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EN
Human activity has been impacting the environment for thousands of years. Progressing environmental pollution caused by human economic activity is associated with an increase in the concentration of trace elements and the formation of an excess of polycyclic aromatic hydrocarbons (PAHs). PAHs have always been present in the environment, but the development of civilisation and technology has resulted in their increase. PAHs easily penetrate plants, animals and the human body, which makes them a serious threat to human health and agriculture. Reducing the amount of polycyclic aromatic hydrocarbons in the soil is possible by introducing a microbiological preparation in the form of Effective Microorganisms (EM) into the soil. Some strains of microorganisms in EM can decompose chemical compounds, including PAHs. Through biodegradation, EM transforms harmful substances into less toxic forms. EM stimulates the activity of soil microflora, which naturally participates in the decomposition processes of organic substances, which contributes to improving soil quality and environmental protection. The following work presents the results of own research on analysing the impact of Effective Microorganisms on changes in the content of PAHs in the soil. It was observed that 75% of test samples in the form of soils after wheat cultivation in which EM was added had lower contents of 3,4,5-ring PAHs than their control samples. The work aims to analyse the potential of EM as a preparation that supports the natural capabilities of the ecosystem to reduce the amount of pollutants in the form of PAHs in the soil.
EN
Occurrence, distribution, and toxicity assessment of 16 Polycyclic Aromatic Hydrocarbons (PAHs) prioritized by the US Environmental Protection Agency in pyrolysis products – pyrolysis oil and pyrolysis wax – of different plastics are characterized. PP, HDPE, LDPE, PVC, PS (respectively, polypropylene, high- and low-density polyethylene, polyvinylchloride and polystyrene) and their mixture named 5P are chosen as a feed material for pyrolysis. Pyrolysis process is carried out in a custom-built laboratory batch reactor with the pyrolysis temperature of 450 °C for PP, PVC, PS and 500 °C for HDPE and LDPE. 5P mixture is pyrolyzed at 500 and 700 °C. PAHs quantification is used to determine the toxicity equivalency quantity TEQ (BaP) for each pyrolysis product and to establish the degree of toxicity. The highest total concentration of 16 PAHs in pyrolysis oil is found to decrease in the order of PVC > PP > PS > LDPE > HDPE. According to TEQ (BaP), the toxicity of the most toxic pyrolysis oils correlates with the aforementioned order of the total concentration, i.e., being lowest for HPDE and highest for PVC. For pyrolysis wax, the highest total concentration of 16 PAHs is for PVC > PS > LDPE > PP > HDPE, while TEQ (BaP) value decreases as PVC > LDPE > PP > PS > HDPE. The PAHs concentration and TEQ (BaP) values of 5P mixture show similar trends in both products (oil, wax), i.e., they both increase with increasing pyrolysis temperature.
PL
Dieta stanowi główne źródło wielopierścieniowych węglowodorów aromatycznych (WWA) dla człowieka. Związki te zwykle występują w żywności jako mieszanina kongenerów absorbowanych ze środowiska lub powstających w wysokotemperaturowych procesach jej przetwarzania (głównie grillowanie i wędzenie). Ze względu na specyficzną budowę WWA wykazują genotoksyczne działanie, co jest szczególnie niebezpieczne ze względu na ich synergistyczne i/lub addytywne oddziaływanie na organizm. W pracy opisano uregulowania prawne dotyczące zarówno metod badania WWA, jak i ich maksymalnych dopuszczalnych stężeń w żywności. Przedstawiono przegląd zawartości WWA w różnych grupach produktów spożywczych. Najwyższe stężenia WWA występują w olejach jadalnych, grillowanym I wędzonym tłustym mięsie, jak również produktach zbożowych, zwłaszcza opiekanych.
EN
Diet is the main source of polycyclic aromatic hydrocarbons (PAHs) for humans. These compounds usually occur in food as a mixture of congeners absorbed from the environment or formed in high-temperature food processing (mainly grilling and smoking). Due to their specific structure, PAHs exhibit genotoxic effects on organisms. This is particularly dangerous due to their synergistic and/or additive effects on the body. The paper describes legal regulations concerning methods of testing both PAHs and their maximal allowable concentrations in food. Also, an overview of the content of PAHs in various food products is presented. The highest concentrations of PAHs are recorded in edible oils, grilled and smoked fatty meat, as well as cereal products, especially toasted.
PL
Celem badań było porównanie skuteczności usuwania WWA ze środowiska wodnego w wyniku sorpcji na biowęglach otrzymanych z pomiotu kurzego oraz komunalnych osadów ściekowych. Proces sorpcji prowadzono dla dawek biowęgli 50 i 100 mg/l. Dla każdej dawki biowęgla czas kontaktu z WWA wynosił 90 i 120 minut. Najlepsze wyniki uzyskano dla dawki biowęgla 100 mg/l i czasu kontaktu 120 minut. Dla biowęgla z pomiotu kurzego i z osadu ściekowego stężenie benzo(a)pirenu obniżyło się odpowiednio o 87,2 i 78,7% natomiast dla czterech WWA normowanych w wodzie przeznaczonej do spożycia sumaryczne stężenie obniżyło się odpowiednio o 83,5 i 80,2%. Dla pozostałych WWA większą sorpcję zaobserwowano dla dibenzo(a,h)antracenu, stężenie tego związku obniżyło się o 83,2%. Najmniejsze zmiany wykazano dla naftalenu, którego stężenie zmniejszyło się o 68,5%. Nie wykazano istotnych statystycznie różnic pomiędzy sorpcją na biowęglu z pomiotu kurzego i osadu ściekowego.
EN
The aim of the study was to compare the effectiveness of removing PAHs from the aquatic environment as a result of adsorption on biochars obtained from chicken manure and municipal sewage sludge. The sorption process was carried out for doses of biochars of 50 and 100 mg/L. For each dose of biochar, the contact time with PAHs was 90 and 120 minutes. The best results were obtained for a biochar dose of 100 mg/L and a contact time of 120 minutes. For biochar from chicken manure and sewage sludge, the concentration of benzo(a)pyrene decreased by 87.2 and 78.7%, respectively, while for four PAHs standardized in drinking water, the total concentration decreased by 83.5 and 80.2%, respectively. For the remaining PAHs, higher sorption was observed for dibenzo(a,h)anthracene, the concentration of this compound decreased by 83.2%. The smallest changes were shown for naphthalene, the concentration of which decreased by 68.5%. There were no statistically significant differences between sorption on biochar from chicken manure and sewage sludge.
EN
Indoor activities involving cooking and warming, outdoor sources, smoking, and candle and in-cense burning may introduce a massive portion of polycyclic fragrant hydrocarbons. These are well known for their mutagenicity and carcinogenicity and are omnipresent in urban situations as a result of the combustion of fuel. Due to small particle size, penetration has been suspected to be one major source of indoor polycyclic aromatic hydrocarbons. In the current study, the manufacturing of three types of filters (electrostatic charge-based, pomegranate peel biochar-based, and birds’ feathers-based) was carried out. Their efficiency was tested to remove molecules bounded PAHs and also other geno-toxic compounds associated with these particles. The electrostatic filter was more efficient (27.42%) than pomegranate peel-based and birds’ feathers-based filters (13.86% and 8.32%, respectively). The carcinogenetic effects of PAHs emitted from outdoor and indoor pollutants can be reduced using these kinds of filters.
EN
Polycyclic aromatic hydrocarbons (PAHs) are significant pollutants found in petroleum products. There is ample literature on the biodegradation of PAHs containing less than five rings, but little has been done on those with more than five rings. Coronene (CRN), a seven-ring-containing PAH, has only been shown to be degraded by one bacterial strain. In this study, a bacterial strain 10SCRN4D was isolated through enrichment in the presence of CRN and 10% NaCl (w/v). Analysis of the 16S rRNA gene identified the strain as Halomonas caseinilytica. The strain was able to degrade CRN in media containing 16.5–165 μM CRN with a doubling time of 9–16 hours and grew in a wide range of salinity (0.5–10%, w/v) and temperature (30–50°C) with optimum conditions of pH 7, salinity 0.5%–10% (w/v), and temperature 37°C. Over 20 days, almost 35% of 16.5 μM CRN was degraded, reaching 76% degradation after 80 days as measured by gas chromatography. The strain was also able to degrade smaller molecular weight PAHs such as benzo[a]pyrene, pyrene, and phenanthrene. This is the first report of Halomonas caseinilytica degrading CRN as the sole carbon source in high salinity, and thus highlights the potential of this strain in bioremediation.
EN
Rising carbon dioxide emissions are driving climate change and there is growing pressure to find alternative energy sources. Co-combustion of waste with fuels is still occurring in some regions of the world, and it is important to know the compounds emitted from such combustion. This study investigated the emissions from the combustion of wood pellets with waste. The wood pellet was combusted with different additions of polyethylene terephthalate plastic and medium-density fiberboard (10 and 50%), in a low-power boiler (18W). Phenols, alkylphenols, phthalates, biomass burning markers, and polycyclic aromatic hydrocarbon emissions were determined. Gas chromatography coupled with a mass spectrometry detector was used to analyze these compounds after extraction and derivatization in the particulate matter and gas phase. The emissions of biomass burning markers and phthalates were the highest among all the compounds determined for MDF addition. The total emission of these compounds was 685 mg/h and 408 mg/h for 10% addition and 2401 mg/h and 337 mg/h for 50% addition, respectively. For the co-combustion of biomass with PET, PAHs and phenols had the highest emission; the emission was 197 mg/h and 114.5 mg/h for 10% addition and 268 mg/h and 200 mg/h for 50% addition, respectively. In our opinion, the obtained results are insufficient for the identification of source apportionment from household heating. After further study, tested compounds could be treated as markers for the identification of the fuel type combusted in households.
PL
Rosnąca emisja dwutlenku węgla powoduje zmiany klimatyczne przez co rośnie presja na poszukiwanie alternatywnych źródeł energii. Współspalanie odpadów z paliwami nadal występuje w niektórych regionach świata, dlatego istotna jest wiedza na temat związków emitowanych z takiego spalania. W niniejszej pracy zbadano wpływ dodatku odpadów na emisję ze współspalania z biomasą. Pelet drzewny współspalano z różnymi dodatkami plastiku z politereftalanu etylenu i płyty pilśniowej średniej gęstości (10 i 50%), w kotle małej mocy (18 W). Oznaczono emisję fenoli, alkilofenoli, ftalanów, markerów spalania biomasy oraz wielopierścieniowych węglowodorów aromatycznych. Do analizy tych związków po ekstrakcji i derywatyzacji w fazie pyłowej i gazowej zastosowano chromatografię gazową sprzężoną ze spektrometrem mas. Emisja znaczników spalania biomasy oraz ftalanów była najwyższa spośród wszystkich związków oznaczonych dla dodatku MDF. Całkowita emisja tych związków wynosiła odpowiednio 685 mg/h i 408 mg/h dla 10% dodatku oraz 2401 mg/h i 337 mg/h dla 50% dodatku. Dla współspalania biomasy z PET największą emisję miały WWA i fenole; emisja wynosiła odpowiednio 197 mg/h i 114,5 mg/h dla 10% dodatku oraz 268 mg/h i 200 mg/h dla 50% dodatku. Naszym zdaniem uzyskane wyniki są niewystarczające do identyfikacji źródeł zanieczyszczeń z ogrzewania gospodarstw domowych. Po dalszych badaniach, badane związki mogłyby być traktowane jako markery do identyfikacji rodzaju paliwa spalanego w gospodarstwach domowych.
EN
The lipophilic biomarker distributions in lipids of Neogene lignites and lignitic shales in western Pomerania and the midlands of Poland are presented. Twenty-six lignite samples and seven lignitic shales were obtained from twenty-four boreholes. Their extracts were separated, using thin-layer chromatography, and the saturate and aromatic fractions were analyzed by gas chromatography-mass spectrometry. The molecular compositions of n-alkanes, isoprenoids, n-alkylcyclohexanes, n-alkylbenzenes, tri- and tetracyclic diterpenoids, pentacyclic triterpenoids, as well as polycyclic aromatic hydrocarbons (PAHs) with up to five rings, were determined. The samples displayed n-alkane distributions in the range of C14–C35 and high odd-over-even carbon number predominances (CPI(25–33) from 2.9 to 7.9). Diterpanes consisted primarily of phyllocladane, abietane, isopimarane, labdane, and kaurane structures, although their abundances varied among the samples. Hopanes exhibited the biological and geochemical characteristics of low-maturity organic matter. Minor oleanane triterpenoids from angiosperms were also found. A few samples displayed evidence of biodegradation on the basis of the advanced isomerization of αβ-hopanes and the presence of short-chained n-alkanes, n-alkylcyclohexanes, and n-alkylbenzenes. A more mature stage of the above biomarkers also may have resulted in part from the oxidation of organic matter. The lignite source materials were derived from conifer and angiosperm flora as well as microbial remnants. The contribution from marine phytoplankton was excluded on the basis of the lack of C27 steroids. PAHs were predominantly perylene or phenanthrene, with minor other analogues. Thus, the data support progressive lacustrine/lagoonal sedimentation in the palaeoenvironmental mires.
PL
W artykule przedstawione zostały zagadnienia związane z opracowaniem metodyki chromatograficznego oznaczania wielopierścieniowych węglowodorów aromatycznych w próbkach gleb. Do tego celu stosowano chromatograf cieczowy serii Vanquish Core firmy Thermo Scientific wyposażony w detektor fluorescencyjny (FLD) i detektor UV-ViS. W ramach prowadzonych badań określono optymalne parametry pracy chromatografu, takie jak: objętość próbki, rodzaj eluentów, szybkość przepływu eluentów, gradient eluentów w trakcie analizy chromatograficznej i czas analizy, oraz dobrano kolumnę chromatograficzną umożliwiającą selektywny rozdział analitów. Następnie wykonano kalibrację układu chromatograficznego i walidację metody analitycznej oznaczania WWA, stosując roztwory kalibracyjne opracowane na podstawie roztworu wzorcowego PAH-Mix nr ref. 722393 firmy Macherey-Nagel. Walidacja metody analitycznej obejmowała wyznaczenie liniowości, odchylenia standardowego, względnego odchylenia standardowego, granicy wykrywalności (LOD) i granicy oznaczalności (LOQ) badanych WWA. Chromatograficzna metoda identyfikacji WWA w próbkach gleb wymaga przeprowadzenia analitów z matrycy stałej do matrycy ciekłej (etap izolacji), oczyszczenia próbki z substancji przeszkadzających oraz zagęszczenia ekstraktu (etap wzbogacania). W celu opracowania metody oznaczania WWA w próbkach gleb sprawdzono 3 metody przygotowania próbek do analizy chromatograficznej HPLC: metodę A (metoda QuEChERS), metodę B (ekstrakcja rozpuszczalnikiem w aparacie Soxhleta) i metodę C (ekstrakcja rozpuszczalnikiem wspomagana wytrząsaniem). Otrzymane ekstrakty były następnie oczyszczane na wybranym materiale sorpcyjnym: MgSO4 i PSA (metoda A), CN/SiOH (metoda B) i Al2O3 (metoda C). Do przetestowania wybranych metod przygotowania próbek gleby do analizy chromatograficznej HPLC wykorzystano glebę wzorcową PAHs by HPLC40g (SQC017-40G) firmy Sigma Aldrich, o znanych stężeniach analitów. Oczyszczone ekstrakty poddano analizie chromatograficznej HPLC, obejmującej identyfikację oraz ilościowe oznaczenie poszczególnych WWA, oraz obliczono stopnie odzysku analitów. Na podstawie analiz chromatograficznych i stopni odzysku wytypowano optymalną metodykę przygotowania próbek gleb do analizy chromatograficznej pod kątem oznaczania wielopierścieniowych węglowodorów aromatycznych. Opracowaną metodykę oznaczania WWA w próbkach gleb przetestowano na rzeczywistych próbkach gruntu pobranych z 2 otworów badawczych zlokalizowanych na terenie kopalni ropy naftowej usytuowanej w południowo-wschodniej Polsce.
EN
The article presents issues related to the development of a methodology for the chromatographic determination of polycyclic aromatic hydrocarbons in soil samples. For this purpose, a Vanquish Core series liquid chromatograph by Thermo Scientific equipped with a fluores­cence detector (FLD) und UV-ViS detector was used. As part of the research, the optimal parameters of the chromatograph work were determined, such as sample volume, type of eluents, eluent flow rate, eluent gradient during the chromatographic analysis and analysis time, and the chromatographic column was selected to enable selective separation of analytes. Then, the chromatographic system was calibrated and the analytical method for PAH determination was validated using calibration solutions prepared on the basis of the PAH-Mix standard solution ref. 722393 from Macherey-Nagel. The validation of the analytical method included the determination of results linearity, standard deviation and relative standard deviation, as well as limit of detection (LOD) and limit of quantification (LOQ) of the tested method. The chromatographic method of identifying PAHs in soil samples requires the transfer analytes from a solid matrix to a liquid matrix (isolation stage), removal of interfering substances from the sample and concentration of extracts (enrichment stage). Soil samples were tested with 3 methods of sample preparation for HPLC analysis: method A (QuEChERS method), method B (solvent extraction in a Soxhlet apparatus), method C (solvent extraction with shaking). The obtained extracts were then purified on the selected sorption material: MgSO4 and PSA (method A), CN/SiOH (method B) and Al2O3 (method C). Standard soil PAHs by HPLC40g (SQCo17-40g) from Sigma Aldrich with known analyte concentrations was used to test selected methods of preparing soil samples for HPLC chromatographic analysis. The purified extracts were subjected to HPLC chromatographic analysis including identification and quantification of individual PAHs, and the recovery rates of the analytes were calculated. On the basis of chromatographic analyzes and degrees of recovery, the most optimal methodology for preparing soil samples for chromatographic analysis for the determination of polycyclic aromatic hydrocarbons was selected. The developed methodology for determination of PAHs in soil samples was tested on real soil samples collected from 2 boreholes located in an oil mine site in south-eastern Poland.
EN
The aim of the research was to determine the factors defining the growth and development of Lolium perenne and Trifolium repens upon petroleum contamination. The top layer of clay soil contaminated with petroleum products resulting from an oil pipeline failure was collected for the tests. The control was the same type of uncontaminated soil with the addition of, under laboratory conditions, tissue paper. The research was conducted in two stages. The first concerned the germination process and seedlings parameters (Petri dishes). The germination energy (GE) and the germination capacity (GC) of seeds were determined. The seedling’s development was also evaluated based on ‘WinRhizo PRO 2009’ software. Then, in the second stage, pot tests were carried out, where the growth and development of species in the first year after sowing were temporarily measured. The parameters studied were the number, height, green and dry masses of the plants. A Gompertz regression model describing seed species germination and number species as time dependent dynamic was applied. The data were analysed statistically using variance analysis (ANOVA) and the PCA (principal component analysis) method. The results of our study indicated that admixture of petroleum into the soil does not seriously affect the development dynamics of Lolium perenne seedlings. The diesel oil contamination mostly affects the germination of the Trifolium repens by a statistically significant increase of the maximum value of germination and increasing the maximum growth rate.
EN
The Southwest Nigeria has witnessed tremendous increase in the output of municipal wastes in the recent years. Non availability of government policy on solid wastes management or its lack of effectiveness where it exists makes unabated open burning the predominant means of municipal solid waste disposal in the region. Open burning of municipal wastes being a major source of anthropogenic air emissions was investigated for atmospheric loading of some hazardous organic pollutants using the emission inventory method. The specific pollutants considered in this study were volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polychlorinated dibenzo –p- dioxin (PCDDs) and polychlorinated dibenzo furan (PCDF). The estimated release of VOCs, PAHs, PCBs, PCDD and PCDF from open burning of municipal wastes in the region over the 5-year period investigated were 64000 tonnes, 988 tonnes, 43 tonnes, 0.56 tonnes and 0.2 tonnes respectively. Given the serious human health implications associated with these hazardous organic pollutants, the study suggested conversion of wastes to energy as a possible solution since the region also faces energy challenges.
PL
W artykule omówiono metody wykorzystywane w biodegradacji wielopierścieniowych węglowodorów aromatycznych występujących w osadach czynnych i dennych. Przeanalizowano ich skuteczność i wpływ na oczyszczanie środowiska z zanieczyszczeń WWA.
EN
The article discusses the methods used in the biodegradation of polycyclic aromatic hydrocarbons found in active and bottom sediments. Their effectiveness and influence on the purification of the environment from PAH pollution were analyzed.
PL
Ropa naftowa jest i w najbliższej przyszłości nadal będzie podstawowym naturalnym surowcem gospodarczym na świecie. Wykorzystanie produktów uzyskiwanych z ropy naftowej stanowi siłę napędową gospodarki każdego kraju. Z przerobu ropy naftowej uzyskuje się wiele produktów, półproduktów i surowców, które znajdują zastosowanie w wielu gałęziach przemysłu, w tym petrochemicznym. Istotną rolę w tej dziedzinie gospodarki większości krajów odgrywają plastyfikatory naftowe, stosowane jako dodatek zmiękczający w procesach wulkanizacji kauczuków, szczególnie kauczuków syntetycznych butadienowych – styrenowo (SBR), oraz jako składnik mieszanek gumowych w procesie ich wytwarzania i wulkanizacji. Kierunki rozwoju plastyfikatorów naftowych dla przemysłu gumowego determinuje wiele dokumentów i aktów prawnych oraz szereg wymagań wynikających ze specyfiki procesów wytwórczych, a także z warunków eksploatacji wyrobów gumowych, w tym szczególnie: • posiadanie wymaganego dla danego zestawienia składu chemicznego oraz charakteryzowanie się odpowiednimi właściwościami fizykochemicznymi; • wykazywanie dobrej kompatybilności ze stosowanym kauczukiem; • odznaczanie się niską lotnością w warunkach procesu produkcji kauczuków oraz w procesach wytwarzania mieszanek gumowych i ich wulkanizacji; • niewykazywanie działania toksycznego. Plastyfikatory naftowe stosowane w kompozycjach kauczukowych (SBR) nazywane są również olejami-wypełniaczami. Składają się z cząstek węglowodorów zawierających od 25 do 35 atomów węgla i dzielą się na aromatyczne, naftenowe i parafinowe w zależności od udziału węgli w strukturach aromatycznych, naftenowych i parafinowych. Istotną rolę w badaniach eksperymentalnych opisanych w niniejszej monografii odgrywają plastyfikatory wysokoaromatyczne, otrzymywane jako produkt uboczny w trakcie rafinacji rozpuszczalnikowej destylatów próżniowych z ropy naftowej w procesie wytwarzania olejów bazowych, które zyskały duże znaczenie w procesie produkcji opon samochodowych. Plastyfikatory wysokoaromatyczne DAE charakteryzują się najwyższą zawartością węglowodorów aromatycznych i związaną z tym wysoką zawartością wielopierścieniowych związków aromatycznych oraz benzo[a]pirenu. Wprowadzenie przez ustawodawstwo Unii Europejskiej Dyrektywy 76/769/ EEC, a następnie Rozporządzenia 1907/2006 miało na celu zmniejszenie zawartości wielopierścieniowych węglowodorów aromatycznych (WWA) w oponach, co doprowadziło do wytwarzania przez przemysł naftowy plastyfikatorów naftowych o niskiej zawartości WWA z wykorzystaniem różnych procesów produkcyjnych, aby zaspokoić potrzeby globalnego przemysłu oponiarskiego. Po roku 2010 rynek światowy plastyfikatorów naftowych ze względu na ich mutagenne i rakotwórcze działanie eliminuje ze stosowania plastyfikator DAE. Stworzony system REACH w Unii Europejskiej uchwalony przez Parlament Europejski i Radę w dniu 18 grudnia 2006 roku Rozporządzenia numer 1907/2006 w sprawie rejestracji, oceny, udzielenia zezwoleń i stosownych ograniczeń w zakresie chemikaliów, wprowadzając zapisy 27 poprawki do Dyrektywy 76/769/EEC wprowadza zakaz stosowania ekstraktów wysokoaromatycznych o przekroczonym limicie zawartości wielopierścieniowych węglowodorów aromatycznych od dnia 1 stycznia 2010 roku. W części eksperymentalnej zamieszczono wyniki badań nad opracowaniem i wdrożeniem na skalę przemysłową technologii produkcji plastyfikatora TDAE spełniającego wymagania w zakresie rakotwórczości i mutagenności. Istotnym etapem przeprowadzonych badań eksperymentalnych były technologiczne próby przemysłowe dotyczące badań plastyfikatora TDAE wykonane na instalacji Furfurol w Zakładzie Produkcyjnym Spółki ORLEN OIL Sp. z.o.o. w Płocku. Wiodącą rolę w uzasadnieniu celu i tez pracy odgrywają badania selektywnej rafinacji rozpuszczalnikowej ciężkich ekstraktów pod kątem wytworzenia plastyfikatora aromatycznego TDAE spełniającego wymagania Rozporządzenia 1907/2006 UE. W wyniku przeprowadzonych prac technologiczno-badawczych pojawiła się możliwość wprowadzenia do cyklu produkcyjnego, obok olejów bazowych, plastyfikatora TDAE o nazwie handlowej Elasticol, wytwarzanego na bloku olejowym PKN ORLEN S.A. Również ważnym, kluczowym elementem wykonanych badań eksperymentalnych było zastosowanie procesu odparafinowania rozpuszczalnikowego dla pozyskania różnych plastyfikatorów TDAE. Proces odparafinowania rozpuszczalnikowego z użyciem różnych rozpuszczalników pozwolił na opracowanie technologii produkcji zmodyfikowanego plastyfikatora TDAE spełniającego wymagania jakościowe i wymagania Rozporządzenia 1907/2006 UE z możliwością poprawy właściwości niskotemperaturowych. Autor dokonał rejestracji technologii w Urzędzie Patentowym pod wspólnym tytułem: Sposób wytworzenia zmodyfikowanego plastyfikatora naftowego TDAE przeznaczonego do produkcji kauczuku i gumy, szczególnie opon samochodowych. Z uwagi na szeroki zakres wiedzy interdyscyplinarnej dotyczącej obszernego zakresu pracy sformułowane wnioski pogrupowano na: ogólne, szczegółowe, metodologiczne i perspektywiczne.
EN
Crude oil is and will continue to be in the near future the basic natural economic resource in the world. The use of products derived from crude oil is the driving force of the economy in every country. Many products, semi-finished products, and raw materials are obtained from the processing of crude oil and used in many industries, including the petrochemical industry. Petroleum plasticisers play an important role in this area of the country’s economy as a softening additive in the vulcanisation of rubbers, especially synthetic styrene-butadiene rubber (SBR), and as a component of rubber compounds in their production and vulcanisation. The development of petroleum plasticisers for the rubber industry is determined by many documents and laws, as well as a number of requirements resulting from the nature of the production and operating conditions of rubber products. In particular, they must: • have the chemical composition required for a given combination and have appropriate physicochemical properties, • exhibit compatibility with the selected rubber, • demonstrate low volatility during the processes of rubber production, rubber compound production, and vulcanisation, and • not show any toxic effects. Petroleum plasticisers used in rubber compositions (SBR) are also called filler oils, which consist of hydrocarbon particles containing from 25 to 35 carbon atoms and are divided into aromatic, naphthenic, and paraffinic types depending on the proportion of carbons in the structures the aromatic, naphthenic and paraffin. An important role in the experimental research of this dissertation is played by highly aromatic plasticisers, a by-product of refining solvents of vacuum distillates from crude oil in the production of base oils, which have gained a lot of significance in the production of car tyres. DAE highly aromatic plasticisers have the highest content of aromatic hydrocarbons and the associated high content of polycyclic aromatic compounds and benzo[a]pyrene. The European Union’s introduction of EU Directive 76/769/EEC and Regulation 1907/2006 was aimed at reducing the content of polycyclic aromatic hydrocarbons (PAH) in tyres, which led to the oil industry’s production of petroleum plastics with low PAH content using various production processes to meet the needs of the global tyre industry. After DAE plasticisers were banned due to their mutagenic and carcinogenic activity, the global plasticisers market in 2010 created the REACH system in the European Union. Caused the adoption by the European Parliament and the Council on December 18, 2006, Regulation No. 1907/2006 in on registration, evaluation, authorization and related restrictions on chemicals, introducing provision 27 to Directive 76/769/EEC of the amendment to prohibit the use of highly aromatic extracts exceeding the limit for polycyclic aromatic hydrocarbon content. The experimental part contains the results of research on the development and industrial-scale implementation of TDAE plasticiser production technology that meets the requirements for carcinogenicity and mutagenicity. An important stage of experimental research is the technological industrial trials concerning the TDAE plasticiser tests carried out on the Furfurol installation in the production plant of ORLEN OIL Sp. z.o.o. in Płock, Poland. The main justification of the purpose and theses of the work are the investigations of selective solvent refining of heavy extracts in terms of the production of TDAE aromatic plasticisers meeting the requirements of EU Regulation 1907/2006. As a result of the work, it is possible to introduce into the production cycle, in addition to the base oils, a TDAE plasticiser with the trade name Elasticol, on the oil block of PKN ORLEN S.A. Another important element of the experimental research is the use of a solvent dewaxing process to obtain various TDAE plasticisers. The process of solvent dewaxing with various solvents allowed for the development of production technology of a modified TDAE plasticiser that meets the quality requirements of EU Regulation 1907/2006 with the potential for improving its low-temperature properties. In addition, the author has registered this technology in the Patent Office under the common title, Manufacture of a modified TDAE plasticiser intended for the production of caoutchouc and rubber, especially car tyres. Due to the broad knowledge of the interdisciplinary, extensive scope of the work, its conclusions were grouped into general, detailed, methodological, and perspective.
EN
The permanganate index (PI), oil and grease (O&G), and 17 polycyclic aromatic hydrocarbons (PAHs) were analyzed in surface sediment and water samples collected at 13 sites along the western coast of Suez Bay (SB). PI and O&G in the SB coastal seawater ranged from 9.6 mg O2 l−1 and 17.0 mg l−1 to 16.0 mg O2 l−1 and 37.0 mg l−1, respectively. The level of polycyclic aromatic hydrocarbons (PAH) in water and sediment in the SB offshore area was determined by gas chromatography/flame ionization detection. The concentration ranged from 0.574 to 16873.2 ng g−1 in the sediment and 0.502 to 43.540 ng l−1 in water. The collected data were compared with values reported in the literature. The possible source and origin of pollution was also assessed based on the determined relative PAH levels at the study sites, the ratio of low molecular mass PAHs (LPAHs) to high molecular mass PAHs (HPAHs), and molecular indices of samples.
EN
The Bay of Cartagena (Colombia) is a site of commercial interest owing to its privileged location for maritime operations; however, the discharge of wastewaters from industrial activities and domestic sewage are affecting the water quality, and consequently, the biodiversity of coastal ecosystems. The polycyclic aromatic hydrocarbons (PAHs) are found in sediments and water of main ports, causing severe damage to the ecosystem. Thus, alternatives for the treatment of the Bay of Cartagena’s water and sediments are needed. In this paper, we performed the exergetic analysis of removing PAHs from water and sediments in the Bay of Cartagena using an adsorption-based treatment process with chitosan microbeads and magnetic nanoparticles (CM-TiO2/Fe3O4). The outcomes of exergy of utilities, irreversibilities and exergy losses were calculated using process data and exergy of substances. The Aspen plus V10 software provided the physical exergies, while chemical exergies were gathered from the literature. Overall exergy efficiency of 0.3% was determined for the seawater and sediment treatment facility. A sensitivity analysis was performed to identify the impact and viability of different design alternatives.
EN
Polycyclic aromatic hydrocarbons (PAHs) are formed from anthropogenic activities, i.e. industrial emissions, incomplete combustion of petroleum, coal and other fossil fuels and other industrial and domestic activities. Research areas of this study are four representative locations in the industrial complex, in the city of Banja Luka, Republic of Srpska, Bosnia and Herzegovina. The main objective of the paper is to determine the ecological risk and to assess probable sources of PAHs contamination in soil and groundwater. The results of this study reflect the effects of coal combustion (pyrogenic origin), petrogenic and biomass origin and may provide basic data for the remediation of PAHs in the location. The ecological risk in soil (at depths of 30, 100, 200, 300 and 400 cm) and groundwater is determined. The mean values of ecological risk in soil and groundwater decreased with soil depth. Values of RQ(NCs) for groundwater were found at high ecological risk, for Ant, Chr, DahA, Acy, Pyr, BaA, Phe, Flo, Nap, Ace and Fluo, with values 28.57, 20.59, 300.00, 242.86, 185.71, 1700.0, 76.67, 53.33, 15.83, 100.00 and 57.14, respectively. Σ16PAH indicated high ecological risk for most PAHs, which decreased with soil depth. The value of RQ(NCs) for ΣPAHs in groundwater indicates high ecological risk (ΣPAHs ≥ 800 and RQ(MPCs) ≥ 1). This is the first study on the ecological risk of PAHs in soil and groundwater in industrial soils in Banja Luka and provides baseline information for further studies and additional investigations of this industrial complex.
EN
The major processes for introducing polycyclic aromatic hydrocarbons (PAHs) in food are smoking and grilling of different products. But in addition, PAHs can permeate in the food chain due to their high lipophilicity and ability to be accumulated in specific tissue, through contaminated animal feed. Further, when some parts of these animals are marketed as food, the accumulated PAHs can go to the human organism. Some of them are classified as highly toxic, carcinogenic and mutagenic for animal and human organisms so they are under consideration of International and European legislation. This work reports development and validation of simple and fast GC/MS method for 16 PAHs determination. Comparison of two methods for sample preparation in pork meat matrix standard extraction/saponification procedure and modified QuEChERS method is also done. In addition, this paper report the calibration step of instrument and a recovery study for 16 PAHs in model pork meat, using modified QuEChERS procedure for sample pretreatment. The calibration step with accessible and suitable for use in real laboratory conditions internal standard (chrysene D12) is done in the range 10–100 ppb using toluene as solvent. The obtained results show very good linearity (R2 5 0.99 to 1.00). For the recovery study six model samples were spiked with 16 PAHs and they all are subjected to QuEChERS procedure. The recovery is calculated and the obtained data (71–120%) is in a good correlation with requirements of international legislation. Finally, LOD values for all 16 investigated compounds of modified GC/MS method and for the instrument were determined.
PL
Wielopierścieniowe węglowodory aromatyczne (WWA) występują powszechnie w środowisku, a rozwój technologiczny powoduje, że rośnie stopień narażenia człowieka na te zanieczyszczenia. Stanowią one bardzo liczną grupę związków organicznych charakteryzujących się obecnością dwóch lub więcej sprzężonych pierścieni aromatycznych w cząsteczce. Wiele WWA to związki genotoksyczne i rakotwórcze. Związki te mogą się tworzyć zarówno w samej żywności (pierwotnie), jak i podczas procesów jej przemysłowego przetwarzania, utrwalania czy przygotowywania do spożycia. W przeciągu ostatnich kilkunastu lat udało się przeprowadzić wiele badań jakościowych i ilościowych WWA w różnych produktach żywnościowych. Celem artykułu jest charakterystyka głównych WWA oraz aktualna ocena występowania i zawartości WWA w artykułach spożywczych produkcji krajowej w odniesieniu do wymagań w ustawodawstwie Unii Europejskiej.
EN
Polycyclic aromatic hydrocarbons (PAHs) are commonly found in the environment, and technological development increases human exposure to these pollutants. They are a large group of organic compounds characterized by the presence of two or more conjugated aromatic rings in the molecule. Many PAHs are genotoxic and carcinogenic. These compounds can form in the food itself (initially), as well as during the processes of its industrial processing, preparation for consumption or preservation. Over the past several years, many qualitative and quantitative tests of PAHs have been carried out in various food products. The purpose of the article is to characterize the main PAHs and to evaluate the occurrence and content of PAHs in food products of domestic production in relation to the requirements of the European Union legislation.
EN
The paper deals with the problem of groundwater pollution with polycyclic aromatic hydrocarbons (PAHs) in the "Cieszyńskie Žrádla Tufowe” Natura 2000 area. The concentration of 16 PAHs was measured with the use of the GC-MS method in seven water samples collected from the area of four enclaves belonging to the nature reserve. The results of analyses were compared with both the hydrogeochemical background and the limit value of PAHs concentration in drinking water, defined in the Regulation of the Minister for Health. Additionally, in order to determine the origin of contamination, PAH ratios for selected compounds were calculated. The paper also highlights the importance of the PAHs monitoring in groundwater.
EN
The paper provides an analysis of current Polish regulations on polycyclic aromatic hydrocarbons (PAH) in water. The issue was also described in relation to international law. Inconsistency in regulations in terms of definitions of the sum of PAH is highlighted. The influence of PAH concentrations on the classification of water chemical status and the assessment of drinking water quality was analyzed based on the results of concentrations of six PAHs: benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenzo(ah)anthracene, benzo(ghi)perylene and indeno(1,2,3-cd)pyrene. The PAH concentrations were determined in 36 water samples, including 28 samples of spring water and eight samples of snowmelt. The results obtained for most of the samples revealed elevated concentrations of benzo(a)pyrene. The authors underline the fact that a separate assessment of benzo(a)pyrene, the sum of six PAHs, and the sum of four PAHs unveil inconsistency in water quality evaluation. The results also suggest that only benzo(a)pyrene should be considered in the classifications mentioned, since its determination gives the actual view on the water quality in terms of PAH concentrations. The assessments for the sum of six PAHs and four PAHs in accordance with existing regulations indicate higher quality classes, meaning a better water quality in comparison with the concentration of benzo(a)pyrene itself.
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