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Article

Preliminary Study of the Occurrence of Microplastics in the Sediments of the Rzeszów Reservoir Using the Laser Direct Infrared (LDIR) Method

by
Wojciech Strojny
*,
Renata Gruca-Rokosz
and
Maksymilian Cieśla
Department of Chemistry and Environmental Engineering, Faculty of Civil and Environmental Engineering and Architecture, Rzeszow University of Technology, 35-959 Rzeszow, Poland
*
Author to whom correspondence should be addressed.
Sustainability 2023, 15(24), 16653; https://doi.org/10.3390/su152416653
Submission received: 6 November 2023 / Revised: 4 December 2023 / Accepted: 6 December 2023 / Published: 7 December 2023
(This article belongs to the Special Issue Sustainability in Water Resources, Water Quality, and Architecture)
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Abstract

:
This paper reports preliminary findings on microplastic (MP) presence in Rzeszów Reservoir sediment, Poland, considering ecotoxicological risks. Sediment samples were collected from three shoreline stations, and a custom density-based method was used for MP extraction. The extracted pollutants were identified using the Laser Direct Infrared (LDIR) method, both quantitatively and qualitatively. At stations R1, R2, and R3, a contamination of 120,000, 70,000, and 7500 MPs/kg of dry mass was determined. A total of nine types of plastics were identified: polypropylene (PP), polyamide (PA), polyethylene (PE), polystyrene (PS), polyurethane (PU), polyethylene terephthalate (PET), polyacrylonitrile (PAN), polyvinyl chloride (PVC), and rubber, with PU being the most prevalent. Spatial variation occurred in MP abundance, polymer diversity, and particle size. The station closest to the reservoir tributary was characterized by the highest abundance of MPs, the greatest variety of polymers, and the largest MPs. The calculated PHI (Polymer Hazard Index) indicated a very high ecotoxicological risk at all stations classified in the highest risk category V on a five-degree scale. Further research is needed to assess Rzeszów Reservoir’s MP contamination and its ecological consequences.

1. Introduction

Over the last fifty years, global plastic production has increased fifty-fold. It is estimated that 9200 million tonnes of plastic have been produced worldwide, of which over 6900 million tonnes were landfilled or, more worryingly, have contributed to environmental pollution [1]. Plastic consumer goods have significantly improved the quality of life. Convenient and durable products have opened up new manufacturing opportunities and created new industries [2]. Plastics are used by the packaging industry to make bottles, containers, and plastic bags to extend the shelf life of food [3]. Plastic materials and components are also widely used in the automotive industry. Plastic components are not only durable but also reduce the weight of vehicles and improve aerodynamics, resulting in better fuel economy and, consequently, lower CO2 emissions [4]. Plastics have also brought widespread benefits in construction, electronics, and medicine but have also created pollution problems [5]. The use of plastic waste as a raw material for reprocessing and energy recycling has been a growing trend in recent years [6]. However, due to the still-low consumer awareness of plastic products, a large amount of plastic waste is released into the environment in an uncontrolled manner [7,8]. It is worth noting that in some cases, plastic is very difficult to recycle. Sometimes, it is not suitable for reuse. The accumulated impurities in the waste degrade the quality of the recyclate. Methods of recovering plastic from waste involve the use of solvents and detergents, which generate wastewater. This makes plastics different from other recyclable materials in that they cannot always be fully reused. An example of a non-recyclable form of plastic is microplastics (MPs) [9,10]. Environmental exposure to plastic waste leads to the formation of microplastics, which are particles characterised by a high surface area to mass ratio and small size. Erekes-Merdano and coauthors (2015) define their size as less than 5 mm [11]. MPs are ubiquitous in the environment [12]. To date, they have been detected in marine environments [13], freshwater [14,15], soil [16], air [17], and even in the human body [18]. As researchers have pointed out, microplastics may have carcinogenic potential and impact the health of the population [19]. A characteristic feature of MPs is their ease of adsorption of other hazardous anthropogenic pollutants, their fragmentation, and their long retention time [20].
As pollutants with potentially harmful effects on aquatic organisms, microplastics pose new challenges for the sustainable management of water resources. Their presence can lead to the disruption of ecosystems and affect the health of aquatic biota. This applies to both marine and inland waters [21]. The problem of marine pollution by plastic waste is estimated to cause huge financial losses. In the case of the Mediterranean, the figure is around EUR 641 million per year. These costs are due to the cleaning of coastlines, rivers, and harbours from litter and plastics, the loss of value of tourist sites, the degradation of fisheries and aquaculture activities, the cost of greenhouse gas emissions, and health costs [22]. Inland reservoirs are also at risk. They are often the source of drinking water after pre-treatment. The presence of contaminants generates both treatment costs and health risks. Finding sustainable solutions to reduce the impact of plastics on the aquatic environment is an urgent problem whose costs are being paid today [23].
Environmental samples are usually not suitable for direct analysis of the presence of MPs in them [24]. One of the most important steps prior to their analysis is the development of efficient methods for the extraction of MPs. The chemical digestion and mechanical sorting of sample components are often required at an early stage, depending on the intended method of determination. Prata and coauthors (2021) describe methods and workflows using common chemicals [25]. The corrosion resistance of plastics, even in high and low pH environments, allows the environmental sample matrix to be decomposed into simple substances without a significant quantitative reduction in the MPs content in the sample [26]. Some of the most common methods used to prepare samples for analysis are the Fenton process and density separation [27]. The dispersion of a sample in a high-density medium, usually a saturated salt solution, allows the separation of its mineral components from the usually much lighter organic substances, including MPs. However, this is not the only method available [28]. Zhao and coworkers (2022) describe a separation method using a hydrocyclone. Methods using chromatography, hydrophobic, and electrostatic properties are also known [29].
The continuous improvement in analytical techniques will allow a more effective monitoring of microplastics and, thus, support the implementation of specific actions for the protection of water and the natural environment. It should also be noted that the lack of available standards and regulations for the extraction of microplastics is an additional challenge, which highlights the importance of developing consistent analytical protocols in this field [30]. The multi-step extraction of MPs from environmental matrices carries a risk of their loss, e.g., during digestion, handling, or filtration. This paper presents a modified density separation method using a custom-developed device that allows the efficient separation of MPs from the matrix of bottom sediment samples or suspended sediments characterised by high organic matter content, where current methods have not been successful. Transferred to a microscope slide, MPs can be efficiently identified quantitatively and qualitatively using, among others, the LDIR (Laser Direct Infrared) method. The development of an extraction method and separator for MPs is an important achievement in the development of analytical techniques for the analysis of MPs in the environment.
The main objective of this work was to preliminarily assess the presence and distribution of MPs in the bottom sediments of the Rzeszów Reservoir using a new separation method and to determine the ecotoxicological risk of MPs. For this purpose, the LDIR (Laser Direct Infrared) method was used, which is based on the analysis of the infrared absorption properties of polymer microparticles and allows the precise determination of their type and size. At the moment, there is a gap in the knowledge of microplastics in this reservoir, and this article tries to fill that gap.

2. Methods

2.1. Study Area

The study focused on the Rzeszów Reservoir in south-eastern Poland. The reservoir was created in 1974 by damming the Wisłok River along 63 + 760 km of its course. It is supplied by two main tributaries: the Wisłok and the Strug. The main function of the reservoir is to ensure the proper functioning of the water supply system of the city of Rzeszów. The catchment area of the Rzeszów Reservoir covers 2025 km2 and includes a large part of the Podkarpackie Voivodeship. The difference in water level between the main tributary of the Wisłok River at its source and the reservoir mouth is 616 m above sea level. The Wisłok flows through the lower foothills, which are mainly agricultural, the upper parts are forested, while in the middle part, there are industrial centres (glassworks, tanneries, refineries). The catchment area of the smaller tributary, the Strugu, is predominantly agricultural, traditionally consisting of fragmented agricultural land with a high population density. The Rzeszow Reservoir is under strong anthropogenic pressure from local agriculture, which causes extensive soil erosion. As a result, mineral substances and diffuse chemical pollutants accumulate in the reservoir [31].
Bottom sediment samples for the study were collected in the nearshore zone from three study sites located in different zones of the reservoir (Figure 1). Sampling at different distances from the dam allowed analysis of possible changes in the abundance and distribution of MPs along the reservoir.

2.2. Methodology of the Studies

The steps involved in the separation of MPs from bottom sediment samples are shown in Figure 2. The MP extraction process was carried out using a density separator registered with the Patent Office under number P.444159 and a modified density method registered under number P.444160. The collected bottom sediment samples were first dried in glass dishes at 60 °C for 48 h. A small amount of sediment of known weight was then transferred to a separator and suspended in 100 mL of deionised water. The sample prepared in this way was first sonified for 10 min at an amplitude of 42 kHz. Sonification was chosen as the method to prepare the sediment for chemical digestion because of its effectiveness in breaking up agglomerates and releasing microplastics from the sediment matrix. By breaking up the agglomerates, a larger reaction surface is created, which increases the efficiency of the Fenton process carried out in the next step. Amplitude and time have been optimised in pilot studies.
In the next step, 30 mL of a 30% H2O2 solution and 0.28 g of FeSO4∙2H2O were added to the separator and the Fenton reaction was carried out at 50 °C for 24 h. A magnetic stirrer with a Teflon mixing element was used to evenly distribute the reactants and maximise the degradation efficiency of the sample matrix. Concentrations and process conditions were chosen based on the work of [25].
The post reaction mixture was sonified again at the same time and with the same instrument parameters as the first time. Then, 10 g of KOH was added to the separator and the sample was left on the stirrer for five hours. At this point, the chemical preparation of the sample was complete, and the separation of the mixture continued.
For this purpose, the upper part of the separator was attached to the separator and the surface between the plates was sealed with a lubricant made from solidified natural fats. The separator was filled with a saturated K2CO3 solution to approximately 1/4 of the height of the upper chamber. The final density of the separating solution was 1.46 g/cm3. The set up prepared in this way was left for 24 h to separate particles with a density lower than that of the separating solution (including MPs).
The upper contents of the separator were then filtered using a vacuum filtration system through a silver filter of 0.45 µm pore size and 25 mm diameter. The remains on the filter were washed with 200 mL of hot deionised water and 100 mL of 96% ethanol. The filtrate was transferred to a sedimentation funnel and sonified again in 96% ethanol for two minutes at 20 kHz amplitude.
One hour after sonication, the sample concentrate collected in a silicone tube was separated using two spring clamps and transferred to a microscope slide. After evaporation of the ethanol from the slide, the sample was analysed on an Agilent 8700 LDIR microscope using Clarity firmware. The particles analysed ranged in size from 30 µm to 4900 µm. For each position, two 0.2 g sediment samples were analysed, and the results were summed. The results, therefore, refer to the presence of microplastics in 0.4 g of dry sediment.
To ensure maximum protection against the potential contamination of the sample, appropriate procedures and protocols were followed for the laboratory equipment and materials used at each stage of the study. Only cotton lab coats were used during the work. All liquids and solids were stored in glass containers. Dishes and equipment were protected with aluminium foil during the transport of samples and chemical reactions. All equipment, except the Teflon mixing element and silicone hose, was made of glass or metal. To ensure reliable results, Teflon and silicone were excluded from the analysis summary. The K2CO3 salt solution was filtered through a glass fibre filter with a pore size of 0.45 µm before use. This provided results that reflected the actual presence of MPs in the sediments of the studied reservoir.

2.3. Assessment of Ecotoxicological Risk

To assess the potential risk from MPs deposited in sediment, both their concentration and chemical composition were taken into account. The chemical toxicity of various types of polymers allows for the evaluation of their environmental harm. Assessments of potential ecotoxicological risk were conducted based on the Polymer Hazard Index (PHI) values [32], which were calculated using the formula:
PHI = Σ P n ·   S n
where Pn is the percent of specific polymer types, and Sn is the hazard scores of polymer types of MPs derived from [33].
Based on the knowledge of PHI values, it is possible to perform an assessment of ecotoxicological risk (Table 1).

3. Results

The study revealed the presence of MP particles in bottom sediments at all test sites. A total of nine types of plastic were identified: polypropylene (PP), polyamide (PA), polyethylene (PE), polystyrene (PS), polyurethane (PU), polyethylene terephthalate (PET), polyacrylonitrile (PAN), polyvinyl chloride (PVC), and rubber. The number and type of MPs at each site are shown in Table 2.
Most of the MPs identified were in the form of irregular fragments and fibres (mostly polyamide). However, no spherical MPs were observed. Figure 1 shows microscopic images of selected MPs along with their sizes. Please note that this is an artificial light source which will not reflect the true colours of microplastics in natural light.
In the sediment sample analysed, a total of 48 microplastic particles were detected at site R1, 28 at site R2, and only 3 at site R3, giving values of 120,000, 70,000, and 7500 MPs per kg of sediment dry mass, respectively. Selected particles for which high magnification images could be obtained are shown in Figure 3.
Figure 4 shows the contribution of each polymer type to the total contamination of the MPs. The main contaminant at sites R1 and R2 was PU, while at site R3, it was rubber. Furthermore, not only was the highest abundance of MPs found in the bottom sediments at site R1 in the zone of the reservoir most affected by inflow, but also the highest abundance of different polymer types. The lowest levels of MPs, both in terms of quantity and quality, were found at site R3, which is closest to the dam.
Variation in the size of the identified MPs was also observed. The bottom sediments at site R1, located in the upper part of the reservoir, were characterised by the highest proportion of particles with the largest surface area, while at site R3, near the dam, the sizes of the MPs were the smallest (Figure 5 and Figure 6).
Table 3 shows the calculated values of the PHI, which provides information on the ecotoxicological risk. At all study sites, the risk from MPs was very high and was classified in the highest hazard category of V, indicating a significant risk from MP contamination of bottom sediments in the studied reservoir. The highest PHI value was obtained for sediments from site R2, which was not characterised by the highest MP contamination in terms of quantity, and the significant ecotoxicological risk was determined by the type of polymer contamination.

4. Discussion

The results of the study showed that the sediments of the Rzeszów dam reservoir were characterised by significant MP contamination, with spatial variation observed in the pollutants studied, both in terms of quantity and quality.
It was found that the abundance of MPs in the studied sediments was closely related to the direction of water flow (Table 2). The highest abundance of MPs (per kg of sediment dry weight) was found at site R1 near the inflow, with 120,000 MPs, and the lowest abundance was found in the downstream zone of R3, with 7500 MPs. The processes of contaminant transport and deposition in bottom sediments are closely linked to the dynamics of the water flow (change in velocity and turbulence) [34], so the highest concentration of MPs at site R1 was certainly a consequence of the slower water flow in the reservoir compared to the river feeding it. The results also showed that the quantitative distribution of deposited MPs in the bottom sediments of the studied reservoir was consistent with the transport and deposition processes of suspended sediments observed in other studies. According to Cieśla et al. (2022) [35], the process of suspended sediment accumulation is most intensive in the tributary zone, while relatively less sediment is deposited in the dam area. This suggests that sedimentary particulate matter is the medium responsible for the transport and deposition of MPs in the bottom sediments of dam reservoirs.
A clear spatial variation was also observed in the quantity of the MPs. Sediments in the tributary zone (station R1) were characterised by the highest number of identified polymer types. The most abundant MPs were polyurethane (PU: 57,500 MPs/kg), polyamide (PA: 40,000 MPs/kg) and polypropylene (PP: 10,000 MPs/kg). High amounts of PU (50,000 MPs/kg), rubber (10,000 MPs/kg), and PVC (5000 MPs/kg) were found at the site located in the central part of the reservoir (R2). In contrast, the least variation in the composition of MPs was found at a site close to the dam (R3). Only two types of MPs were identified at this site, rubber (5000 MPs/kg) and polyethylene terephthalate (PET: 2500 MPs/kg). The presence of rubber identified at sites R2 and R3 is most possibly related to the proximity to a major road. As a result of vehicle use, tyres are subjected to progressive abrasion, resulting in the release of rubber microparticles [36]. The significant amount of PU contamination at sites R1 and R2 is probably a consequence of the industrial activities carried out in the vicinity of the reservoir. The area around the Rzeszów reservoir is highly urbanised and industrialised, and materials containing this type of polymer are widely used in both industry and construction, e.g., as a component of sealants or insulation. It is also worth noting that MPs present in bottom sediments can originate not only from water transport but also from direct deposition on the reservoir surface from the air [37]. For example, MPs falling directly on to the surface of a reservoir can result from the dispersal of plastic pollutants from a number of different sources, such as industry or waste incineration, but also from airborne particles (in the form of aerosols) that can be easily transported over long distances by wind (dry deposition) [38]. After falling to the surface of the reservoir, the plastic microparticles can interact with suspended matter and then sink to the bottom to become a component of the sediments [39]. Confirmation of such a mechanism of deposition of MPs in the bottom sediments of reservoirs is certainly provided by the presence in these sediments of polymers such as PP or PE, which have a density lower than water. The ability of these MPs to float should therefore prevent them from sinking and being deposited in the bottom sediments. However, under favourable conditions, suspended particles of MPs can interact with biological material to form aggregates of much larger size [40]. The results of a study by Cieśla et al. (2022) [35] have shown that organic matter produced inside reservoirs intensifies the flocculation process and thus the aggregation of fine grains of sedimenting particulate matter. This may be due to the fact that primary production includes both the production of phytoplankton biomass and the production of transparent exopolymer particles (TEP) which, due to their high viscosity, act as biological glue and are responsible for the formation of rapidly sinking aggregates that determine the rate of accumulation of suspended matter in bottom sediments. Exopolymer particles have also been shown to promote the binding of chemical contaminants in water, including MP particles [41]. Thus, a key factor controlling the environmental fate of MPs in inland aquatic ecosystems is not only their buoyancy, but also the overall factors influencing the metabolism of the aquatic ecosystem. It can be assumed that particles suspended in water form a kind of micro-ecosystem in which many processes take place, including colonisation by living organisms, interactions between particles and, most importantly, sorption of MP pollution. The contamination rate of MPs in the bottom sediments of the Rzeszów Dam reservoir was compared with the sediment contamination of selected aquatic ecosystems in different parts of the world (Table 4).
The literature review showed that the abundance of MPs in bottom sediments in different parts of the world varies over a very wide range. This is certainly related to the lack of standardised procedures for sampling and extraction of MPs from environmental matrices, as well as the variety of analytical methods used. It is also worth noting the differences in the presentation of results. Some studies report average values, and others report maximum and minimum values. The MPs contamination rates obtained in our study were very high and consistent with few ecosystems in the world (Haave et al., 2019 [44]; Ballent et al., 2016 [50]).
The highest level of MP contamination described in the literature was for sediments from a sewage outfall in an urban fjord in Norway (Haave et al., 2019 [44]). In this study, an FTIR method was used to identify twenty different types of polymers ranging from 12,000 to 200,000 MPs/kg sediment dry weight, of which more than 95% were particles smaller than 100 μm. Importantly, the high deposition of small particles coincided with areas of organic deposition, confirming the role of organic matter in the transport of MPs into the bottom sediments. The sizes of the identified MPs particles, as in our study, reached values unattainable by visual methods. Therefore, when comparing the results of different studies on MPs contamination, special attention should be paid to the standards and guidelines for sampling and analytical methods used.
An extremely important and crucial step is ensuring the accuracy and reliability of the results obtained in the process of extracting MPs from environmental samples and distinguishing them from other sample components. This is one of the biggest challenges for scientists working in this field. This is because MPs are similar to plant fibres, zooplankton or sand particles, even when observed under magnification. These, in turn, are present in the sample even after prior chemical digestion or filtration [58]. Therefore, methods for the separation of MPs from different environmental matrices are constantly being improved. Very rarely is the material collected from the environment suitable for direct analysis. Usually, a labour-intensive and multi-step preparation of the material is required. Physical, mechanical and chemical methods are used, as well as techniques that use differences in the physical properties of microplastics [59]. The MP separation methods developed so far apply to environmental matrices that are relatively ‘easy’ to analyse, i.e., sand-rich marine sediments and soils. However, as this study has shown, they are not applicable to more ‘challenging’ matrices, such as organic-rich bottom sediments and suspended matter in water from dam reservoirs or lakes. It is, therefore, clear that a universal and standardised method for the extraction and identification of MPs is still lacking. This gap is filled by the modified separation method presented in this paper in combination with LDIR, which allows the extraction and identification of plastic particles in a wide range of sizes.
Another important aspect of the occurrence of MPs is their negative environmental impact and potential hazards due to their toxicity. Due to their highly organophilic nature and high surface area to mass ratio, MPs can absorb other environmentally harmful substances (e.g., hydrophobic organic pollutants and heavy metal ions) during migration and transformation [60]. MPs are not only pollutants in their own right but can also act as carriers of toxic organic substances. MPs can travel long distances and exhibit the characteristics of long-term environmental persistence and relatively poor biodegradability. They can also be accidentally ingested by small aquatic organisms and thus transferred to other organisms higher up the trophic chain [61,62].
The synergistic effects of MPs and contaminants have significant effects on aquatic organisms, including fish (organ damage and even death) [63]. Aquatic mammals, usually at the top of the trophic chain, are particularly vulnerable to the adverse effects of MPs due to biomagnification and bioaccumulation. Scientists point to cytotoxic effects, adverse effects on the intestinal epithelium, induction of inflammation, and immunosuppression in these animals. However, it is still unclear whether these effects are a direct result of the polymer particles or the organochlorine, organophosphorus or heavy metal contaminants they absorb [64]. In addition, MPs have the potential to affect not only fauna but also flora. A controlled experiment on wetland plants showed a correlation between the presence of MPs and a reduction in chlorophyll synthesis, a reduction in plant weight and height, and a significant reduction in soil potassium, total nitrogen and phosphorus [65].
The literature review also indicates that the various types of additives and fillers used in the manufacture of plastics can also have a negative impact on the environment. To meet functional requirements, chemical additives such as plasticisers, flame retardants, antioxidants, stabilisers, lubricants and fillers are added to plastics. In general, these substances do not degrade, are also biologically toxic, have a long half-life and are bioaccumulative [66].
Commonly used organic additives in plastics (e.g., phthalates, polybrominated diphenyl ethers and phenolic compounds) are typical endocrine disruptors and can interfere with endogenous hormone synthesis in animals and humans [67]. Recent studies suggest that bioavailable plastic particles can even enter the human bloodstream. Fragments of polystyrene, polyethylene terephthalate, polyethylene and polymethyl methacrylate have been found in the blood of volunteers. The mechanism by which this occurs is still unknown, but it is thought that MPs may enter via the gastrointestinal and respiratory tracts [68].
It has been shown that the amount of plastic in freshwater reservoirs is highly dependent on the pollution of their tributaries. The characteristics of MPs (size and material type) in reservoirs are very similar to their tributaries [69]. Watercourses that are the outlets of wastewater treatment systems are particularly vulnerable [70]. One of the functions of retention reservoirs is to supply households with pre-treated water for consumption. Although there is no standard for the quality of tap water with regard to the presence of MPs, it is known to be a real problem [71]. This is evidenced by the presence of polymer particles in tap water documented by Tong et al. (2020) [72]. There is therefore an urgent need to expand research into the migration of MPs particles and their real risk to the environment and human health. It has also been shown that the toxicity of MPs depends not only on their chemical composition but also on their shape and size. The cytotoxic effect of fragments with an irregular, jagged shape and a developed surface is greater than that of spherical MPs [73]. Studies also suggest that in environments contaminated with MPs of different characteristics, those with the smallest size are more likely to bioaccumulate [74]. The results of the study in the Rzeszów Reservoir, where MPs of irregular, jagged or thread-like shape (Figure 3) and small size were generally identified, are therefore of great concern. In the total identified MPs, particles with a size < 50 μm2·103 represented 91% of the cases, with particles with an area in the range of 3–6 μm2 ·103 being the most numerous group (27%) (Figure 5). This is a particularly important issue, not only for the reservoir studied, where the ecotoxicological risk of MPs has been classified as the highest category of V, but also in a wider global context. Understanding the magnitude of human exposure to these contaminants could have major public health implications in the future [68].

5. Conclusions

The sediments accumulated at the bottom of the Rzeszow Dam Reservoir show a significant abundance of microplastics, placing them in the highest ecotoxicological hazard class. The most common microplastics in the reservoir are fibres and irregular fragments, while the most common polymers are polyurethane and polyamide. Spatial variability is evident in both the quantity and size of MP particles. The region closest to the reservoir inflow has the highest accumulation of MPs, characterized by a correspondingly larger average surface area of identified microplastics.
By identifying the types of microplastics and determining their distribution in the reservoir, our research provides important information that can support sustainable management decisions.
The results suggest that suspended particulate matter plays an important role in the deposition of MPs in the bottom sediments of the reservoir. This underlines the importance of understanding the dynamics of particulate matter in the context of microplastic distribution.
The use of a modified density separation method with an original instrument proves to be an efficient means of isolating MPs from the matrix of bottom sediment samples or suspended sediments characterised by high organic matter content.
The Laser Direct Infrared (LDIR) method proves to be a useful tool for the identification of MPs, especially those with sizes beyond the range of visual methods. Its effectiveness in environmental studies is confirmed by the results obtained.

Author Contributions

Conceptualization, W.S., R.G.-R. and M.C.; sampling and analysis, W.S.; methodology, W.S., R.G.-R. and M.C.; calculations and statistics, W.S., R.G.-R. and M.C.; writing—original draft, W.S., R.G.-R. and M.C. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are available on request from the corresponding author.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. Locations of studied reservoir and research stations.
Figure 1. Locations of studied reservoir and research stations.
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Figure 2. Stages of sample preparation for analysis.
Figure 2. Stages of sample preparation for analysis.
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Figure 3. Selected microscopic images of identified MPs: (a) PU particle; (b) acrylate particle; (c) PVC particle; (d) PP particle; (e) rubber particle.
Figure 3. Selected microscopic images of identified MPs: (a) PU particle; (b) acrylate particle; (c) PVC particle; (d) PP particle; (e) rubber particle.
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Figure 4. Contribution of each polymer type to overall MPs.
Figure 4. Contribution of each polymer type to overall MPs.
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Figure 5. Contribution of particles of a certain size to overall MPs.
Figure 5. Contribution of particles of a certain size to overall MPs.
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Figure 6. Particle size distribution of MPs at individual sites.
Figure 6. Particle size distribution of MPs at individual sites.
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Table 1. Hazard category for MP pollution [32].
Table 1. Hazard category for MP pollution [32].
PHIHazard Category
0–1I
1–10II
10–100II
100–1000IV
>1000V
Table 2. Number and type of MPs per study site.
Table 2. Number and type of MPs per study site.
Type of PlasticStation
R1R2R3
Rubber-42
PET--1
PU2320-
PA162-
PP4--
PE2--
PS1--
PVC12-
Acrylates (PAN)1--
Table 3. Potential risk assessment of MPs in sediments of Rzeszów Reservoir.
Table 3. Potential risk assessment of MPs in sediments of Rzeszów Reservoir.
StationPolymerScore (Sn)PHI
Value		Risk Category
R1Polyurethane (PU)13,8447133V
Polyamide (PA)63
Polypropylene (PP)1
Polyethylene (PE)11
Polystyrene (PS)30
Polyvinyl chloride (PVC)10,551
Polyacrylonitrile (PAN)12,379
R2Rubber162810,879V
Polyurethane (PU)13,844
Polyamide (PA)63
Polyvinyl chloride (PVC)10,551
R3Rubber16281086V
Polyethylene terephthalate (PET)4
Source: Lithner et al. (2021) [33].
Table 4. Abundance of MPs (MPs/kg) in sediment from different aquatic ecosystems.
Table 4. Abundance of MPs (MPs/kg) in sediment from different aquatic ecosystems.
ObjectsMinMaxMethodReferences
MarineBeibu Gulf
(China)		 264 ± 2 *3D Raman spectroscopy(Jiao et al., 2021) [8]
Coastline of Ireland 5483D Raman Spectroscopy(Marques Mendes et al., 2021) [42]
Lagoon of Venice (Italy)6722175ESEM-EDS(Vianello et al., 2013) [43]
Byfjorden (Norway)12,000200,000FTIR(Haave et al., 2019) [44]
Harbor of Cartagena (Spain)16.57 ± 2.96 *23.78 ± 4.59 *Microscopy(Bayo et al., 2022) [45]
Mele Bay (Vanuatu) 7300 ± 33,300 *Microscopy,
ATR-FTIR		(Bakir et al., 2020) [46]
Caspian Sea (Iran)28542SEM, FTIR(Ghayebzadeh et al., 2020) [47]
Lake/ReservoirLake Onega (Russia) 2188.7 ± 1164.4 *Microscopy(Zobkov et al., 2020) [48]
Edgbaston Pool (UK)250300Microscopy(Vaughan et al., 2017) [49]
Lake Ontario (Canada)50028,000Microscopy(Ballent et al., 2016) [50]
Lake Chiusi
(Italy)		112234UV-microscope, SEM(Fisher et al., 2016) [51]
Ox-Bow Lake (Nigeria)3477593Microscopy(Oni et al., 2020) [52]
RiverAntuã River (Portugal)18629Microscopy(Rodrigues et al., 2018) [53]
Vaal River
(South Africa)		29.63 *1028.57 *Microscopy(Saad et al., 2022) [54]
Fuhe River (China) 1049± 462 *Microscopy(Zhou et al., 2021) [55]
Yellow River (China) 6166 ± 2914 *LDIR(Qian et al., 2023) [56]
Rhine River (Germany)683763FTIR(Klein et al., 2015) [57]
* Average values.
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Strojny, W.; Gruca-Rokosz, R.; Cieśla, M. Preliminary Study of the Occurrence of Microplastics in the Sediments of the Rzeszów Reservoir Using the Laser Direct Infrared (LDIR) Method. Sustainability 2023, 15, 16653. https://doi.org/10.3390/su152416653

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Strojny W, Gruca-Rokosz R, Cieśla M. Preliminary Study of the Occurrence of Microplastics in the Sediments of the Rzeszów Reservoir Using the Laser Direct Infrared (LDIR) Method. Sustainability. 2023; 15(24):16653. https://doi.org/10.3390/su152416653

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Strojny, Wojciech, Renata Gruca-Rokosz, and Maksymilian Cieśla. 2023. "Preliminary Study of the Occurrence of Microplastics in the Sediments of the Rzeszów Reservoir Using the Laser Direct Infrared (LDIR) Method" Sustainability 15, no. 24: 16653. https://doi.org/10.3390/su152416653

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