National Institute of Oceanography (CSIR), 8-44-1/5, Plot No. 94, Chinawaltair, Visakhapatnam, 530003, India.
Anal Chim Acta. 2010 Feb 5;659(1-2):137-43. doi: 10.1016/j.aca.2009.11.043. Epub 2009 Nov 24.
Diffusion coefficients of Cd-humate complexes are dependent on pH and [Cd]/[Humic] Acid (HA)] ratio in a Cd-HA system. These two factors mainly control the mass transport and complexation kinetics of Cd that may influence bioavailability and toxicity of Cd species in environmental systems. Determination of diffusion coefficients of Cd-HA systems by Scanned stripping voltammetry and dynamic light scattering techniques can provide a better understanding of the systems and can be very useful for extracting other speciation parameters of the systems. This study revealed that Cd(2+) ion along with small dynamic Cd complexes was predominantly present in a Cd-HA system at pH 5 with high diffusion coefficients. HA molecules were in aggregated form at pH 5. However, HA molecules were in disaggregated form at pH 6 and concentrations of Cd(2+) ion and small Cd-dynamic complexes decreased with a decrease in diffusion coefficients of Cd complexes at this pH due to formation of Cd-humate complexes. No further decrease in the hydrodynamic radii of HA was observed with the increase of pH from 6 to 7. The Cd-humate system partially lost its lability at pH 7. Conditional stability constants were calculated for Cd-humate complexes by combining the diffusion coefficient data obtained by two techniques. The log K values calculated in this study are in good agreement with the data available from the literature.
Cd-腐殖酸配合物的扩散系数取决于 Cd-HA 体系中的 pH 值和 [Cd]/[腐殖酸](HA)比值。这两个因素主要控制 Cd 的物质传输和络合动力学,这可能会影响环境系统中 Cd 物种的生物利用度和毒性。通过扫描剥离伏安法和动态光散射技术测定 Cd-HA 体系的扩散系数,可以更好地了解这些体系,并且对于提取体系的其他形态参数非常有用。本研究表明,在 pH 5 时,Cd(2+)离子与小动态 Cd 配合物主要存在于 Cd-HA 体系中,具有较高的扩散系数。在 pH 5 时,HA 分子呈聚集态。然而,在 pH 6 时,HA 分子呈解聚态,由于 Cd-腐殖酸配合物的形成,Cd(2+)离子和小 Cd-动态配合物的浓度降低,Cd 配合物的扩散系数也随之降低。随着 pH 值从 6 增加到 7,HA 的水动力半径没有进一步减小。在 pH 7 时,Cd-腐殖酸体系部分失去了其不稳定性。通过结合两种技术获得的扩散系数数据,计算了 Cd-腐殖酸配合物的条件稳定常数。本研究中计算的 log K 值与文献中可用的数据吻合良好。