Critical evaluation of key parameters in single particle ICP-MS data processing for the correct determination of platinum nanoparticles in complex environmental and biological matrices.

There is an urgent need for the harmonization of critical parameters in single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) and they have been deeply studied and optimized in the present work using platinum nanoparticles (PtNPs) as a representative case of study. Special attention has been paid to data processing in order to achieve an adequate discrimination between signals. Thus, a comparison between four different algorithms has been performed and the method for transport efficiency calculation has also been thorougly evaluated (finding the use of a well-characterized solution of the same targeted analyte (30 nm PtNPs) as adequate). The best results have been obtained after the application of a deconvolution approach for the data processing and using 5 ms as dwell time and 40,000 data points for data acquisition. Under the optimized conditions, a correct discrimination between NP events and background signal up to 100 or 750 ng L-1 of added ionic Pt was reached for 30 and 50 nm PtNPs, respectively. The suitability of the developed method for the characterization of PtNPs in relevant environmental (water samples) and biological (cell culture media) matrices has also been demonstrated.

Assessment by a multi-technique approach of PtNPs' transformations in waters under relevant environmental concentrations and conditions.

Once released to the environment, platinum nanoparticles (PtNPs) can undergo different transformations and are affected by several environmental conditions. An only analytical technique cannot provide all the information required to understand those complex processes, so new analytical developments are demanded. In the present work, the potential of asymmetric flow field flow fractionation hyphenated to inductively coupled plasma mass spectrometry (AF4-ICP-MS) for these studies, has been investigated, and classical dynamic and electrophoretic light scattering (DLS & ELS) have been used as complementary techniques. The role of ionic strength, ionic water composition, and natural organic matter (NOM) in the behaviour of PtNPs of different sizes (5 and 50 nm) has been specifically studied. Dynamic and electrophoretic light scattering have been used to track changes in the hydrodynamic diameters (dh) and polydispersity index (PdI) for 50 nm PtNPs (5 nm cannot be studied by DLS) and Z-potential values (for all sizes) to monitor aggregation. AF4-ICP-MS has been also employed to have a solid insight of aggregation at low environmental concentrations for different sizes of PtNPs simultaneously. The information gathered with those techniques was useful to observe changes as the ionic strength increases, which induces aggregation. Also, it was observed that this aggregation process was attenuated in the presence of organic matter. This approach, based on complementary analytical techniques, is needed for a comprehensive study of such complex interactions of NPs in the environment. AF4-ICP-MS is still under-exploited but shows a great potential for this purpose, especially low size NPs and concentrations.

A method based on asymmetric flow field flow fractionation hyphenated to inductively coupled plasma mass spectrometry for the monitoring of platinum nanoparticles in water samples.

An analytical methodology based on asymmetric flow field flow fractionation hyphenated to inductively coupled plasma mass spectrometry (AF4-ICP-MS) has been developed for monitoring citrate coated platinum nanoparticles (PtNPs) of different sizes (5, 30, and 50 nm) in water samples. Several factors have been optimized, such as carrier composition, AF4 separation program, focusing step or cross flow values. Under the optimum conditions, PtNPs can be fractionated in about 30 min in a single run with quantitative recoveries of the membrane (100 ± 7%, n = 5). The optimized method has been successfully applied to study transformations, not only in size but also surface modifications, of PtNPs in synthetic and natural water samples over time. The effect of organic matter was specifically studied, and it was found to be a critical parameter. The analytical strategy followed in this work can be very useful to develop further environmental studies involving PtNPs.

Analytical strategy based on asymmetric flow field flow fractionation hyphenated to ICP-MS and complementary techniques to study gold nanoparticles transformations in cell culture medium.

An analytical methodology based on asymmetric flow field flow fractionation (AF4) hyphenated to inductively coupled plasma mass spectrometry (ICP-MS) has been developed to study gold nanoparticles (AuNPs) in cell culture medium (Dulbecco's Modified Eagle Medium, DMEM, containing 10% fetal bovine serum, FBS, and antibiotics) used for in vitro toxicological studies. AF4-ICP-MS separation of AuNPs was performed using a regenerated cellulose membrane (molecular weight cut-off, MWCO, of 10 kDa). The carrier composition and the AF4 separation program were optimized. Under the optimum conditions, AuNPs of different types, i.e. phosphate buffered saline (PBS) and citrate stabilized, and sizes (10, 30 and 40 nm), without and with cell culture medium could be separated. The developed method allowed to detect transformations in AuNPs and dissolved gold species (Au3+) induced by this medium, such as an increase in the hydrodynamic volume and oxidation. Centrifugal ultrafiltration (CU), transmission electron microscopy (TEM) and Ultraviolet-visible (UV-vis) absorption spectrophotometry have been used as complementary techniques to study these processes. This information is of major interest to have a correct interpretation of the in vitro toxicological studies of NPs, which are more and more demanded due to the increasing concerns about the safe use of these materials and their impacts. This work demonstrates the potential of hyphenated techniques based on AF4 to achieve this relevant information.

Methodology for monitoring gold nanoparticles and dissolved gold species in culture medium and cells used for nanotoxicity tests by liquid chromatography hyphenated to inductively coupled plasma-mass spectrometry.

An analytical methodology based on coupling reversed-phase liquid chromatography (HPLC) to an inductively coupled plasma mass spectrometry (ICP-MS) has been developed for the characterization and identification of gold nanoparticles (AuNPs) and gold dissolved species (Au3+) in culture medium (Dulbecco's Modified Eagle Medium, DMEM) and HeLa cells (a human cervical adenocarcinoma cell line) used in nanotoxicity tests. The influence of the culture medium was also studied and the method applied for nanotoxicity tests. It was also observed that AuNPs can undergo an oxidation process in the supernatants and only a small amount of AuNPs and dissolved Au3+ was associated with cells. To evaluate the biological impact of AuNPs, a classical viability assay onto HeLa cells was performed using cellular media DMEM in the presence of increasing dosage of 10nm AuNPs. The results showed that 10nm AuNPs exhibit a slight toxic effect.

Multiresidue determination of organochlorines in fish oil by GC-MS: a new strategy in the sample preparation.

A rapid, economic and environmentally friendly analytical methodology has been implemented for the determination of alpha-, beta-, gamma- and delta-HCH, p,p'-DDT, p,p'-DDD and p,p'-DDE, PCBs congeners #28, #52, #101, #153, #138 and #180 and Hexachlorobenzene in fish oil. 1,2,3,4-Tetrachloronaphtalene was used as internal standard. The sample preparation, consisting of a single step of clean-up and fractionation, took place in a column filled with different layers of neutral and sulphuric acid modified silica. The analytes were eluted by vacuum with of hexane. Significant reduction in terms of solvents, sorbents, and analysis time was achieved in comparison with literature. Gas chromatography coupled to mass spectrometry was used for the separation and determination of the analytes. The instrumental limits of detection were from 0.1 to 1.3ngmL(-1) and the response of the detector was linear up to 200ngmL(-1). The separation proved to be precise (RSD<3.7% in peak area) and robust in terms of peak area, peak efficacy and resolution. The methodology was validated with two certified reference materials of cod liver oil, BCR 598 and BCR 349, obtaining no statistically significant differences between the concentrations found and certified. For the analytes that were not certified, aliquots of the reference materials were spiked and the recoveries obtained were satisfactory. These results were consistent with those found previously for DDTs by gas chromatography with an electron-capture detector. The methodology was applied to the analysis of three fish oil pills sold in Spain as a dietary supplement of vitamins and omega-3 fatty acids. The sum of the analytes studied was from 64 to 80ngg(-1). The most abundant compounds are PCBs, followed by DDTs in all samples.