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Monitoring of residues of sulfonylurea in soil under real conditions by using high pressure liquid chromatography

dc.contributor.advisorSuturović, Zvonimir
dc.contributor.otherKravić, Snežana
dc.contributor.otherSuturović, Zvonimir
dc.contributor.otherKondić-Špika, Ankica
dc.creatorGrahovac, Nada
dc.date.accessioned2016-12-30T15:34:24Z
dc.date.available2016-12-30T15:34:24Z
dc.date.available2020-07-03T13:55:54Z
dc.date.issued2016-12-26
dc.identifier.urihttp://nardus.mpn.gov.rs/handle/123456789/7195
dc.identifier.urihttp://www.cris.uns.ac.rs/DownloadFileServlet/Disertacija147852127902538.pdf?controlNumber=(BISIS)102385&fileName=147852127902538.pdf&id=7029&source=NaRDuS&language=srsr
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dc.identifier.urihttp://www.cris.uns.ac.rs/DownloadFileServlet/IzvestajKomisije147852129774798.pdf?controlNumber=(BISIS)102385&fileName=147852129774798.pdf&id=7030&source=NaRDuS&language=srsr
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dc.description.abstractU okviru doktorske disertacije razvijena je brza i selektivna metoda za određivanje i praćenje ostataka herbicida na bazi sulfonilurea (nikosulfuron, oksasulfuron, tribenuron metil, tritosulfuron, triasulfuron, rimsulfuron i prosulfuron) u zemljištu primenom visoko pritisne tečne hromatografije sa UV detektor sa nizom fotoosetljivih dioda (HPLC-UV-DAD). Razdvajanje sulfonilurea je izvedeno uz primenu Zorbax Eclipse XDB-C18 kolone. U cilju definisanja odgovarajućih uslova analize, ispitan je i definisan uticaj najznačajnijih eksperimentalnih faktora. Usvojeni su sledeći optimalni uslovi gradijentne elucije: mobilna faza acetonitril (A) i 0,1% sirćetna kiselina (B) t = 0 min, 52% A; t = 2-2,5 min, 47% A; t = 2,5-5 min, 52% A, pri konstatnom protoku od 1 mL min-1 i temperaturi kolone od 250C. Na osnovu odziva analitičkog signala, njegove reproduktivnosti i linearnosti, talasna dužina od 240 nm je usvojena kao odgovarajuća. Utvrđeno je da je uticaj matriksa bio izražen te je stoga za kvantitativno određivanje sadržaja SU u uzorcima zemljišta primenom HPLC-UV-DAD metode korišćena MMC kalibraciona kriva. Pri analizi ekstrakata nekontaminiranog zemljišta ostvarena je granica kvantitativnog određivanja za nikosulfuron, oksasulfuron, tribenuron metil, tritosulfuron, triasulfuron, rimsulfuron i prosulfuron od 3,16 μg kg-1, 3,40 μg kg-1, 3,76 μg kg-1, 4,13 μg kg-1, 3,60 μg kg-1, 3,04 μg kg-1 i 2,97 μg kg-1, redom. Za potrebe osetljivijih, selektivnijih i tačnijih određivanja SU u zemljištu, definisana je metoda uz primenu tečne hromatografije sa tandemskom masenom spektrometrijom (HPLC-MS-MS). HPLC-MS-MS je korišćena kao referntna tehnika za proveru rezultata koji su dobijeni primenom HPLC uz UV-DAD detektor. Definisan je efikasan postupak za pripremu uzoraka zemljišta u cilju hromatografskog određivanja SU. Najefikasnija ekstrakcija ostvarena je primenom smeše dihlormetanacetonitril (2:1, v/v), zakišeljene sirćetnom kiselinom (0,8%, v/v), uz dodatak uree (0,3 g/ 10g zemljišta). Postupak mikrotalasne estrakcije u zatvorenom sistemu omogućio je najbolje uslove za ekstrakciju SU. U cilju izdvajanja SU, iz matriksa ekstrakata zemljišta, primenjena je ekstrakcija na čvrstoj fazi (SPE) sa silika gelom kao adsorbensom. Definisana metoda za određivanje ispitivanih SU, kao i razvijeni postupak pripreme uzoraka, uspešno je primenjen u analizi realnih uzoraka zemljišta. Veoma dobre vrednosti testa povrata ostvarene pri analizi primenom HPLC-UV-DAD metode, potvrdile su pre svega ispravnost postupka pripreme uzoraka, a delom i kompletne metode. Tačnost razvijene metode za određivanje SU u zemljištu potvrđena je paralelnim analizama uzoraka zemljišta korišćenjem HPLC-MS-MS. Primenom Studentovog t-testa (upareni), utvrđeno je da se rezultati paralelnih analiza statistički značajno ne razlikuju (P=95%). Istraživanja u okviru disertacije obuhvatila su i praćenje disipacije nikosulfurona, rimsulfurona, oksasulfurona i prosufurona u različitim komercijalnim dozama primene tokom 50 dana u polju na tri različite dubine (0-15 cm, 15-30 cm i 30-45 cm), kao i laboratorijskim uslovima na dve temperature (250C i 300C). Vreme polurazgradnje (DT50) ispitivanih SU (nikosulfuron, oksasulfuron i prosulfuron) definisano Mitttag-Lefler-ovom funkcijom u ogledima u laboratorijskim uslovima na 250C iznosilo je 0,65 dana (50 g ha-1 a.k.), 0,64 dana (160 g ha-1 a.k.) i 0,66 dana (30 g ha-1 a.k.), redom, a na 300C za nikosulfuron 0,20 dana (50 g ha-1 a.k.) i prosulfuron 0,49 dana (50 g ha-1 a.k.). DT50 za ispitivane SU u polju, takođe definisano Mitttag-Lefler-ovom funkcijom, iznosilo je 72 minuta (0,05 dana), 0,23 dana, 0,12 dana i 0,15 dana, za nikosulfuron, rimsulfuron, oksasulfuron i prosulfuron, redom. Značajno veća disipacija koja je utvrđena istraživanjima u okviru ove disertacije najverovatnije je uzrokovana uticajem abiotičkih i biotičkih procesa, kao i faktora spoljašnje sredine.sr
dc.description.abstractIn this thesis a fast and selective method for determination and monitoring of residues sulfonylurea herbicides (SU) (nicosulfuron, oxasulfuron, tribenuron methyl, tritosulfuron, triasulfuron, rimsulfuron and prosulfuron) in soil, by applying high-performance liquid chromatography with UV detector with diode array diodes (HPLC-UV-DAD) was developed. The separation of the sulfonylurea was performed by use of a Zorbax Eclipse XDB-C18 column. In order to define appropriate conditions of analysis, the influence of the most significant the experimental factors was investigated and defined. The following optimal conditions for gradient elution: mobile phase acetonitrile (A) and 0.1% acetic acid (B) t = 0 min, 52% A; t = 2-2.5 min, 47% A; t = 2.5-5 min, 52% A were adopted at a constant flow rate of 1 mL min-1 and column temperature of 250C. On basis of the response of the analytical signal, its reproducibility and linearity, the wavelength of 240 nm was adopted as an appropriate. The influence of the matrix was expressed and therefore for the quantitative determination of investigated SU in soil samples application of HPLCUV- DAD methods was used MMC calibration curve. In the analysis of extracts of nocontaminated soil limits of quantitation for nicosulfuron, oxasulfuron, tribenuron methyl, tritosulfuron, triasulfuron, rimsulfuron and prosulfuron was achieved 3.16 μg kg-1, 3.40 μg kg-1, 3.76 μg kg-1, 4.13 μg kg-1, 3.60 μg kg-1, 3.04 μg kg-1 and 2.97 μg kg-1, respectively. The method by using liquid chromatography-tandem mass spectrometry (HPLC-MSMS) was defined in order to find more sensitive, more selective and more accurate way to determine concentration SU in soil. HPLC-MS-MS was used as the reference technique for checking results that have been obtained by HPLC with UV-DAD detector. An efficient procedure preparation of soil samples for the purpose chromatographic determination of SU was defined. Using a mixture of dichloromethane-acetonitrile (2: 1, v / v), acidified with acetic acid (0.8%, v / v), with the addition of urea (0.3 g / 10 g soil) was applied as the most effective way for extraction SU. Microwave extraction process in a closed system allowed the best conditions for the extraction of SU. In order to extract SU from matrix exctracts soil the solid phase the extraction (SPE) with silica gel as an adsorbent was used. The defined method for determination of investigated SU, as well as the developed procedure of sample preparation, was successfully applied in the analysis of real samples of soil. The correctness of procedure of sample preparation was confirmed with very good values of recovery test which was applied in the analysis by using HPLC-UVDAD. The accuracy of the developed method for determination of SU was confirmed by coupled analysis soil samples using HPLC-MS-MS. The results of parallel analysis does not differ significantly at 95% confidence level. It was obtained using Student t-test (paired). The method developed in this thesis was used for monitoring the dissipation of nicosulfuron, rimsulfuron, oxasulfuron prosufuron, in different commercial doses of application during 50 days in field at three different depths (0-15 cm, 15- 30 cm and 30-45 cm) and for laboratory conditions at two temperatures (25ºC and 30ºC). The half-life time (DT50) of investigated SU were calculated by use of Mitttag-Lefler function in experiments under laboratory conditions at 25ºC. The values of DT50 for nicosulfuron, prosufuron and oxasulfuron read: 0.65 days (50 g ha-1 a.k.), 0.64 days (160 g ha-1 a.k.) and 0.66 days (30 g ha-1 a.k.), respectively. In the same type of experiments at 30ºC we get DT50 for nicosulfuron equals 0.20 days (50 g ha-1 a.k.) and for prosulfuron equals 0.49 days (50 g ha-1 a.k.). The values of DT50 on experiments in field were obtain also by use of Mitttag-Lefler's function, and half-life times for nicosulfuron, rimsulfuron, oxasulfuron and prosufuron from the commercially recommended doses, equal 72 minutes (0.05 days), 0.23 days, 0.12 days and 0.15 days, respectively. Significantly greater dissipation which was determined in this thesis was probably caused by the influence of abiotic and biotic processes as well as environmental factors.en
dc.languagesr (latin script)
dc.publisherУниверзитет у Новом Саду, Технолошки факултетsr
dc.rightsopenAccessen
dc.sourceУниверзитет у Новом Садуsr
dc.subjectTečna hromatografijasr
dc.subjectLiquid chromatographyen
dc.subjectmikrotalasna ekstrakcijasr
dc.subjectsulfonilurea herbicidisr
dc.subjectzemljištesr
dc.subjectdisipacijasr
dc.subjectmicrowave extractionen
dc.subjectsulfonylurea herbicidesen
dc.subjectsoilen
dc.subjectdissipationen
dc.titlePraćenje ostataka sulfonilurea u zemljištu u realnim uslovima primenom visoko-pritisne tečne hromatografijesr
dc.title.alternativeMonitoring of residues of sulfonylurea in soil under real conditions by using high pressure liquid chromatographyen
dc.typedoctoralThesissr
dc.rights.licenseBY-NC
dcterms.abstractСутуровић, Звонимир; Кравић, Снежана; Сутуровић, Звонимир; Кондић-Шпика, Aнкица; Граховац, Нада; Праћење остатака сулфонилуреа у земљишту у реалним условима применом високо-притисне течне хроматографије; Праћење остатака сулфонилуреа у земљишту у реалним условима применом високо-притисне течне хроматографије;
dc.identifier.fulltexthttp://nardus.mpn.gov.rs/bitstream/id/40738/IzvestajKomisije6914.pdf
dc.identifier.fulltexthttp://nardus.mpn.gov.rs/bitstream/id/40737/Disertacija6914.pdf


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