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Identification of Micro- and Submicron (Nano) Plastics in Water Sources and the Impact of COVID-19 on Plastic Pollution / JAVIER GALLARDO

Swansea University Author: JAVIER GALLARDO

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DOI (Published version): 10.23889/SUthesis.63499

Abstract

One of the most significant environmental issues that our society may deal with this century could be plastics. The world's water bodies, as well as land and air, are becoming more and more contaminated by plastic due to the ongoing and expanding manufacturing of these synthetic materials, as w...

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Published: Swansea, Wales, UK 2023
Institution: Swansea University
Degree level: Doctoral
Degree name: Ph.D
Supervisor: Sarp, Sarper.
URI: https://cronfa.swan.ac.uk/Record/cronfa63499
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fullrecord <?xml version="1.0" encoding="utf-8"?><rfc1807 xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns:xsd="http://www.w3.org/2001/XMLSchema"><bib-version>v2</bib-version><id>63499</id><entry>2023-05-18</entry><title>Identification of Micro- and Submicron (Nano) Plastics in Water Sources and the Impact of COVID-19 on Plastic Pollution</title><swanseaauthors><author><sid>b7b6df0d7fbaf9b6b2d47399e0d4ed43</sid><firstname>JAVIER</firstname><surname>GALLARDO</surname><name>JAVIER GALLARDO</name><active>true</active><ethesisStudent>false</ethesisStudent></author></swanseaauthors><date>2023-05-18</date><abstract>One of the most significant environmental issues that our society may deal with this century could be plastics. The world's water bodies, as well as land and air, are becoming more and more contaminated by plastic due to the ongoing and expanding manufacturing of these synthetic materials, as well as the lack of an effective strategy for managing plastic waste. The fact that plastics break down into smaller particles (micro and nanoplastics) by action of environmental physical and chemical reactions, and do not degrade biologically in a reasonable time, is a cause of concern as plastics are believed to cause harm in animals, plants and humans.To identify the types of plastics prevalent in aquatic habitats, a number of procedures have been developed, from sampling to identification. After a water body has been sampled using nets, pumps, or other tools, depending on the type of sample taken, it is usually necessary to treat the samples for separation and purification. The next stage is to employ analytical techniques to identify the synthetic contaminants. The most common approaches are microscopy, spectroscopy, and thermal analysis. This thesis gives an overview of where in the environment microplastics (MPs) and nanoplastics (NPs) can be found and summarizes the most important technologies applied to analyse the importance of plastics as a contaminant in water bodies. The development of standardised analytical procedures is still necessary as most of them are not suitable for the identification of particles below 50 μm due to resolution limitations. The preparation and analysis of samples are usually time-consuming factors that shall be considered. Particularly for MP and NP analysis in aqueous samples, thermal analysis methods based on sample degradation are generally not considered to be the most effective approach. Nevertheless, Pyrolysis - Gas Chromatography Time-of-Flight Mass Spectrometry (Py-GCToFMS) is used in this thesis to propose a novel approach as due to its unique detection abilities, and with a novel filtration methodology for collection, it enables the identification of tiny particle sizes (&gt;0.1 μm) in water samples.PTFE membranes were selected to filter the liquid samples using a glass filtration system. This way, the synthetic particles will be deposited on the membranes and will allow the study and analysis of the precipitated material. PTFE is a readily available, reasonably priced, and adaptable product that makes sample preparation quick and simple.The three plastics under study—polypropylene (PP), polystyrene (PS), and polyvinyl chloride (PVC)—can be identified from complex samples at trace levels thanks to the employment of these widely used membranes and the identification of various and specific (marker) ions. The technique was examined against a range of standards samples that contained predetermined concentrations of MPs and NPs. Detection levels were then determined for PVC and PS and were found to be below &lt;50 μg/ L, with repeatable data showing good precision (RSD &lt;20 %). The examination of a complex matrix sample taken from a nearby river contributed to further validate this innovative methodology; the results indicated the existence of PS with a semi-quantifiable result of 250.23 g/L. Because of this, PY-GCToFMS appears to be a method that is appropriate for the task of identifying MPs and NPs from complex mixtures.This thesis also focuses on the environmental challenge that disposable plastic face masks (DPFMs) pose, which has been made significantly worse due to the COVID-19 pandemic. By the time this thesis was written, the production of disposable plastic facemasks had reached to approximately 200 million a day, in a global effort to tackle the spread of the new SARS-CoV-2 virus. This thesis investigates the emissions of pollutants from several different DPFM brands (medical and non-medical) that were submerged in water to replicate the conditions in the environment after these DPFMs have been discarded. The DPFM leachates were filtered using inorganic membranes type and characterized using Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDS), Light/Optical Microscopy (LM/OM), Inductively coupled plasma mass spectrometry (ICP-MS) and Liquid chromatography–mass spectrometry (LC-MS). Micro and nano scale polymeric fibres, particles, siliceous fragments and leachable inorganic and organic chemicals were observed from all of the tested DPFMs. For non-medical DPFMs, traces of concerning heavy metals were detected in association with silicon containing fragments (i.e. lead up to 6.79 μg/L). ICP-MS also confirmed the presence of other leachable metals like cadmium (up to 1.92 μg/L), antimony (up to 3.93 μg/L) and copper (up to 4.17 μg/L). LC-MS analysis identified organic species related to plastic additives; polyamide-66 monomer and oligomers (nylon-66 synthesis), surfactant molecules, and dye-like molecules were all tentatively identified in the leachate. The question of whether DPFMs are safe to use daily and what implications may be anticipated after their disposal into the environment is brought up by the toxicity of some of the chemicals discovered.The previous approach is expanded to medical DPFMs with the utilisation of Field Emission Gun Scanning Electron Microscope (FEG-SEM) in order to get high resolution images of the micro and nanoparticles deposited on the membranes. It is also incorporated the use of 0.02 μm pore size inorganic membranes to better identify the nanoparticles released.Separated aqueous samples were also obtained by submerging medical DPFMs for 24 hours to be analysed using ICP-MS and LC-MS.Both particles and fibres in the micro and nano scale were found in all 6 DPFMs brands of this study. EDS analysis revealed the presence of particles containing different heavy metals like lead, mercury, and arsenic among others. ICP-MS analysis results confirmed traces of heavy metals (antimony up to 2.41 μg/L and copper up to 4.68 μg/L). LC-MS analysis results identified organic species related to plastic additives and contaminants; polyamide-66 monomer and oligomers (nylon-66 synthesis), surfactant molecules, and polyethylene glycol were all tentatively identified in the leachate. 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spelling v2 63499 2023-05-18 Identification of Micro- and Submicron (Nano) Plastics in Water Sources and the Impact of COVID-19 on Plastic Pollution b7b6df0d7fbaf9b6b2d47399e0d4ed43 JAVIER GALLARDO JAVIER GALLARDO true false 2023-05-18 One of the most significant environmental issues that our society may deal with this century could be plastics. The world's water bodies, as well as land and air, are becoming more and more contaminated by plastic due to the ongoing and expanding manufacturing of these synthetic materials, as well as the lack of an effective strategy for managing plastic waste. The fact that plastics break down into smaller particles (micro and nanoplastics) by action of environmental physical and chemical reactions, and do not degrade biologically in a reasonable time, is a cause of concern as plastics are believed to cause harm in animals, plants and humans.To identify the types of plastics prevalent in aquatic habitats, a number of procedures have been developed, from sampling to identification. After a water body has been sampled using nets, pumps, or other tools, depending on the type of sample taken, it is usually necessary to treat the samples for separation and purification. The next stage is to employ analytical techniques to identify the synthetic contaminants. The most common approaches are microscopy, spectroscopy, and thermal analysis. This thesis gives an overview of where in the environment microplastics (MPs) and nanoplastics (NPs) can be found and summarizes the most important technologies applied to analyse the importance of plastics as a contaminant in water bodies. The development of standardised analytical procedures is still necessary as most of them are not suitable for the identification of particles below 50 μm due to resolution limitations. The preparation and analysis of samples are usually time-consuming factors that shall be considered. Particularly for MP and NP analysis in aqueous samples, thermal analysis methods based on sample degradation are generally not considered to be the most effective approach. Nevertheless, Pyrolysis - Gas Chromatography Time-of-Flight Mass Spectrometry (Py-GCToFMS) is used in this thesis to propose a novel approach as due to its unique detection abilities, and with a novel filtration methodology for collection, it enables the identification of tiny particle sizes (>0.1 μm) in water samples.PTFE membranes were selected to filter the liquid samples using a glass filtration system. This way, the synthetic particles will be deposited on the membranes and will allow the study and analysis of the precipitated material. PTFE is a readily available, reasonably priced, and adaptable product that makes sample preparation quick and simple.The three plastics under study—polypropylene (PP), polystyrene (PS), and polyvinyl chloride (PVC)—can be identified from complex samples at trace levels thanks to the employment of these widely used membranes and the identification of various and specific (marker) ions. The technique was examined against a range of standards samples that contained predetermined concentrations of MPs and NPs. Detection levels were then determined for PVC and PS and were found to be below <50 μg/ L, with repeatable data showing good precision (RSD <20 %). The examination of a complex matrix sample taken from a nearby river contributed to further validate this innovative methodology; the results indicated the existence of PS with a semi-quantifiable result of 250.23 g/L. Because of this, PY-GCToFMS appears to be a method that is appropriate for the task of identifying MPs and NPs from complex mixtures.This thesis also focuses on the environmental challenge that disposable plastic face masks (DPFMs) pose, which has been made significantly worse due to the COVID-19 pandemic. By the time this thesis was written, the production of disposable plastic facemasks had reached to approximately 200 million a day, in a global effort to tackle the spread of the new SARS-CoV-2 virus. This thesis investigates the emissions of pollutants from several different DPFM brands (medical and non-medical) that were submerged in water to replicate the conditions in the environment after these DPFMs have been discarded. The DPFM leachates were filtered using inorganic membranes type and characterized using Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDS), Light/Optical Microscopy (LM/OM), Inductively coupled plasma mass spectrometry (ICP-MS) and Liquid chromatography–mass spectrometry (LC-MS). Micro and nano scale polymeric fibres, particles, siliceous fragments and leachable inorganic and organic chemicals were observed from all of the tested DPFMs. For non-medical DPFMs, traces of concerning heavy metals were detected in association with silicon containing fragments (i.e. lead up to 6.79 μg/L). ICP-MS also confirmed the presence of other leachable metals like cadmium (up to 1.92 μg/L), antimony (up to 3.93 μg/L) and copper (up to 4.17 μg/L). LC-MS analysis identified organic species related to plastic additives; polyamide-66 monomer and oligomers (nylon-66 synthesis), surfactant molecules, and dye-like molecules were all tentatively identified in the leachate. The question of whether DPFMs are safe to use daily and what implications may be anticipated after their disposal into the environment is brought up by the toxicity of some of the chemicals discovered.The previous approach is expanded to medical DPFMs with the utilisation of Field Emission Gun Scanning Electron Microscope (FEG-SEM) in order to get high resolution images of the micro and nanoparticles deposited on the membranes. It is also incorporated the use of 0.02 μm pore size inorganic membranes to better identify the nanoparticles released.Separated aqueous samples were also obtained by submerging medical DPFMs for 24 hours to be analysed using ICP-MS and LC-MS.Both particles and fibres in the micro and nano scale were found in all 6 DPFMs brands of this study. EDS analysis revealed the presence of particles containing different heavy metals like lead, mercury, and arsenic among others. ICP-MS analysis results confirmed traces of heavy metals (antimony up to 2.41 μg/L and copper up to 4.68 μg/L). LC-MS analysis results identified organic species related to plastic additives and contaminants; polyamide-66 monomer and oligomers (nylon-66 synthesis), surfactant molecules, and polyethylene glycol were all tentatively identified in the leachate. The toxicity of some of the chemicals found raises the question of whether DPFMs are safe to be used on a daily basis and what consequences are to be expected after their disposal into the environment. E-Thesis Swansea, Wales, UK Chemical Engineering, Environmental Science 17 4 2023 2023-04-17 10.23889/SUthesis.63499 COLLEGE NANME COLLEGE CODE Swansea University Sarp, Sarper. Doctoral Ph.D EPSRC doctoral training grant, European Regional Development Fund (EPIR51312X/1 ) 2023-09-28T15:44:30.2777615 2023-05-18T14:09:47.6635827 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemical Engineering JAVIER GALLARDO 1 63499__27524__9da034914a8444ea9e44d9141a92b58f.pdf 2023_Delgado-Gallardo_J.final.63499.pdf 2023-05-18T16:43:50.7494142 Output 13196390 application/pdf E-Thesis – open access true Copyright: The Author, Javier Delgado Gallardo, 2023. true eng
title Identification of Micro- and Submicron (Nano) Plastics in Water Sources and the Impact of COVID-19 on Plastic Pollution
spellingShingle Identification of Micro- and Submicron (Nano) Plastics in Water Sources and the Impact of COVID-19 on Plastic Pollution
JAVIER GALLARDO
title_short Identification of Micro- and Submicron (Nano) Plastics in Water Sources and the Impact of COVID-19 on Plastic Pollution
title_full Identification of Micro- and Submicron (Nano) Plastics in Water Sources and the Impact of COVID-19 on Plastic Pollution
title_fullStr Identification of Micro- and Submicron (Nano) Plastics in Water Sources and the Impact of COVID-19 on Plastic Pollution
title_full_unstemmed Identification of Micro- and Submicron (Nano) Plastics in Water Sources and the Impact of COVID-19 on Plastic Pollution
title_sort Identification of Micro- and Submicron (Nano) Plastics in Water Sources and the Impact of COVID-19 on Plastic Pollution
author_id_str_mv b7b6df0d7fbaf9b6b2d47399e0d4ed43
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author JAVIER GALLARDO
author2 JAVIER GALLARDO
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description One of the most significant environmental issues that our society may deal with this century could be plastics. The world's water bodies, as well as land and air, are becoming more and more contaminated by plastic due to the ongoing and expanding manufacturing of these synthetic materials, as well as the lack of an effective strategy for managing plastic waste. The fact that plastics break down into smaller particles (micro and nanoplastics) by action of environmental physical and chemical reactions, and do not degrade biologically in a reasonable time, is a cause of concern as plastics are believed to cause harm in animals, plants and humans.To identify the types of plastics prevalent in aquatic habitats, a number of procedures have been developed, from sampling to identification. After a water body has been sampled using nets, pumps, or other tools, depending on the type of sample taken, it is usually necessary to treat the samples for separation and purification. The next stage is to employ analytical techniques to identify the synthetic contaminants. The most common approaches are microscopy, spectroscopy, and thermal analysis. This thesis gives an overview of where in the environment microplastics (MPs) and nanoplastics (NPs) can be found and summarizes the most important technologies applied to analyse the importance of plastics as a contaminant in water bodies. The development of standardised analytical procedures is still necessary as most of them are not suitable for the identification of particles below 50 μm due to resolution limitations. The preparation and analysis of samples are usually time-consuming factors that shall be considered. Particularly for MP and NP analysis in aqueous samples, thermal analysis methods based on sample degradation are generally not considered to be the most effective approach. Nevertheless, Pyrolysis - Gas Chromatography Time-of-Flight Mass Spectrometry (Py-GCToFMS) is used in this thesis to propose a novel approach as due to its unique detection abilities, and with a novel filtration methodology for collection, it enables the identification of tiny particle sizes (>0.1 μm) in water samples.PTFE membranes were selected to filter the liquid samples using a glass filtration system. This way, the synthetic particles will be deposited on the membranes and will allow the study and analysis of the precipitated material. PTFE is a readily available, reasonably priced, and adaptable product that makes sample preparation quick and simple.The three plastics under study—polypropylene (PP), polystyrene (PS), and polyvinyl chloride (PVC)—can be identified from complex samples at trace levels thanks to the employment of these widely used membranes and the identification of various and specific (marker) ions. The technique was examined against a range of standards samples that contained predetermined concentrations of MPs and NPs. Detection levels were then determined for PVC and PS and were found to be below <50 μg/ L, with repeatable data showing good precision (RSD <20 %). The examination of a complex matrix sample taken from a nearby river contributed to further validate this innovative methodology; the results indicated the existence of PS with a semi-quantifiable result of 250.23 g/L. Because of this, PY-GCToFMS appears to be a method that is appropriate for the task of identifying MPs and NPs from complex mixtures.This thesis also focuses on the environmental challenge that disposable plastic face masks (DPFMs) pose, which has been made significantly worse due to the COVID-19 pandemic. By the time this thesis was written, the production of disposable plastic facemasks had reached to approximately 200 million a day, in a global effort to tackle the spread of the new SARS-CoV-2 virus. This thesis investigates the emissions of pollutants from several different DPFM brands (medical and non-medical) that were submerged in water to replicate the conditions in the environment after these DPFMs have been discarded. The DPFM leachates were filtered using inorganic membranes type and characterized using Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDS), Light/Optical Microscopy (LM/OM), Inductively coupled plasma mass spectrometry (ICP-MS) and Liquid chromatography–mass spectrometry (LC-MS). Micro and nano scale polymeric fibres, particles, siliceous fragments and leachable inorganic and organic chemicals were observed from all of the tested DPFMs. For non-medical DPFMs, traces of concerning heavy metals were detected in association with silicon containing fragments (i.e. lead up to 6.79 μg/L). ICP-MS also confirmed the presence of other leachable metals like cadmium (up to 1.92 μg/L), antimony (up to 3.93 μg/L) and copper (up to 4.17 μg/L). LC-MS analysis identified organic species related to plastic additives; polyamide-66 monomer and oligomers (nylon-66 synthesis), surfactant molecules, and dye-like molecules were all tentatively identified in the leachate. The question of whether DPFMs are safe to use daily and what implications may be anticipated after their disposal into the environment is brought up by the toxicity of some of the chemicals discovered.The previous approach is expanded to medical DPFMs with the utilisation of Field Emission Gun Scanning Electron Microscope (FEG-SEM) in order to get high resolution images of the micro and nanoparticles deposited on the membranes. It is also incorporated the use of 0.02 μm pore size inorganic membranes to better identify the nanoparticles released.Separated aqueous samples were also obtained by submerging medical DPFMs for 24 hours to be analysed using ICP-MS and LC-MS.Both particles and fibres in the micro and nano scale were found in all 6 DPFMs brands of this study. EDS analysis revealed the presence of particles containing different heavy metals like lead, mercury, and arsenic among others. ICP-MS analysis results confirmed traces of heavy metals (antimony up to 2.41 μg/L and copper up to 4.68 μg/L). LC-MS analysis results identified organic species related to plastic additives and contaminants; polyamide-66 monomer and oligomers (nylon-66 synthesis), surfactant molecules, and polyethylene glycol were all tentatively identified in the leachate. The toxicity of some of the chemicals found raises the question of whether DPFMs are safe to be used on a daily basis and what consequences are to be expected after their disposal into the environment.
published_date 2023-04-17T15:44:31Z
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