Organic Aerosol Formation from the Reactive Uptake of IEPOX 3499

Organic Aerosol Formation from the Reactive Uptake of IEPOX 3499

$WPRV &KHP 3K\V ± Atmospheric Open Access ZZZDWPRVFKHPSK\VQHW GRLDFS Chemistry $XWKRU V && $WWULEXWLRQ /LFHQVH and Physics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± 3XEOLVKHG LQ $WPRV &KHP 3K\V 'LVFXVV 2FWREHU 5HYLVHG )HEUXDU\ ± $FFHSWHG )HEUXDU\ ± 3XEOLVKHG $SULO $EVWUDFW 7KH UHDFWLYH SDUWLWLRQLQJ RI FLV DQG WUDQV β,(32; ,QWURGXFWLRQ ZDV LQYHVWLJDWHG RQ K\GUDWHG LQRUJDQLF VHHG SDUWLFOHV ZLWK RXW WKH DGGLWLRQ RI DFLGV 1R RUJDQLF DHURVRO 2$ IRUPD $ VLJQLILFDQ SRUWLRQ RI WKH RUJDQLF DHURVRO 2$ SURGXF WLRQ ZDV REVHUYHG RQ GU\ DPPRQLXP VXOIDWH $6 KRZHYHU WLRQ IURP LVRSUHQH D QRQPHWKDQH K\GURFDUERQ HPLWWHG WR SURPSW DQG HIILFLHQ 2$ JURZWK ZDV REVHUYHG IRU WKH FLV DQG WKH DWPRVSKHUH LQ YDVW DPRXQWV LV DWWULEXWHG WR WKH KHWHURJH β WUDQV ,(32; RQ $6 VHHGV DW OLTXLG ZDWHU FRQWHQWV RI ±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¶V /DZ SDUWLWLRQLQJ RI ,(32; DGGLWLRQ RI DYDLODEOH QXFOHRSKLOHV LQ WKH FRQGHQVHG SKDVH ZDV PHDVXUHG RQ 1D&O SDUWLFOHV LRQLF VWUHQJWK ∼0 WR − HJ DGGLWLRQ RI ZDWHU WR SURGXFH WHWUROV VXOIDWH WR SURGXFH EH × 0 DWP − $ VPDOO TXDQWLW\ RI 2$ + RUJDQRVXOIDWHV DQG VR RQ 0LQHUDWK HW DO (GGLQJVDDV ZDV SURGXFHG ZKHQ 1+ ZDV SUHVHQW LQ WKH SDUWLFOHV EXW WKH HW DO 6XUUDWW HW DO 7KLV SURSRVHG PHFKDQLVP − −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− + − HJ >1+ @ × >62 @RU>1+ @ >12 @ ∼ /LQ HW DO + 7KH DTXHRXV 1+ PD\ SRVVLEO\ DFW DV FDWDO\VW IRU 2$ IRUPDWLRQ DV KDV EHHQ VKRZQ IRU D QXPEHU RI DWPRVSKHUL FDOO\ LPSRUWDQW UHDFWLRQV 1R]LHUH HW DO 6DUHHQ HW DO (UYHQV DQG 9RONDPHU <X HW DO :H VWXG\ + UHDFWLRQ ZLWK 1+ DV D SRWHQWLDO UDWHOLPLWLQJ PHFKDQLVP 6FKHPH )RUPDWLRQ RI ,(32; LVRPHUV IURP UHOHYDQW LVRSUHQH IRU WKH ,(32; UHDFWLRQ 7KH UROH RI FDWLRQ DQG DQLRQ FRP K\GUR[\ K\GURSHUR[LGH SUHFXUVRUV LQ WKH ORZ12 SKRWRR[LGDWLRQ SRVLWLRQV LQ WKH VHHG IRU 2$ IRUPDWLRQ LV VWXGLHG E\ XVLQJ RI LVRSUHQH 7KH H[SHFWHG GRPLQDQW SDWKZD\ LV VKRZQ LQVLGH WKH DPPRQLXP VXOIDWH DPPRQLXP FKORULGH VRGLXP VXOIDWH DQG ER[ 7KH QDPLQJ FRQYHQWLRQ LV EDVHG RQ 3DXORW HW DO E VRGLXP FKORULGH VHHGV 0DWHULDOV DQG PHWKRGV /LQ HW DO %XGLVXOLVWLRULQL HW DO ,W VKRXOG EH QRWHG WKDW WKH LQGLUHFW GHILQLWLR RI ³SDUWLFOH DFLGLW\´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◦ XODWH 2$ IRUPDWLRQ IURP ,(32; LQ FRQMXQFWLRQ ZLWK SDUWLFOH PHQWV ZHUH SHUIRUPHG DW URRP WHPSHUDWXUH ± & DQG + >+ @ 2QH LPSRUWDQW GLVWLQFWLRQ EHWZHHQ SUHYLRXV FKDPEHU LQ WKH GDUN 3ULRU WR WKH VWDUW RI H[SHULPHQWV WKH FKDPEHU LQYHVWLJDWLRQV ZKLFK KDYH DOO EHHQ FRQGXFWHG XQGHU GU\ FRQ ZDV WKRURXJKO\ IO VKHG ZLWK GU\ SXULILH DLU XQWLO SDUWLFOH − GLWLRQV UHODWLYH KXPLGLW\ 5+ DQGWKH 6RXWKHDVWHUQ FRQFHQWUDWLRQV DUH JP )RU KXPLG H[SHULPHQWV 86$ ORFDWLRQ LV WKH SUHYDOHQFH RI SDUWLFOH OLTXLG ZDWHU RQ WKH ZDWHU YDSRU ZDV LQMHFWHG XQWLO WKH GHVLUHG UHODWLYH KXPLG DPPRQLXP VXOIDWH VHHGV :DWHU LV D XELTXLWRXV DQG DEXQGDQW LW\ 5+ ZDV DFKLHYHG LQ WKH FKDPEHU E\ I RZLQJ GU\ SXUL FRPSRQHQW RI WKH DWPRVSKHUH WKHUHIRUH WKH HIIHFW RI OLTXLG ILH DLU RYHU D 1DILR PHPEUDQH KXPLGLILH )& 3HUPD ◦ ZDWHU RQ WKH XSWDNH RI 2$ SUHFXUVRUV KDV LPSRUWDQW LPSOL SXUH //& ZKLFK LV NHSW PRLVW E\ UHFLUFXODWLQJ & XOWUD FDWLRQV IRU PXFK RI WKH JOREH 7KH FU\VWDOOLQH DPPRQLXP SXULILH 0 30 ZDWHU 0LOOL4 0LOOLSRUH &RUS 7HPSHU VXOIDWH VHHGV XVHG LQ GU\ FKDPEHU H[SHULPHQWV PD\ QRW KDYH DWXUH DQG 5+ ZHUH PHDVXUHG E\ D 9DLVDOD +00 SUREH DGHTXDWH OLTXLG ZDWHU IRU ,(32; WR SDUWLWLRQ LQWR WKH DTXHRXV FDOLEUDWHG ZLWK VDWXUDWHG VDOW VROXWLRQV LQ WKH 5+ UDQJH RI ± + + −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◦ LRQV LH FKDQJLQJ WKH DFLGLW\ RU LRQLF VWUHQJWK ZKLFK KDV GHQXGHU NHSW DW & VXFK WKDW WKH VHHG SDUWLFOHV HQWHU WKH EHHQ GHPRQVWUDWHG WR FKDQJH WKH HIIHFWLYH +HQU\¶V /DZ SDU FKDPEHU K\GUDWHG /LTXLG ZDWHU LV H[SHFWHG WR HYDSRUDWH WLWLRQLQJ FRHIILFLHQ RI JO\R[DO .DPSI HW DO 'HVSLWH IURP WKH VHHG SDUWLFOHV DFFRUGLQJ WR WKH VDOW¶V HIIORUHVFHQF WKHVH LPSRUWDQW LQWHUDFWLRQV WKH HIIHFW RI OLTXLG ZDWHU RQ 2$ EHKDYLRU /HH DQG +VX DW WKH 5+ RI WKH FKDPEHU HJ IRUPDWLRQ IURP ,(32; KDV QRW EHHQ V\VWHPDWLFDOO\ H[SORUHG LQ D GU\ FKDPEHU LW LV H[SHFWHG WKDW WKH K\GUDWHG SDUWLFOHV LQ WKH ODERUDWRU\ ZLOO HQWHU WKH FKDPEHU IXOO\ GULHG 3DUWLFOHV ZHUH DOORZHG WR :H UHSRUW KHUH WKH UHDFWLYH XSWDNH RI WZR LVRPHUV RI HTXLOLEUDWH XQWLO WKHLU YROXPH FRQFHQWUDWLRQV DUH VWDEOH SULRU ,(32; WKH FLV DQG WUDQV β,(32; 3DXORW HW DO E WR RUJDQLF LQMHFWLRQV ZKLFK WRJHWKHU FRPSULVH PRUH WKDQ RI WKH LVRPHU GLV 7ZR LVRPHUV RI LVRSUHQH HSR[\GLROV FLV DQG WUDQV β WULEXWLRQ %DWHV HW DO :H V\QWKHVL]HG DXWKHQWLF VWDQ ,(32; ZHUH V\QWKHVL]HG YLD SURFHGXUHV DGDSWHG IURP $WPRV &KHP 3K\V ± ZZZDWPRVFKHPSK\VQHW T. Nguyen et al.: Organic aerosol formation from the reactive uptake of IEPOX 3499 Zhang et al. (2012) and purifie with normal-phase column hydroperoxide (ISOPOOH), which has been documented to chromatography until the estimated purity based on nuclear yield mainly m/z 63 and a negligible amount of m/z 183 magnetic resonance (NMR) of the cis and trans β-IEPOX upon CID (Paulot et al., 2009b). ISOPOOH (m/z 203 → isomers are 99 % and > 92 %, respectively. Details of the syn- m/z 63), was not expected, nor observed, during IEPOX in- thesis and NMR spectra are reported in Bates et al.

View Full Text

Details

  • File Type
    pdf
  • Upload Time
    -
  • Content Languages
    English
  • Upload User
    Anonymous/Not logged-in
  • File Pages
    14 Page
  • File Size
    -

Download

Channel Download Status
Express Download Enable

Copyright

We respect the copyrights and intellectual property rights of all users. All uploaded documents are either original works of the uploader or authorized works of the rightful owners.

  • Not to be reproduced or distributed without explicit permission.
  • Not used for commercial purposes outside of approved use cases.
  • Not used to infringe on the rights of the original creators.
  • If you believe any content infringes your copyright, please contact us immediately.

Support

For help with questions, suggestions, or problems, please contact us