Synthesis and characterization of Zr- and Hf-doped nano-TiO2 as internal standards for analytical quantification of nanomaterials in complex matrices

TY - JOUR

T1 - Synthesis and characterization of Zr- and Hf-doped nano-TiO2 as internal standards for analytical quantification of nanomaterials in complex matrices

AU - Ellis, Laura-Jayne

A2 - Papadiamantis, Anastasios

A2 - Weigel, Stefan

A2 - Valsami-Jones, Eugenia

PY - 2018/6/1

Y1 - 2018/6/1

N2 - The reliable quantification of nanomaterials (NMs) in complex matrices such as food, cosmetics and biological and environmental compartments can be challenging due to interactions with matrix components and analytical equipment (vials and tubing). The resulting losses along the analytical process (sampling, extraction, clean-up, separation and detection) hamper the quantification of the target NMs in these matrices as well as the compatibility of results and meaningful interpretations in safety assessments. These issues can be overcome by the addition of known amounts of internal/recovery standards to the sample prior to analysis. These standards need to replicate the behaviour of target analytes in the analytical process, which is mainly defined by the surface properties. Moreover, they need to carry a tag that can be quantified independently of the target analyte. As inductively coupled plasma mass spectrometry is used for the identification and quantification of NMs, dopingwith isotopes, target analytes or with chemically related rare elements is a promising approach. We present the synthesis of a library of TiO2 NMs doped with hafnium (Hf) and zirconium (Zr) (both low in environmental abundance). Zirconia NMs doped with Hf were also synthesized to complement the library. NMs were synthesized with morphological and size properties similar to commercially available TiO2. Characterization included: transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy, X-ray diffraction spectroscopy, Brunauer–Emmett–Teller total specific surface area analysis, cryofixation scanning electron microscopy, inductively coupled plasma optical emission spectroscopy and UV–visible spectrometry. The Ti : Hf and Ti :Zr ratios were verified and calculated using Rietveld refinement. The labelled NMs can serve as internal standards to track the extraction efficiency from complex matrices, and increase method robustness and traceability of characterization/quantification.

AB - The reliable quantification of nanomaterials (NMs) in complex matrices such as food, cosmetics and biological and environmental compartments can be challenging due to interactions with matrix components and analytical equipment (vials and tubing). The resulting losses along the analytical process (sampling, extraction, clean-up, separation and detection) hamper the quantification of the target NMs in these matrices as well as the compatibility of results and meaningful interpretations in safety assessments. These issues can be overcome by the addition of known amounts of internal/recovery standards to the sample prior to analysis. These standards need to replicate the behaviour of target analytes in the analytical process, which is mainly defined by the surface properties. Moreover, they need to carry a tag that can be quantified independently of the target analyte. As inductively coupled plasma mass spectrometry is used for the identification and quantification of NMs, dopingwith isotopes, target analytes or with chemically related rare elements is a promising approach. We present the synthesis of a library of TiO2 NMs doped with hafnium (Hf) and zirconium (Zr) (both low in environmental abundance). Zirconia NMs doped with Hf were also synthesized to complement the library. NMs were synthesized with morphological and size properties similar to commercially available TiO2. Characterization included: transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy, X-ray diffraction spectroscopy, Brunauer–Emmett–Teller total specific surface area analysis, cryofixation scanning electron microscopy, inductively coupled plasma optical emission spectroscopy and UV–visible spectrometry. The Ti : Hf and Ti :Zr ratios were verified and calculated using Rietveld refinement. The labelled NMs can serve as internal standards to track the extraction efficiency from complex matrices, and increase method robustness and traceability of characterization/quantification.

KW - Nanosafety

KW - Nanomaterials

KW - Reference Materials

KW - hydrolysis/oxidation methods

KW - Hydrothermal

KW - Titania

KW - zirconia

U2 - 10.1098/rsos.171884

DO - 10.1098/rsos.171884

M3 - Article

VL - 5

JO - Royal Society Open Science

JF - Royal Society Open Science

SN - 2054-5703

IS - 171884

M1 - L-JAE, 0000-0003-2781-4509

ER -