Chemisorption and reaction characteristics of methyl radicals on Cu(110)

Methyl radicals are generated by pyrolysis of azomethane, and the condition for achieving neat adsorption on Cu(110) is described for studying their chemisorption and reaction characteristics. The radical-surface system is examined by X-ray photoemission spectroscopy, ultraviolet photoemission spectroscopy, temperature-programmed desorption, low-energy electron diffraction (LEED), and high-resolution electron energy loss spectroscopy under ultrahigh vacuum conditions. It is observed that a small fraction of impinging CH3 radicals decompose into methylene possibly on surface defect sites. This type of CH2 radical has no apparent effect on CH3(ads) surface chemistry initiated by dehydrogenation to form active CH2(ads) followed by chain reactions to yield high-mass alkyl products. All thermal desorption products, such as H-2, CH4, C2H4, C2H6, and C3H6, are detected with a single desorption peak near 475 K. The product yields increase with surface coverage until saturation corresponding to 0.50 monolayer of CH3(ads). The mass distribution is, however, invariant with initial CH3(ads) coverage, and all desorbed species exhibit first-order reaction kinetics. LEED measurement reveals a c(2 x 2) adsorbate structure independent of the amount of gaseous exposure. This strongly suggests that the radicals aggregate into close-packed two-dimensional islands at any exposure. The islanding behavior can be correlated with the reaction kinetics and is deemed to be essential for the chain propagation reactions. Some relevant aspects of the CH3/Cu(111) system are also presented. The new results are compared with those of prior studies employing methyl halides as radical sources. Major differences are found in the product distribution and desorption kinetics, and these are attributed to the influence of surface halogen atoms present in those earlier investigations.

潮棕壤不同利用方式营养元素随剖面深度的变化特征

对中国科学院沈阳生态实验站潮棕壤水稻田、玉米地、撂荒地和人工林地营养元素随剖面深度变化的研究表明,4种土地利用方式的有机C、全N、全S及DTPA浸提态Fe、Mn、Cu、Zn等具有随剖面深度增加而下降的趋势,交换性Ca、Na及交换性盐基总量在土层间的分异不明显。有机C、全N、碱解N、NO3--N、全S及DTPA浸提态微量元素在0~10 cm和0~20 cm的含量与0~100 cm含量的比值分别为0.1和0.2以上,表明这些养分指标具有明显的表聚性特征;NH4+-N、全P、速效S无明显的表聚性;交换性Mg、Na及交换性盐基总量在0~20cm与0~100 cm含量的比值小于0.2,反映了供试潮棕壤较强的淋溶作用。不同土地利用方式营养元素在土壤剖面中的分布差异及表聚性特征,主要受到植物循环的影响,另外还受到淋溶及人为干扰的影响。

Photo-induced reactions in the ion-molecule complex Mg+-OCNC2H5

Ion - molecule complexes of magnesium cation with ethyl isocyanate were produced in a laser- ablation supersonic expansion nozzle source. Photo- induced reactions in the 1: 1 complexes have been studied in the spectral range of 230 - 410 nm. Photodissociation mass spectrometry revealed the persistent product Mg+ from nonreactive quenching throughout the entire wavelength range. As for the reactive channels, the photoproducts, Mg+OCN and C2H5+, were produced only in the blue absorption band of the complex with low yields. The action spectrum of Mg+(OCNC2H5) consists of two pronounced peaks on the red and blue sides of the Mg+ 3(2)P <-- 3(2)S atomic transition. The ground state geometry of Mg+ - OCNC2H5 was fully optimized at B3LYP/6- 31 - G** level by using GAUSSIAN 98 package. The calculated absorption spectrum of the complex using the optimized structure of its ground state agrees well with the observed action spectrum. Photofragment branching fractions of the products are almost independent of the photolysis photon energy for the 3P(x,y,z) excitations. The very low branching ratio of reactive products to nonreactive fragment suggests that evaporation is the main relaxation pathway in the photo- induced reactions of Mg+ (OCNC2H5). (C) 2003 American Institute of Physics.

Capillary electrophoretic analysis of arsenic species with indirect laser induced fluorescence detection

The development of a method for determining arsenic species by capillary zone electrophoresis (CZE) with indirect laser-induced fluorescence (LIF) is described in this paper. The buffer pH, the concentration of fluorescein, the nature and the concentration of the background electrolytes (BGEs) were defined. When 2.0 mM NaHCO3 (pH 9.28) with 10(-7) M fluorescein was used as the buffer, arsenite (As(lll), dimethylarsonic acid (DMA), monomethylarsonic acid (MMA), and arsenate (As(V)) were all separated from one another. The limits of detection for the four arsenic species were p p in the range of 0.12-0.54 mg/L. This method was used in the analysis of spiked arsenic species in tap and mineral water to demonstrate its usefulness. The results showed that both the recovery and the reproducibility of the developed method were acceptable.

根系产生的有机酸对根际土壤养分活化的影响(英文)

本试验以采自中国东北3个地点的4种土壤,即棕色针叶林土、暗棕壤、黑土与黑钙土为材料,对根系分泌的两种有机酸及水在活化根际矿质养分方面的作用进行了模拟与比较。结果表明:有机酸能够活化养分,其程度主要取决于有机酸的数量和类型以及供试土壤的理化和生物化学性质;对于所有土壤类型,柠檬酸对Fe, Mn, Cu和Zn的活化效率明显高于苹果酸,而对于P, K, Ca 和Mg的活化效率并不是很高,有时甚至较苹果酸为低;所有元素的溶液浓度均随所加柠檬酸数量的增加而增加。图2表3参9。

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.

营养元素调控下南瓜组培根化感作用的初步研究

通过调节B5培养基中的组分,研究了金钩南瓜组培根在五种营养元素(P、Mg、Fe、Cu、B)四个浓度梯度(1/2 B5、B5、3/2 B52、B5)培养下化感作用的响应模式以及对黑籽和金钩南瓜两种受体幼苗生长的影响。结果表明:不同营养元素对受体植物幼苗生长的影响不一致,与元素含量显著相关,而且依赖于受体选择。五种营养元素在亏缺(1/2 B5)和正常(B5)条件下南瓜组培根过滤液对受体植物幼苗生长均表现为抑制作用;而适量增加营养元素的条件下(3/2 B5和2 B5),一般表现为促进作用,但2 B5含量下,B元素导致金钩南瓜的自毒作用,而Fe能引发金钩南瓜组培根过滤液对黑籽南瓜的抑制作用。因此理论上初步得出P和Mg元素可以降低南瓜根系的毒害作用,而Fe、Cu和B元素对南瓜根系的化感调控作用与品种选择有关,这对调控施肥、降低设施农业中葫芦科作物的连作障碍具有一定的参考意义。

柠条锦鸡儿组培苗继代培养中矿质元素的吸收规律

比较柠条锦鸡儿在MS、WPM、B5三种基本培养基中对P、K、Ca、Mg、Mn、Cu等主要矿质元素的吸收规律,用向量分析方法找出三种基本培养基中的限制因子。结果表明:矿质养分整体供应水平是影响柠条锦鸡儿组培苗吸收矿质元素的关键因子;除此之外,MS培养基的Ca、P水平偏低,WPM和B5培养基的主要限制因子分别为K、Mn和Ca、P、K。

平阴玫瑰花芽分化期叶片矿质元素含量动态变化

分析了平阴玫瑰叶片中P,K,Ca,Mg,Fe,Cu,Zn,Mn,B共9种矿质营养元素在花芽分化的7个生长时期含量动态变化及其相关性。结果表明,在平阴玫瑰花芽分化期间P,K,Zn,Cu大体上呈下降趋势;Ca除现蕾前含量陡然下降外,随叶片成熟含量呈现上升趋势;Mg,Fe,Mn,B含量波动频繁且变化各异。P与K,Zn,Cu均达到极显著正相关;K与Fe,Zn,Cu也达到极显著正相关;Fe与Mn,Zn与Cu之间均达到极显著正相关。平阴玫瑰叶片中9种矿质营养元素含量按高低排序为:Ca>K>P>Mg>Fe>Mn>B>Zn>Cu。

三种不同光谱学方法测定转基因抗虫棉组织营养元素含量

采用火焰原子吸收、火焰原子发射光谱法及分光光度法分析了三种不同转基因抗虫棉在不同生育时期不同组织内的11种营养元素含量的变化。结果表明,与非转基因对照比较,转基因抗虫棉植株体的营养化学组成发生了一定程度的改变,这种改变与转基因抗虫棉的品种、部位及生育时期相关。转基因抗虫棉全N含量的变化最为显著,其中转Bt抗虫棉Z30增幅最高达21%,这可能与外源基因导入及杀虫蛋白的表达有关。Mg,Na和Cu含量的显著改变仅特异的发生在某个转基因抗虫棉品种的某一组织内。外源抗虫基因导入对转基因抗虫棉植株内有机C、全P、全S、K、Ca、Fe、Zn含量的扰动是微小的,从而推测,转基因抗虫棉对这些营养元素的利用和积累能力没有显著改变。

土地利用对潮棕壤电导率影响的研究

对中国科学院沈阳生态实验站潮棕壤水稻田、玉米地、撂荒地和人工林地4种土地利用方式经过14年后土壤电导率在土体10个土层中的剖面分布进行比较研究,结果表明:不同土地利用方式及不同深度土层土壤电导率差异显著。表层,玉米地土壤电导率显著低于其他3种土地利用方式;150 cm深度内土壤电导率平均值为林地>撂荒地>玉米地>水稻田。水稻田土层具有相对较高的土壤电导率,可能主要受植稻过程中土壤淋溶及复盐基作用的影响;林地深层相对较高的土壤电导率可能主要受树木根系分布的影响。不同土地利用方式下土壤剖面中电导率与有机C、全量N、P、S、有效态N、P、S、pH、交换性Ca、Mg、K、Na、CEC、DTPA浸提态Fe、Mn、Cu、Zn之间具有不同的相互关系,反映了不同土地利用方式下元素的生物地球化学循环对土壤电导率的影响。由此,土壤电导率可作为指征不同土地利用方式对土壤性质影响可行的土壤化学指标。表4,参13。

文冠果叶片养分元素含量的动态变化及再吸收特性

以文冠果叶片为试材,运用原子吸收光谱法分析了叶片养分元素含量的季节动态变化和再吸收效率。结果表明:N、P、K均呈下降趋势,是"稀释效应"和养分再吸收导致;Mg呈"单峰"曲线走势,与Mg的生理功能有关;Fe、Mn呈"V"字型走势,Cu呈"W"型,Zn呈"N"型,与树体吸收特性和不同的物候期有关。总体来看,养分元素含量顺序是:N>P>K>Mg>Fe>Zn>Mn>Cu,且不同时期又有所不同。大量元素之间存在显著的相关关系;微量元素间相关关系不显著(Fe、Zn除外),Fe与N显著负相关,与拮抗作用有关。C/N呈升高趋势,差异显著;N/P呈降低趋势,差别不大。养分再吸收效率由大到小的顺序是:Mg>N>K>P,差异显著。微量元素由于移动性较差,不能被再吸收。N、P、K、Mg养分再吸收效率反映了文冠果较高的养分保存能力和养分利用效率。

污水灌溉对土壤重金属含量、酶活性和微生物类群分布的影响

以沈阳张士灌区长期污灌的农田土壤为对象,研究了土壤重金属、土壤酶活性、微生物生物量和种群分布特征,分析了土壤微生物参数与土壤重金属和土壤性质的相关关系。结果表明,虽然已停止污灌十余年,张士灌区农田土壤仍存在Cd、Zn、Cu等多种重金属污染。土壤Cd污染最严重,含量达1.75~3.89 mg.kg-1。土壤耕作层(0~30cm)Zn、Cu、Pb总含量随土层深度增加逐渐减少,而Cd元素的垂直分布呈向下迁移的趋势。Cd、Zn、Cu、Pb等4种重金属含量水平分布特征相似,均为1号样地>2号样地>3号样地>4号样地。相关性分析表明,张士灌区土壤酶活性、微生物生物量和种群分布受重金属污染和土壤养分的影响,土壤养分含量(有机碳、N、P、K)对微生物的正面效应大于重金属对微生物的负面效应。土壤全量Cd和速效K对微生物参数的影响最为明显,Cd含量与多酚氧化酶活性和微生物生物量(Cmic)呈极显著负相关,与纤维素酶活性呈极显著正相关(P<0.01),速效K含量与多酚氧化酶活性、微生物生物量以及可培养微生物种群数量均呈极显著正相关(P<0.01)。

杂种樱桃(P.avium×P.pseudocerasus)叶片离体再生体系的建立

以先锋与对樱桃的种间杂交种F8的组培苗为试材进行离体再生,研究建立了F8叶片再生体系,以WPM为基本培养基,附加6-BA及IAA的培养基芽再生效果最好,在1~7 mg/L 6-BA、0.5~3.0 mg/L IAA的浓度组合中,离体叶片均可以再生。其中3.0 mg/L 6-BA+2.0 mg/L IAA组合叶片离体再生效果最好,再生频率可达90%,叶片平均再生芽数可达5.22个。