同位素示踪法测定稀土在土壤中的吸附,解吸和扩散

对９种不同性质土壤测定结果表明，ＲＥ的吸附或解吸均与Ｌａｎｇｍｕｉｒ方程有极好的拟合性。土壤ＲＥ吸附容量在１．５－１５ｍｇ／ｇ之间，它与土壤中伊利石的相对含量呈明显正相关土壤ＲＥ解吸量与吸附量之间呈显著指数曲线关系，曲线转折点的ＲＥ吸附量称为土壤特征吸附量，以它表征ＲＥ在土壤中运移难易，比土壤吸附容量表征更有意义。     

CO在轻微氧化的Mo(100)表面上的吸附和反应

应用ＨＲＥＥＬＳ和ＴＤＳ研究了１２０Ｋ时ＣＯ在轻微氧化的Ｍｏ（１００）上的吸附和脱附状况。１２０Ｋ时,ＣＯ在轻微氧化的Ｍｏ（１００）上存在顶位垂直吸附（ν＾－ｃｏ＝２０１６～２０５０ｃｍ＾－１）、四重空位倾斜吸附（ν＾－ｃｏ＝１０８８ｃｍ＾－１）和通过π键与表面发生作用的倾斜吸附（ν＾－ｃｏ＝１０６６ｃｍ＾－１）。当表面温度升高时,顶位吸附的ＣＯ在低覆盖度下发生解离,但在较高覆盖度下,可以同时发生     

超大孔Fe和V－Ti分子筛的合成

水热法合成了具有超大孔ＭＣＭ－４１分子筛结构的含Ｐｅ和Ｖ－Ｔｉ分子筛，通过ＸＲＤ、骨架ＩＲ、ＥＳＲ、￣（２９）ＳｉＭＡＳＮＭＲ、紫外漫反射等测试表征证实，Ｆｅ原子在ＦｅＭＣＭ－４１分子筛骨架上，Ｖ和Ｔｉ同时进入Ｖ－ＴｉＭＣＭ－４１分子筛骨架。ＦｅＭＣＭ－４１的骨架红外谱除Ｆｅ分子筛的特征吸收峰６６０ｃｍ￣（－１）外，还显示９６０ｃｍ￣（－１）峰，ＥＳＲ谱出现高对称八面体环境Ｆｅ（Ⅲ）信号（ｇ＝２．０）和扭曲四面体环境Ｆｅ（Ⅲ）信号（ｇ＝４．２），而Ｖ－ＴｉＭＣＭ－４１的骨架红外９６０ｃｍ￣（－１）峰强度分别随分子筛中钛或钒的含量线性增强。约在ｇ＝１．９８处出现的超精细结构ＥＳＲ信号表明Ｖ以分散的不流动的Ｖ￣（４＋）形式存在，化学分析结果表明骨架上Ｔｉ和Ｖ原子相互间不排斥。     

聚芳醚酮膜的溶剂吸附与诱导结晶行为

研究了聚芳醚酮系列在１，２－二氯乙烷中的吸附，及溶剂与温度诱导结晶行为。得到６０℃时的最大吸附量Ｃ∞及假扩散系数Ｄ为：ＰＥＥＫ，Ｃ∞＝４６％，Ｄ＝３．１０×１０＾－１２ｍ＾２·ｓ＾－１；ＰＥＥＫＫ，Ｃ∞＝５０％，Ｄ＝６．５７×１０＾－１２ｍ＾２·ｓ＾－１；ＰＥＫＫ，Ｃ∞＝５５％，Ｄ＝９．４１×１０＾－１２ｍ＾２·ｓ＾－１。实验表明，吸附及脱附行为均与分子链刚性或羰基含量有关，膜的分子链受溶剂作用而     

镧积累对黄褐土中主要微生物类群数量的影响

模拟在黄褐土中长期使用稀土产生的镧积累，获得了三种主要土壤微生物类群和三种主要生理类群的剂量—反应曲线。土壤中５％～５０％吸附容量的镧都对细菌总数产生抑制作用，２０％吸附容量以下的镧对放线菌产生刺激作用，直至５０％吸附容量对真菌都产生强烈刺激作用，３０％时产生最大刺激作用。镧积累在吸附容量１０％以下时对好气性纤维素分解细菌产生刺激作用，直至５０％都对纤维素分解真菌产生刺激作用；１０％吸附容量以下对氨化微生物刺激作用不明显，但１０％以上对其产生强烈的抑制作用。     

La,Ce,Nd和Pr对RE（NiCoMnTi）5贮氢合金电化学性能的作用机理

系统地研究了稀土（ＲＥ＝Ｌａ１－ｘ－ｙ－ｚＣｅｘＮｄｙＰｒｚ）对贮氢合金ＲＥ（ＮｉＣｏＭｎＴｉ）５电化学性能的影响。结果表明，Ｌａ、Ｃｅ、Ｎｄ和Ｐｒ比例对合金性能有显著影响，ＲＥ＝Ｌａ０．４Ｃｅ０．１Ｎｄ０．２Ｐｒ０．３时，对应合金具有最高放电容量，为２９０ｍＡｈ／ｇ，并有较好的循环寿命。从原子结构和性质角度分析了Ｌａ，Ｃｅ，Ｎｄ和Ｐｒ作用的机理。     

2—（5—溴—2—吡啶偶氮）—5—二乙氨基酚树脂相分光光度法测定铁矿中…

本文介绍了２－（５－溴－２－吡啶偶氮）－５－二乙氨基酚（５－Ｂｒ－ＰＡＤＡＰ）与稀土元素在ｐＨ８．０～１１．０时，形成１：４红紫色络合物，加入非离子表面活性剂Ｔｗｅｅｎ－８０＾［１］后，可被７１７型强碱性阴离子树脂定量吸附，其最大吸收位于６２０ｎｍ处；摩尔吸光系数为９．２×１０＾５Ｌ·ｍｏｌ＾－１·ｃｍ＾－１；ＲＥｘＯｙ含量在０～１０μｇ／５０ｍｌ范围内符合比尔定律；回收率达到９９％～１０３％。     

八乙墓卟啉和四苯基卟啉合钌（Ⅱ）及锇（Ⅱ）的二氧加合物的红外光谱

ＯＥＰ（八乙基卟啉阴离子）和ＴＰＰ（四苯基卟啉阴离子）合钌（Ⅱ）和锇（Ⅱ）的二氧加合物由ｍａｔｒｉｘ分离技术得到（Ｔ＝２０－４３Ｋ，Ｐ＝１０－５－１０－６ｔｏｒｒ）．为了确定ｖ（Ｏ２）带的归属应用了同位素取代法１６Ｏ２／１８Ｏ２．ＩＲ谱说明对于钌的两种加合物（指ＯＥＰ和ＴＰＰ）都有两种异构体，其Ｖ（１６Ｏ２）频率为：Ｒｕ（ＯＥＰ）Ｏ２，１１４１和１１０３ｃｍ－１；Ｒｕ（ＴＰＰ）Ｏ２，１１６７和１１１４ｃｍ－１．Ｏｓ（ＴＰＰ）Ｏ２只生成一种异构体，ｖ（１６Ｏ２）＝１０９０ｃｍ－１，异构体ｖ（１６Ｏ２）：［Ｒｕ（ＯＥＰ）Ｏ２］，１１４１ｃｍ－１，［Ｒｕ（ＴＰＰ）Ｏ２］，１１６７ｃｍ－１，这些加合物约在１００Ｋ时分解，它们的结构指定为ｅｎｄｏｎ，而异构体［Ｒｕ（ＯＥＰ）Ｏ２］，１１０３ｃｍ－１，［Ｒｕ（ＴＰＰ）Ｏ２］，１１１４ｃｍ－１和［Ｏｓ（ＴＰＰ）Ｏ２］，１０９０ｃｍ－１，在２４０—２７０Ｋ分解，它们的结构指定为桥联二聚体．在加合物中，将ＯＥＰ换成ＴＰＰ引起的钌加合物ｖ（Ｏ２）频率的改变比铁和钴加合物更大．ｖ（Ｏ２）相对强度的变化顺序为：Ｆｅ（Ⅱ）→Ｒｕ（Ⅱ）→Ｏｓ（Ⅱ）．     

纳米级TiO_2粉体的制备研究Ⅰ.pH值的影响

采用无机盐作为前驱物，利用溶胶凝胶超临界流体干燥（ＳＣＦＤ）法，制备出大孔、高比表面纳米级ＴｉＯ２超细粉。详细考察了初始水凝胶ｐＨ值对ＴｉＯ２超细粉形貌、晶相、颗粒大小、比表面积及孔结构等的影响。实验结果发现：当在酸性环境中，所制得的ＴｉＯ２超细粉的比表面积随着ｐＨ值的减小而增大；而在碱性环境中，则随着ｐＨ值的增大而增大。ＴｉＯ２超细粉的比表面积和孔体积由ｐＨ为６．５时的ＳＢＥＴ＝１４２．２ｍ２·ｇ１，ＶＰＮ＝０．４５ｃｍ３·ｇ１，增大到ｐＨ值为１３．０时的ＳＢＥＴ＝４２５．６ｍ２·ｇ１，ＶＰＮ＝１．７９ｃｍ３·ｇ１，且颗粒分布均匀狭窄，颗粒间的三维网络织构更为规整清晰。     

酸性溶液中甲基红在钢表面的吸附

甲基红等有机染料类化合物可以作为金属缓蚀剂[1- 2 ] 。本文依据电化学测量结果 ,拟建立一种吸附模型 ,以便于讨论酸性水溶液中甲基红在钢表面的吸附等温式 ,解释甲基红在钢表面的吸附行为及其对钢电化学腐蚀的影响。1　实验部分所用试剂见文献 (2 )。工作电极为钢电极(2 0 #碳钢 ) ,以环氧树脂封涂绝大部分 ,余 0 3ｃｍ2(1 2ｃｍ×0 2 5ｃｍ)作为研究表面。使用前用水磨砂纸磨光亮 ,并用蒸馏水洗净 ,擦干备用。以大面积铂片为辅助电极 ,饱和甘汞电极 (ＳＣＥ)为参比电极 ,试验所测的所有电极电位均是相对于ＳＣＥ的数值。极化曲线、交…     

前沿分析法研究对-羟基苯甲酸印迹整体柱的热力学行为

采用矩形前沿分析法对原位聚合的对-羟基苯甲酸印迹整体柱的热力学吸附等温线进行了测定. 印迹整体柱的吸附等温线是分别以乙腈、甲醇、 四氢呋喃和含有体积分数分别为1%, 3%, 5%和7%乙酸的乙腈为流动相以及在以甲醇为流动相时柱温分别为20, 40和50 ℃的条件下测定的. 吸附等温线表明, 印迹整体柱对模板分子的吸附能力比其结构类似物(邻-羟基苯甲酸)的吸附能力强. 用双Langmuir方程对不同条件下得到的实验数据进行拟合, 得到模板分子和邻-羟基苯甲酸在印迹整体柱各种吸附位点上的饱和吸附量和键合常数, 结果表明, 流动相中乙酸含量、有机溶剂的性质和柱温对模板分子容量因子的影响比对邻-羟基苯甲酸的大, 造成印迹聚合物的选择性随条件的变化而发生了明显的改变.     

Adsorption of phthalic acid and salicylic acid and their effect on exchangeable Al capacity of variable-charge soils

Low-molecular-weight (LMW) organic acids may be adsorbed by soils and the adsorption could affect their biodegradation and efficiency in many soil processes. In the present study, the adsorption of phthalic acid and salicylic acid and their effect on the exchangeable Al capacity of variable-charge soils were investigated. The results indicated that phthalic acid and salicylic acid were adsorbed by four variable-charge soils to some extent, oxisols showed a greater adsorption capacity for organic acids than ultisols, and the ability of the four variable-charge soils to adsorb the organic acids at different pH generally followed the order Kunming oxisol > Xuwen oxisol > Jinxian ultisol > Lechang ultisol, which was closely related to their content of free iron oxides and amorphous iron and aluminum oxides. The adsorption of organic acids induced a decrease in the zeta potentials of soils and oxides. Goethite has greater adsorption capacity for organic acid than Xuwen oxisol and the adsorption of organic acids resulted in a bigger decrease in the zeta potential of goethite suspensions. After free iron oxides were removed, less organic acid was adsorbed by Xuwen oxisol and no change was observed in zeta potential for the soil suspension after organic acid was added. The presence of phthalic acid increased the capacity of exchangeable Al and the increment in the four variable-charge soils also followed the order Kunming oxisol > Xuwen oxisol > Lechang ultisol and Jinxian ultisol. The presence of salicylic acid increased the capacity of exchangeable Al in Kunming oxisol, Xuwen oxisol, and Jinxian ultisol, but decreased it in Lechang ultisol due to less adsorption of the acid and formation of soluble Al-salicylate complexes in solution. After free iron oxides were removed, less effect of organic acid on exchangeable Al was observed for Xuwen oxisol, which further confirmed that the iron oxides played a significant role in organic acid adsorption and had a consequent effect on the capacity of exchangeable Al in variable-charge soils. Therefore, the higher the content of iron oxides, the greater the adsorption of organic acids by soils and the greater the increase in soil exchangeable Al induced by the organic acids.     

FTIR Studies of the Adsorption of Acetic Acid on Silicas

A range of cesium doped silica samples (0.15 – 0.90 mmol g^–1) have been characterized using a combination of deuterium exchange and adsorption of acetic acid. FTIR results show a strong correlation between the carboxylate formation on acetic acid adsorption and catalyst activity. Cesium loadings of > 0.3 mmol g^–1 do not give any increased acetic acid adsorption, suggesting a saturation of the silica exchange capacity. Deuterium exchange studies demonstrate that 35% of the surface silanol groups on the fresh silica are rapidly exchanged with deuterated water at room temperature.     

Behavior of <Superscript>134</Superscript>Cs, <Superscript>90</Superscript>Sr,and <Superscript>238</Superscript>Pu in different Syrian soils

The experiment aimed to evaluate the vertical migration of ¹³⁴Cs, ⁹⁰Sr and ²³⁸Pu in the main types of Syrian soils; entisol, inceptisol, alluvial (rock outcrops) and gypsiferous soils, using soil columns through which the aqueous solution of the radionuclides percolated. The results show that the vertical migration of the studied radionuclides through the soil profile depend on the radionuclide and the soil type. More than 97% of ¹³⁴Cs and ²³⁸Pu concentrated in the upper 2 cm of the entisol, inceptisol, and alluvial soils, whereas only 46.2% to 68.6% of the ⁹⁰Sr was retained in the upper 2 cm of these soils. The vertical migration of the studied radionuclides in the gypsiferous soil was different from the other soils. The distribution of the radionuclides in the gypsiferous soil was irregular through the soil profile and reached the deeper layer of the soil. This may be due to its physical characteristics; poor structure stability, high permeability and low retention capacity.     

Influence of the mobile phase composition on the adsorption isotherms of an amino-acid derivative on immobilized bovine serum albumin

Summary The saturation capacity of columns packed with bovine serum albumin immobilized on silica has been determined for the N-benzoyl derivative of leucine at different compositions of a 1-propanol/water mobile phase. In all cases it has been found that the equilibrium adsorption data are well accounted for by a biLangmuir isotherm. The experimental data are consistent with the assumption that the column saturation capacity of the chiral selective sites as well as the saturation capacity of the non-selective sites are independent of the 1-propanol concentration in the range 0–10%.     

Adsorption and desorption of copper and zinc in the surface layer of acid soils

The environmental and health effects of the contamination of soils by heavy metals depend on the ability of the soils to immobilize these contaminants. In this work, the adsorption and desorption of Cu and Zn in the surface layers of 27 acid soils were studied. Adsorption of Cu(II) from 157-3148 mumol L(-1) solutions was much greater than adsorption of Zn(II) from solutions at the same concentration. For both Cu and Zn, the adsorption data were fitted better by the Freundlich equation than by the Langmuir equation. Multiple regression analyses suggest that Cu and Zn adsorption depends to a significant extent on pH and CEC: for both metals these variables accounted for more than 80% of the variance in the Freundlich pre-exponential parameter K(F), and pH also accounted for 57% of the variance in 1/n for Zn and, together with carbon content, for 41% of the variance in 1/n for Cu. The percentage of adsorbed metal susceptible to desorption into 0.01 M NaNO3 was greater for Zn than for Cu, but in both cases depended significantly on pH, decreasing as pH increased. In turn, both pH(H2O) and pH(KCl) are significantly correlated with cation exchange capacity. Desorption of metal adsorbed from solutions at relatively low concentration (787 mumol L(-1)) exhibited power-law dependence on Kd, the quotient expressing distribution between soil and soil solution in the corresponding adsorption experiment, decreasing as increasing Kd reflected increasing affinity of the soil for the metal. The absence of a similarly clear relationship when metal had been adsorbed from solutions at relatively high concentration (2361 mumol L(-1)) is attributed to the scant between-soil variability of Kd at these higher concentrations. In general, adsorption was greater and subsequent desorption less in cultivated soils than in woodland soils.     

The effect of sorption properties of soil minerals on the vertical migration rate of cesium in soil

The vertical distribution of¹³⁷Cs is shown for two types of soil: silly loamy “supposed” soil and silly lessive one, slightly eroded, occuring in the vicinity of Lublin (Eastern Poland). Based on the distribution data the vertical migration rates of¹³⁷Cs are calculated for both soils. These rates are found to be 0.045 and 0.3 cm/year respectively. The percent contribution of¹³⁷Cs originating from the damaged reactor in Chernobyl is also calculated. The kinetics of cesium adsorption and its adsorption isotherms on minerals separated from the tested soils are also studied. The sorption of Cs on soil minerals markedly affects the migration rate of¹³⁷Cs in soil. The experimental results indicate that, among the extracted mineral fractions, the largest adsorption takes place on marls from the silly loamy soil. This work is supplemented by results of a physicochemical analysis of the studied soils.     

Simulation of temperature and moisture fields around a single borehole ground heat exchanger: effects of moisture migration and groundwater seepage

This paper aims to investigate the effects of moisture migration and groundwater seepage on the heat transfer capacity of ground heat exchangers in stratified soils. A three-dimensional unsteady groundwater flow and heat transport model was established using finite volume method. Sixteen cases with different model considerations and initial soil conditions were simulated based on the proposed model. A group of 8 cases considering only transverse moisture migration and another group considering both transverse and longitudinal moisture migration were compared. The heat and moisture fields after 30 days of operation reveal that considering the change of saturation caused by vertical moisture transfer, the soil temperature field will be affected, but borehole outlet temperature was less influenced. The absolute value of outlet temperature difference between corresponding cases in the two groups is only about 0.2 °C. The position of groundwater seepage and arrangement of unsaturated soil layers with different degrees of saturation on heat transfer capacity of vertical ground heat exchanger were further explored. The results show that the longitudinal moisture migration would be made more influential by the existence of seepage layer, because the average relative deviation of inlet and outlet temperature difference between the corresponding cases of Group 1 and Group 2 was 1.34% when setting seepage layer and was 0.44% when without seepage layer. Heat transfer performance of borehole heat exchanger is also affected by the location of seepage layer. The average relative deviation of inlet and outlet temperature difference between the reference case and cases with seepage in the top, middle and bottom layers is 34.18%, 25.08% and 16.82%, respectively. The arrangement of unsaturated soil layers also has a certain effect. When the soil layer with low degree of saturation is located in the upper layer of soil, heat transfer capacity is better.

     

Microwave-assisted solvent extraction of the herbicide methabenzthiazuron from soils and some soil natural organic and inorganic constituents. Influence of environmental factors on its extractability

A microwave-assisted solvent extraction (MASE) method for the determination of methabenzthiazuron (MBT) in soil samples by HPLC-DAD (diode array detection) was evaluated. Spiked soil samples having different physico-chemical properties, and selected soil-derived matrices with diverse MBT adsorption capacity, characterized by their Freundlich equation Kf values, were used to verify the method applicability to a broad range of different soils. The spiking procedure was considered a crucial point to reproduce as closely as possible the solute-soil adsorption taking place in the natural environment. Ageing effects, where the compound could diffuse into inaccessible locations within the soil matrix in view of its great stability, were considered of particular concern. In spite of the heterogeneous physico-chemical properties of soils under study, recoveries were greater than 90%. Performance of the MASE procedure correlated highly with the adsorption capacity of soil-derived matrices: the lowest recoveries were for illite (67-73%), among the mineral surfaces, and for a humic acid (67-72%), among the organic fractions. Intra-assay variation for each type of sample soil range from 0.40 to 3.89%(RSD). Limits of detection and quantification were 0.047 and 0.15 microg g(-1), respectively. Analyte residence time was not a very significant factor on the extractability.     

毛细管电泳-电致化学发光法测定土壤中的多抗霉素B

以稀土铕离子(Ⅲ)掺杂的类普鲁士蓝膜(Eu-PB)修饰铂电极为工作电极,采用毛细管电泳-电致化学发光法(CE-ECL)对土壤中的多抗霉素B进行检测.分别对毛细管电泳分离条件和电致化学发光检测条件进行优化,并探讨了体系产生电致化学发光的机理.在优化实验条件下,多抗霉素B可在4 min内得到分离,其ECL强度值与多抗霉素B...