Envr 725Slide 2Slide 3Gas/Particle partitioning of toxics organics on different aerosolsNew UNC Aerosol Smog ChamberDual 270m3 chamber fine particle t 1/2 >17 hFrom a Modeling perspective Equilibrium Organic Gas-particle partitioning provides a context for addressing SOA FormationSlide 8Slide 9Slide 10Slide 11Overall kinetic MechanismSlide 13Slide 14Slide 15Slide 16Particle phase pinonaldehyde dimers from acid a-pinene +O3Chemical SystemSlide 20Slide 21UNC outdoor chamber groupSlide 23Slide 24Slide 25Slide 26Slide 27Slide 28Slide 29Introduction to Environmental Physical Organic ChemistryClass objectives:Slide 32ThermodynamicsVapor pressureVapor pressure and Henry’s lawAdditional PrinciplesHomework, quizzes, examsSlide 38Slide 39Slide 40LearningSlide 42Slide 43Slide 44Combustion Formation of PAHSlide 46Slide 47Slide 48Slide 49Slide 50Slide 51Slide 52Slide 53Slide 54Slide 55Professor Grimmer fractionated the exhaust extractsSlide 57Slide 58Slide 59Slide 60Slide 61Slide 62Slide 63Slide 64What did Grimmer see when exposed rats and mice to the different fractions?Slide 66Slide 67Slide 68Slide 69Analysis of reaction productsPFBHA O-(2,3,4,5,6-pentafluorobenzyl) -hydroxylamine for carbonyl groupsPentafluorobenzyl bromide (PFBBr) derivatization for carboxylic and hydroxyl groupsBSTFA for carbonyl, hydroxyl, and/or carboxylicSlide 74Thermal desorption particle beam mass spectrometry (Paul Ziemann)Slide 76Combustion Formation of Dioxins from Polychlorinated phenolSlide 78Slide 79Slide 80Slide 81Slide 82Environmental Fate of Chlorinated Dioxins and Furans (Czuczwa and Hites, 1984)US coal consumption vs chlorinated aromatic productionChlorinated aromatic production vs dioxin and furan conc. in lake core samplesPCBs in the U.S. Great LakesPolychlorinated biphenyls (PCBs)Slide 88Slide 89Slide 90Slide 91What do we do now, when new compounds are introduced into the environment...??An example is a new compound called D5. It is a silicon-oxygen compoundNew compounds are introduced into the environment ... Toxicity? Where will it go?Slide 951. There is a general concern that if we observe abnormalities in wildlife, similar kinds of mechanisms may exist in humans.Mercury poisoning off the coast of Minamata, Japan is an example2. Toxic loadsSlide 99Slide 100Slide 1013. Pesticide exposures4. The end points may not only be cancer, but compromised immune systems and generally poorer health.4. Immune systems & Mother’s milk4. Mother’s milkSlide 106Slide 1075. PCBs and lower intelligenceSlide 109Slide 110Slide 1116. DDT and immune system damageSlide 1137. Sexual impairmentSlide 1157a. Sexual impairment7b. Sexual impairment8. Endocrine disruptersSlide 1199. Other chemicalsSlide 121Slide 1229. PhthalatesSlide 124Recommendations1Envr 725Tues. and Thurs- 3 credit hours, room 0015 MHRC 11:00 am to 12:15 pmSnow days call 942 4880 or cell 919 614 4730http://www.unc.edu/courses/2007spring/envr/725/001/Envr725.html Rich Kamens; 966 5452[email protected]http://airsite.unc.edu/~kamens/2Textbook Environmental Organic Chemistry by René P. Schwarzenbach, Philip M. Gschwend, and Dieter M. Imboden, John Wiley & Sons, Inc., New York, 2003, ISBN 0-471-35053-2, pages:1313.3UNC outdoor chamber4Gas/Particle partitioning of toxics organics on different aerosols5New UNC Aerosol Smog Chamber6Dual 270m3 chamber fine particle t 1/2 >17 h7From a Modeling perspective Equilibrium Organic Gas-particle partitioning provides a context for addressing SOA FormationNumerical fittingSemi-explicit8Link gas and particle phasesC=OOcis-pinonaldhydeparticleC=OOGas phase reactionsTSPCCKgasipartip9 [ [ iigasgas] + [part] ] + [part] [ [ iipartpart]] KR Tp M wpLo7 5 0 11 09.fo mKp = kon/koffkonkoffparticlekonkoffC=OO10CHOOOCH3OOOCriegee2Criegee1OOO-pineneO3COOHCOOHpinic acid+ otherproductsOpinonic acidCHOOCOOH+ CO, HO2, OHCOOHOnorpinonaldehydenorpinonic acidMechanism11pinonaldehydeOHOOO2+(a)(b)(c)(d)(e)pinonaldehydeacetoneOOO.NO2NOOO.pinald-ooOHpinonic acidOpinO2OO.NO2NOorganic nitrate+HO2+NO2pinald-PAN=o=o=o=o=o=o=oOO.O2=oOO=C8=OC8-oo.O2NO2NOO+ h+ +CO+HO2=oOO.NO2NO=o=o+HO2+ hNO2NO=oOO.C8-oo. (C8O2)+CO+HO2NO2NO(f)(g)CO2+ pinO2H2O++HO2O2OOH3C-OO.+oxygenated products+NO2+H3C-OONO2PAN (stab-oxy)+HO2norpinonaldehydeOOHO=o+pin-ooH+OHOOO.=oNO2NO+CO2norpinaldPAN+NO2+HO2norpinonic acid+norpin-ooHOOONO2=o+O2ONO2=o+=oONO2+organic nitrate12Overall kinetic Mechanism linked gas and particle phase rate expressions1314Particle Phase reactionsparticleC=OOcis-pinonaldhydeC=OOpolymersGas phase reactions15Particle Phase reactionsparticleC=OOcis-pinonaldhydeC=OOpolymersGas phase reactions16Particle Phase reactionsC=OOcis-pinonaldhydeC=OOpolymersGas phase reactions17M Na+ (ESI-QTOF Tolocka et al, 2003)Particle phase pinonaldehyde dimers from acid -pinene +O318Chemical System-pinene+ NOx+ sunlight + ozone----> aerosols190.95 ppm -pinene + 0. 44ppm NOxO3NONO2NO2modeldataTime in hours ESTppmV20Gas phase pinonaldehdyeOOmg/m3Time in hours EST21Particle phasemodel TSPmg/m3Particle phasemodel TSPmg/m3Measured particle mass vs. modeldataTime in hours EST22UNC outdoor chamber group23Air Pollution in Northern Thailand2425260 50 100 150 200 250 300 ug/m312-Ma20-Ma28-Ma05-Ap13-Ap21-Ap29-Ap05/0705/15PM2.5 standard NuiPM2.5 concentrations27282930Introduction to Environmental Physical Organic ChemistryEnvironmental chemistry may be defined as "the study of sources, reactions, transport, effects, and fates of chemical species in water, soil, and air environments, and the effects of technology thereon.” Manahan, 199431Class objectives:Highlight some important areas in environmental chemistrypresent some of the common techniques that environmental chemists use to quantify process that occur in the environmentIt is assumed that everyone has courses in organic and physical chemistry.32Class objectives:Partitioning is a thread that runs through the courseLinear free energy relationships will be used to help quantify equilibrium and kinetic processes33Thermodynamicsui = uo1 +RT ln pi/p*iLfi = i Xipi*pure liquidRT ln fi hx /fiopure liq = RT lnfi H2O /fiopure liqfi hx = fi H2Oln Kp = a 1/T+b34ambambmfusiLTTTRSppis)()(lnln**Vapor pressure)]()(ln.*lnTTTTpbbiL58119 How to calculate boiling points35Vapor pressure and Henry’s lawKPCP ViawiiwiwsatsatsatsatiL*iw  Solubility and activity coefficientsOctanol-water partitioning