Investigating the behavior of ultratrace levels of nanoparticulate and ionic silver in a seawater mesocosm using single particle inductively coupled plasma - mass spectrometry

Michail Ioannis Chronakis; Emmanouil Mavrakis; Roberto Álvarez-Fernández García; Maria Montes-Bayón; Jörg Bettmer; Paraskevi Pitta; Manolis Tsapakis; Ioanna Kalantzi; Anastasia Tsiola; Spiros A Pergantis

doi:10.1016/j.chemosphere.2023.139109

Investigating the behavior of ultratrace levels of nanoparticulate and ionic silver in a seawater mesocosm using single particle inductively coupled plasma - mass spectrometry

Chemosphere. 2023 Sep:336:139109. doi: 10.1016/j.chemosphere.2023.139109. Epub 2023 Jun 1.

Affiliations

¹ University of Crete, Department of Chemistry, Environmental Chemical Processes Laboratory, Voutes, 70013, Heraklion, Greece; Federal Institute for Materials Research and Testing (BAM) - Division 1.1 - Inorganic Trace Analysis, Richard-Willstätter-Str. 11, 12489 Berlin, Germany.
² University of Crete, Department of Chemistry, Environmental Chemical Processes Laboratory, Voutes, 70013, Heraklion, Greece.
³ University of Oviedo, Faculty of Chemistry, Dept. of Physical and Analytical Chemistry and Instituto de Investigación Sanitaria Del Principado de Asturias (ISPA), Oviedo, Spain.
⁴ Hellenic Centre for Marine Research, Institute of Oceanography, Gournes, Heraklion, Greece.
⁵ University of Crete, Department of Chemistry, Environmental Chemical Processes Laboratory, Voutes, 70013, Heraklion, Greece. Electronic address: spergantis@uoc.gr.

PMID: 37270041
DOI: 10.1016/j.chemosphere.2023.139109

Abstract

Silver nanoparticles (AgNPs) nowadays appear in close to 24% of consumer products that contain engineered nanomaterials. Thus, they are expected to be released into the environment, where their fate and effect are still undetermined. Considering the evidenced efficacy of the single particle Inductively Coupled Plasma - Mass Spectrometry (sp ICP-MS) technique in the study of nanomaterials, this work reports on the use of sp ICP-MS along with an online dilution sample introduction system for the direct analysis of untreated and spiked seawater samples, as part of a larger scale experiment studying the fate of Ag (ionic and nanoparticles) in seawater mesocosm systems. Silver nanoparticles coated with branched polyethyleneimine (BPEI@AgNPs) or ionic silver (Ag⁺) were introduced gradually into the seawater mesocosm tanks at very low, environmentally relevant concentrations (50 ng Ag L^-1 per day, for 10 consecutive days, up to a total of 500 ng Ag L^-1), and samples were collected and analyzed daily, within a consistent time window. Using very low detector dwell time (75 μs) and specialized data treatment, information was obtained on the nanoparticles' size distribution and particle number concentration, as well as the ionic silver content, of both the AgNPs and the Ag⁺ treated seawater mesocosm tanks. The results for the AgNP treated samples indicated the rapid degradation of the added silver particles, and the subsequent increase of ionic silver, with recoveries close to 100% for the first days of the experiment. On the other hand, particle formation was observed in the Ag⁺ treated seawater tanks, and even though the number concentration of silver-containing nanoparticles increased throughout the experiment, the amount of silver per particle remained relatively constant from the early days of the experiment. In addition, the online dilution sample introduction system for the ICP-MS proved capable of handling the untreated seawater matrix without significant contamination issues and downtime, while the low dwell time and data treatment procedure developed were shown to be suitable for the analysis of nanomaterials at the low nm-scale, despite the complex and heavy matrix introduced into the ICP-MS.

MeSH terms

Ions
Mass Spectrometry / methods
Metal Nanoparticles* / analysis
Particle Size
Seawater
Silver* / analysis
Spectrum Analysis

Substances

Silver
Ions