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).     

Stochastic evaluation of fluvial to marginal marine sealing facies

Hydrocarbon top seal analyses are particularly difficult in fluvial and marginal marine settings. Although these settings often contain beds comprised of a low-permeability, clay-rich lithology associated with high quality seals, their presence does not guarantee an effective seal because individual beds within the stratal unit may be laterally discontinuous. Lateral facies changes, truncation of fine-grained beds, or the presence of crevasse splays may provide cross-stratal migration pathways, reducing the effective sealing capacity to a magnitude less than the closure height.     

基于公平性的水环境容量分配研究——以沱江流域为例

公平与效益是容量分配的两个重要原则.在我国目前采用的水环境容量无偿分配方式下,公平原则是需遵循的首要原则,在公平的基础上追求效益.以沱江流域为对象,综合考虑涉及区域的社会、经济、自然等客观因素,筛选指标确定系数对流域容量进行分配.应用经济学中衡量收入公平的基尼系数概念,对分配结果的公平性进行评估,给出综合体现社会性、经济性和历史性的水环境容量分配方案.     

基于非线性动力学模型的旅游生态容量分析

近年来,大量增加的游客给景区的旅游生态容量带来了较大的压力,矛盾日渐突出。为了实现景区的环境保护与可持续发展,研究游客活动量与景区旅游生态容量之间的关系是十分必要的。本文从非线性动力学观点出发,构建二者非线性动力学模型,并进行平衡态分析。研究结果表明:(1)系统要达到可持续发展,必须建立在景区环境的自我更新能力及人工恢复程度之和大于外界污染水平,且游客的增长率必须保持在较低水平的基础上;(2)景区旅游生态容量的承载力是有限的,所能容纳的游客也是有限的,超过一定的限度就会引起生态系统失衡。采取严格控制游客量,加强对景区内外环境的保护和改善、提升游客素养等措施,对于系统的协调发展至关重要。     

海上风电嵌岩桩水平抗力影响因素研究

桩基础是我国海上风电工程中应用最为广泛的基础形式,其中嵌岩桩因其施工难度大,承载力高备受关注。与其他类型的桩基础不同,嵌岩桩的水平承载力不仅受到围岩强度的影响,更与其成桩质量与灌浆材料的强度相关。采用有限元方法分析了嵌岩深度、桩基直径与壁厚、桩身倾斜度等多种因素对嵌岩桩水平承载力的影响,提出了确定嵌岩桩水平极限抗力的标准。研究表明：桩与围岩间的灌浆环会先于桩身发生破坏,因此可将灌浆环受拉破坏作为判断嵌岩桩达到水平极限承载力的标准;桩身倾斜度对嵌岩桩的水平极限承载力影响较大,直径和壁厚的增加,均能提高桩基的水平承载力。     

真空预压联合碎石桩加固港口吹填堆场地基的试验研究

在港口工程建设中,快速加固超软弱的吹填地基,采用真空预压法是一个经济有效的方法,再联合以碎石桩加固则能进一步提高地基的承载力、减少地基工后沉降.通过真空预压联合碎石桩加固地基的现场试验以及观测资料的分析,得出真空预压联合碎石桩加固后地基的承载力特征值由原天然地基的60 kPa左右提高到220 kPa,计算结果表明打碎石桩后的地基变形模量Esp与真空预压后的Ea相比提高了1倍,联合碎石桩加固后的地基沉降量比仅经过真空预压的地基减少1/3.     

水流挟沙力分析与探讨

水流挟沙力是悬沙输运计算中非常重要的问题之一,其计算形式常采用基于重力理论的经验和半经验公式.本文针对目前广泛采用的2种挟沙力关系式,选用4组实验水槽数据和2组天然河道实测资料分别讨论其关联性.结果表明,不论指数m在其取值范围内取何值,2个表达式皆存在一定的函数关联性.且当指数m取1和2/3时,直接表现出很强的线性关联.在挟沙力计算中采用流速的平方关系式,物理意义清晰,形式简单.在实际应用时,适当选取系数,挟沙力采用形式简单的平方关系式是完全可行的.     

昆承湖水流水质计算分析

在模拟昆承湖水流流场的基础上,模拟化学需氧量(CODMn)在湖水中的扩散情况;同时,利用昆承湖实测资料和水质的浓度场计算结果,得到其枯季环境容量.可以看出,昆承湖的流速较小,且方向由西北流向东南,可能是受长江径流和湖底西北高东南低的地形特征影响;从昆承湖的CODMn浓度实测值和计算值中,可以看出小于其水环境质量标准限值.这将进一步为实现常熟市湖泊水环境质量的不断提高、生态状况的持续改善与科学管理提供依据.