长期施肥对黑土中Cu、Cd含量及其剖面分布的影响

以经过8个不同施肥处理的黑土样品为材料,研究长期不同施肥处理下,黑土中Cu、Cd含量的差异。采用原子吸收分光光度法和Tessier-连续提取法,研究黑土中全Cu、全Cd和有效Cu、有效Cd的含量差异。结果表明,有机肥的长期施用,会使土壤中Cu、Cd与有机质发生络合并使Cu、Cd在土壤表层累积;秸秆和氮磷钾(S+NPK)化肥的长期配合施用,有利于作物对有效Cu和Cd的吸收,从而使Cu、Cd在土壤中没有明显积累;NP及NPK处理下,二铵、氯化钾肥对土壤中Cu、Cd积累的影响不明显。长期耕作不施肥(CK)处理时,因无外源Cu、Cd,以及作物对有效Cu、Cd的长期吸收,土壤中Cu、Cd含量低于不耕作不施肥(休闲)处理的。从垂直剖面上看,Cu、Cd主要积累在黑土表层,而表层以下不同施肥处理间Cu、Cd含量的差异和变幅不大。有机肥料能明显地向土壤中带入Cu、Cd,造成Cu、Cd在土壤表层的积累,并由于植物体的吸收对人体造成潜在危害,而其他化学肥料对土壤中Cu和Cd积累的影响不明显。本研究为人们的生产实践提供了施肥理论和依据,并且对土壤的污染防治也具有现实意义。

Electrocatalytic properties of Cu-Zr amorphous alloy towards the electrochemical hydrogenation of nitrobenzene

The Cu-Zr amorphous alloy was studied as an electrocatalyst towards the electrochemical hydrogenation of nitrobenzene. The electrocatalyst was activated by chemical etching in HF solution. Resulted changes in the morphology, chemical composition and crystalline structure of the electrocatalyst surface were characterised by scanning electron microscopy, X-ray diffraction and Auger electron spectroscopy. The electrocatalytic properties of the Cu-Zr amorphous alloy were assessed by voltammetric measurements. Due to the formation and aggregation of Zr residue modified Cu nanocrystals on the surface caused by the selective dissolution of Zr components in the chemical etching, the activated amorphous alloy is an effective electrocatalyst for the electrochemical reduction reaction of nitrobenzene with aniline as the main product. The positive shift of the peak potential and accompanying increase in the value of peak current in voltammograms with increasing Cu content and decreasing Zr content of the alloy surface in the chemical etching are indicative of improved electrocatalytic activity. (C) 2002 Elsevier Science B.V. All rights reserved.

Asymmetric cyclopropanation of styrene catalyzed by Cu-(chiral Schiff-base) complexes

Asymmetric cyclopropanation of olefins was carried out with chiral copper-Schiff base complexes derived from copper acetate monohydrate, substituted salicylaldehydes and a chiral amino alcohol. Substituents on salicylaldehyde framework demonstrate a significant effect on the steroselectivities. Those with electron-withdrawing properties enhance the selectivities, whereas bulky sustituents in ortho position to the phenol hydroxy group decrease the selectivities. An ee of more than 98% was achieved for the reaction of styrene with diazoacetate. (C) 2000 Elsevier Science Ltd. All rights reserved.

On-line voltammetric monitoring of dissolved Cu and Ni in the Gulf of Cadiz, south-west Spain

Geochemical processes in estuarine and coastal waters often occur on temporally and spatially small scales, resulting in variability of metal speciation and dissolved concentrations. Thus, surveys, which are aimed to improve our understanding of metal behaviour in such systems, benefit from high-resolution, interactive sampling campaigns. The present paper discusses a high-resolution approach to coastal monitoring, with the application of an automated voltammetric metal analyser for on-line measurements of dissolved trace metals in the Gulf of Cadiz, south-west Spain. This coastal sea receives metal-rich inputs from a metalliferous mining area, mainly via the Huelva estuary. On-line measurements of dissolved Cu, Zn, Ni and Co were carried out on-board ship during an eight-day sampling campaign in the study area in June 1997. A pumping system operated continuously underway and provided sampled water from a depth of ca. 4 m. Total dissolved metal concentrations measured on-line in the Gulf of Cadiz ranged between <5 nM Cu (<3 nM Ni) ca. 50 km off-shore and 60–90 nM Cu (5–13 nM Ni) in the vicinity of the Huelva estuary. The survey revealed steep gradients and strong tidal variability in the dissolved metal plume extending from the Huelva estuary into the Gulf of Cadiz. Further on-line measurements were carried out with the automatic metal monitor from the bank of the Odiel estuary over a full tidal cycle, at dissolved metal concentrations in the μM range. The application confirmed the suitability of the automated metal monitor for coastal sampling, and demonstrated its adaptability to a wide range of environmental conditions in the dynamic waters of estuaries and coastal seas. The near-real time acquisition of dissolved metal concentrations at high resolution enabled an interactive sampling campaign and therefore the close investigation of tidal variability in the development of the Huelva estuary metal plume.

山杏种皮黑色素与Cu~(2+)和Zn~(2+)络合性质的研究

【目的】研究山杏种皮黑色素与Cu2+和Zn2+络合的相关性质,为山杏种皮黑色素以及其他植物黑色素的开发利用提供依据。【方法】采用电位滴定、紫外-可见光差示吸收光谱和红外光谱对山杏种皮黑色素与Cu2+和Zn2+的络合物进行分析。【结果】Cu2+和Zn2+与山杏种皮黑色素络合后,均能促进山杏种皮黑色素酸性位点的去质子化作用,但Cu2+的促进作用更强,结合更为牢固;随pH值升高,山杏种皮黑色素中解离出的络合位点增多,络合Cu2+能力增强。【结论】Cu2+和Zn2+主要与山杏种皮黑色素中羰基发生络合作用,氨基和羟基参与了络合。

石油烃、Cu~(2+)单一与复合污染对沙蚕的毒性效应

在实验室模拟条件下研究了石油烃、Cu2+单一与复合污染对沙蚕的毒性效应.试验的结果表明,沙蚕的死亡率与石油烃、Cu2+的浓度呈显著相关关系.其半数致死浓度LC50分别为:30.2～116.26μg/L(石油烃);449.52～1130.34μg/L(Cu2+).沙蚕体内Cu2+的积累量随着暴露溶液中Cu2+浓度的上升而增加,当Cu2+的浓度>500μg/L时,这一变化十分显著;而沙蚕体内石油烃的含量随着暴露溶液中石油烃浓度的升高无显著变化.而Cu2+和石油烃复合污染对沙蚕的毒性作用较为复杂,在不同的处理中,表现出了协同和拮抗两种作用方式.同时,在Cu2+与石油烃复合污染条件下,沙蚕体内Cu2+的积累量也有显著变化.在复合处理组中,当Cu2+的浓度达到500μg/L时,Cu2+在沙蚕体内的积累量与Cu2+单一污染相比,Cu2+在沙蚕体内积累量相比显著降低.

有机质对Cu~(2+)在棕壤及其各粒级微团聚体中吸附解吸特性的影响

采用平衡液吸附法和NH4AC、EDTA溶液解吸法,研究了有机质对Cu2+在棕壤及其各粒级微团聚体中(<10μm,10～50μm,50～250μm)的吸附解吸过程中的影响,为寻求有效控制土壤中Cu2+环境行为的对策措施提供理论支撑。研究结果表明,各粒级微团聚体中有机质对Cu2+的吸附能力随粒级的减小而增强,原土仅次于<10μm微团聚体。就吸附机制而言,去除有机质后的原土及其各粒级微团聚体在不同吸附机制控制下的吸附能力也有所变化,表现为:去除有机质后,棕壤及各粒级微团聚体对Cu2+的静电吸附能力增强,络合吸附能力和专性吸附的能力均有所降低。分析表明,原土及其不同粒级微团聚体对Cu2+的吸附能力及稳定性的差异,与其重要组成成分有机质有关。