Organic geochemical approach in identification and monitoring of the fate of oil type pollutants in river sediments on the Vrbas river model (Banja Luka)

Cilj istraživanja u okviru ove doktorske disertacije je da se korišćenjem bioloških markera, n-alkana i policikličnih ugljovodonika tipa sterana i terpana rasvetle izvori zagađenja naftnom zagađujućom supstancom u životnoj sredini na primeru interakcije između rečnih i priobalnih sedimenata (zemljišta). Analizirani su uzorci rečnih i uzorci priobalnih sedimenata iz rečnog i priobalnog područja reke Vrbas, na području grada Banja Luka (Bosna i Heregovina). Alkanska frakcija izolovanih ekstrakata pokazuje bimodalnu raspodelu n-alkana. Niži homolozi dominiraju u rečnim sedimentima sa maksimumima na C15, dok u priobalnim sedimentima dominiraju viši n-alkani, sa maksimumima na C29 odnosno C31. Više koncentracije sterana i terpana sa naftnom raspodelom dominiraju u rečnim sedimentima (u odnosu na priobalne), što je dokaz da niži n-alkani pripadaju naftnim izvorima. Više koncentracije ugljovodonika u rečnim sedimentima u poređenju sa priobalnim sedimentima, dodatno potvrđuju ovu činjenicu. Isto tako, ovo zapažanje daje dokaz o naftnom zagađenju u samom rečnom toku, kao i o njegovoj migraciji u priobalne sedimente. Mnogi izvori zagađenja su teško prepoznatljivi, jer se zagađujuće supstance prenose na velike razdaljine u složenim sredinama. Posebno su mehanizmi naftne migracije u sedimentima slabo poznati. U drugom delu istraživanja proučavana su uzorci dva sedimenta iz pojasa kruga gradske toplane i tri sedimenta smeštena na udaljenosti od približno 100, 200 i 300 m od uzoraka iz toplane u smeru toka reke Vrbas. Iz ovih uzoraka su izolovani zasićeni ugljovodonici i određen je grupni sastav hromatografijom na koloni. n-Alkani, terpani i sterani su analizirani gasno hromatografskom-maseno spektrometrijskom (GC-MS) tehnikom. Rezultati su pokazali da se količina nižih n-alkana povećava tokom migracije, što ukazuje na migracioni mehanizam. Rezultati sterana otkrivaju geohromatografsku migraciju nafte, gde stereoizomeri koji se najbrže eluiraju pokazuju najduži put migracije. Promene u distribuciji bioloških markera posledica su migracije naftnog polutanta pomoću vode.The aim of the research within this doctoral dissertation, on the example of interaction between river and coastal sediments, an attempt was made to contribute to the use of biological markers, n-alkanes, and polycyclic alkanes of sterane and terpane type, in assessing the source of oil pollutants in the environment. Samples of river sediments of the river Vrbas and samples of near coastal sediments (soils), in the part of the river that belongs to the city of Banja Luka (Bosnia and Herzegovina) were investigated. In the alkane fractions of isolated extracts, bimodal distribution of the n-alkanes was identified. The lower homologues dominated in the river sediments with maximum at C15, but the higher n-alkanes dominated in the soils samples, with maximum at n-C29 or at n-C31. The higher concentration of steranes and terpanes with oil type distributions in the river sediments (compared to the coastal sediments) represents evidence that lower n-alkanes originate from the oil sources. The higher content of total hydrocarbons in the river sediments when compared to the coastal sediments, further confirms this conclusion. At the same time, these fundamental considerations provide evidence that oil pollution occurred in the water flow and then oil pollutants migrated towards the coastline. Many pollution sources are difficult to identify because pollutants are transported far away into complex environments. In particular, the mechanisms of petroleum migration in sediments are poorly known. Here, we studied samples from two sediments from the circuit of a heating plant and samles from three sediments located at 100, 200 and 300 m away from the plant. Saturated hydrocarbons were isolated and group composition was determined by column chromatography. n-Alkanes, terpanes and steranes were analyzed by gas chromatography-mass spectrometry (GC-MS). Results show that the amount of short n-alkanes increases during migration, which indicates the migration mechanism. Results on steranes reveal a geochromatographic migration of the oil, where the fastest eluting stereoisomers display the longest migration path. Changes in the distribution of biological markers are explained by migration in water

Application of alkane biological markers in the assessment of the origin of oil pollutants in the soil and recent river sediments (River Vrbas, Bosnia and Herzegovina)

In this paper, an attempt was made to contribute to the use of biological markers, n-alkanes, and polycyclic alkanes of the sterane and terpane type, in the assessment of the source of oil pollutants in the environment using the example of the correlation between recent river and coastal sediments,. Four samples of recent river sediments of the Vrbas River and four samples of adjacent bank sediments (soils), in the part of the River that belongs to the city of Banja Luka (Bosnia and Herzegovina) were analyzed. In the alkane fractions of isolated extracts, a bimodal distribution of the n-alkanes was observed. Lower homologues dominated in the recent river sediments with maximum at C15, but higher n-alkanes dominated in the soil samples, with a maximum at n-C29 or at n-C31. The higher concentration of steranes and terpanes with oil type distributions in the recent/fresh river sediments (compared to the bank sediments) represents evidence that lower n-alkanes originate from oil sources. The higher content of total hydrocarbons in the recent river sediments than in the bank sediments further confirms this conclusion. At the same time, these fundamental considerations provide evidence that oil pollution primarily occurred in the water flow and then the oil pollutants propagated towards the riverbank

Supplementary material for the article: Samelak, I.; Balaban, M.; Vidović, N.; Koljančić, N.; Antić, M.; Šolević-Knudsen, T.; Jovančićević, B. Application of Alkane Biological Markers in the Assessment of the Origin of Oil Pollutants in the Soil and Recent River Sediments (River Vrbas, Bosnia and Herzegovina). Journal of the Serbian Chemical Society 2018, 83 (10), 1167–1175. https://doi.org/10.2298/JSC180501061S

Supplementary material for: [https://doi.org/10.2298/JSC180501061S]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2237

Sadržaj mineralnih materija u sremušu (Allium ursinum) sa različitih lokaliteta Republike Srpske

Allium ursinum is a plant, more known as sremus, crijemus, wild or bearded onion. In nutrition it is used as a vegetable (salad and spice), and in human medicine, as an auxiliary agent. It is significant due to its nutritional and healing value. Since diet is largely used seasonally and in fresh state, as a salad, it can be a significant source of some nutrients, such as mineral matter, which are of great importance for human health. Considering the polemics about sremus as a "source of health" we decided to analyze content of mineral matter, macro and micro elements in sremus, with four different locations of the northwest part of Repulic of Srpska. Sodium concentrations were determined from 31,065 to 32,905 mg / kg, potassium from 4703.06 to 4803.485mg / kg, calcium from 1532.545 to 1559.095 mg / kg. Microelements included nickel (0.358 to 0.388 mg / kg), cobalt, aluminum. Mineral matter was determined by atomic absorption spectrophotometry ICP OES spectroscopy after wet digestion.Allium ursinum u narodu je poznatiji kao sremuš, crijemuš, divlji ili medvjeđi luk. U ishrani se koristi kao povrće (salata i začin), a u humanoj medicini kao pomoćno sredstvo. Značajan je zbog svoje nutritivne i ljekovite vrijednosti. Pošto se u ishrani najvećim dijelom koristi sezonski u vrijeme prispjeća i u svježem stanju, kao salata, može da bude značajan izvor pojedinih hranjivih materija, kao npr. mineralnih materija, koje su od velikog značaja za zdravlje ljudi. Obzirom na dosta polemike o sremušu kao „izvoru zdravlja“ odlučili smo da u ovom radu analiziramo sadržaj mineralnih materija, makro i mikro elemenata u sremušu, sa četiri različite lokacije sjeverozapadnog dijela Republike Srpske. Određene su koncentracije natrijuma od 31,065 do 32,905 mgkg-1, kalijuma od 4703,06 do 4803,485mgkg-1, kalcijuma od 1532,545 do 1559,095 mg/kg. Od mikroelemenata određeni su nikl (0,358 do 0,388 mgkg-1), kobalt, aluminijum. Mineralne materije su određivane atomskom apsorpcionom spektrofotometrijom ICP OES spektroskopijom nakon vlažne digestije

Korelacija sadržaja ukupnih fenola sa antioksidativnom aktivnošću crvenih vina sa područja regije Banja Luka

In this paper, the antioxidant activity of 3 red wine samples was determined using 1,1- diphenyl-2- picrylhydrazil (DPPH)- radical scavenging assay, 2,2’- azino- bis- (3- ethylbenzothiazoline-6- sulfonic acid) (ABTS) radical scavenging assay, so as Briggs- Raushers oscillatory reactions. Correlation of these antioxidant methods with the total phenol content in these red wine samples was also performed. The total phenol content was found to vary from 1790,67- 3209,97 mgGAE/Lwine. Antioxidant activity determined by DPPH method 15,45- 17,08 mmolTrolox/Lwine, ABTS method 23,21- 24,14 mmolTrolox/Lwine, and Briggs- Raushers oscillatory reactions 1,826- 3,848 mmolTrolox/Lwine respectively. The total phenol content shows signifficant correlation with ABTS method (0,55), and very signifficant correlation with Briggs- Raushers oscillatory reactions (0,99)U ovom radu određena je antioksidativna aktivnost 3 uzorka crvenih vina primjenom gašenja 1,1- difenil- 2- pikrilhidrazil (DPPH)- stabilnog radikala, 2,2’- azino- bis- (3-etilbenzotiazolin- 6- sulfonska kiselina) (ABTS) stabilnog radikala, kao i Briggs- Rausherove oscilatorne reakcije. Urađena je i korelacija ovih antioksidativnih metoda sa sadržajem ukupnih fenola u navedenim uzorcima crvenih vina. Sadržaj ukupnih fenola se mijenjao u rasponu 1790,67- 3209,97 mgGAE/L. Antioksidativna aktivnost dobijena DPPH testom od 15,45- 17,08 mmolTrolox/L vina, ABTS testom od 23,21- 24,14 mmolTrolox/L vina, te Briggs - Rausherovom oscilatornom metodom 1,826- 3,848 mmolTrolox/Lvina respektivno. Sadržaj ukupnih fenola pokazuje značajnu korelaciju sa ABTS testom (0.55), te vrlo visoku korelaciju sa Briggs- Rausherovim oscilatornim reakcijama (0.99)

Neenzimski antioksidativni status paradajza sorte „Volovsko srce“ sa područja Lijevče Polja

The results of determination of non- enzymatic antioxidant capacity tomato variety “volovsko srce” are presented in this paper. Content of total phenols is between 88.81 to 138.44 µgGAE/gFW, total flavonoids from 59.25 to 66.95 µgQc/gFW, and flavonols from 94.49 to 243.47 µgQc/gFW respectively. The content of lycopene in the samples ranged from 136.32 to 600,3 µg/100gFW, while we determined and the content of vitamin C , which is 12.6 to 15.87 mg/100gFW for 3 different sample probes. The results of antioxidant activity of ethanolic extract of tomato variety “volovsko srce” obtained using DPPH and ABTS methods as compared to Trolox equivalent antioxidant capacity are: DPPH ranged from 1.81 to 2.54 µmol Trolox/gFW, for ABTS from 0.19 to 2.23 µmol Trolox/gFW. The results are in agreement with literature data , but it is most likely to some differences due to different ways of breeding samples.Rezultati određivanja neenzimskih antioksidativnih kapaciteta paradajza sorte „Volovsko srce“ prikazani su u ovom radu. Sadržaj ukupnih fenola se kreće u rasponu od 88.81 do 138.44 µgGAE/gFW, ukupni flavonoidi od 59.25 do 66.95 µgQc/gFW, te flavonoli od 94.49 do 243.47 µgQc/gFW respektivno. Sadržaj likopena u uzorcima se kretao od 136.32 do 600,3 µg/100gFW, dok je određen i sadržaj vitamina C koji iznosi 12.6 do 15.87 mg/100gFW za 3 različita uzorka. Rezultati antioksidativne aktivnosti etanolnih ekstrakata paradajza sorte „volovsko srce“ određeni su primjenom DPPH i ABTS metoda u odnosu na Trolox ekvivalent i iznose: DPPH u rasponu od 1.81 do 2.54 µmol Trolox/gFW, za ABTS od 0.19 do 2.23 µmol Trolox/gFW. Rezultati su u saglasnosti sa literaturnim podacima, ali je, najvjerovatnije, do određenih razlika došlo zbog različitog načina uzgoja ispitivanih uzoraka

Supplementary material for the article: Samelak, I.; Balaban, M.; Vidović, N.; Koljančić, N.; Antić, M.; Šolević-Knudsen, T.; Jovančićević, B. Application of Alkane Biological Markers in the Assessment of the Origin of Oil Pollutants in the Soil and Recent River Sediments (River Vrbas, Bosnia and Herzegovina). Journal of the Serbian Chemical Society 2018, 83 (10), 1167–1175. https://doi.org/10.2298/JSC180501061S

Supplementary material for: [https://doi.org/10.2298/JSC180501061S]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2237

Organic geochemical approach in identification and monitoring of the fate of oil type pollutants in river sediments on the Vrbas river model (Banja Luka)

Cilj istraživanja u okviru ove doktorske disertacije je da se korišćenjem bioloških markera, n-alkana i policikličnih ugljovodonika tipa sterana i terpana rasvetle izvori zagađenja naftnom zagađujućom supstancom u životnoj sredini na primeru interakcije između rečnih i priobalnih sedimenata (zemljišta). Analizirani su uzorci rečnih i uzorci priobalnih sedimenata iz rečnog i priobalnog područja reke Vrbas, na području grada Banja Luka (Bosna i Heregovina). Alkanska frakcija izolovanih ekstrakata pokazuje bimodalnu raspodelu n-alkana. Niži homolozi dominiraju u rečnim sedimentima sa maksimumima na C15, dok u priobalnim sedimentima dominiraju viši n-alkani, sa maksimumima na C29 odnosno C31. Više koncentracije sterana i terpana sa naftnom raspodelom dominiraju u rečnim sedimentima (u odnosu na priobalne), što je dokaz da niži n-alkani pripadaju naftnim izvorima. Više koncentracije ugljovodonika u rečnim sedimentima u poređenju sa priobalnim sedimentima, dodatno potvrđuju ovu činjenicu. Isto tako, ovo zapažanje daje dokaz o naftnom zagađenju u samom rečnom toku, kao i o njegovoj migraciji u priobalne sedimente. Mnogi izvori zagađenja su teško prepoznatljivi, jer se zagađujuće supstance prenose na velike razdaljine u složenim sredinama. Posebno su mehanizmi naftne migracije u sedimentima slabo poznati. U drugom delu istraživanja proučavana su uzorci dva sedimenta iz pojasa kruga gradske toplane i tri sedimenta smeštena na udaljenosti od približno 100, 200 i 300 m od uzoraka iz toplane u smeru toka reke Vrbas. Iz ovih uzoraka su izolovani zasićeni ugljovodonici i određen je grupni sastav hromatografijom na koloni. n-Alkani, terpani i sterani su analizirani gasno hromatografskom-maseno spektrometrijskom (GC-MS) tehnikom. Rezultati su pokazali da se količina nižih n-alkana povećava tokom migracije, što ukazuje na migracioni mehanizam. Rezultati sterana otkrivaju geohromatografsku migraciju nafte, gde stereoizomeri koji se najbrže eluiraju pokazuju najduži put migracije. Promene u distribuciji bioloških markera posledica su migracije naftnog polutanta pomoću vode.The aim of the research within this doctoral dissertation, on the example of interaction between river and coastal sediments, an attempt was made to contribute to the use of biological markers, n-alkanes, and polycyclic alkanes of sterane and terpane type, in assessing the source of oil pollutants in the environment. Samples of river sediments of the river Vrbas and samples of near coastal sediments (soils), in the part of the river that belongs to the city of Banja Luka (Bosnia and Herzegovina) were investigated. In the alkane fractions of isolated extracts, bimodal distribution of the n-alkanes was identified. The lower homologues dominated in the river sediments with maximum at C15, but the higher n-alkanes dominated in the soils samples, with maximum at n-C29 or at n-C31. The higher concentration of steranes and terpanes with oil type distributions in the river sediments (compared to the coastal sediments) represents evidence that lower n-alkanes originate from the oil sources. The higher content of total hydrocarbons in the river sediments when compared to the coastal sediments, further confirms this conclusion. At the same time, these fundamental considerations provide evidence that oil pollution occurred in the water flow and then oil pollutants migrated towards the coastline. Many pollution sources are difficult to identify because pollutants are transported far away into complex environments. In particular, the mechanisms of petroleum migration in sediments are poorly known. Here, we studied samples from two sediments from the circuit of a heating plant and samles from three sediments located at 100, 200 and 300 m away from the plant. Saturated hydrocarbons were isolated and group composition was determined by column chromatography. n-Alkanes, terpanes and steranes were analyzed by gas chromatography-mass spectrometry (GC-MS). Results show that the amount of short n-alkanes increases during migration, which indicates the migration mechanism. Results on steranes reveal a geochromatographic migration of the oil, where the fastest eluting stereoisomers display the longest migration path. Changes in the distribution of biological markers are explained by migration in water

Class III peroxidase and polyphenol oxidase activities in

In this study, changes in Class III peroxidase (POX) and polyphenol oxidase (PPO) activity in Phragmites australis (Cav.) Trin. Ex Steud. Utricularia vulgaris L. and Salvinia natans (L.) from the Bardača wetland during one vegetation season (June-October) were monitored. The highest activities of soluble and ionic cell wall bound peroxidases (solPOX and ionPOX, respectively) were measured for Phragmites communis (leaf > root > rhizome), followed by Utricularia vulgaris (whole plant), then Salvinia natans (whole plant). The results showed that during the vegetation period (August-September) the activity of solPOX, ionPOX and PPO in Phragmites communis increased, but the activity decreased drastically in October. For Salvinia natans and Utricularia vulgaris, a different seasonal distribution was obtained in the PPO activity, i.e. with a maximum activity during July and a minimum one during September. Different seasonal trends in enzyme activities are probably the result of abiotic stress caused by changing physic-chemical environmental conditions and different adaptive capacities of the studied species to habitat conditions. Correlations between physicochemical environmental parameters and enzyme activities indicate the possibility of using POX and PPO activities as an important bioindicatos of environmental status.The paper examined changes in the activity of Class III Peroxidase (POX) and polyphenol oxidase (PPO) in Phragmites australis (Cav.) Trin. Ex Steud. Utricularia vulgaris L. and Salvinia natans (L.) from two sites on Bardača wetland during one vegetation season (June-September). The results showed differences in POX and PPO activities between emergent, submersed and floating plants, depending on both the sampling period and the site. The obtained differences in enzyme activities are probably a reflection of the influence of different types of abiotic stress on plants in their natural habitat, but also specific adaptive characteristics of each of the investigated species. The obtained results indicate that the activities of POX and PPO in examined water macrophytes can be used as bioindicators of environmental conditions

Geochromatographic migration of oil pollution from a heating plant to river sediments

Many pollution sources are difficult to identify because pollutants are transported far away into complex environments. In particular, the mechanisms of petroleum migration in sediments are poorly known. Here, we studied two sediments from the circuit of a heating plant and three sediments located at 100, 200 and 300 m away from the plant. Saturated hydrocarbons were isolated and group composition was determined by column chromatography. n-Alkanes, terpanes and steranes were analyzed by gas chromatography-mass spectrometry. Results show that the amount of short n-alkanes increases during migration, which indicates the migration mechanism. Results on steranes reveal a geochromatographic migration of the oil, where the fastest eluting stereoisomers display the longest migration path. Changes in the distribution of biological markers are explained by migration in water