Chemistry Department, Florida Institute of Technology, 150 West University Boulevard, Melbourne, Florida 32901, USA.
Environ Sci Technol. 2013 Jan 15;47(2):757-64. doi: 10.1021/es302305f. Epub 2012 Dec 28.
This study investigated the possible natural formation of silver nanoparticles (AgNPs) in Ag(+)-fulvic acid (FA) solutions under various environmentally relevant conditions (temperature, pH, and UV light). Increase in temperature (24-90 °C) and pH (6.1-9.0) of Ag(+)-Suwannee River fulvic acid (SRFA) solutions accelerated the appearance of the characteristic surface plasmon resonance (SPR) of AgNPs. The rate of AgNP formation via reduction of Ag(+) in the presence of different FAs (SRFA, Pahokee Peat fulvic acid, PPFA, Nordic lake fulvic acid, NLFA) and Suwannee River humic acid (SRHA) followed the order NLFA > SRHA > PPFA > SRFA. This order was found to be related to the free radical content of the acids, which was consistent with the proposed mechanism. The same order of AgNP growth was seen upon UV light illumination of Ag(+)-FA and Ag(+)-HA mixtures in moderately hard reconstituted water (MHRW). Stability studies of AgNPs, formed from the interactions of Ag(+)-SRFA, over a period of several months showed that these AgNPs were highly stable with SPR peak reductions of only ~15%. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements revealed bimodal particle size distributions of aged AgNPs. The stable AgNPs formed through the reduction of Ag(+) by fulvic and humic acid fractions of natural organic matter in the environment may be transported over significant distances and might also influence the overall bioavailability and ecotoxicity of AgNPs.
本研究在各种与环境相关的条件下(温度、pH 值和紫外光),考察了银离子(Ag(+))-富里酸(FA)溶液中银纳米颗粒(AgNPs)可能的自然形成。Ag(+) -苏万尼河富里酸(SRFA)溶液的温度(24-90°C)和 pH 值(6.1-9.0)的升高加速了 AgNPs 特征表面等离子体共振(SPR)的出现。在不同 FA(SRFA、Pahokee 泥炭富里酸、PPFA、北欧湖富里酸、NLFA)和苏万尼河腐殖酸(SRHA)存在下,通过还原 Ag(+)形成 AgNP 的速度遵循 NLFA > SRHA > PPFA > SRFA 的顺序。该顺序与酸的自由基含量有关,这与提出的机制一致。在中等硬度重制水中,Ag(+) -FA 和 Ag(+) -HA 混合物经紫外光照射后,AgNP 的生长也呈现出相同的顺序。在几个月的时间里,对由 Ag(+) -SRFA 相互作用形成的 AgNPs 的稳定性研究表明,这些 AgNPs 具有高度稳定性,SPR 峰值降低仅约 15%。透射电子显微镜(TEM)和动态光散射(DLS)测量表明,老化 AgNPs 的粒径分布呈双峰模式。在环境中,天然有机物的腐殖酸和富里酸部分通过还原 Ag(+)形成的稳定 AgNPs 可能会被运输到很远的距离,也可能会影响 AgNPs 的整体生物利用度和生态毒性。
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