Ultrasonic preparation of nano-nickel/activated carbon composite using spent electroless nickel plating bath and application in degradation of 2,6-dichlorophenol

Ni was effectively recovered from spent electroless nickel （EN） plating baths by forming a nano-nickel coated activated carbon composite. With the aid of ultrasonication, melamine- formaldehyde-tetraoxalyl-ethylenediamine chelating resins were grafted on activated carbon （MFT/AG）. PdC12 sol was adsorbed on MFT/AC, which was then immersed in spent electroless nickel plating bath; then nano-nickel could be reduced by ascorbic acid to form a nano-nickel coating on the activated carbon composite （Ni/AC） in situ. The materials present were carefully examined by Fourier transform infrared spectroscopy, X-ray diffraction, field emission scanning electron microscopy, X-ray photoelectron spectroscopy and electro- chemistry techniques. The resins were well distributed on the inside and outside surfaces of activated carbon with a size of 120 ± 30 nm in MFT/AC, and a great deal of nano-nickel particles were evenly deposited with a size of 3.8 ± 1.1 nm in Ni/MFT. Moreover, Ni/AC was successfully used as a catalyst for ultrasonic degradation of 2.6-dichloronhenol.     

Enhanced U(VI) bioreduction by alginate-immobilized uranium-reducing bacteria in the presence of carbon nanotubes and anthraquinone-2,6-disulfonate

Uranium-reducing bacteria were immobilized with sodium alginate, anthraquinone-2, 6-disulfonate (AQDS), and carbon nanotubes (CNTs). The effects of different AQDS-CNTs contents, U(IV) concentrations, and metal ions on U(IV) reduction by immobilized beads were examined. Over 97.5% U(VI) (20 mg/L) was removed in 8 hr when the beads were added to 0.7% AQDS-CNTs, which was higher than that without AQDS-CNTs. This result may be attributed to the enhanced electron transfer by AQDS and CNTs. The reduction of U(VI) occurred at initial U(VI) concentrations of 10 to 100 mg/L and increased with increasing AQDS-CNT content from 0.1% to 1%. The presence of Fe(III), Cu(II) and Mn(II) slightly increased U(VI) reduction, whereas Cr(VI), Ni(II), Pb(II), and Zn(II) significantly inhibited U(VI) reduction. After eight successive incubation-washing cycles or 8 hr of retention time (HRT) for 48 hr of continuous operation, the removal efficiency of uranium was above 90% and 92%, respectively. The results indicate that the AQDS-CNT/AL/cell beads are suitable for the treatment of uranium-containing wastewaters.     

Rain‐washing of foliar deposits of Dimilin®WP‐25 formulated in four different carrier liquids

Abstract

Dimilin^® WP‐25, a wettable powder formulation of diflubenzuron (DFB) [1‐(4‐chlorophenyl)‐3‐(2,6‐difluorobenzoyl) urea], was formulated in four different carrier liquids, viz., water; a light petroleum paraffinic oil, ID 585; a heavy paraffinic oil, Sunspray^® 7N; and a 1:2 mixture of a light petroleum aromatic solvent (Cyclosol^® 63) and canola oil; to provide four end‐use mixtures, Dim‐W, Dim‐585, Dim‐7N and Dim‐Cy‐C respectively, each containing 28 g of DFB per litre. Balsam fir branch tips clipped from greenhouse‐grown seedlings, and sugar maple branch tips clipped from field‐grown young trees, were exposed to uniform‐sized droplets (ranging in diameters from 135 to 190 μm) of the four end‐use mixtures which were atomized using a monodispersed droplet generator. Droplets were collected on the fir and maple branch tips and the initial residue per g fresh weight of foliage was determined by high‐performance liquid chromatography (HPLC). The branch tips were exposed to cumulative rainfall of 3, 6 and 10 mm at an intensity of 5 mm/h and at time intervals of 1, 12, 36 and 72 h after DFB treatment, to test the influence of ‘ageing’ of foliar residues on rainfastness. Foliar samples were collected for residue determination just before the onset of rainfall, and at 0.5 h post‐rain. DFB was quantified by the HPLC method. In the case of fir foliage, the Dim‐W formulation was the most susceptible to rain‐washing and the rainfastness did not increase with the ageing period of foliar deposits. In contrast, the three oil‐based mixtures showed greater rainfastness depending upon the carrier liquid and the ageing period. Rainfastness decreased in the order of Dim‐Cy‐C > Dim‐7N > Dim‐585 > Dim‐W. In contrast, the data on maple foliage indicated that the ageing of deposits increased the rainfastness of all the 4 end‐use mixtures. Dim‐585 was the most susceptible to rain washing, and rainfastness decreased in the order of Dim‐W > Dim‐Cy‐C > Dim‐7N > Dim‐585.     

1,4-二氯苯在褐土中的残留量变化及对几种土壤酶活性的影响

1,4-二氯苯(1,4-DCB)作为农药和化工产品生产的原料和中间体,在环境中的含量越来越多.采用气相色谱法对不同浓度1,4-DCB处理后土壤中药物残留量进行了测定;对1,4-DCB处理后褐土土壤中几种重要的氧化还原酶(多酚氧化酶、过氧化氢酶、脱氢酶)和脲酶活性进行测定,用其改变来反应1,4-DCB残留对土壤生态系统的影响.结果发现:在1,4-DCB处理30 d后,土壤中1,4-DCB残留保持在44%~50%;1,4-DCB处理后土壤中多酚氧化酶活性呈现先升高后降低的现象,酶活性峰值因作用时间和作用浓度不同而不同.与多酚氧化酶活性改变趋势不同,1,4-DCB处理后土壤脱氢酶活性降低.两种酶活性与1,4-DCB处理浓度之间均具有一定的浓度-效应和时间-效应关系.与多酚氧化酶和脱氢酶活性变化结果不同,1,4-DCB处理后土壤脲酶和过氧化氢酶的活性则随着处理浓度升高和处理时间延长而升高.因此,土壤中不同酶活性对1,4-DCB污染产生了不同的响应.     

改性Ti/SnO2-Sb电极催化降解1,4-二氯苯废水试验研究

采用聚合物前驱体法制备了未掺杂、掺杂Cu、掺杂Bi、掺杂Ni的4种Ti/Sn O2-Sb电极,运用SEM和XRD分析电极表面形貌及结构,通过线性极化扫描、循环伏安等测试考察其电化学性能,同时进行1,4二氯苯(p-DCB)降解实验进一步探究电极的电催化氧化特性.SEM和XRD结果表明,掺杂金属可改善电极表面形貌,增大其比表面积;电化学测试表明,Ti/Sn O2-Sb电极的析氧电位并未因金属掺杂而有明显改变,掺杂金属后,Ti/Sn O2-Sb电极具有更优的电催化活性和稳定性.p-DCB降解实验表明,改性Ti/Sn O2-Sb电极对p-DCB的降解效率明显提高,其中Ti/Sn O2-Sb-Cu电极的电催化处理效果最优,电解2 h后p-DCB的去除率即达到87.6%,且p-DCB的降解反应遵循一级反应动力学规律.     

The use of the tergal gland defensive secretion in male intrasexual aggression of the rove beetle,Aleochara curtula (Coleoptera: Staphylinidae), measured by closed-loop-stripping-analyses and tandem bioassay — mass fragmentography

Summary 2-methyl-1,4-benzoquinone as a target compound of the tergal gland secretion of the rove beetle,Aleochara curtula, was quantified from the reservoirs of individual beetles. Males store less secretion than females, and they evaporate more of the secretion as measured by adsorption from the air (closed-loop-stripping-analysis). The amount of emitted quinone is increased during aggressive interactions of rival males. The pulsed emission of the secretion during aggression is demonstrated by a novel technique combining observation of behavior with the on-line measurement of target fragment ions by mass-spectrometry (tandem bioassay — mass fragmentography). The emission of the secretion is used as a weapon in combats between males and may result in the repulsion of subordinate males from the mating site, but may also serve to mimic females chemically in order to avoid aggressive encounters.     

Application of a Second-Order Kinetic Model to a Complex Melt Polymerization Reaction

A novel copolymer system has been synthesized using methyl hydroquinone diacetate (MHQDA), 1,4 naphthalene dicarboxylic acid (1,4 NDCA), and polybutylene terephthalate (PBT) using the melt polymerization technique. The optimum kinetic parameters pertinent to this system are reported in this study. A simple second-order reaction sequence summarizes catalyzed and uncatalyzed reactions between MHQDA, 1,4 NDCA, and PBT. The kinetic parameters for the copolymerization reaction were determined using a new second-order model. This technique was used to compute the moles of acetic acid generated in the polymerization process. The model was compared to that of the experimentally determined data. Close comparison (percentage error of less than 5%) was obtained between the experimental and theoretical data. The kinetic data support block copolyester formation. The thermal data also supports formation of block polymers.     

Degradation of Monophenylheptamethylcyclotetrasiloxane and 2,6-cis-Diphenylhexamethylcycloterasiloxane in Londo Soil

The natural degradation of monophenylheptamethylcyclotetrasiloxane and 2,6-cis-diphenylhexamethylcyclotetrasiloxane in soil was evaluated under laboratory conditions. Both monophenyl and 2,6-cis underwent rapid degradation in dry soil generating the same products in varying proportions. During the first 24 hr, approximately 99% of the two materials underwent significant chemical transformations forming silanols of various structures, dimethyl cyclic siloxanes of the structure (Me₂SiO)x, and rearrangement products (geometrical isomers) of diphenylhexamethylcyclotetrasiloxane. Among the silanols, the following were identified as trimethylsilyl derivatives: HOSiMe₂OH, HOSiMePhOH, HOSiMe₂OSiMe₂OH, HOSiMePhOSiMe₂OH, HOSiMePhOSiMePhOH, HOSiMe₂OSiMe₂OSiMe₂OH, HOSiMePhOSiMe₂OSiMe₂OH, HOSiMe₂OSiMePhOSiMe₂OH, HOSiMePhSiMe₂OSiMePhOH, HOSiMePhOSiMePhOSiMe₂OH, HOSiMePhOSiMe₂OSiMe₂OSiMe₂OH, HOSiMe₂OSiMePhOSiMe₂OSiMe₂OH, HOSiMePhOSiMe₂OSiMePhOSiMe₂OH, HOSiMePhOSiMePhOSiMe₂OSiMe₂OH, HOSiMePhOSiMe₂OSiMe₂OSiMePhOH, HOSiMe₂OSiMePh-OSiMePhOSiMe₂OH. Derivatization was carried out using bis(trimethylsilyl)trifluoroacetamide. Gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry (atmospheric pressure chemical ionization) analyses were used to derive structures. Structures were confirmed by gas chromatography-mass spectrometry comparisons of synthetic standards. Degradation was slower in wet soil. Nevertheless, in 14 days, the chemical transformation was essentially found to be complete as soil was allowed to dry. Detection of phenol as one of the degradation products revealed the occurrence of carbon–silicon bond cleavage promoted by soil.     

NO3自由基与3种环醚的大气化学反应动力学研究

在自制的大气反应烟雾箱模拟实验装置中,利用相对速率法研究了3种工业常用溶剂四氢呋喃、1,3-二氧五环、1,4-二氧六环与NO3自由基在298 K±1 K和1.01×105 Pa条件下的反应,目的是通过了解这些挥发性有机化合物（volatile organiccompounds,VOCs）在大气中的降解反应动力学来评估这些化合物对环境可能造成的影响.利用配有氢火焰离子化检测器（FID）的气相色谱（GC）检测反应物浓度变化,测得NO3自由基与四氢呋喃的反应速率常数为（5.36±1.93）×10-15cm3·（molecule·s）-1,与文献报道值在误差范围内非常吻合,验证了实验装置和实验方法的可靠性.实验首次测定了298 K±1K和1.01×105 Pa条件下1,3-二氧五环以及1,4-二氧六环与NO3自由基反应的速率常数,分别为（1.84±0.70）×10-15cm3·（molecule·s）-1和（3.20±0.67）×10-16 cm3.（molecule·s）-1.利用所测反应速率常数估算这些化合物在大气中的平均寿命都在1 d甚至十几d,因此,其排放可能会对区域大气环境产生一定的影响.     

一株高效1,4-雄烯二酮降解菌的筛选、鉴定及其降解转化特性研究

从养殖场废水中筛选出1株1,4-雄烯二酮（ADD）高效降解菌株ADD3,经过16S rDNA序列同源性分析,鉴定该菌株为芽孢杆菌（Bacillus sp.）.通过单因素实验研究了不同实验条件对菌株ADD3降解特性的影响,采用高效液相色谱与质谱联用技术（UPLC-MS/MS）和高效液相色谱与四级杆飞行时间高分辨率质谱联用技术（UPLC-QTof-MS）鉴定转化产物.结果表明：菌株ADD3通过共代谢方式转化ADD,在MH肉汤培养基中降解500 μg·L^-1 ADD的半衰期为3.6 h;葡萄糖、乙酸钠、蔗糖和淀粉对菌株ADD3降解ADD均有一定的促进作用,其中,最佳碳源为淀粉,最佳浓度为1000 mg·L^-1;最佳pH和温度分别为7和40℃.实验中共鉴定出5种产物,降解机理主要包括加氢还原、脱氢氧化和羟基化,TP1（雄烯二酮）为主要产物.研究结果可为探索微生物转化ADD的机理、优化去除ADD的研究提供参考,并为构造相关工程菌提供一些基础数据.