Separation, detection and characterization of nanomaterials in municipal wastewaters using hydrodynamic chromatography coupled to ICPMS and single particle ICPMS

Engineered nanoparticles (ENP) are increasingly being incorporated into consumer products and reaching the environment at a growing rate. Unfortunately, few analytical techniques are available that allow the detection of ENP in complex environmental matrices. The major limitations with existing techniques are their relatively high detection limits and their inability to distinguish ENP from other chemical forms (e.g. ions, dissolved) or from natural colloids. Of the matrices that are considered to be a priority for method development, ENP are predicted to be found at relatively high concentrations in wastewaters and wastewater biosolids. In this paper, we demonstrate the capability of hydrodynamic chromatography (HDC) coupled to inductively coupled plasma mass spectrometry (ICPMS), in its classical and single particle modes (SP ICPMS), to identify ENP in wastewater influents and effluents. The paper first focuses on the detection of standard silver nanoparticles (Ag NP) and their mixtures, showing that significant dissolution of the Ag NP was likely to occur. For the Ag NP, detection limits of 0.03 μg L−1 were found for the HDC ICPMS whereas 0.1 μg L−1 was determined for the HDC SP ICPMS (based on results for the 80 nm Ag NP). In the second part of the paper, HDC ICPMS and HDC SP ICPMS were performed on some unspiked natural samples (wastewaters, river water). While nanosilver was below detection limits, it was possible to identify some (likely natural) Cu nanoparticles using the developed separation technology

Detection and characterization of ZnO nanoparticles in surface and waste waters using single particle ICPMS

The increasing production of ZnO nanoparticles (nZnO) makes their analysis and characterization extremely important from an ecological risk perspective, especially at the low concentrations at which they are expected to be found in natural waters. Single particle ICPMS (SP-ICPMS) is one of the few techniques available to detect and characterize nanoparticles at environmentally relevant concentrations. Unfortunately, at the very low particle concentrations where SP-ICPMS is performed, significant dissolution of the nZnO generally increases background levels of dissolved Zn to the point where measurements are not generally possible. By hyphenating SP-ICPMS with an ion-exchange resin, it was possible to characterize and quantify nZnO in order to gain insight into the nature of the nZnO in natural waters. Spiked and unspiked water samples were analyzed using a SP-ICPMS that was coupled to a column containing a strong metal binding resin (Chelex 100). In addition to the detection of ZnO nanoparticles and the determination of a size distribution in natural waters, it was possible to partition the dissolved Zn among free and/or labile and strongly bound Zn fractions. In two natural waters, a high proportion (ca. 93–100%) of dissolved Zn was measured, and the residual ZnO particles were mainly composed of small agglomerates (average sizes ranging from 133.6 to 172.4 nm in the surface water and from 167.6 to 216.4 nm in the wastewater effluent). Small numbers of small nanoparticles were also detected in nonspiked waters

Quantification of ZnO nanoparticles and other Zn containing colloids in natural waters using a high sensitivity single particle ICP-MS

Inductively coupled plasma mass spectrometry in single particle mode (SP-ICP-MS) is becoming a powerful tool of choice for the quantification and characterization of metallic nanoparticles (NP) at very low concentrations. Nonetheless, this technique has relatively high size detection limits for highly soluble nanoparticles (e.g. ZnO, CuO) or NP that are measured in the presence of high background concentrations of dissolved metal. In order to evaluate whether SP-ICP-MS could be used to measure a soluble NP under environmentally relevant conditions, an ion-exchange column (IEC) was coupled to a highly-sensitive sector-field ICP-MS (IEC-SP-ICP-MS) and then used to detect both spiked ZnO NP and natural Zn containing colloids in natural waters. The use of an ion exchange column, short dwell times (50 µs) and a high sensitivity instrument gave size detection limits for the measurement of ZnO NP of ca. 8.2 nm in pure water, 14.3 nm in a river water and 17.7 nm in a rainwater. IEC-SP-ICP-MS measured ca. 4.4 × 105 mL−1 zinc containing particles in a river water sample and ca. 1.0 × 105 mL−1 particles in a local rainwater

Quantification and characterization of Ti-, Ce- and Ag5 nanoparticles in global surface waters and precipitation

Nanoparticle (NP) emissions to the environment are increasing as a result of anthropogenic activities, prompting concerns for ecosystems and human health. In order to evaluate the risk of NPs, it is necessary to know their concentrations in various environmental compartments on regional and global scales; however, these data have remained largely elusive due to the analytical difficulties of measuring NPs in complex natural matrices. Here, we measure NP concentrations and sizes for Ti-, Ce-, and Ag-containing NPs in numerous global surface waters and precipitation samples, and we provide insights into their compositions and origins (natural or anthropogenic). The results link NP occurrences and distributions to particle type, origin, and sampling location. Based on measurements from 46 sites across 13 countries, total Ti- and Ce-NP concentrations (regardless of origin) were often found to be within 104 to 107 NP mL–1, whereas Ag NPs exhibited sporadic occurrences with low concentrations generally up to 105 NP mL–1. This generally corresponded to mass concentrations of <1 ng L–1 for Ag-NPs, <100 ng L–1 for Ce-NPs, and <10 μg L–1 for Ti-NPs, given that measured sizes were often below 15 nm for Ce- and Ag-NPs and above 30 nm for Ti-NPs. In view of current toxicological data, the observed NP levels do not yet appear to exceed toxicity thresholds for the environment or human health; however, NPs of likely anthropogenic origins appear to be already substantial in certain areas, such as urban centers. This work lays the foundation for broader experimental NP surveys, which will be critical for reliable NP risk assessments and the regulation of nano-enabled products

Release of TiO2 nanoparticles from painted surfaces in cold climates : characterization using a high sensitivity single-particle ICP-MS

Paints and coatings represent one of the major applications of TiO2 nanoparticles (NPs). While it has been previously shown that NPs are released from painted surfaces, there is still a lack of experimental data on their release rates under natural conditions and on the size distributions of the NPs following release. This study quantifies TiO2 NP release from painted surfaces under natural weathering conditions and identifies the main seasonal factors that contribute to increased NP release. First, an analytical methodology using a highly sensitive single particle inductively coupled plasma mass spectrometer (SP-ICP-MS) was developed that improved the size detection limit (SDL) of the technique down to <20 nm for TiO2 NPs. Precipitation (rain, snow) was collected after it came into contact with painted panels that were exposed to natural weathering. NPs that were released from the paint, as well as those pre-existing in the precipitation were thoroughly characterized with respect to their size distributions, particle number concentrations and total metal content. During the 10 week winter exposure, 3 × 1011 NP per m2 were released, corresponding to <0.001% of the TiO2 NP load on the panels, with most of the NPs found in the 20–60 nm range. Significantly fewer NPs were released during the summer than the winter, in spite of the fact that there was more precipitation in the summer. Controlled lab weathering experiments revealed that NP release was significantly enhanced for wet surfaces, particularly, when the samples underwent freeze–thaw cycles. The results also indicated that NP release and loss (i.e. through agglomeration, sedimentation or sorption, etc.) are dynamic processes that are a function of the physical and chemical properties of the external medium. Although NP release is a primary determinant in environmental risk, subsequent NP behavior leading to losses or re-suspension can be equally critical

Synthèse d'hydroxyapatite et de silices greffées pour l'élimination de métaux toxiques en solution aqueuse

TOULOUSE3-BU Sciences (315552104) / SudocSudocFranceF

Sample preparation for the analysis of nanoparticles in natural waters by single particle ICP-MS

With the significant increase in the production and use of nanoparticles (NP), concern is increasing over their release into their environment. Single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) is emerging as one of the best techniques for detecting the very small NP at very low concentrations in natural waters. However, there is no unified protocol for the preparation of natural water samples for SP-ICP-MS analysis. In order to minimize nebulizer blockage, filtration is often used with the expectation that 0.45 μm membranes will not remove significant quantities of 1–100 nm NP. Nonetheless, there are limited data on its effect on the concentrations or size distributions of the NP. To that end, we examined the interactions between six different membrane filters and silver (Ag) and cerium oxide (CeO2) NP in aqueous samples. For Ag NP, the highest recoveries were observed for polypropylene membranes, where 55% of the pre-filtration NP were found in rainwater and 75% were found in river waters. For CeO2 NP, recoveries for the polypropylene membrane attained 60% in rainwater and 75% in river water. Recoveries could be increased to over 80% by pre-conditioning the filtration membranes with a multi-element solution. Similar recoveries were obtained when samples were centrifuged at low centrifugal forces (≤1000×g)

Measurement of CeO2 Nanoparticles in Natural Waters Using a High Sensitivity, Single Particle ICP-MS

As the production and use of cerium oxide nanoparticles (CeO2 NPs) increases, so does the concern of the scientific community over their release into the environment. Single particle inductively coupled plasma mass spectrometry is emerging as one of the best techniques for NP detection and quantification; however, it is often limited by high size detection limits (SDL). To that end, a high sensitivity sector field ICP-MS (SF-ICP-MS) with microsecond dwell times (50 &micro;s) was used to lower the SDL of CeO2 NPs to below 4.0 nm. Ag and Au NPs were also analyzed for reference. SF-ICP-MS was then used to detect CeO2 NPs in a Montreal rainwater at a concentration of (2.2 &plusmn; 0.1) &times; 108 L&minus;1 with a mean diameter of 10.8 &plusmn; 0.2 nm; and in a St. Lawrence River water at a concentration of ((1.6 &plusmn; 0.3) &times; 109 L&minus;1) with a higher mean diameter (21.9 &plusmn; 0.8 nm). SF-ICP-MS and single particle time of flight ICP-MS on Ce and La indicated that 36% of the Ce-containing NPs detected in Montreal rainwater were engineered Ce NPs

Detection and Characterization of ZnO Nanoparticles in Surface and Waste Waters Using Single Particle ICPMS

The increasing production of ZnO nanoparticles (nZnO) makes their analysis and characterization extremely important from an ecological risk perspective, especially at the low concentrations at which they are expected to be found in natural waters. Single particle ICPMS (SP-ICPMS) is one of the few techniques available to detect and characterize nanoparticles at environmentally relevant concentrations. Unfortunately, at the very low particle concentrations where SP-ICPMS is performed, significant dissolution of the nZnO generally increases background levels of dissolved Zn to the point where measurements are not generally possible. By hyphenating SP-ICPMS with an ion-exchange resin, it was possible to characterize and quantify nZnO in order to gain insight into the nature of the nZnO in natural waters. Spiked and unspiked water samples were analyzed using a SP-ICPMS that was coupled to a column containing a strong metal binding resin (Chelex 100). In addition to the detection of ZnO nanoparticles and the determination of a size distribution in natural waters, it was possible to partition the dissolved Zn among free and/or labile and strongly bound Zn fractions. In two natural waters, a high proportion (ca. 93–100%) of dissolved Zn was measured, and the residual ZnO particles were mainly composed of small agglomerates (average sizes ranging from 133.6 to 172.4 nm in the surface water and from 167.6 to 216.4 nm in the wastewater effluent). Small numbers of small nanoparticles were also detected in nonspiked waters

Improvements to Single Particle ICPMS by the Online Coupling of Ion Exchange Resins

Single particle ICPMS (SP-ICPMS) is becoming a very promising technique for nanoparticle detection and characterization, especially at very low concentrations (∼10^–12–10^–10 M). Nonetheless, the ability of the technique to detect smaller nanoparticles is presently limited by the setting of threshold values for the discrimination of nanoparticles from the dissolved metal background. In this study, a new approach to attaining lower particle size detection limits has been developed by the online coupling of an ion exchange column (IEC) with SP-ICPMS (IEC-SP-ICPMS). The IEC effectively removes the continuous signal of dissolved metal, allowing for both lower detection limits and an improved resolution of solutions containing multiple particles. The feasibility and the efficiency of this coupling were investigated using silver nanoparticles in the presence of various concentrations of Ag⁺ and other major ions (Mg²⁺, Ca²⁺, Na⁺, K⁺, and Cl^–). The online elimination of the dissolved metal made data processing simpler and more accurate. Following the addition of 1 to 4 μg L^–1 of Ag⁺ spikes, symmetric particle size distributions were obtained using IEC-SP-ICPMS, whereas the use of SP-ICPMS alone led to asymmetric distributions, especially for nanoparticle sizes below 60 nm. Although this proof of principle study focused on nanosilver, the technique should be particularly useful for any of the metal based nanoparticles with high solubilities