Digitalni repozitorijum
Univerziteta u Beogradu
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Hemometrijska karakterizacija teških metala u zemljištu i izdancima pionirskih vrsta koje rastu u blizini zagađenih voda u neposrednoj okolini rudarsko-metalurškog kompleksa u Boru: aspekti fitoekstrakcije i biomonitoringa : doktorska disertacija
Petrović, Jelena, 1973-
Tošić, Snežana, 1965-
Alagić, Slađana, 1962-
Stevanović, Zoran, 1967-
Milić, Snežana, 1961-
Predmet i cilj ove doktorske disertacije je procena autentičnih biljnih fitoekstrakcionih ibiomonitoring potencijala u odnosu na teške metale, u odabranim pionirskim biljnim vrstama kojerastu pored zagađenih voda u neposrednoj blizini rudarsko-metalurškog kompleksa u Boru i tokorišćenjem hemometrijskog pristupa i izračunavanjem rata bioakumulacije za svaki metal(oid) unadzemnim biljnim delovima (bioakumulacioni faktori izraženi kroz takozvane odnose mobilnosti,MR). Hemometrijski pristup realizovan je najsavremenijim analitičkim metodama za detekciju ikvantifikaciju metal(oid)a, kao što je masena spektrometrija sa indukovano spregnutom plazmomuz prethodno mikrotalasno rastvaranje pripremljenih uzoraka, koje su dalje bile kombinovane sastatističkim metodama kao što su: Pearson-ova korelaciona studija, hijerarhijska klaster analiza(HCA) i jednosmerna analiza varijanse (One-Way ANOVA). Posmatrani metal(oid)i bili su: Cu,Zn, Pb, As i Cd, a kao test-biljke za navedenu procenu, iskorišćene su dve zeljaste višegodišnjebiljne vrste: mlečika suncogled (Euphorbia helioscopia L.) i obična kopriva (Urtica dioica L.), jersu jedino one bile pronađene na svih pet lokacija od interesa (osim koprive na jednoj od njih).Preciznije rečeno, kod ovih biljaka uzorkovani su i dalje analizirani njihovi nadzemni delovi(izdanci), kao i odgovarajući uzorci zemljišta/sedimenta. Dodatno, izvršena je i analiza nekihvažnih zemljišnih parametara kao što su: pH, električni konduktivitet, EC, organska materija, OM iukupni N i P, kao i procena njihovog uticaja na procese usvajanja i akumulacije ispitivanihmetal(oid)a u sakupljenim biljnim izdancima.Rezultati ove disertacije i primenjeni hemometrijski pristup, kao i izračunavanjeodgovarajućeg bioakumulacionog faktora za svaki metal(oid) u obe biljne vrste sa svake lokacije,obezbedili su brojne korisne informacije o fitoekstrakcionim i fitomonitoring potencijalimaispitivanih pionirskih vrsta, gde su najvažnije sledeće:1) Prvo, pronađena je i analizirana biljka, tj. mlečika suncogled (Euphorbia helioscopia L.), za kojuranije nisu postojali literaturni podaci u odnosu na njene praktične fitoremedijacione ifitomonitoring potencijale.2) Kada su u pitanju ispitivani uzorci zemljišta/sedimenta, rezultati statističke metode One-wayANOVA, pružili su dokaz da su detektovane koncentracije svakog pojedinog zemljišnogmetal(oid)a značajno varirale, osim u slučaju Cd, gde su koncentracije varirale samo minimalno.Rezultati ove disertacije su takođe ukazali i na izuzetno visoke koncentracije Cu u svim uzorcimaprikupljenim pored zagađenih voda u Boru i njegovoj najbližoj okolini i najvažnije - ovekoncentracije bile su mnogo veće od propisanih graničnih (LV)- i remedijacionih (RV)- vrednosti, atakođe su bile u opsegu fitotoksičnih (zemljišnih) koncentracija. Fitotoksične koncentracije su biledostignute i u slučaju zemljišnog As na dve lokacije u urbano/industrijskoj (UI) zoni. I u ovomslučaju, odgovarajući LV i RV, su bili prevaziđeni i to u velikoj meri. LV i RV za Cd su takođe biliprevaziđeni na istim UI lokacijama. Na jednoj od njih, LV i RV za Zn su takođe bili prevaziđeni,kao i za Pb na drugoj. Sve ostale koncentracije (u zemljištu/ sedimentu) nisu bile na nivoima koji bise mogli smatrati povišenim, ili alarmantnim.3) Ovi nalazi su dalje sugerisali da, generalno, najveći rizik za sve žive organizme, a posebno zaprisutnu vegetaciju, može doći od zemljišnog Cu (na svim istraživanim mestima), a zatim i As (namestima iz UI zone). Ipak, uprkos ovoj činjenici, obe ispitivane biljne vrste su normalno rasle nasvojim prirodnim staništima, bez ispoljavanja bilo kakvih vidljivih simptoma toksičnosti Cu, ili As,što ih dalje kvalifikuje kao perspektivne kandidate za obnavljanje vegetacije na ugroženim mestima.Štaviše, obe biljne vrste bile su u stanju da tolerišu ekstremno visoke koncentracije Cu u svojimizdancima. Praktično, u svim izdancima, ovaj element je bio najobilniji i sve detektovanekoncentracije bile su na nivou fitotoksičnosti. Fitotoksične koncentracije su takođe bile otkrivene zaPb (u većini slučajeva) i za As (u nekoliko slučajeva). Sve ostale koncentracije metal(oid)a uizdancima, bile su na normalnim nivoima, a redosled obilnosti je bio: Cu > Zn > Pb > As > Cd (zasvaku biljnu vrstu, na svakoj lokaciji). One-way ANOVA je dodatno pokazala veliki broj statističkiznačajnih razlika između detektovanih koncentracija pojedinih metal(oid)a u obe biljke. Najmanjestatistički značajnih razlika (kod obe biljke) nađeno je u slučaju Cd i naročito As.4) U najvećem broju slučajeva, najveća koncentracija svakog pojedinog metal(oid)a u ispitivanimizdancima, bila je zabeležena u slučaju mlečike suncogled (na svakoj lokaciji), što je ukazalo dageneralno, ova biljna vrsta može razviti efikasnije mehanizme za usvajanje i akumulacijumetal(oid)a (preko lista, ili putem korena) od koprive, a posebno u pogledu Cu. Međutim, u osnovi,sposobnosti obe ispitivane biljke za usvajanje preko korena, tj. iz zemljišta/sedimenta nisu bile nanekim značajnijim nivoima, jer su vrednosti većine izračunatih MR bile mnogo niže od 1.Najefektniji rezultati uočeni su u slučaju Cu kod mlečike suncogled sa dve UI lokacije, gde sudetektovane koncentracije u izdancima bile iznad nivoa odgovarajućih koncentracija u zemljištu(MR > 1). One su takođe bile iznad nivoa koji je karakterističan za biljke hiperakumulatore, što jeposebno interesantno za fitoremedijaciju, praktično, fitoekstrakciju. Kako su obe UI lokacije bilekarakteristične i po niskim vrednostima pH zemljišta, jasno je da je, u Cu ekstrakciji, mlečikasuncogled bila najefikasnija u okolnostima kiselog zemljišta, što je dodatno bilo potvrđeno irezultatima izvedene Pearson-ove korelacione studije, dok je kopriva bila najefikasnija na mestimasa najvećim vrednostima EC (situacija sa ostalim metal(oid)ima nije bila tako uniformna ijednostavna). Takođe, bilo je jasno da su koncentracije skoro svih ispitivanih metal(oid)a uizdancima bile u negativnim korelacijama sa pH zemljišta, a u pozitivnim korelacijama sasadržajem OM, dok je situacija sa EC zemljišta, kao i sa zemljišnim P i N bila komplikovanija.Interesantno - zemljišni N bio je u pozitivnim korelacijama sa detektovanim koncentracijama svihmetal(oid)a u izdancima koprive i u negativnim korelacijama sa koncentracijama metal(oid)a uizdancima mlečike suncogled. Međutim, poslednje pomenute korelacije nisu bile na statističkiznačajnim, tj. pouzdanim nivoima. Rezultati iste statističke metode takođe su potvrdili dakoncentracije metala u izdancima nisu uvek bile u pozitivnim korelacijama sa odgovarajućimkoncentracijama u zemljištu (osim u slučaju As u mlečiki suncogled, gde je uočena jaka pozitivnakorelacija sa zemljišnim As), ali su u isto vreme bile u značajnim pozitivnim korelacijama sa nekimdrugim zamljišnim metalima: As-Pb, As-Cd i Cd-Pb kod mlečike suncogled i Zn-Cd kod koprive.Ovo sve ukazuje da, u većini slučajeva, koncentracije metal(oid)a u izdancima nisu bile u nekojznačajnijoj meri zavisne od odgovarajućih zemljišnih koncentracija, kao i da su neki metal(oid)i biliu kompeticiji pri usvajanju preko korena (korelacije sa negativnim predznakom), a neki ne(korelacije sa pozitivnim predznakom). Ovo u konačnom sugeriše da su obe biljne vrste usvajalemetal(oid)e pre svega u skladu sa svojim individualnim potrebama i takođe, sve ovo ide u prilogopšte poznate činjenice da biljke usvajaju metale ne samo preko korena, već i preko lista.5) Isti nalazi dalje indikuju da su obe biljne vrste, u slučajevima izuzetno visokih (praktično -rizičnih) zemljišnih koncentracija, za većinu metal(oid)a, usvojile strategiju njihovog ograničenogusvajanja (preko korena). U suštini i pored svih razlika u usvajanju i akumulaciji metala između dverazličite ispitivane biljne vrste (koje su bile uočene kroz primenjene analize), na bazi veoma niskihizračunatih vrednosti MR ( 1), može se reći da su se, u odnosu na većinu metal(oid)a, obe biljnevrste, ponašale kao tolerantne, ali nehiperakumulatorske vrste, a moguće čak i kao ekskluderi.6) Dobijeni rezultati, uključujući i rezultate HCA, korišćenjem Ward-ove metode, koji se odnose naklasifikaciju lokacija po zagađenosti, potvrdili su da izdanci obe ispitivane biljke ne mogu tačno daodraze postojeću situaciju u zemljištu, što ih dalje ne može preporučiti kao pouzdano sredstvo ufitomonitoringu zagađenja zemljišta.7) Međutim, u slučaju zagađenja atmosferskog porekla, obe vrste mogu biti od koristi, jer surezultati HCA sa primenjenom metodom povezivanja srednjih vrednosti između grupa, pokazali daobe biljne vrste imaju veoma dobar potencijal da odraze poreklo metal(oid)a u svojim izdancima(tj., predominantno iz - zemljišta/sedimenta, ili pak – iz atmosfere), pa su tako pružile i jednuadekvatnu ilustraciju opšteg stepena zagađenosti u konkretnoj oblasti, u konkretno vreme(uzorkovanja), što znači da one mogu poslužiti kao precizno sredstvo u praćenju zagađenja jednogsezonskog i pre svega atmosferskog karaktera, praktično tokom kompletnog vegetacionog perioda iu osnovi, za procenu generalnog kvaliteta životne sredine. Ova poslednja metoda je takođe pružilauvid i u moguće izvore metal(oid)a u ispitivanoj oblasti, tako da je kombinacija ove poslednjepomenute vrste HCA i izračunavanja Pearson-ovih koeficijenata, uspešno ukazala:- da se poreklo Cu u uzorcima zemljišta/sedimenta, u značajnom stepenu razlikuje u odnosu naostale ispitivane metal(oid)e, kao i da se najmanje može pripisati zagađenju koje dolazi izatmosfere, a pre svega iz topionice kao glavnog izvora ove vrste zagađenja u regionu Bora; porekloCu u zemljištu/sedimentu je predominantno prirodno, tj. geološko, ali svakako manjim delom potičei od povremenih izlivanja zagađenih voda iz neposredne blizine; ostali metal(oid)i su takođerazličitog porekla – i geološkog i antropogenog, ali pre svega atmosferskog, pa tek zatim i poreklomod izlivanja zagađenih voda,- da je poreklo metal(oid)a u izdancima mlečike suncogled bilo najviše u vezi sa otpadnimgasovima emitovanim iz topionice, pri čemu su prednjačili metal(oid)i kao što su: Cu, As i Cd, štopraktično znači da je mlečika usvajala metal(oid)e pre svega iz atmosfere (tj. preko listova), amanjim delom iz podloge (osim u slučajevima usvajanja Cu iz kiselog zemljišta) i- da su izdanci koprive, iz atmosfere usvajali pre svega Zn i As (najvećim delom), dok su metali Cdi Pb verovatno poticali iz oba izvora: iz tla i iz atmosfere (i to prilično ujednačeno); konačno,najveći deo Cu u koprivi sa izabranih mesta u Borskom regionu bio je poreklom iz podloge na kojojsu biljke rasle.
Tehnološko inženjerstvo - Hemija, hemijska tehnologija i hemijsko inženjersto / Technological engineering - Chemistry, chemical technology, and chemical engineering Datum odbrane: 25.09.2023.
The objective and goal of this doctoral dissertation is the evaluation of authenthic plantphytoextraction and biomonitoring potentials with regard to heavy metals in the selected pionirplant species, which are growing near polluted water bodies in the close vicinity of themining/metallurgical complex in Bor, using a chemometric approach and the calculation ofbioaccumulation rates for each metal(oid) in the aboveground plant parts (bioaccumulation factorsexpressed through the so called mobility ratios, MRs). Chemometric approach was realized by themost current analytical methods for metal(oid)s detection and kvantification such as inductivelycoupled plasma-mass spectrometry with previous microwave digestion of the samples, whichfurther were combined with the statistical methods such as: Pearson’s correlation study, hierarchicalcluster analysis (HCA), and one-way analysis of variance (One-Way ANOVA). The observedmetal(oid)s were: Cu, Zn, Pb, As, and Cd, while the two herbaceous perennial plant species: sunspurge (Euphorbia helioscopia L.), and common nettle (Urtica dioica L.) were used as the test-plants for the mentioned evaluation, because only they were found at all five locations of interest(except the common nettle at one of them). Precisely speaking, from these plants were collected andthen analyzed their aboveground parts (shoots), as well as the corresponding samples ofsoil/sediment. In addition, the analysis of some important soil parameters such as: pH, electricalconductivity, EC, organic matter, OM, and the total N, and P, was done, as well as the estimation oftheir influence on the processes of the uptake and accumulation of the investigated metal(oid)s inthe collected plant shoots.The results of this dissertation and the applied chemometric approach, as well as thecalculation of related bioaccumulation factot for each metal(oid) in both plant species from eachlocation, provided numerous informative data on the phytoextraction and biomonitoring potentialsof the investigated pioneer species, where the most important are the following:1) Firstly, it was found and analyzed the plant, namely, the sun spurge (Euphorbia helioscopia L.),for which, there was no any literature data regarding their practical phytoextraction andphytomonitoring potentials.2) As for the investigated samples of soil/sediment, the results of the statistical method One-wayANOVA, offered evidence that the detected concentrations of each individual soil metal(oid) variedsignificantly, except in the case of Cd, where the concentrations varied only minimally. The resultsof this dissertation also pointed to the extremely high concentrations of Cu in all samples collectednear polluted water boddies in Bor and its close vicinity, and most importantly – theseconcentrations were much higher than the defined limit (LV)- and remediation (RV)-values, andalso, they were in the range of phytotoxic (soil) concentrations. Phytotoxic concentrations werereached in the case of soil As at the two locations in urban/industrial (UI) zone, too. In this case, therelated LV, and RV were exceeded in a high quantity. LV, and RV for Cd were also surpassed atthe same UI locations. At one of them, LV, and RV for Zn were surpassed too, as well as for Pb atthe other. All other concentrations (in soil/sediment) were not at the levels that could be consideredelevated or alarming.3) These findings are further suggested that, generally, the greatest risk for all living organisms, andespecially for the present vegetation, may come from the soil Cu (at all investigated sites), and thenfrom the soil As (at the sites from UI zone). However, inspite of this fact, the growth of bothinvestigated plant species was normal at their natural habitats, without the expression of any ofvisible toxicity symptoms of Cu or As, which further qualifies them as prospective candidates forrevegetation of endangeres sites. What is more, both plant species were capable to tolerateextremely high Cu concentrations in their shoots. Practically, in all shoots, this element was themost abundant and all detected concentrations were at the level of phytotoxicity. Phytotoxicconcentrations were also found for Pb (in most cases), and for As (in several cases). All otherconcentrations of metal(oid)s in the shoots were at normal levels; the order of abundance was: Cu >Zn > Pb > As > Cd (for each plant species, at each location). Additionally, one-way ANOVAshowed a great number of statistically significant differences between the detected concentrations ofindividual metal(oid)s in both plants. The minimum of statistically significant differences (for bothplants) was found in the case of Cd, and especially As.4) In most cases, the highest concentration of each individual metal(oid) in the investigated shootswas recorded in the case of sun spurge (at each location), which pointed that, in general, this plantspecies can develop more efektive mechanisms for the uptake and accumulation of metal(oid)s (vialeaf or via root) than nettle, especially with regard to Cu. However, basically, the capabilities ofboth investigated plants regarding the uptake via root, i.e. from the soil/sediment, were not at somesignificant levels; namely, the values of most calculated MRs were much lower than 1. The mosteffective results were noticed in the case of Cu in sun spurge from the two UI locations, where thedetected shoot concentrations were above the corresponding soil concentrations (MRs > 1). Theywere also above the level charachteristic for plant hyperaccumulators, which is especiallyinteresting for phytoremediation, practically, phytoextraction. Given that both UI locations werecharachterised with their low values of soil pH, it is clear that in Cu extraction, sun spurge was themost efficient in the circumstances of acidic soils, which was additionally confirmed also by theresults of the performed Pearson correlation study; the nettle was the most efficient at the sites withthe highest EC values (the situation with other metal(oid)s was not so uniform and simple). It wasalso clear that the concentrations of almost all investigated metal(oid)s in the shoots were innegative correlations with soil pH, but in positive correlations with OM content, whereas thesituation with soil EC, as well as wit soil P, and N was more complicated. Interestingly – soil N wasin positive correlations with the detected concentrations of all metal(oid)s in nettle shoots and innegative correlations with the metal(oid)s concentrations in the shoots of sun spurge. However, therecently mentioned correlations were not at the statistically significant, i.e. confident levels. Theresults of the same statistical method also confirmed that the concentrations of metal(oid)s in theshoots were not always in positive correlations with the corresponding soil concentrations (exceptin the case of As in sun spurge, where a strong positive correlation with soil As was noticed), butsimultaneously, they were in significant positive correlations with some other soil metal(oid)s: As-Pb, As-Cd, and Cd-Pb in the case of sun spurge, and Zn-Cd in the case of nettle. This all points that,in most cases, the concentrations of metal(oid)s in shoots were not dependent, in some significantextent, on the corresponding soil concentrations, as well as that some metal(oid)s were incompetition during the root uptake (correlations with negative sign), whereas some of them werenot (correlations with positive sign). In final, this all suggests that both plant species assimilatedmetal(oid)s predominately in accordance with their individual needs, and also, this all is in favourof a well known fact that plants assimilate metal(oid)s not only via root but also via leaf.5) The same findings indicate further that, in the cases of very high (practically - dangerous) soilconcentrations, both plant species adopted a strategy of limited root uptake, for most metal(oid)s.Mainly, regardless all differences in metal(oid)s uptake and accumulation between the two differentplant species (that were perceived through the applied analyses), on the basis of very low values ofthe calculated MRs ( 1), it can be said, that, regarding most metals, both plant species acted astolerant but nonaccumulator species, possible even as excluders.6) The obtained results, including the results of HCA, using the Ward's method, which are related tothe classification of location according to their contamination, confirmed that the shoots of bothinvestigated plants can not reflect accurately, the existing situation in the soil, which further, can notrecommend them as a confident tool in soil phytomonitoring.7) However, in the case of contamination of atmospheric origin, both species can be of use, becausethe results of HCA with the applied method of average linkage between groups, showed that bothplant species have a very good potential to reflect the origin of metal(oid)s in their shoots (i.e.,predominately from the soil/sediment, or from the atmosphe). They offered an adequate illustrationof a general extent of contamination in the concrete area, in the actual time (of sampling), whichmeans that they can serve as an accurate tool in the screening of contamination of a seasonal and theatmospheric character, practically, during the complete vegetation period, and basically, for theestimation of a general environmental quality. Also, the last method offered an insight into thepossible sources of metal(oid)s in the examined area, so that, the combination of the last kind ofHCA and the calculation of Pearson's coefficients is successfully pointed that:- the origin of Cu in the soil/sediment samples differ, in a significant extent, from the otherinvestigated metal(oid)s, as well as that it can be less ascribed to the contamination of atmosphericorigin, and above all – to the smelter plant as the main source of this kind of contamination in theregion of Bor; the origin of Cu in the soil/sediment is predominately natural, i.e., geogenic, but in aless part it comes from the occasional overflows of polluted waters in the close vicinity; the rest ofmetal(oid)s are also of different origin – geogenic and anthropogenic, but primarily, they come fromthe atmosphere and then from the occasional overflows of polluted waters,- the origin of metal(oid)s in the shoots of sun spurge is mostly linked to tho waste gases emmitedfrom the smelter, where Cu, As, and Cd, were leading metal(oid)s, which means that the sun spurgeassimilated metal(oid)s predominately from the atmosphere (via leaves), and in a less extent, fromthe ground (except in the cases of Cu assimilation from the acidic soil) and- the shoots of the common nettle assimilated Zn, and As mostly from the atmosphere, while Cd iPb originated probably from both sources, i.e., from the ground and from the atmosphere (preetyevenly); finally, the greatest part of Cu in the nettle from the selected sites in the Bor region, wasfrom the ground where the plants were growing.
srpski
2023
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Creative Commons CC BY-NC-ND 3.0 AT - Creative Commons Autorstvo - Nekomercijalno - Bez prerada 3.0 Austria License.
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chemometry, phytoremediation, phytoextraction, biomonitoring, sun spurge (Euphorbia helioscopia L.), common nettle (Urtica dioica L.), heavy metal(oid)s, soil/sediment, biological accumulation
hemometrija, fitoremedijacija, fitoekstrakcija, biomonitoring, mlečika suncogled (Euphorbia helioscopia L.), obična kopriva (Urtica dioica L.), teški metal(oid)i, zemljište/sediment, biološka akumulacija
148231177
9821