 74 to 116 kJ mol⁻¹. Simple regression equations of log K_OA versus relative retention times (RRTs) on gas chromatography (GC), and log K_OA versus molecular connectivity indexes (MCI) were obtained, for which the correlation coefficients (r²) were greater than 0.985 at 283.15 K and 298.15 K. Thus the K_OA values of the remaining PBBs can be predicted by using their RRTs and MCI according to these relationships.     

Pyrolysis of permethrin and formation of precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) under non-oxidative conditions

This article reports the computational and experimental results of the thermal decomposition of permethrin, a potential source of dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). We have performed a quantum chemical analysis by applying density functional theory to obtain the decomposition pathways of permethrin and the formation mechanism of dibenzofuran. We have conducted the pyrolysis experiments in a tubular reactor and identified the pyrolysis products to demonstrate the agreement between the experimental measurements and quantum chemical calculations. The initiation of the decomposition of permethrin involves principally the aromatisation of permethrin into 3-phenoxyphenylacetic acid, 2-methylphenyl ester (J) and concomitant loss of 2HCl. This rearrangement is followed by the rupture of the O–CH₂ linkage in J, with a rate constant derived from the quantum chemical results of 1 × 10¹⁵ exp(−68 kcal/mol/RT) s⁻¹ for temperatures between 700 and 1300 K. This is confirmed by finding that the rate constant for unimolecular rearrangement of permethrin into J is 1.2 × 10¹² exp(−53 kcal/mol/RT) s⁻¹ over the same range of temperatures and exceeds the direct fission rate constant at all temperatures up to 850 ± 120 °C as well as by the experimental detection of J prior to the detection of the initial products incorporating diphenyl ether, 1-methyl-3-phenoxybenzene, 3-phenoxybenzaldehyde and 1-chloromethyl-3-phenoxybenzene. As the temperature increases, we observe a rise in secondary products formed directly or indirectly (via phenol/phenoxy) including aromatics (naphthalene), biphenyls (biphenyl, 4-methyl-1,1′-biphenyl) and dibenzofuran (DF). In particular, we discover by means of quantum chemistry a direct route from 2-phenoxyphenoxy to naphthalene. We detect no polychlorinated dibenzo-p-dioxins and dibenzofurans. Unlike the case of oxidative pyrolysis [Tame, N.W., Dlugogorski, B.Z., Kennedy, E.M., 2007b. Formation of dioxins in fires of arsenic-free treated wood: Role of organic preservatives. Environ. Sci. Technol. 41, 6425–6432] where significant yields of both PCDD and PCDF were obtained, under non-oxidative conditions the thermal decomposition of permethrin does not form appreciable amounts of PCDD or PCDF and the presence of oxygen (and/or a sizable radical pool) appears necessary for the formation of dibenzo-p-dioxin itself or PCDD/F from phenol/phenoxy.     

Important role of reaction field in photodegradation of deca-bromodiphenyl ether: Theoretical and experimental investigations of solvent effects

Photolysis of deca-bromodiphenyl ether (BDE-209) was investigated in tetrahydrofuran, dichloromethane, isopropanol, acetone, ethanol, methanol, acetonitrile and dimethylsulfoxide. Noticeable differences of the photolytic rates and quantum yields were found in the diverse solvents. Different to the previous deductions, hydrogen donating efficiency and electron donating efficiency of solvents were not the decisive factors for the photolytic rate in this study, which was proved by the fast photolysis of BDE-209 in CCl₄, a solvent without hydrogen and difficult to donate electrons. Besides hydrogen addition process, intermolecular polymerization might occur during the photolysis. Density functional theory (DFT) calculation was performed to understand the molecular properties of BDE-209 in different solvents. The lowest singlet vertical excitation energy (E_ex) and the average formal charge on Br () of BDE-209, reflecting the difficulty for the excitation of BDE-209 and for the departing of Br atom, respectively, were changed by the reaction fields formed by the different solvents. E_ex and linearly correlated with the photolytic activity (log k). This study is helpful to better understand the photolytic behavior of BDE-209 in different media.     

Perfluorosulfonates and perfluorocarboxylates in snow and rain in Dalian,China

Samples of precipitation events (snow and rain) in Dalian, a typical coastal town in China, were analyzed for perfluorosulfonates (PFSAs) and perfluorocarboxylates (PFCAs) to investigate atmospheric contamination by these compounds. In the snow event on December 16, 2006, samples were collected from 21 different sites and in another 6 precipitation events, samples were collected from a single location. Four PFSAs (C4, C6, C8, C10) and seven PFCAs (C6–12) were analyzed. Among the homologues, perfluorooctane sulfonate (PFOS) concentrations were the highest with a geometric mean (GM) of 145 ng/L (n = 21) during the snow event on December 16, 2006, followed by perfluorooctanoate (PFOA) with a GM of 24.7 ng/L (n = 21). Concentrations of perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS) and perfluoroheptanoate (PFHpA) were more than two orders of magnitude lower than that of PFOS. Other PFSAs and PFCAs were found to be below the limit of detection in all the samples. In other 6 precipitation events, PFSAs and PFCAs were detected approximately in the same order of magnitude in both snow and rain. The results indicate that wet deposition may be a potential transport mechanism of perfluorinated chemicals in the environment.     

北京市春季大气颗粒物污染特性研究

为研究北京市春季大气颗粒物污染特性,2008年3月至2008年5月,对北京市西三环大气颗粒物进行采样分析.测定了总悬浮颗粒物(TSP)与可吸入颗粒物(PM10)的日平均质量浓度,使用扫描电子显微镜(SEM)观察大气颗粒物的微观形貌,并通过X射线能谱仪(EDX)对样品中的元素组成进行分析.结果表明,TSP和PM10日平均质量浓度以初春最高,春天次之,春夏交际最低;PM10/TSP以春夏交际最高,初春次之,春天最低;大气颗粒物形态有规则和不规则2类,以不规则形态居多,同时发现花粉颗粒存在.EDX分析表明,大气颗粒物所附着的重金属中Pb所占的质量分散最高,并且集中吸附在细粒子颗粒物上.     

土壤中零价铁还原3-氯硝基苯的作用

利用零价铁在常温常压下对土壤中的3-氯硝基苯的还原,对反应物和产物随时间的变化及反应的各个影响因素进行了研究。实验结果表明,零价铁能够有效地将3-氯硝基苯还原为3-氯苯胺,反应过程中没有检测到脱氯产物。其反应速率随铁粉用量、反应体系含水量的增加以及反应温度的升高而升高,随土壤初始pH值的升高而降低。在土壤中3-氯硝基苯含量约为2.5×10^-6 mol/g,铁粉使用量为25 mg/g,反应体系中含水量为0.75 mL/g,pH值为6.8时,在恒温生化培养箱(25±1)℃反应5 h后,3-氯硝基苯的还原率达到92.75％。     

生物法同时脱硫脱硝试验研究

采用轻质陶粒生物滴滤塔处理摸拟燃煤烟气中二氧化硫和氮氧化物的试验研究,探讨生物法同时脱硫脱硝的影响因素及生物降解宏观动力学。研究结果表明,生物法能有效同时去除烟气中的二氧化硫和氮氧化物,烟气同时脱硫脱硝效率分别可达99.9%和88.9%。为获得最佳烟气同时脱硫脱硝效果,二氧化硫和氮氧化物进气负荷应分别＜140 g/（m³·h）和20 g/（m³·h）,循环液pH=7～8,空床停留时间为30.28 s,喷淋密度为8.81 L/（m³·h）。     

花叶芦竹水平潜流人工湿地脱氮性能研究

采用花叶芦竹水平潜流人工湿地处理生活污水,对其脱氮性能进行研究。结果表明：在HRT＝5 d,对TOC,NH⁺₄-N,NO^-₂-N,NO^-₃-N和TN的去除效果分别达到92％、93％、84％、51％和88％,相应空白湿地的去除率分别为91％、85％、-232％、-203％和66％。大部分TOC在湿地的前端被去除。花叶芦竹可以直接吸收氮素,向湿地输送氧气,通过根系分泌物提供碳源。因此,花叶芦竹人工湿地具有很好的硝化反硝化能力,实现了良好的脱氮性能。     

新型转式垃圾焚烧过程中脱氯脱硫机理的研究

为了探讨有机垃圾焚烧过程钙基添加剂对HCl,SO_x生成特性的影响,分别在自行设计的中空水冷转式垃圾焚烧炉和固定床加热炉中进行了一系列的实验,研究结果表明新型转式焚烧炉具有强化传热传质特性,能提高HCl、SO_x的脱除率,可抑制有害气体的生成;同时也研究了 HCl,SO₂气体同时存在时,钙基添加剂对脱氯脱硫效率的影响规律。