Kinetic and equilibrium studies of copper-dissolved organic matter complexation in water column of the stratified Krka River estuary (Croatia)

An interaction of dissolved natural organic matter (DNOM) with copper ions in the water column of the stratified Krka River estuary (Croatia) was studied. The experimental methodology was based on the differential pulse anodic stripping voltammetric (DPASV) determination of labile copper species by titrating the sample using increments of copper additions uniformly distributed on the logarithmic scale. A classical at-equilibrium approach (determination of copper complexing capacity, CuCC) and a kinetic approach (tracing of equilibrium reconstitution) of copper complexation were considered and compared. A model of discrete distribution of organic ligands forming inert copper complexes was applied. For both approaches, a home-written fitting program was used for the determination of apparent stability constants (K_i^equ), total ligands concentration (L_iT) and association/dissociation rate constants (k_i¹,k_i^- 1).A non-conservative behaviour of dissolved organic matter (DOC) and total copper concentration in a water column was registered. An enhanced biological activity at the freshwater–seawater interface (FSI) triggered an increase of total copper concentration and total ligand concentration in this water layer. The copper complexation in fresh water of Krka River was characterised by one type of binding ligands, while in most of the estuarine and marine samples two classes of ligands were identified. The distribution of apparent stability constants (log K₁^equ: 11.2–13.0, log K₂^equ:8.8–10.0) showed increasing trend towards higher salinities, indicating stronger copper complexation by autochthonous seawater organic matter.Copper complexation parameters (ligand concentrations and apparent stability constants) obtained by at-equilibrium model are in very good accordance with those of kinetic model. Calculated association rate constants (k₁¹:6.1–20 × 10³ (M s)^− 1, k₂¹: 1.3–6.3 × 10³ (M s)^− 1) indicate that copper complexation by DNOM takes place relatively slowly. The time needed to achieve a new pseudo-equilibrium induced by an increase of copper concentration (which is common for Krka River estuary during summer period due to the nautical traffic), is estimated to be from 2 to 4 h.It is found that in such oligotrophic environment (dissolved organic carbon content under 83 µM_C, i.e. 1 mg_CL^− 1) an increase of the total copper concentration above 12 nM could enhance a free copper concentration exceeding the level considered as potentially toxic for microorganisms (10 pM).     

珠江口及附近海域夏季氮的化学形式分布研究

根据1998年夏季对珠江河口及附近海域的水质调查，研究了氮的各种化学形式的空间分布特征、相关系数和环境条件的影响。结果表明：珠江河口中，无机氮含量很高，占总氮的85％；而硝酸氮占无机氮的95％，NO2^--N和NH4^ -N含量很低。在外海，则以有机氮为主，占总氮的80％。NH4^ -N和NO2^--N在伶仃洋河口中部出现最大值，在外海的值最小；其它形式的氮从伶仃洋内河口到外海，其浓度都逐渐降低。NO3^--N是各种形式氮中的主要因素，它与各形式氮之间具有良好的相关性；NH4^ -N和NO2^--N与其它形式氮之间的相关性都很差，而其余各种形式氮之间都有较好的相关性。涨潮时不利于污染物的扩散；与小潮相比，大潮时伶仃洋河口中部表层氮的浓度偏高。     

自然金的化学分离方法

作者用物理方法和化学方法相结合分离了九个矿区的自然金,效果良好,其纯度一般达99％以上。X光、化学分析和物性测试表明,化学处理对自然金的物性、化学成分和结构无明显影响。文中分别对几种矿物组合的化学分离方法作了具体介绍。     

Tafoni on coastal slopes,South Devon,U.K.

Cavernous weathering (tafoni development) occurs on coastal slopes in greenschist bedrock at elevations up to 40 m above sea level. The freshly weathered surfaces of the cavern interiors are irregular in morphology, discordant to major rock structure, formed by substantially weakened rock and associated with granular weathering debris. The weathering debris contains soluble elements in proportions similar to those present in seawater, and the penetration of elements associated with sea salts into the weathering surface to estimated depths of at least 0·1–0·2 m is indicated by the presence of chlorine. Scanning electron microscopy and microprobe analyses suggest that rock breakdown occurs principally through limited chemical weathering at grain boundaries. The mechanism for the emplacement of marine salts within sheltered rock surfaces in the tafoni is postulated to be a combination of dry deposition under turbulent atmospheric conditions and wetting by coastal fog.     

Physicochemical properties of fine aerosols at Plan d'Aups during ESCOMPTE

The physical and chemical properties of aerosol particles were investigated at Plan d'Aups, one of the ESCOMPTE sites located in the St. Baume mountain area (700 m a.s.l.), 50 km east of Marseilles (France). The site is ideally located for assessing the vertical and horizontal extent of the pollution plume from the Marseilles–Berre area.Our study showed that polluted air masses from the Marseilles–Berre area are advected to Plan d'Aups in the early afternoon. Average daily concentration of particles reaches up to 40 μg m⁻³ while 1-h average particle number concentration is greater than 30,000 cm⁻³. Most of the particle mass is composed of SO₄²⁻ and organic carbon (OC). The chemical properties of the particles revealed that an additional source, possibly from the industrial area of Gardanne, contributes to the aerosol mass. This last source is characterised by significant emissions of elements, such as Zn, V, Al and Si.In addition to transport, we found that gas-to-particle conversion takes place at the interface between the free troposphere and the boundary layer. We estimated that on average, 30% of the particle number is accounted for by direct nucleation. This is potentially a major aerosol source to the free troposphere.     

Effect of chemical fertilizers on the fractionation of Cu,Cr and Ni in contaminated soil

Effect of chemical fertilizers (urea, NH₄Cl, Ca(NO₃)₂, KCl and KH₂PO₄) on the fractionation of Cu, Cr and Ni was studied by a 4-month incubation experiment. Using sequential extraction procedure, it was found that the application of fertilizers could change the distribution of Cu, Cr and Ni in the fractions of soil. Applying urea (CO(NH₂)₂) significantly decreased the concentrations of Cu, Cr and Ni in water soluble plus exchangeable (WE) fraction, but increased those in Fe–Mn oxides bound (FM) fraction (p < 0.01). However, application of NH₄Cl caused an increase in the WE fraction by 27.7% for Cu, 111.5% for Cr and 20.4% for Ni. The CO(NH₂)₂ raised the soil pH from 4.51 to 4.96, whereas NH₄Cl lowered the pH of soil by 0.44 units. The WE fraction of the three heavy metals was significantly increased, while the FM fraction was significantly decreased by adding KCl (p < 0.01). Moreover, the supply of KH₂PO₄ reduced the WE and carbonate bound (CB) fractions of Cu, Cr and Ni in the soil, however, it raised Cu and Ni in the residual (RS) fraction and Cr in the FM fraction. In addition, the mobility index indicated that KCl and NH₄Cl increased the mobility of Cu, Cr and Ni in the soil, whereas urea and KH₂PO₄ decreased the mobility of the three metals in the soil. These results suggest that applying chemical fertilizers does not only provide plant nutrients, but may also change the speciation and mobility of heavy metals in the soil.     

化学试剂管理数据库的设计与开发——以华东地质学院化学试剂管理数据库为例

论述了采用客户／服务器模型设计、实现化学试剂管理数据库的方法和技术。通过网络平台完成院各部门的年度化学试剂申报、统计和管理工作，可以充分发挥校园网的通讯优势。解决了长期存在的化学试剂手工管理所带来的效率低、申报不及时甚至重复申报等问题。     

农业生态的化学元素分类及其与作物优质高产的关系

利用国家科学技术成果，并根据国内外研究现状，将103个化学元素分成对作物生长发育、增产起显著作用、起一定作用、起有害作用和起未知作用4个农业生态元素类型，进而论述了它们与作物优质高产的关系。