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.     

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.     

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.     

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.     

棉秆基活性炭的制备及其对2,4-二硝基苯酚的吸附

以棉秆为原料，以KOH为活化剂，制备了高比表面棉秆基生物质活性炭。分析了制得的活性炭的元素组成、表面官能团、吸附能力等物化性能，探讨了浸渍比，活化温度，活化时间等工艺参数对制备活性炭得率、表面官能团、碘值、亚甲基蓝值等性能的影响，并通过静态吸附实验比较了不同条件下制备活性炭对2，4-二硝基苯酚的吸附性能，探讨了典型炭样品对2，4-二硝基苯酚的等温吸附特性。结果表明，KOH活化棉秆基生物质活性炭的表面物化性质随浸渍比、活化温度等工艺参数变化而变化，活化适宜条件为浸渍比1：3、活化温度800℃、活化时间90 min，在此条件下制得的炭样的碘值为1 251 mg/g，亚甲基蓝吸附值为478 mg/g，分别是国家一级品标准的1.25倍与3.54倍；对2，4-二硝基苯酚的Langmuir最大吸附量为747 mg/g，与Freundlich模型相比，Langmuir模型能较好地描述2，4-二硝基苯酚在炭样上的吸附行为，表明制备活性炭样品表面吸附位的能量分布较为均一。     

2,4-二硝基酚的超声波及协同降解研究

以 2 ,4 二硝基酚为研究对象 ,探讨了超声功率、氧化剂H2 O2 与Fenton试剂等因素对其超声降解效率的影响 .2 ,4 二硝基酚在超声波 (US)、US H2 O2 和US Fe2 H2 O2 体系中的降解均符合一级反应动力学模式 .超声波和Fe2 H2 O2 体系在 2 ,4 二硝基酚的降解过程中存在着协同效应 ,而在Cu2 H2 O2 和超声波体系中未观察到相似的协同效应 .     

二氯苯醌对斑马鱼胚胎发育及超氧化物歧化酶的影响

2,6-二氯-1,4-苯醌（2,6-dichloro-1,4-benzoquinone,2,6-DCBQ）作为一种新型消毒副产物,因其高检出率及高含量的特点而备受人们关注.本研究以斑马鱼胚胎为实验材料探究了2,6-DCBQ的发育毒性.结果发现：斑马鱼胚胎在8~24 hpf（器官发育形成时期）对2,6-DCBQ暴露最为敏感,死亡率最高;2,6-DCBQ安全浓度为27.15 μg·L^-1,属于极度危险外源化学物.在本实验中,2,6-DCBQ对斑马鱼的生长没有显著影响,但高浓度（100和150 μg·L^-1）2,6-DCBQ会显著增加斑马鱼胚胎及仔鱼的畸形率.在实验过程中还发现,高浓度（≥ 80 μg·L^-1）2,6-DCBQ会明显抑制斑马鱼胚胎的心率.此外,≥ 30 μg·L^-1 2,6-DCBQ可提高超氧化物歧化酶（Superoxide dismutase,SOD）的活性,并影响Cu/ZnSOD和MnSOD的正常转录.本研究较全面地探究了2,6-DCBQ对斑马鱼早期发育阶段的发育毒性,可为2,6-DCBQ的毒性研究提供可靠证据.     

Degrader density determines spatial variability of 2,6-dichlorobenzamide mineralisation in soil

The metabolite 2,6-dichlorobenzamide (BAM) is a frequent groundwater pollutant produced during degradation of the herbicide 2,6-dichlorobenzonitrile (dichlobenile). Spatial variability of BAM mineralisation is uncharacterized in surface soil, however, and factors controlling the heterogeneity remain unknown. We addressed these issues by sample-to-sample comparisons of BAM mineralisation rates and a range of soil characteristics at spatial scales ranging from meters to centimetres. For mineralisation assays nano-molar concentrations of labelled BAM were added to determine mineralisation rates under realistic conditions. We found a significant variability of BAM mineralisation which increased with decreasing spatial scale. BAM mineralisation rates were correlated to the density of BAM-degrading bacteria but not to water content, TOC, NH₄⁺, NO₃⁻, or pH. The genus Aminobacter, which contains the only BAM degraders known, was detected in MPN samples of BAM degraders by a specific PCR assay targeting the 16S rRNA gene, confirming a role of Aminobacter in BAM mineralisation.     

Accelerated anaerobic dechlorination of DDT in slurry with Hydragric Acrisols using citric acid and anthraquinone-2,6-disulfonate (AQDS)

The application of electron donor and electron shuttle substances has a vital influence on electron transfer,thus may affect the reductive dechlorination of 1,1,1-trichoro-2,2-bis(p-chlorophenyl)ethane(DDT) in anaerobic reaction systems.To evaluate the roles of citric acid and anthraquinone-2,6-disulfonate(AQDS) in accelerating the reductive dechlorination of DDT in Hydragric Acrisols that contain abundant iron oxide,a batch anaerobic incubation experiment was conducted in a slurry system with four treatments of(1) control,(2) citric acid,(3) AQDS,and(4) citric acid + AQDS.Results showed that DDT residues decreased by 78.93%–92.11% of the initial quantities after 20 days of incubation,and 1,1-dichloro-2,2-bis(4-chlorophenyl)-ethane(DDD) was the dominant metabolite.The application of citric acid accelerated DDT dechlorination slightly in the first 8 days,while the methanogenesis rate increased quickly,and then the acceleration effect improved after the 8th day while the methanogenesis rate decreased.The amendment by AQDS decreased the Eh value of the reaction system and accelerated microbial reduction of Fe(III) oxides to generate Fe(II),which was an efficient electron donor,thus enhancing the reductive dechlorination rate of DDT.The addition of citric acid + AQDS was most efficient in stimulating DDT dechlorination,but no significant interaction between citric acid and AQDS on DDT dechlorination was observed.The results will be of great significance for developing an efficient in situ remediation strategy for DDT-contaminated sites.     

pH和盐对活性炭纤维吸附2,4-二硝基酚的影响

研究了pH和盐对活性炭纤维ST-8和ST-13吸附2,4-二硝基酚的影响。结果表明,在pH0～14范围内,吸附量先随着pH的增大而增大,然后吸附量随着pH的增大而减小,在pH11时吸附量最小但不为零;在pH11～14范围内,吸附量随着pH增大而增大;ST-8和ST-13吸附2,4-二硝基酚的最佳pH分别为2和3。盐的存在对吸附2,4-二硝基酚有利,低pH时,氯化钠的作用是盐析效应;在pH较大时,氯化钠的作用是屏蔽效应。