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.     

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.     

无标度网络上队列资源分配研究

研究了节点队列资源有限的条件下,无标度网络上的信息流动力学过程,发现了网络由自由流通到拥塞的相变现象,提出了一种基于节点度的队列资源分配模型.模型的核心是使节点i的队列长度与k^β_i成正比(k_i为节点i的度,β为分配参数).仿真结果表明,在网络使用最短路径算法进行信息包传送的条件下,β近似等于1.25时队列资源分配最合理,网络容量最大,且该最佳值与队列总资源多少以及网络的规模无关.     

珠江口八大口门径、潮作用动力过程研究

根据2006—2007年期间在珠江口八大口门进行的丰水期大、中、小潮3个航次、平水期和枯水期各1个航次的全潮同步水文观测资料,分析了八大口门的潮流特性、涨落潮通量等特征,并建立了逐时潮差与流量的相关关系。在丰水期小潮期间,八大口门受强热带风暴碧利斯带来的强降雨的影响,潮流特性、断面流量等水文特征出现较大的变化,逐时潮差与流量的相关关系与其他航次相比表现出不同的规律。在无强径流影响下,逐时潮差与流量的相关关系用线性方程拟合,相关性较好;但在强径流影响下,则采用二次多项式拟合较为合适,且拟合曲线的左右侧表现出涨、落潮过程的区别。     

东海陆扰海域铜、铅、锌、镉重金属排海通量及海洋环境容量估算

汇总并分析了20世纪80年代初以来东海陆扰海域重金属排海通量年变化规律及主要来源,应用多介质海洋环境中重金属迁移-转化模型,估算了东海陆扰海域重金属海洋环境容量。20世纪80年代初以来,东海陆扰海域铜、铅、锌、镉排海总量整体上呈不对称的倒"U"形变化趋势,基本符合"环境库兹涅茨曲线",20世纪90年代达到最大值,当前排海总量仍高于20世纪80年代初期的水平。东海陆扰海域铜、铅、锌、镉污染物主要来源于以河流为主的陆源排放,其中88.0%左右来源于河流排放,7.5%左右来源于排污口,只有4.5%左右来源于大气沉降。长江流域排海通量占东海陆扰海域排海总量的比例最大,平均为92.4%左右,钱塘江流域平均只有3.9%左右,闽江流域平均只有3.7%左右。东海陆扰海域铜、铅、锌、镉污染物海洋环境容量分别约为17.0,4.7,113.1,0.71 kt/a。当前铅、锌、镉污染物排海总量没有超过东海陆扰海域海洋环境容量,但铜的排海总量超过其海洋环境容量大约8%。     

青岛市地质资源环境承载能力评价关键技术与应用

通过了解青岛市地质资源分布特征和区域地质环境条件,从地质资源和地质环境2个方面科学合理选取评价因子,建立评价指标体系,开展青岛市地质资源环境承载能力评价。评价结果显示,青岛市地质资源相对较匮乏,地质资源环境承载能力整体以强和较强为主,地质资源环境承载能力较弱的地区主要分布在环胶州湾地区、东部崂山山区及西海岸新区的西南部,地质资源环境承载能力弱的地区主要分布在李沧区以北及周边。分别从生产生活空间、农业生产空间及生态环境空间等方面提出了青岛市地质资源环境优化配置建议,为青岛市地质资源合理利用与地质环境安全保障提供科学依据。评价结果能够为区域国土空间规划提供建议。