Chen Zhuo, Westerhoff Paul, Herckes Pierre
Department of Civil and Environmental Engineering, Arizona State University, Tempe, Arizona 85287-1604, USA.
Environ Toxicol Chem. 2008 Sep;27(9):1852-9. doi: 10.1897/07-560.1.
The growing usage of nanomaterials is causing emerging concern regarding their environmental behavior in aquatic environments. A major need is the capability to detect and quantify nanomaterials in complex water matrices. Carbon60 fullerene is of special interest because of the widespread application of nanocarbon technology. The present study focuses on how to separate and concentrate fullerenes from water containing salts and organic matter and then quantify their concentrations using liquid chromatography coupled with mass spectrometry (LC/MS). The stable aqueous C60 aggregates (nC60) prepared in the present study were approximately 60 to 70 nm in diameter and had an ultraviolet (UV) extinction coefficient of 0.0263 L/mg-cm at 347 nm, which equated to a UV detection limit of 0.4 mg/L based upon an absorbance of 0.01 cm(-1). Ultraviolet analysis is not applicable to use in waters containing salts or organics (e.g., tap water) because of their interferences and potential to aggregate nC60. The LS/MS analysis detected C60 as single fullerene rather than aggregates. Three techniques were developed to separate and concentrate nC60 from ultrapure and tap water into toluene to facilitate LC/MS determination: Evaporation of sample to dryness; extraction using 20% NaCl into toluene; and solid-phase extraction. The first two methods had limitations for use in complex water matrices, but aqueous nC60 concentration as low as 300 ng/L in water were quantified using solid-phase extraction (SPE) separation method. This is the first publication on the application of extraction methods for nC60 from ultrapure and tap waters and determination of detection limits by LC/MS.
纳米材料使用的不断增加引发了人们对其在水生环境中环境行为的新关注。一个主要需求是能够在复杂的水基质中检测和量化纳米材料。由于纳米碳技术的广泛应用,碳60富勒烯特别受关注。本研究重点关注如何从含有盐和有机物的水中分离和浓缩富勒烯,然后使用液相色谱-质谱联用(LC/MS)对其浓度进行量化。本研究制备的稳定的水相C60聚集体(nC60)直径约为60至70纳米,在347纳米处的紫外(UV)消光系数为0.0263 L/mg-cm,基于0.01 cm(-1)的吸光度,这相当于0.4 mg/L的UV检测限。由于盐或有机物(如自来水)的干扰以及使nC60聚集的可能性,紫外分析不适用于含有这些物质的水。LC/MS分析检测到的C60为单个富勒烯而非聚集体。开发了三种技术将超纯水和自来水中的nC60分离并浓缩到甲苯中,以方便LC/MS测定:将样品蒸发至干;用20% NaCl萃取到甲苯中;以及固相萃取。前两种方法在复杂水基质中的使用存在局限性,但使用固相萃取(SPE)分离方法可对水中低至300 ng/L的水相nC60浓度进行量化。这是关于从超纯水和自来水中萃取nC60的方法应用以及通过LC/MS测定检测限的首次发表。