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Emerging investigator series: automated single-nanoparticle quantification and classification: a holistic study of particles into and out of wastewater treatment plants in Switzerland.

ABSTRACT: Single particle inductively coupled plasma time-of-flight mass spectrometry (sp-ICP-TOFMS), in combination with online microdroplet calibration, allows for the determination of particle number concentrations (PNCs) and the amount (i.e. mass) of ICP-MS-accessible elements in individual particles. Because sp-ICP-TOFMS analyses of environmental samples produce rich datasets composed of both single-metal nanoparticles (smNPs) and many types of multi-metal NPs (mmNPs), interpretation of these data is well suited to automated analysis schemes. Here, we present a new data analysis approach that includes: 1. automatic particle detection and elemental mass determinations based on online microdroplet calibration, 2. correction of false (randomly occurring) multi-metal associations caused by measurement of coincident but distinct NPs, and 3. unsupervised clustering analysis of mmNPs to identify unique classes of NPs based on their element compositions. To demonstrate the potential of our approach, we analyzed water samples collected from the influent and effluent of five wastewater treatment plants (WWTPs) across Switzerland. We determined elemental masses in individual NPs, as well as PNCs, to estimate the NP removal efficiencies of the individual WWTPs. From WWTP samples collected at two points in time, we found an average of 90% and 94% removal efficiencies of single-metal and multi-metal NPs, respectively. Between 5% to 27% of detected NPs were multi-metal; the most abundant particle types were those rich in Ce-La, Fe-Al, Ti-Zr, and Zn-Cu. Through hierarchical clustering, we identified NP classes conserved across all WWTPs, as well as particle types that are unique to one or a few WWTPs. These uniquely occurring particle types may represent point sources of anthropogenic NPs. We describe the utility of clustering analysis of mmNPs for identifying natural, geogenic NPs, and also for the discovery of new, potentially anthropogenic, NP targets.

SUBMITTER: Mehrabi K

PROVIDER: S-EPMC8136323 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:We fabricated a suite of polymeric electrospun nanofiber mats (ENMs) and investigated their performance as next-generation passive sampler media for environmental monitoring of organic compounds. Electrospinning of common polymers [e.g., polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), and polystyrene (PS), among others] yielded ENMs with reproducible control of nanofiber diameters (from 50 to 340 nm). The ENM performance was investigated initially with model hydrophilic (aniline and nitrobenzene) and hydrophobic (selected PCB congeners and dioxin) compounds, generally revealing fast chemical uptake into all of these ENMs, which was well described by a one compartment, first-order kinetic model. Typical times to reach 90% equilibrium (t90%) were ?7 days under mixing conditions for all the ENMs and <0.5 days for the best performing materials under static (i.e., no mixing) conditions. Collectively, these short equilibrium timescales suggest that ENMs may be used in the field as an equilibrium-passive sampler, at least for our model compounds. Equilibrium partitioning coefficients (KENM-W, L kg-1) averaged 2 and 4.7 log units for the hydrophilic and hydrophobic analytes, respectively. PAN, PMMA and PS were prioritized for additional studies because they exhibited not only the greatest capacity for simultaneous uptake of the entire model suite (log?KENM-W ?1.5-6.2), but also fast uptake. For these optimized ENMs, the rates of uptake into PAN and PMMA were limited by aqueous phase diffusion to the nanofiber surface, and the rate-determining step for PS was analyte specific. Sorption isotherms also revealed that the environmental application of these optimized ENMs would occur within the linear uptake regime. We examined the ENM performance for the measurement of pore water concentrations from spiked soil and freshwater sediments. Soil and sediment studies not only yielded reproducible pore water concentrations and comparable values to other passive sampler materials, but also provided practical insights into ENM stability and fouling in such systems. Furthermore, fast uptake for a suite of structurally diverse hydrophilic and moderately hydrophobic compounds was obtained for PAN and PS, with t90% ranging from 0.01 to 4 days with mixing and KENM-W values ranging from 1.3 to 3.2 log units. Our findings show promise for the development and use of ENMs as equilibrium-passive samplers for a range of organic pollutants across soil/sediment and water systems.

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Emerging investigator series: automated single-nanoparticle quantification and classification: a holistic study of particles into and out of wastewater treatment plants in Switzerland.

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