Modeling of microplastics degradation in aquatic environments using an experimental plan.

The aim of this article is to apply advanced predictive modeling techniques to understand the degradation process of microplastics in aquatic environments. Utilizing a Fractional Factorial Central Composite Experimental Plan, this study seeks to develop precise predictive statistical models that enable forecasting the quantity of pollutants generated during the degradation of microplastics under various environmental conditions. This tool was applied to model changes in DOC (dissolved organic carbon) and DEHP (bis(2-ethylhexyl) phthalate) values during the degradation of microplastics in aquatic ecosystems. The methods were developed using data derived from laboratory tests conducted using the GC-MS technique. The obtained approximating functions, considering factors such as degradation time, water temperature, and particle size, significantly reduced the analysis time. A two-stage verification of the approximating functions was conducted, considering the accuracy of the function form, its adequacy, the statistical significance of input variables, and their correlation with DOC and DEHP. The employed a Fractional Factorial Central Composite Experimental Plan allowed for the simultaneous reduction in the number of experiments and prediction of the influence of variables on the output values. Precise predictive models support understanding of the microplastic degradation process, facilitating the development of effective strategies for managing this pollution.

Elimination of a Mixture of Microplastics Using Conventional and Detergent-Assisted Coagulation.

The research described here investigated the suitability of coagulation process in the elimination of microplastics from tap water. The purpose of the study was to assess the effects of microplastic type (PE1, PE2, PE3, PVC1, PVC2, and PVC3), tap water pH (3, 5, 7, and 9), coagulant doses (0, 0.025, 0.05, 0.1 and 0.2 g/L), and microplastic concentration (0.05, 0.1, 0.15, and 0.2 g/L) on elimination efficiency with coagulation utilizing Al and Fe coagulants as well coagulation combined with a detergent (SDBS) addition. This work also explores the elimination of a mixture of two microplastics (PE and PVC) that are significant in terms of the environment. The effectiveness of conventional and detergent-assisted coagulation was calculated as a percentage. The fundamental characteristics of microplastics were also determined via LDIR analysis, and on the basis of these findings, particles that were more coagulation-prone were identified. The maximum reduction in MPs was achieved with tap water's neutral pH and a coagulant dosage of 0.05 g/L. The addition of SDBS increased the loss of the plastic microparticles' efficacy. A removal efficiency of greater than 95% (Al-coagulant) and 80% (Fe-coagulant) was achieved for each of the microplastics tested. The removal efficiency of the microplastic mixture with SDBS-assisted coagulation was obtained at a level of 95.92% (AlCl3·6H2O) and 98.9% (FeCl3·6H2O). After each coagulation procedure, the mean circularity and solidity of the unremoved particles increased. This confirmed that particles with irregular shapes are easier to completely remove.

Removal of Phosphorus with the Use of Marl and Travertine and Their Thermally Modified Forms-Factors Affecting the Sorption Capacity of Materials and the Kinetics of the Sorption Process.

The paper presents new reactive materials, namely marl and travertine, and their thermal modifications and the Polonite® material, analyzing their phosphorus removal from water and wastewater by sorption. Based on the experimental data, an analysis of the factors influencing the sorption capacity of the materials, such as the material dose, pH of the initial solution, process temperature, surface structure, and morphology, was performed. Adsorption isotherms and maximum sorption capacities were determined with the use of the Langmuir, Freundlich, Langmuir-Freundlich, Tóth, Radke-Praunitz, and Marczewski-Jaroniec models. The kinetics of the phosphorus sorption process of the tested materials were described using reversible and irreversible pseudo-first order, pseudo-second order, and mixed models. The natural materials were the most sensitive to changes in the process conditions, such as temperature and pH. The thermal treatment process stabilizes the marl and travertine towards materials with a more homogeneous surface in terms of energy and structure. The fitted models of the adsorption isotherms and kinetic models allowed for an indication of a possible phosphorus-binding mechanism, as well as the maximum amount of this element that can be retained on the materials' surface under given conditions-raw marl (43.89 mg P/g), raw travertine (140.48 mg P/g), heated marl (80.44 mg P/g), heated travertine (282.34 mg P/g), and Polonite® (54.33 mg P/g).

Experimental and computational hazard prediction associated with reuse of recycled car tire material.

The paper presents research on the emission of pollutants from used car tires in the form of microparticles. Due to the large amount of waste generated in the form of used car tires, a method is being sought to utilize this material as secondary raw material. More and more frequently, this waste is used in civil engineering. To do this, it is necessary to determine the environmental impact of this waste. 2 g of microplastic samples with fractions of 3000-8000, 1000-3000, 1000, and 600 µm were incubated in water protected from light. The influence of pH (3, 7, and 10), incubation time (1, 3, 5, 7, and 14 d) and temperature (20, 60, and 90 °C) on the degree of emission of selected phthalic acid esters and other tire components was investigated. Additionally, the influence of the decomposition of the analyzed material on the emission of methane and carbon dioxide at the temperature of 20 °C during 30, 180, and 360 days was investigated. The analysis of the amount of released substances was carried out using a gas chromatograph coupled with a mass spectrometer. Greenhouse gas analysis was performed using a gas chromatograph with a Barrier Discharge Ionization Detector. The research carried out confirmed that, depending on the environmental conditions, tire particles leach out, among others, phthalates, benzenediamine, phenol, benzothiazole, and benzene. Influence of particle size, pH value, incubation time, and temperature on the degree of emission of selected plasticizers was investigated. An innovative aspect of the research was the use of artificial neural networks to identify the validity of using machine algorithms in environmental research. An additional negative aspect of the implementation of tire particles in the water-soil environment is the emission of carbon dioxide and methane that are greenhouse gases.

The Use of an Ultrasonic Field in Support of Classical Methods of Oxidising Component Leached from Microplastics in Bottom Sediments.

The work detailed here examined the impact of selected unit methods and ultrasonic removal of the widespread plastic additive di(2-ethylhexyl) phthalate (DEHP) from the bottom sediments of a body of water. To this end, hydrogen peroxide and a classic or modified Fenton process were used, supplemented by an ultrasonic field. The latter had a vibration frequency of 20 kHz and an acoustic wave intensity of 3.97 W/cm2. The impact of process parameters such as reaction environment, reaction time, initial impurity content, aging of the impurity, influence of processes on the content of organic matter and dissolved organic carbon, and elution of selected components from the matrix were all analysed. It emerged that the most effective process by which to remove DEHP from a solid matrix involved a modified Fenton process assisted by an ultrasonic field. The highest average degradation efficiency achieved in this way was 70.74%, for C0 = 10 mg/kg d.w. and t = 60 min.

Reactive Materials in the Removal of Phosphorus Compounds from Wastewater-A Review.

Modern technologies designed to treat wastewater containing phosphorus compounds are based on the processes of adsorption and precipitation. In addition, more environmentally friendly and cheaper materials are being sought to ensure greater conformity with overarching assumptions of green chemistry and sustainable development. Against that background, this paper offers a review and analysis of available information on the considered reactive materials that have the capacity to remove phosphorus from wastewater. These materials are categorised as natural (with a sub-division in line with the dominant sorption groups of Al/Fe or Ca/Mg), waste, or man-made. Notably, most studies on sorbents have been carried out in laboratory systems via experimentation under static conditions. Among the natural materials, opoka has the highest sorption capacity of 181.20 g P/kg, while red mud (in the waste material category) is most efficient at binding phosphorus with a level of 345.02 g P/kg. Finally, among the group of commercial materials, Rockfos® has the highest sorption capacity of 256.40 g P/kg. In addition, this paper recognises the effect of composition, pH, and physical properties on a reactive material's capacity to absorb phosphorus, as well as the possibility for further potential use in the production of fertilisers.

Trophic degradation predispositions and intensity in a high-flow, silted reservoir.

The objective of the work was to demonstrate the relationship between the natural environmental characteristics of a reservoir and its catchment and severity of trophic degradation. The shallow, highly-silted Rzeszów Reservoir (SE Poland) was the object of study. The impact on degradation of internal supply from accumulated bottom sediments was also assessed, using water and sediment sampled in 2013 and 2014. A high value for trophic state was identified for the reservoir on the basis of TSI indexes, while assessed natural resilience to degradation and analysis of the catchment as a supplier of biogenic and organic matter both indicate high susceptibility to cultural eutrophication. Obtained values for equilibrium phosphate concentrations under anoxic conditions (EPC-0) point to the possibility of a more intensive process of internal supply in phosphorus. However, the presence of sediments poor in organic matter suggest no major threat of ongoing eutrophication. Desludging and/or dredging are likely to entail elimination from the ecosystem of a large part of the pollutants accumulated in sediments, as well as the internal supply of phosphate to the water column. However, as external sources are responsible for the advanced degradation of Rzeszów Reservoir, any attempts at reclamation within the water will fail to yield persistent effects if appropriate protective procedures in the catchment are not implemented.

Application of material from used car tyres in geotechnics-an environmental impact analysis.

This work begins with a literature-based discussion of the hazardous-waste problem represented by car tyres as hazardous waste, along with possible ways in which they might be utilised or managed. The impact of the material on the environment is characterised in the process, not least in the context of pollutants leached to the aquatic environment. Input in terms of new research results concerns the impact on water and soil of material from used car tyres being used in geotechnics. Specifically, tyre bales comprising 100-140 car vehicle tyres compressed into a lightweight block and secured by galvanised steel tie wires running around the length and depth of the bale, were researched, having been immersed in basins with alkaline and acidic water following initial preparation and pre-washing. The aim was to in some sense simulate-respectively-conditions in which rain and surface/ground water are involved, or else acid rain. To do that, the tyre bales were placed in the water for 120 days, with emerging leachate analysed after set intervals of time, with a view to changes in key physicochemical parameters of water being noted, as well as signs of the leaching of both undesirable components and priority substances, from tyres into the aqueous medium. Washing of the tyre bales was shown to induce slight pollution of water, with limited exceedance of normative values in respect of OWO content. However, this increase was not due to leaching of the Persistent Organic Pollutants tested for, but may rather have reflected contamination of tyres used, e.g., of soil at the place of previous storage. In general, waste water arising does not therefore contain substances that would stand in the way (legally) of its being discharged into a combined sewer system. Similar conclusions were arrived at through analysis of the leaching of pollutants from tyre bales exposed in the aforementioned pools of water of neutral and acidic reaction. Wastewater arising was not enriched significantly in impurities (be these metals, PAHs, phthalates, selected anions or cations), and there were therefore no exceedances of standards imposed for wastewater discharged to either waters or soil.

The use of alternative catalysts in processes of the chemical degradation of di-n-butyl phthalate in aqueous solutions.

The work detailed here investigated the efficiency of oxidising technologies in clearing aqueous solutions of di-n-butyl phthalate (DBP), a known endocrine-disrupting compound (EDCs). Specifically, this paper addresses the use of the classic Fenton process, and the development of a modification of Fenton's reagent targeted at the degradation of di-n-butyl phthalate in aqueous solution. The modification in question entailed the use of alternative catalysts or a mixture thereof. Hence oxidation by hydrogen peroxide (at various different concentrations), the classic Fenton process, was tested for the removal of DBP, alongside versions modified in terms of the quantitative and qualitative composition of a mixture of catalysts, and the presence of metal ions, as well as the factors of time, pH and initial DBP concentration. Given that it did not exceed 31%, the degradation of DBP we achieved using H2O2 could not be regarded as satisfactory. In contrast, the addition of 2.5 mM L-1 of Fe2+ was found to mediate almost complete elimination of the phthalate from the model solution. Also confirmed by experimentation were the benefits of using homogeneous catalysts (compounds of copper(II) and manganese(II)) as alternatives to Fe2+ in the Fenton reagent. A key experimental achievement was to confirm the applicability of a catalyst formed from a mixture of 2 or 3 types of transition metal ion. A Fenton reaction extended to ions like Mn2+ and Cu2+ in particular is seen to eliminate factors/parameters discouraging practical industrial use of the classic Fenton process.

A new concept for risk analysis relating to the degradation of water reservoirs.

This paper presents a proposal for a procedure by which to analyse the risk of reservoirs being degraded. The body of water assessed for its susceptibility to degradation in line with the proposed procedure is Myczkowce Reservoir, SE Poland. This reservoir has a maximum capacity of ten million m3 and helps provide hydropower, by serving as a surge tank located above the main Solina Reservoir. On the basis of an assessment of its morphometric and hydrological parameters, Myczkowce Reservoir was assigned to the low-resilience category where risk of degradation was concerned. The primary factors responsible for that are limited capacity in relation to shoreline length, a lack of thermal stratification, and a high value for the Schindler index. These and other environmental parameters provided for Myczkowce's assignment to the category of susceptible to the impact of matter supplied by its catchment, with this reflecting the instantaneous nature of the basin, high values for the Ohle coefficient, average catchment slope, and the lack of a septic system. The designated risk level supported Myczkowce's assignment to a category characterised by an "unacceptable" risk of degradation. The proposed method taking two parameters (resilience and susceptibility) into account represents the first universal method for assessing reservoirs without reference to risks such as drought, flooding, or lack of water supply for human consumption. The risk depends only on the reservoir and catchment parameters.

Production pathways for CH4 and CO2 in sediments of two freshwater ecosystems in south-eastern Poland.

This paper presents the results of research into pathways leading to the production of methane (CH4) and carbon dioxide (CO2) in sediments of two eutrophic reservoirs (Maziarnia and Nielisz), located in south-eastern Poland. In seeking to identify the pathways in question, use was made of analysis of stable carbon isotopes in CH4 and CO2 dissolved in pore water. This determined that CH4 is mainly produced through acetate fermentation, though the hydrogenotrophic methanogenic process may also be of importance, especially in deeper layers of sediments. Both the presence of autochthonous organic matter and increased pH values are shown to favour acetate fermentation. In turn, methanogenesis in sediments is assessed as capable of accounting for the generation of a considerable amount of CO2. Indeed, the role of methanogenesis in CO2 production is increasingly important further down in the layers of sediment, where allochthonous organic matter is predominant.

The influence of environmental factors on the carbon dioxide flux across the water-air interface of reservoirs in south-eastern Poland.

Studies concerning the emission of carbon dioxide (CO2) were carried out in 2009-2012 for six reservoirs located in four provinces of south-eastern Poland. The CO2 flux across the water-air interface was measured using the "static chamber" method. The measured fluxes of CO2 (FCO2) ranged from -30.64 to 183.78mmol/m2/day, and the average values varied in the range from -3.52 to 82.11mmol/m2/day. In most of the cases, emission of CO2 to the atmosphere was observed. The obtained values of CO2 fluxes were comparable to values typical for other temperate reservoirs. Analysis of the influence of selected environmental factors on the FCO2 showed that it depends on parameters characterizing both the sediments and surface water. The CO2 flux at the water-air interface was positively correlated with parameters of bottom sediments such as porosity, content of organic carbon and total nitrogen; and negatively with pH value and δ13C of organic carbon. In the case of the parameters characterizing surface water, positive dependences on the concentrations of nitrate and total nitrogen, and negative relationships with water temperature and chlorophyll a concentrations, were found.

The qualitative and quantitative analysis of the coupled C, N, P and Si retention in complex of water reservoirs.

The Solina-Myczkowce complex of reservoirs (SMCR) accounts about 15 % of the water storage in Poland. On the base of historical (2004-2006 years) data, the mass balance of nitrogen, phosphorus, total organic carbon and dissolved silicon were calculated. Large, natural affluents were the main source of the biogenic compounds in the studied ecosystem, delivering 90 % of TOC, 87 % of TN and 81 % of TP and DSi load. Moreover, results show that SMCR is an important sink for all the analysed biogenic elements. About 15-30 % of external loads were retained in the reservoir mainly in upper Solina. Due to the intensive processes of primary production, inorganic forms of nitrogen and phosphorus were mainly retained. Internal production of organic matter lead to an amount of the organic matter deposited in the sediments greater than was anticipated on the basis of the mass balance calculations. A constant load of dissolved silicon originating only from natural sources did not contribute to supplement deficits of Si present in the body of water in the reservoirs, promoting disturbances in N:C:P:Si ratios and another growth condition for other types of algae.

Determination of nitrate isotopic signature in waters of different sources by analysing the nitrogen and oxygen isotopic ratio.

A reference study on both the nitrogen content in waters and nitrogen and oxygen isotopic signatures characterising nitrate from different sources was conducted within the San River catchment area. Three kinds of catchments were studied: (1) forested and uncultivated; (2) artificially fertilised with nitrate; and (3) fertilised with manure and sewage. Moreover, atmospheric water was studied. The obtained values were found to be similar to others in the literature, with the exception of nitrate from the atmosphere, in regard to which influence reflecting the local conditions was to be noted. The isotopic signature of nitrate in the studied water results from the biogeochemical transformation of nitrogen compounds rather than from the mixing of different sources. The obtained results were statistically distinct and can be used as end-member values in further modelling studies connected with the management of nitrate in river waters, especially under middle-eastern European conditions.