Chemistry Department, Florida Institute of Technology, Melbourne, Florida 32901, USA.
Environ Sci Technol. 2011 May 1;45(9):3895-901. doi: 10.1021/es103946g. Epub 2011 Apr 1.
The formation of silver nanoparticles (AgNPs) via reduction of silver ions (Ag(+)) in the presence of humic acids (HAs) under various environmentally relevant conditions is described. HAs tested originated from the Suwannee River (SUW), and included samples of three sedimentary HAs (SHAs), and five soils obtained across the state of Florida. The time required to form AgNPs varied depending upon the type and concentration of HA, as well as temperature. SUW and all three SHAs reduced Ag(+) at 22 °C. However, none of the soil HAs formed absorbance-detectable AgNPs at room temperature when allowed to react for a period of 25 days, at which time experiments were halted. The appearance of the characteristic surface plasmon resonance (SPR) of AgNPs was observed by ultraviolet-visible spectroscopy in as few as 2-4 days at 22 °C for SHAs and SUW. An elevated temperature of 90 °C resulted in the accelerated appearance of the SPR within 90 min for SUW and all SHAs. The formation of AgNPs at 90 °C was usually complete within 3 h. Transmission electron microscopy and atomic force microscopy images showed that the AgNPs formed were typically spherical and had a broad size distribution. Dynamic light scattering also revealed polydisperse particle size distributions. HAs appeared to colloidally stabilize AgNPs based on lack of any significant change in the spectral characteristics over a period of two months. The results suggest the potential for direct formation of AgNPs under environmental conditions from Ag(+) sources, implying that not all AgNPs observed in natural waters today may be of anthropogenic origin.
本文描述了在各种与环境相关的条件下,银离子(Ag(+))在腐殖酸(HAs)存在下被还原形成银纳米颗粒(AgNPs)的过程。所测试的 HAs 源自苏万尼河(SUW),包括三种沉积物 HAs(SHAs)和佛罗里达州各地获得的五种土壤的样本。形成 AgNPs 所需的时间取决于 HA 的类型和浓度以及温度。SUW 和所有三种 SHA 在 22°C 下还原 Ag(+)。然而,在允许反应 25 天的时间内,没有一种土壤 HAs 在室温下形成可检测到吸光度的 AgNPs,此时实验停止。通过紫外-可见光谱在 22°C 下仅在 2-4 天内观察到 SHA 和 SUW 的 AgNPs 的特征表面等离子体共振(SPR)的出现。升高温度至 90°C 导致 SUW 和所有 SHA 的 SPR 在 90 分钟内加速出现。在 90°C 下形成 AgNPs 通常在 3 小时内完成。透射电子显微镜和原子力显微镜图像显示,形成的 AgNPs 通常为球形且具有较宽的尺寸分布。动态光散射还揭示了多分散的颗粒尺寸分布。根据在两个月的时间内光谱特征没有任何明显变化,HAs 似乎胶体稳定了 AgNPs。研究结果表明,在环境条件下,Ag(+) 源可能直接形成 AgNPs,这意味着并非当今在天然水中观察到的所有 AgNPs 都可能具有人为来源。