Management of selected waste generated during cable production.

The subject of the research was the recovery of raw materials from waste generated in the production of cable insulation and the management of aluminum sludge. It was found that 49% (w/w) acetophenone, 6.8% (w/w) α-methylstyrene, and 17.2% (w/w) cumyl alcohol can be recovered from waste with a loss on ignition of 95% and used in various industries. A gas chromatograph equipped with a mass spectrometry detector was used to identify the recovered compounds. A waste distillation process was proposed to remove the water layer and obtain a concentrated acetophenone fraction. A method of neutralizing the water fraction and distillation residues is presented. The proposed waste management method is an alternative method to the currently used thermal transformation method. In turn, aluminum sludge was used to produce aluminum sulfate, which was used in the plant's sewage treatment plant as a coagulant. The effect of this action was a reduction of 67% in the content of total iron, 60% of trivalent iron, and 32% of chemical oxygen demand. The above-mentioned examples of waste management are part of a closed-loop waste management strategy.

Application of gas chromatographic data and 2D molecular descriptors for accurate global mobility potential prediction.

Mobility is a key feature affecting the environmental fate, which is of particular importance in the case of persistent organic pollutants (POPs) and emerging pollutants (EPs). In this study, the global mobility classification artificial neural networks-based models employing GC retention times (RT) and 2D molecular descriptors were constructed and validated. The high usability of RT was confirmed based on the feature selection step performed using the multivariate adaptive regression splines (MARS) tool. Although RT was found to be the most important, according to Kruskal-Wallis ANOVA analysis, it is insufficient to build a robust model, which justifies the need to expand the input layer with 2D descriptors. Therefore the following molecular descriptors: MPC10, WTPT-2, AATS8s, minaaCH, GATS7c, RotBtFrac, ATSC7v and ATSC1p, which were characterized by a high predicting potential were used to improve the classification performance. As a result of machine learning procedure ten of the most accurate neural networks were selected. The external validation showed that the final models are characterized by a high general accuracy score (85.71-96.43%). The high predicting abilities were also confirmed by the micro-averaged Matthews correlation coefficient (MAMCC) (0.73-0.88). To evaluate the applicability of the models, new retention times of selected POPs and EPs including pesticides, polycyclic aromatic hydrocarbons, pharmaceuticals, fragrances and personal care products were measured and used for mobility prediction. Further, the classifiers were used for photodegradation and chlorination products of two popular sunscreen agents, 2-ethyl-hexyl-4-methoxycinnamate and 2-ethylhexyl 4-(dimethylamino)benzoate.

Microplastic in the Baltic Sea: A review of distribution processes, sources, analysis methods and regulatory policies.

Microplastics pollution is an issue of great concern for scientists, governmental bodies, ecological organisations, and the general public. Microplastics pollution is widespread and is a great environmental problem on account of its potential toxicity for marine biota and human health. Today, almost all the world's seas and oceans are polluted with microplastics. The Baltic Sea is a semi-enclosed reservoir of brackish water and is a hotspot for contamination in terms of eutrophication and the presence of organic matter. Microplastics are quite intense, based on data from studies of marine litter and microplastics in the Baltic Sea. The number of microplastics in the Baltic Sea water is 0.07-3300 particles/m3, and in sediments 0-10179 particles/kg. These amounts prove that the waters and sediments of the Baltic Sea are heavily contaminated with microplastics. This article provides a comprehensive review of the microplastic origins and transport routes to the Baltic Sea. The data is presented as the concentration of microplastics in surface waters, sediments, and sea sand. The extraction methods used and the microplastics techniques are also presented. The possibilities and limitations of water and sediment sampling methods for microplastics determination were summarised, taking into account sampling tools, volume and depth. Extraction, separation, filtration, and visual sorting are outlined as sample preparation techniques for microplastic analysis. This review also focuses on the problems of obtaining data relevant to the development of the mathematical models necessary to monitor trends in the spread of microplastics in the Baltic Sea. Finally, several important laws and policies, which are in place in the Baltic States to control and manage microplastic pollution in the region, are highlighted.

Determination of environmental properties and toxicity of octyl-dimethyl-para-aminobenzoic acid and its degradation products.

Octyl-dimethyl-para-aminobenzoic acid (ODPABA) is one of compounds of emerging concern. It undergoes transformations under the influence of oxidizing or chlorinating agents and UV radiation forming products with different properties. There is very little experimental data concerning the environmental fate of ODPABA and its transformation products. Therefore, the purpose of the studies was to determine environmental parameters: water solubility, soil - water partition coefficient, octanol - air partition coefficient, bioconcentration factor as well as half-life in air, water and soil. Based on the results obtained, the persistence and migration possibilities of ODPABA and its transformation products in the aquatic environment were estimated. Moreover, the ecological toxicity of oxidation and chlorination products was investigated. Microtox®, Daphtoxkit F® and Artoxkit M® tests were used to determine toxicity. LC50 for Fish and Daphnia magna was calculated by Ecosar module. Studies have shown that as a result of ODPABA transformations, chloroorganic products are formed, which are lipophilic, are bioconcentrated in organic matter, are characterized by significant environmental persistence, can spread over considerable distances and are toxic. Oxidation products have significantly smaller impact on the environment. They are characterized by higher water solubility, lower bioconcentration factor and are less toxic.

The use of fast molecular descriptors and artificial neural networks approach in organochlorine compounds electron ionization mass spectra classification.

Developing of theoretical tools can be very helpful for supporting new pollutant detection. Nowadays, a combination of mass spectrometry and chromatographic techniques are the most basic environmental monitoring methods. In this paper, two organochlorine compound mass spectra classification systems were proposed. The classification models were developed within the framework of artificial neural networks (ANNs) and fast 1D and 2D molecular descriptor calculations. Based on the intensities of two characteristic MS peaks, namely, [M] and [M-35], two classification criterions were proposed. According to criterion I, class 1 comprises [M] signals with the intensity higher than 800 NIST units, while class 2 consists of signals with the intensity lower or equal than 800. According to criterion II, class 1 consists of [M-35] signals with the intensity higher than 100, while signals with the intensity lower or equal than 100 belong to class 2. As a result of ANNs learning stage, five models for both classification criterions were generated. The external model validation showed that all ANNs are characterized by high predicting power; however, criterion I-based ANNs are much more accurate and therefore are more suitable for analytical purposes. In order to obtain another confirmation, selected ANNs were tested against additional dataset comprising popular sunscreen agents disinfection by-products reported in previous works.

Estimation of physicochemical properties of 2-ethylhexyl-4-methoxycinnamate (EHMC) degradation products and their toxicological evaluation.

The organic UV filters, commonly used in personal protection products, are of concern because of their potential risk to aquatic ecosystems and living organisms. One of UV filters is ethylhexyl-4-methoxycinnamate (EHMC) acid. Studies have shown that, in the presence of oxidizing and chlorinating factors, EHMC forms a series of products with different properties than the substrate. In this study, the toxicities of EHMC and its transformation/degradation products formed under the influence of NaOCl/UV and H2O2/UV systems in the water medium were tested using Microtox® bioassay and by observation of mortality of juvenile crustaceans Daphnia magna and Artemia Salina. We have observed that oxidation and chlorination products of EHMC show significantly higher toxicity than EHMC alone. The toxicity of chemicals is related to their physicochemical characteristic such as lipophilicity and substituent groups. With the increase in lipophilicity of products, expressed as log KOW, the toxicity (EC50) increases. On the basis of physicochemical properties such as vapour pressure (VP), solubility (S), octanol-water partition coefficient (KOW), bioconcentration factor (BCF) and half-lives, the overall persistence (POV) and long-range transport potential (LRTP) of all the products and EHMC were calculated. It was shown that the most persistent and traveling on the long distances in environment are methoxyphenol chloroderivatives, then methoxybenzene chloroderivatives, EHMC chloroderivatives, methoxybenzaldehyde chloroderivatives and methoxycinnamate acid chloroderivatives. These compounds are also characterised by high toxicity.

Studies on the formation of formaldehyde during 2-ethylhexyl 4-(dimethylamino)benzoate demethylation in the presence of reactive oxygen and chlorine species.

In order to protect the skin from UV radiation, personal care products (PCPS) often contain chemical UV-filters. These compounds can enter the environment causing serious consequences on the water ecosystems. The aim of this study was to examine, the effect of different factors, such as UV light, the presence of NaOCl and H2O2 on the formaldehyde formation during popular UV filter, 2-ethylhexyl 4-(dimethylamino)benzoate (ODPABA) demethylation. The concentration of formaldehyde was determined by VIS spectrophotometry after derivatization. The reaction mixtures were qualitatively analyzed using GC/MS chromatography. The highest concentration of formaldehyde was observed in the case of ODPABA/H2O2/UV reaction mixture. In order to describe two types of demethylation mechanisms, namely, radical and ionic, the experimental results were enriched with Fukui function analysis and thermodynamic calculations. In the case of non-irradiated system containing ODPABA and NaOCl, demethylation reaction probably proceeds via ionic mechanism. As it was established, amino nitrogen atom in the ODPABA molecule is the most susceptible site for the HOCl electrophilic attack, which is the first step of ionic demethylation mechanism. In the case of irradiated mixtures, the reaction is probably radical in nature. The results of thermodynamic calculations showed that abstraction of the hydrogen from N(CH3)2 group is more probable than from 2-ethylhexyl moiety, which indicates higher susceptibility of N(CH3)2 to the oxidation.

Formation of chlorinated breakdown products during degradation of sunscreen agent, 2-ethylhexyl-4-methoxycinnamate in the presence of sodium hypochlorite.

In this study, a new degradation path of sunscreen active ingredient, 2-ethylhexyl-4-methoxycinnamate (EHMC) and 4-methoxycinnamic acid (MCA) in the presence of sodium hypochlorite (NaOCl), was discussed. The reaction products were detected using gas chromatography-mass spectrometry (GC-MS). Since HOCl treatment leads to more polar products than EHMC, application of polar extracting agents, dichloromethane and ethyl acetate/n-hexane mixture, gave better results in terms of chlorinated breakdown products identification than n-hexane. Reaction of EHMC with HOCl lead to the formation of C=C bridge cleavage products such as 2-ethylhexyl chloroacetate, 1-chloro-4-methoxybenzene, 1,3-dichloro-2-methoxybenzene, and 3-chloro-4-methoxybenzaldehyde. High reactivity of C=C bond attached to benzene ring is also characteristic for MCA, since it can be converted in the presence of HOCl to 2,4-dichlorophenole, 2,6-dichloro-1,4-benzoquinone, 1,3-dichloro-2-methoxybenzene, 1,2,4-trichloro-3-methoxybenzene, 2,4,6-trichlorophenole, and 3,5-dichloro-2-hydroxyacetophenone. Surprisingly, in case of EHMC/HOCl/UV, much less breakdown products were formed compared to non-UV radiation treatment. In order to describe the nature of EHMC and MCA degradation, local reactivity analysis based on the density functional theory (DFT) was performed. Fukui function values showed that electrophilic attack of HOCl to the C=C bridge in EHMC and MCA is highly favorable (even more preferable than phenyl ring chlorination). This suggests that HOCl electrophilic addition is probably the initial step of EHMC degradation.

Determination of linoleic acid in toothpaste by gas chromatography with flame ionization detection.

A new method for the determination of linoleic acid (LA) in toothpaste by a routine analysis has been proposed. Studies were based on the ISO 5509 procedure, which was modified for the purpose of LA determination in the toothpaste. Gas chromatography (GC) was employed for the qualitative and quantitative determination of linoleic acid methyl ester. The content of LA (5.31%) in sunflower oil added to the toothpaste composition (0.5%) was determined, and then the optimization studies for the determination of LA in the toothpaste samples were carried out. The relative standard deviation (RSD) of the procedure developed was 9.96% (n = 9). The quantitative analysis showed that the content of LA in the toothpaste samples studied was 0.0258 +/- 0.0011%. The detection limit of LA in toothpaste was approximately 0.001%.

Effect of Parameters on Oxychlorination of Tert-Butyl Ethers.

The effect of concentration, molar ratios of reagents, pH, and temperature on formation of chloro-organic products in reaction of tert-butyl ethers with chloride ions and hydrogen peroxide has been determined. A significant effect of Cl(-) ions and H(2)O(2) molar ratios on the rate of chloro-organic product formation has been observed. Studies on oxychlorination of tert-butylethyl ether (ETBE) at pH 7, 3.5, and 2.5 have been carried out. It was found that introduction of hydronium ions into the reaction system considerably hastened the process of chloro-organic product formation. Hydronium ions contribute to the formation of the reactive tert-butyl carbocation, which undergoes secondary reactions in the presence of reactive forms of chlorine and oxygen. Moreover, the effect of temperature on ETBE (tert-butylethyl ether) and MTBE (tert-butylmethyl ether) conversions was verified. The reactions of MTBE and ETBE oxychlorination were carried out at temperatures of 5 degrees C, 20 degrees C, and 35 degrees C.

Experimental and theoretical studies on formation and degradation of chloro organic compounds.

Studies on oxidation of tert-butyl ethers in the presence of chloride ions proved that acid medium favoured formation of chloro organic compounds. 1,2-Dichloro-2-methylpropane, 3-chloro-2-chloromethylpropene were identified among the reaction products. Presence of these compounds was identified both in the case when methyl-tert-butyl ether (MTBE) and ethyl-tert-butyl ether (ETBE) were subjected to reaction. Reaction products were analysed by gas chromatography method with application of -FID, -MS and -AED detectors. On the basis of experimental data, the path of tert-butyl ethers conversion to dichloro products was proposed. It was found that the identified chloro derivatives could be formed both by ionic and radical reactions. In order to confirm this thesis for the proposed scheme of reaction, the theoretical calculations of molecular simulation of the reaction paths were performed.