Geitner, Nicholas K

Ke, Pu Chun

Ladner, David A

Powers, Sean

Tu, Ying

Whelton, Andrew

Xie, Peng

English

Clemson University: TigerPrints

Clemson UniversityTigerPrintsPresentations Environmental Engineering & Earth Sciences7-1-2013Dendritic Polymers as Oil Spill Dispersants:Effectiveness and Toxicity Compared to Corexit9500ADavid A. LadnerClemson UniversityPeng XieClemson UniversityYing TuClemson UniversityNicholas K. GeitnerClemson UniversitySean PowersUniversity of South AlabamaSee next page for additional authorsFollow this and additional works at: https://tigerprints.clemson.edu/envengineering_presThis Poster is brought to you for free and open access by the Environmental Engineering & Earth Sciences at TigerPrints. It has been accepted forinclusion in Presentations by an authorized administrator of TigerPrints. For more information, please contact kokeefe@clemson.edu.Recommended CitationLadner, David A.; Xie, Peng; Tu, Ying; Geitner, Nicholas K.; Powers, Sean; Whelton, Andrew; and Ke, Pu Chun, "Dendritic Polymersas Oil Spill Dispersants: Effectiveness and Toxicity Compared to Corexit 9500A" (2013). Presentations. 12.https://tigerprints.clemson.edu/envengineering_pres/12AuthorsDavid A. Ladner, Peng Xie, Ying Tu, Nicholas K. Geitner, Sean Powers, Andrew Whelton, and Pu Chun KeThis poster is available at TigerPrints: https://tigerprints.clemson.edu/envengineering_pres/12Dendritic polymers as oil spill dispersants: Effectiveness and toxicity compared to Corexit 9500ADavid A. Ladner1*, Peng Xie1, Ying Tu1, Nicholas K. Geitner2, Sean Powers3, Andrew Whelton4, Pu Chun Ke21Department of Environmental Engineering and Earth Sciences, Clemson University2Department of Physics and Astronomy, Clemson University3Department of Marine Sciences, University of South Alabama4Department of Civil Engineering, University of South AlabamaIntroductionWe hypothesize that crude oil can be dis-persed using dendritic polymers. Our objective is to compare dendritic polymers to Corexit 9500A (the dispersant used in the BP oil spill) taking effectiveness and toxicity into consider-ation.0 0.2 0.4 0.6 0.8Oil Alone1.2 kDa HyPEI1.8 kDa HyPEI10 kDa HyPEI70 kDa HyPEI750 kDa HyPEICorexit% Dispersed OilEectiveness measurements with 1:50 dispersant:oil ratio (DOR) show that Corexit is best. Hyperbranched polymers have roughly in-creasing eectiveness with molecular weight, but the 10 kDa size bucks the trend.Video stills from interfacial tension experi-ments with oil alone, 10 kDa HyPEI, and Co-rexit. HyPEI did not cause the dramatic drop breakup that Corexit caused, indicating HyPEI uses a dierent mechanism than inter-facial tension modication for its dispersion capability. (See the videos by scanning the QR code at the bottom right of the poster). Oil aloneOil + 10 kDa HyPEIOil + Corexit0246810121416180 50 100 150 200Interfacial tension (mN/m)Time (s)HY 1200HY 1800HY 10,000HY 70,000HY 750,000oilCorexit, 500 ppm, 3 ul dropEven a low concentration of Corexit is eective at reducing interfacial tension, but the hyperbranched polymers are less eective; no clear trend with mo-lecular weight is observed.Left to right: oil, oil + 1.2 kDa HyPEI, oil + 10 kDa HyPEI, and oil + Corexit in water. Photo taken after mixing and standing 5 minutes. Qualitatively, the hyper-branched polymers disperse oil, though not as well as Corexit. Materials• Hyperbranched polyethylenimine polymer, (HyPEI) with several molecular weights (1.2, 1.8, 10, 70, and 750 kDa)• Corexit 9500A• Louisiana light sweet crude (LLS) oil• Synechocystis sp. • Dunalliela sp.Dispersant performance• Premix the oil and polymer(or dispersant) at different DOR for 24 hours• Add 20 ul premix to 12 ml artificial seawater, mixing at 200 rpm for 30min• Settle for 15 min• Collect 3 ml water sample from bottom of vials              • Extract dispersed oil in water sample with 1.5 ml dichloromethane (DCM)• Test the absorbance at 340nmInterfacial tension• Premix as in performance test • Pendent drop and the axisymmetric drop shape analysis (ASDA) technique, Easy Drop@kruss• Graph interfacial tension change with time Algal growth inhibition• Subculture two algal speceis in culture tubes with 10 ml media• Add combinations of oil premixed with dis-persant at various DORs into triplicate tubes.• Grow under 12-hr light/dark cycle• Measure absorbance daily at 685 nmMethodsDispersion performance resultsInterfacial tension resultsAlgal growth inhibition resultsAmine-terminated HyPEI branches00.10.20.30.40.50.60.70.80.911.11.21.31.41.50 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21Absorbance (685nm)Time (d)SynechosystisSyn. + OilSyn. + CorexitSyn. + Oil + Corexit  1:25Syn. + Oil + Corexit  1:50Syn. + Oil + Corexit  1:100Synechocystis with Corexit. Corexit protected Synechosystis from oil contamination. Corexit alone did not seem to have an adverse eect on algal growth. Synechocystis  with 1.2 kDa HyPEI. 1.2 kDa seems to be a threat for algal growth. The higher the DOR, the greater the threat. 1.2 kDa HyPEI’s toxic-ity reached its climax when it was applied alone without any oil.-0.2-0.100.10.20.30.40.50.60.70.80.911.11.21.31.41.50 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21Absorbance (685nm)Time (d)SynechosystisSyn. + OilSyn. + 1.2 kDa HyPEISyn. + Oil + 1.2 kDa  1:25Syn. + Oil + 1.2 kDa  1:50Syn. + Oil + 1.2 kDa  1:100-0.2-0.100.10.20.30.40.50.60.70.80.911.11.21.31.41.50 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21Absorbance (685nm)Time (d)SynechosystisSyn. + OilSyn. + 10 kDa HyPEISyn. + Oil + 10 kDa  1:25Syn. + Oil + 10 kDa  1:50Syn. + Oil + 10 kDa  1:100Synechocystis  with 10 kDa HyPEI. 10 kDa seems to be a threat for algal growth, but the higher DOR, the  less the threat. Only 1:100 showed higher toxicity than oil.  10 kDa HyPEI’s toxicity reached its climax when it was applied alone without any oil.-0.2-0.100.10.20.30.40.50.60.70.80.911.11.21.31.41.50 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21Absorbance (685nm)Time (d)SynechosystisSyn. + OilSyn. + 750 kDa HyPEISyn. + Oil + 750 kDa  1:25Syn. + Oil + 750 kDa  1:50Syn. + Oil + 750 kDa  1:100Synechocystis  with 750 kDa HyPEI. 750 kDa  HyPEI posed a greater threat and  showed higher toxicity when it was applied without oil. But when it was mixed with oil, it seemed to have no adverse eect on algae growth. (70 kDa results were similar).00.10.20.30.40.50.60.70 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16Absorbance (685nm)Time (d)DunaliellaDun. + OilDun. + 1.2 kDa HyPEIDun. + Oil + 1.2 kDa HyPEI 1:25Dun. + Oil + 1.2 kDa HyPEI 1:50Dun. + Oil + 1.2 kDa HyPEI 1:100Dunaliella with 1.2 kDa HyPEI.  The 1:50 DOR appears protective of algal growth. (Though in this set there was high variability in the other DORs). Dunaliella with 10 kDa HyPEI. The 10 kDa HyPEI and oil combination showed higher toxicity than oil or 10 kDa HyPEI alone and the toxicity of the combination increased with the DOR.   Dunaliella with 750 kDa HyPEI. The 750 kDa HyPEI alone showed the highest toxicity and the toxicity of the oil and 750 kDa HyPEI combination was higher at DOR of 1:25 and 1:100, but showed no eect at DOR of 1:50.00.10.20.30.40.50.60.70 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16Absorbance (685nm)Time (d)DunaliellaDun. + OilDun. + CorexitDun. + Oil + Corexit 1:25Dun. + Oil + Corexit 1:50Dun. + Oil + Corexit 1:100Dunaliella with Corexit. Corexit or oil seem to have no adverse eect on algae growth.-0.100.10.20.30.40.50.60.70 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16Absorbance (685nm)Time (d)DunaliellaDun. + OilDun. + 10 kDa HyPEIDun. + Oil + 10 kDa HyPEI 1:25Dun. + Oil + 10 kDa HyPEI 1:50Dun. + Oil + 10 kDa HyPEI 1:100-0.100.10.20.30.40.50.60.70 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16Absorbance (685nm)Time (d)DunaliellaDun. + OilDun. + 750 kDa HyPEIDun. + Oil + 750 kDa HyPEI, 1:25Dun. + Oil + 750 kDa HyPEI, 1:50Dun. + Oil + 750 kDa HyPEI, 1:100Conclusions• Hyberbranched polymers, especially 10 kDa, were effective at dispersing oil, though not as effective as Corexit 9500. HyPEI did not decrease interfacial tension as well as Corexit.• Corexit addition mitigated algal growth inhibition by oil. Some HyPEI polymers did the same, though the polymers alone often greatly inhibited growth. Scan to view a PDF and videos, or visithttp://clemson.edu/ces/ladnergroup/posters/AEESP2013Environmental Engineering & Earth SciencesRD835182Algal growth inhibition photosa. Water, Dunalliella alone, and Synechocystis aloneb. Synechocystis + oil + 10 kDa HyPEI 1:50c. Dunalliela + oil + 10 kDa HyPEI  at three DORs: 1:25, 1:50, 1:100.d. Dunalliela alone, Dunalliela + oil + 750 kDa HyPEI 1:100, and Dunalliela + Oil + Corexit 1:100e. Oil + 1.2 kDa HyPEI 1:25. a b c d e

Dendritic Polymers as Oil Spill Dispersants: Effectiveness and Toxicity Compared to Corexit 9500A

https://tigerprints.clemson.edu/cgi/viewcontent.cgi?article=1011&amp;context=envengineering_pres

Dendritic Polymers as Oil Spill Dispersants: Effectiveness and Toxicity Compared to Corexit 9500A

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