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Where is the nano? Analytical approaches for the detection and quantification of TiO2 engineered nanoparticles in surface waters†
Environmental Science: Nano ( IF 7.3 ) Pub Date : 2017-12-14 00:00:00 , DOI: 10.1039/c7en00952f
Andreas Gondikas 1, 2, 3, 4 , Frank von der Kammer 1, 2, 3, 4 , Ralf Kaegi 5, 6, 7, 8 , Olga Borovinskaya 8, 9, 10 , Elisabeth Neubauer 1, 2, 3, 4 , Jana Navratilova 1, 2, 3, 4 , Antonia Praetorius 1, 1, 2, 3, 4 , Geert Cornelis 11, 12, 13, 14 , Thilo Hofmann 1, 2, 3, 4
Affiliation  

Detecting and quantifying engineered nanoparticles (ENPs) in complex environmental matrices requires the distinction between natural nanoparticles (NNPs) and ENPs. The distinction of NNPs and ENPs for regulatory purposes calls for cost-efficient methods, but is hampered by similarities in intrinsic properties, such as particle composition, size, density, surface chemistry, etc. Titanium dioxide (TiO2) ENPs, for instance, are produced in very large quantities but Ti also commonly occurs naturally in nano-scale minerals. In this work, we focus on utilizing particle size and composition to identify ENPs in a system with a significant background concentration of the target metal. We have followed independent approaches involving both conventional and state-of-the-art analytical techniques to detect and quantify TiO2 ENPs released into surface waters from sunscreen products and to distinguish them from Ti-bearing NNPs. To achieve this, we applied single particle inductively coupled plasma mass spectrometry with single-element (spICPMS) and multi-element detection (time-of-flight) spICP-TOFMS, together with transmission electron microscopy (TEM), automated scanning electron microscopy (autoSEM), and bulk elemental analyses. A background concentration of Ti-bearing NPs (approximately 5 × 103 particles per ml), possibly of natural origin, was consistently observed outside the bathing season. This concentration increased by up to 40% during the bathing season. Multi-element analysis of individual particles using spICP-TOFMS revealed that Al, Fe, Mn, and Pb are often present in natural Ti-bearing NPs, but no specific multi-element signatures were detected for ENPs. Our data suggests that TiO2 ENPs enter the lake water during bathing activities, eventually agglomerating and sedimenting. We found adhesion of the TiO2 ENPs to the air–water interface for short time periods, depending on wind conditions. This study demonstrates that the use of spICP-TOFMS and spICPMS in combination with other conventional analytical techniques offers significant advantages for discriminating between NNPs and ENPs. The quantitative data produced in this work can be used as input for modeling studies or as a benchmark for analysis protocols and model validations.

中文翻译:

纳米在哪里?用于检测和定量地表水中TiO 2工程纳米颗粒的分析方法

在复杂的环境基质中检测和定量工程化的纳米颗粒(ENP)要求在天然纳米颗粒(NNP)和ENP之间进行区分。为了监管目的,区分NNP和ENP要求采用经济高效的方法,但由于内在特性(例如颗粒组成,尺寸,密度,表面化学等)的相似性而受到阻碍二氧化钛(TiO 2)例如,ENP的产量非常高,但Ti通常也天然存在于纳米级矿物中。在这项工作中,我们专注于利用粒径和成分来识别目标金属背景浓度很高的系统中的ENP。我们采用了独立的方法,涉及常规和最先进的分析技术,以检测和定量TiO 2ENP从防晒产品释放到地表水中,以区别于含钛NNP。为了实现这一目标,我们将单元素电感耦合等离子体质谱(spICPMS)和多元素检测(飞行时间)spICP-TOFMS与透射电子显微镜(TEM),自动扫描电子显微镜( autoSEM)和大量元素分析。含钛纳米颗粒的背景浓度(约5×10 3可能在沐浴季节以外一直观察到可能是天然来源的每毫升颗粒物(每毫升))。在沐浴季节,这种浓度增加了多达40%。使用spICP-TOFMS对单个颗粒进行多元素分析后发现,天然Ti纳米颗粒中经常存在Al,Fe,Mn和Pb,但未检测到ENP特有的多元素特征。我们的数据表明,TiO 2 ENPs在沐浴过程中进入湖水中,最终发生团聚和沉淀。我们发现TiO 2的附着力根据风况,ENP会在短时间内进入气-水界面。这项研究表明,将spICP-TOFMS和spICPMS与其他常规分析技术结合使用可为区分NNP和ENP提供显着的优势。这项工作中产生的定量数据可以用作建模研究的输入,也可以用作分析协议和模型验证的基准。
更新日期:2017-12-14
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