p. 1


# OAR Box 1846 Prepped byOllie Stewart



### Document

Number: 

# 79 ) IV-A- 1 Docket Number: 

# A-90-0 7

Printed 11/18/20087:30:17

AM Sheet 79of 93—P. 2 

# CR C Repdr fNo . 55 1


# CHEMICA L METHOD S FO R TH E MEASUREMEN TO F UNREGULATE D DIESE L EMISSION S

Carbonyls/Aldehyde s Particulat e Characterizatio n

Sulfate s PAH/N0 9 

# PA H
Augus t 198 7

J'i' V FE 3 

## IT199 3 x ' 

# I ' " L

_

# . -— ' { EPAA1BJ30CICE T


# COORDINATIN G RESEARC H COUNCIL , INC . 21 9 PERIMETE R CENTE R PARKWAY, ATLANTA , GEORGI A3034 8P. 3

»» COORDINATIN G RESEARC H COUNCI L INCORPORATE D 2 1 9 PERIMETE R CENTE R PARKWA Y ATLANTA . GEORGI A 3034 6 (404 ) 396-340 0 

## CHEMICA L METHOD S FO

RTHE MEASUREMEN

T O F UNREGULATE

DDIESE L EMISSIONS - CARBONYLS/ALDEHYDE S PARTICULAT E CHARACTERIZATIO N

SULFATE S PAH/NO 2 

### PA H 

## (CRC-APRA C PROJEC T NO . 

## CAPI-1-64 ) I N FORMULATIN G AN D APPROVIN G REPORTS , TH E APPROPRIATE COMMITTE E O F TH E COORDINATIN G RESEARC H COUNCIL , INC
. HA S NO TINVESTIGATE D O R CONSIDERE D PATENT S WHICH
. MAYAPPL YT O TH E SUBJEC

TMATTER
. PROSPECTIV E USER S O F TH E REPOR TAR E RESPONSIBL E FO R PROTECTIN G THEM SELVES AGAINS TLIABILITYFO R INFRINGEMEN TO F PATENTS
. Prepare db

y th e Chemica l Characterizatio nPane l

o f the CR C Program

Grou po

nCompositio no f Diese l Exhaus t Edite dBy : J . M . Pere z R . E . Jas s D . G . Leddy

Augus t 198 7

Ai r Pollutio nResearc hAdvisor y Committe e o f th e Coordinatin g Researc hCouncil , Inc .P. 4

TABL E O F CONTENT S Paig e SECTIO NI - INTRODUCTIO N3 SECTIO NI I - HIG H PERFORMANC E LIQUI D CHROMATOGRAPHI C (HPLC ) DINITROPHENYLHYDRAZIN E (DNPH ) METHO D FO R CARBONY L COMPOUND S A . Scop e 7 B . Definitio n 7 C . Experimenta l 7 D . Sampl e Collectio n 9 E . Sampl e Analysi s 9 F . Precisio n and Accurac y1 0 G . Alternat e Samplin g Procedur e 1 1 SECTIO NII I - DIESE L PARTICULAT E CHARACTERIZATIO N A . Purpos e 1 5 B . Summar y1 5 C . Definitions/Abbreviation s 1 6 D . Experimenta l 1 7 SECTIO N111. 1 - TOTA L PARTICULAT E MAS S A. Procedure s 2 1 B . Measuremen t o f Tota l Particulat e Mas s . 2 3 SECTIO NIII. 2 - SOLVEN T EXTRACTABL E FRACTION S (SEF ) A. Scop e 2 7 B . Extractio n o f SO F 2 7 C . Extractio n o f TO E 2 8 D . Determinatio n o f Sulfat e 2 9 E . Combine d Wate r 3 0 F . Repeatab i 1 it y3 1 SECTIO NI

V - NITRATE D POLYCYCLI C AROMATI C HYDROCARBON S A. Scop e 3 3 B . Backgroun d 3 3 C . Definitions/Abbreviation s 3 3 D . Experimenta l Equipmen t 3 3 E . So l vent s 3 4 F . Procedur e * 3 4 G . Precisio n and Accurac y3 5 H . Alternat e Column Configuratio n 3 5 I . Alternat e Metho d 3 5P. 5

SECTIO NV

- POLYCYCLI C AROMATI C HYDROCARBON S A . Scop e 3 9 B . Backgroun d 3 9 C . Definitions/Abbreviation s 3 9 D . Equipmen t 4 0 E . So l vent s 4 0 F . Procedure s ^.. . 4 1 REFERENCE S 4 9
TABLE S Tabl e I - Physica l Propertie s o f Carbony l Compound s 5 5 Tabl e I I - Storag e Stabilit y5 6 Tabl e II I - Compariso n o f SO F and VacuumRemova l o f Organi c

Fractio n 5 7 Tabl e I V - Elutio n o f Polycycli c Aromati c Hydrocarbon s o n a Bondapa k NH 2 Column 5 8 Tabl e V - HighPerformanc e Liqui d Chromatographyo f Polycycli c Aromati c Hydrocarbons : Fractio n 1 5 9 Tabl e VI - Hig hPerformanc e Liqui d Chromatographyo f Polycycli c

Aromati c Hydrocarbons : Fractio n 2 6 0 Tabl e VI I - Hig hPerformanc e Liqui d Chromatographyo f Polycycli c

Aromati c Hydrocarbons : Fractio n 3 6 1 FIGURE S Figur e 1 - Samplin g Car t (Schemati c Diagram) 6 2 Figur e 2 . - Carbony l Analysi s Metho d 6 3 Figur e 3 - Chromotogra mo f th e Standar d DNPH-Aldehyd e Mixtur e 6 4 Figur e 4 - Formaldehyd e Stabilit y6 5 Figur e 5 - Acrolei n Stabilit y6 6 Figur e 6 - Tota l Aldehyd e Stabilit y6 7 Figur e 7 - Soxhle t (Photograph ) 6 8 Figur e 8 - Mas s o f Boun d Ho O Pe r Gra m H 2 S 0 4 i n a n Aqueou s Solutio n Versu s Relativ e Humidit y(25°C ) 6 9 Figur e 9 - Schemati c o f Nitropyren e Analysi s Syste m7 0 Figur e 1 0 - HPL C PAH Metho d No . 1 7 1 Figur e 1 1 - HPL C Metho d Summar y- Fractionatio n o f th e

Diese l Extrac t 7 2 Figur e 1 2 - HPL C PAH Metho d No. . 2 7 3 Figur e 1 3 - Typica l HPL C Traces , Metho d No . 2 7 4

APPENDICE S APPENDI XA- Membership : Chemica l Characterizatio n Pane l o f th e

CR C Diese l Exhaus t Compositio n Grou p A- l

• n -P. 6



## SECTIO NI INTRODUCTIONP. 7

I . INTRODUCTIO N

Thi s Progres s Repor t summarize s researc h conducte d o n unregulate d diese l emission s method s b yth e Chemica l Characterizatio n Pane l (CCP ) o fth e Coordinatin g Researc h Council' s (CRC ) Diese l Compositio n Grou p ove rth e pas t thre e years . (Membershi p o fth e Chemica l Charactizatio n Pane l i s liste d i n Appendi xA. ) Method s ar e recommende d fo rth e measuremen t o faldehydes/carbonyls , sulfates , particulat e characteri zation , polycycli caromati chydrocarbon s (PAH) an d nitrate d PA H (N0 2 - PAH)
. Mos t o fth e method s propose d ar e th e resul t o fcooperativ e testin g an d ar e considere d t o b e based o n soun d engineerin g practices
. Tw o o fth e methods , PA H an d N0

2 PAH , ar e stil l bein g evaluate d throug h cooperativ e round-robi n study
. Th e PA H metho d wa

s develope d unde rCR C contrac t a t IITR I an d pre viousl yevaluate d i n a round-robi n b yth e group . Currently , a follow u p internationa l round-robi n i s i n progress . Th e N0

2 PA H metho d ha s evolve d primaril ya s th e resul t o fwor k con ducte d a t EPA-RTP
. A n alternat e metho d wa s develope d b

yA
. D
. Little , Inc
. unde rcontrac t fo rth e CRC-APRA C CAPE-3

0 Projec t Group
.P. 8



## SECTIO N

I I
HIGHPERFORMANC E LIQUI DCHROMATOGRAPHI C (HPLC ) DINITROPHENYLHYDRAZINE (DNPH ) METHO DFO RCARBONYL COMPOUND SP. 9

I I . HIG H PERFORMANCE LIQUI D CHROMATOGRAPHIC (HPLC ) DINITRO PHENYLHYDRAZIN E (DNPH ) METHO D FOR CARBONY

L COMPOUND

S
SCOP E Th e procedur e incorporate s an improve d 2,4-dinitrophenylhydrazin e metho d i n whic h C

^ t o C g carbony l compound s ar e collecte d b y bubblin g diese l exhaus t o rdilute d diese l exhaus t throug h an acetonitril e solutio n o fDNP H reagen t an d analyze d b yHPL C usin g U V detectio n a t 36 5 nm . Usin g a n acetonitril e solutio n fo r sampl e collectio n allow s direc t injectio n o fth e sampl e int o th e HPLC , thereb yeliminatin g man yo fth e recover ystep s an d savin g considerabl e sampl e preparatio n manhours
. Th e metho d result s i n quantitativ e sampl e recoveries , improve d accurac yan d provide s fo ra simple , rapi d an d lo wcos t metho d fo raldehyd e analysis
. Th e metho d wa

s reporte d (1) *
. B . DEFINITIO N Carbony l Compound s - Compound s containin g th e C= 0 functiona l chemica l group . Thi s procedur e refer s t o C j t o C g compound s containin g thi s group , specificall yth e compound s shown i n Tabl e I
. Th e metho d coul d als o be applicabl e t o highe rmolecula r weigh t carbony l compounds
. EXPERIMENTA

L 1
. Reagent s - Reagent s use d i n thi s procedur e shoul d b e HPL C Grad e (distille d i n glass ) o rEquivalen t Grad e Solvent s a s indicated : Acetonitril e - Burdic k an d Jackso n Labs , Inc. , Fishe r Scientifi cCo. , J.T
. Bake rChemica l Co
. o requivalent
. 2,4-Dinitrophenylhydrazin e - Aldric h Chemica l Co
. o rJ.T
. Baker , recrystallize d twic e fro m HPL C grad e methano l o r acetonitrile
. Distilled , deionize d wate r(HPL C Grade)
. 2 N HCl - Bes t Source
. Ethano l - Bes t Source
. Perchlori cAci d - Bes t Source
.

* Number

s i n ( ) ar e reference s a t en d o ftext .P.1 0

Aldehyd e Standard s - Individua l aldehyde s fo r standar d preparatio nshoul dbe bes t availabl e grade . 2,4-DNP HDerivative s - Metho do f preparatio ndiscusse di n later'section . 2 . Equipmen t HPL C wit h U

V detectio n (36 5 nm)
. Variou s unit s ar e avail able
. 5uZorba xOD

S 4. 6 m m x25. 0 c

m HPL C column , DuPont Inst
. Co
. Midge t Impinger s (Light-Dut yDiesels ) o r10 0 m LGlas s Impin ger s (Heavy-Dut yDiesels)
. Flowmeter , pump an d mete r— require d fo rsampl e collectio n (Figur e 1)
. L C syringe s a

s required
. Meltin g Poin t Apparatus
. Pretes t Preparatio n a . Aldehyde-DNP HDerivative s - Th e 2,4-DNP Hderivative s ar e prepare db

y reactio no f the individua l aldehyde s wit ha saturate dDNP Hsolutio ni n2 N HCL . Th e derivative s ar e filtered , washe dwit h2 N HC l andH 2 0 , ai r dried , an d store di nseale dvials . Purit y o f th e derivative s i s ' checke dby

meltin g poin t determinations , Tabl e I . Purit y ca nb e improve db y recrystallizatio nfro m absolut e ethano l o r methanol , i f required . Individua l derivative s o r a mixtur e o f th e standard s shoul dals o be checke dfo r purit y

b y HPLC . b . Preparatio no f Solution s an dStandard s - A

6.25ymole/m

L o f 2,4-DNP Hstoc ksolutio ni s prepare dby additio no f 10 0 m L o f acetonitril e t o 12 0 m g o f purifie dDNP H crystals . Dilutio no f th e stoc ksolutio nwit hacetoni tril e i s use dt o prepar e a 1. 6 mole/m L DNP Habsorbin g solutio ni nth e bubblers . Fiv e drop s o f I N HCl0 ^ catalys t i s adde dpe r eac h2 0 m L o f absorbin g solution . Th e aci di s adde djus t prio r t o use . Standar dsolution s o f th e aldehyde s ar e prepare db y injectin g 5. 0 m L o f th e aldehyd e int o a septu m seale d via l containin g 5. 0 m L o f acetonitrile . Th e concentra tion s o f th e stoc ksolution s ar e calculate dfro m th e densitie s o f th e aldehydes . Th e formaldehyd e concen tratio ni s determine dby th e concentratio no f th eP.1 1
-9- . formali n solutio n bytitration
. Standar d derivativ e solution s ar e prepare d b yinjectin g 2. 0 t o 20 u Lo fth e aldehyd e solutio n int o a septu m seale d via l containin g th e derivatizin g reagent . Weighin g soli d DNP H hydra zone s an d dissolvin g the m i n acetonitril e ca n als o b e used t o prepar e standar d derivatives
. D
. SAMPL

E COLLECTIO

N 1
. Samplin g Syste m - Th e samplin g syste m ca n var ydependin g on th e sourc e o faldehydes
. On e system , Figur e 1 , wa s designe d t o sampl e dilute d exhaus t fro m variou s siz e dilutio n tunnel s o rheate d Teflo n Kbag s containin g dilute d exhaust
. Fo r samplin g directl yfro m undilute d exhaus t stream s a shor t (approximatel y2 meter s X0.63 5 c m O.D. ) stainles s stee l lin e shoul d be adde d t o allo wsom e coolin g o fth e exhaus t prio rt o enterin g th e Teflo n coate d heate d line
. 2
. Samplin g - A1.6umole/m L DNP H solutio n i s use d fo remissio n testing
. Thi s i s obtaine d b ydilutin g th e stoc k

solutio n a

s indicate d abov e o rth e solutio n ca n be prepare d bydis - solvin g abou t 3 1 m

g o fpurifie d DNP

H i n 10 0 m Lo facetoni trile
. Fo reac h light-dut ydiese l (LDD ) sampl e t o be taken , th e impinger s ar e prepare d b yaddin g 1 0 m

Lo fth e DNP

H solutio n an d 2 drop s (approximatel y100 uL ) o fth e I N HC104 t o eac h impinger
. Samplers ar e connecte d i n serie s an d place d i n a n ic e bath
. Fo rsamplin g heavy-dut ydiesel s (HDD) , 2 0 m l o f th e DNP H solutio n wit h 4 drop s I N HC104 ar e adde d t o eac h impinger
. Sampl e flo wthroug h th e bubbler s i s maintaine d a t 1/ 2 L/mi n fo rLD

D an d 2- 4 L/mi n HDD
. Normall y10-3 0 Lo f exhaus t (100-30 0 La t 9: 1 dilutio n ratio ) i s adequat e t o obtai n sufficien t sampl e fo ra reliabl e analysi s dependin g o n th e typ e o femissio n source . Th e lowe rth e sourc e con centratio n th e mor

e sampl e tha t i s require d fo rgood quanti tativ e results
. A s a guideline , aldehyd e level s fro m LDD<:HDD<H

D gasolin e engines
. Sample s shoul d b

e analyze d immediatel yo rrefrigerate d unti l used
. SAMPL E ANALYSI S 1
. Analysi s Procedur e - Samples shoul d b e analyze d a

s soo n a

s possible , preferabl ywithi n a fe whours , t o minimiz e th e losse s o fcertai n species
. Th e procedur e fo ranalysi s i s shown i n Figur e 2
. Followin g an acceptabl e HPL C blank , th e calibratio n standard s ar e run .P.1 2

•10 - An exampl e o fa n HPL C trac e fo rth e standard s i s show n i n Figur e 3
. I t shoul d be emphasize d tha t th e appearanc e ma y var ydependin g o n th e HPL C syste m utilized
. However , th e relativ e retentio n time s o fth e peak s shoul d closel yagre e with'thos e shown i n Tabl e I
. I fnot , retentio n time s shoul d b e redetermine d usin g a se t o fstandards
. Th e tim e require d fro m injectio n t o th e appearanc e o fth e interna l standard , benzaldehyde , i s considere d t o be 1.0
. Th e time s fo ral l othe rpeak

s t o elut e ar e normalize d t o it
. I fan automate d syste m i s utilized , th e sample s ca n b e sequence d runnin g a standar d chec k

a t th e en d o fth e serie s o revery4- 6 sample s dependin g o n th e numbe ro fsample s t o b e analyzed
. 2
. Sampl e Stabilit y- The stabilit yo fsample s indicate s tha t losse s o findividua l aldehydes , wit h th e th e exceptio n o f acrolein , ar e onl yabou t 1 0 percen t i n 24 hours
. Experimen tall ydetermine d losse s fo rformaldehyde , acrolei n an d tota l aldehyde s ar e show n i n Figure s 4 , 5 , an d 6
. Th e acrolei n losse s a

s demonstrate d on Figur e 5 ar e concentratio n depen dent
. Highe rconcentration s approac h 35 % los s i n 24 hours
. Fortunately , thi s specie s i s normall ya mino rcomponen t o f th e tota l aldehydes
. Tota l aldehyd e losse s ar e 1 0 percen t o rless
. Typically , samplin g an d analysi s i s complete d withi n 2

4 hours
. Storag e stabilit ybeyon d 24 hours i s shown o n Tabl e II
. Th e dat a showtha t losse s i n tota l aldehyde s withi n an eigh t week perio d were les s tha n 5 percent . Thi s i s primaril ydu e t o acrolei n an d crotonaldehyd e degradation
. F
. PRECISION AN

D ACCURAC

Y Th e metho d precisio n an d accurac ywer e determine d i n a cooperativ e round-robi n conducte d b yth e Chemica l Characterizatio n Pane l o fth e Diese l Exhaus t Compositio n inhous e Grou p o fth e Coordinatin g Researc h Council , Inc. , Ai rPollutio n Researc h Advisor yCommitte e (CRC-APRA C CAPI-1-64)
. The result s ar e describe d i n Referenc e 1
. Th e concentratio n level s o f aldehyde s i n th e stud yar e considere d t o be a wors t cas e situatio n involvin g lo wlevel s o faldehydes
. Reproducibility , i.e. , agreemen t withi n a laboratory , wa s bette rtha n 20 percen t relativ e standar d deviatio n (r.s.d.)
. Agreemen t betwee n labora tories , repeatability , wa s as hig h a s 3

5 percen t r.s.d
. Th e precisio n an d accurac yimprove d a s th e concentratio n o faldehyde s i n th e sample s increased
. Th e concentratio n level s i n th e CR C stud ywer e o fth e orde ro f0.02 ymoles/m l an d shoul d be con sidere d minimu m level s require d t o achiev e 2 0 percen t r.s.d
. reproducibility
. Wit h experienc e an d analysi s o fsample s withi n 24 hours afte rcollection , a precisio n an d accuracyo f1 0 percen t r.s.d
. o rbette rshoul d be achievable
.P.1 3

-11 -
G . ALTERNAT E SAMPLINGPROCEDUR E Bot h Genera l Motor s Researc h an d EPA-RTP hav e develope d pro cedure s utilizin g DNPH-coated silic a cartridge s fo rsamplin g an d analyzin g carbony l compound s i n engin e exhaust
. S.B
. Tejada' s (EPA-RTP ) metho d was presente d a t th e CR C worksho p i n Marc h 1985 (2)

. Basically , th e procedur e involves : 1 . Reagen t purification . 2 . Preparatio no f DNPH-coate dsilic a cartridges . 3 . Impinge r solution . 4 . Cartridg e sampling . 5 . HPL C conditions . One interestin g aspec t o fthi s metho d i s th e presenc e o fa n unidentifie d "compound-x " tha t ma yb e th e decompositio n produc t o facrolei n i n air
. Asecon d advantag e o fthi s procedur e i s th e abilit yt o readil y collec t fiel d samples
. Stabilit yo fformaldehyd e an d acrolei n appea rimprove d o n th e cartridge
. Tejada' s procedur e an d th e metho d fo rpreparin g cartridge s hav e bee n publishe d i n th e literature* 3 '
.P.1 4



### SECTIO NIII. l
TOTA L PARTICULAT E MASSP.1 5

•21 -
III. 1 TOTA

L PARTICULAT

E MAS S

A
. PROCEDURE

S 1
. Operatio n o fth e Engin e - Diese l particulat e ca n b e collec te d 1 n a variet yo ftests . Fo rsteady-stat e particulat e collectio n wit h o rwithou t a dilutio n tunnel , th e engin e operatin g procedure s a s describe d i n SA

E Procedure J1003 (7 ) ar e guideline s fo rengin e operation
. Fo rtransien t tests , th e USEP Aprocedures r8 ) ca n b e use d a

s a guideline
. 2
. Dilutio n Rati o - The dilutio n rati o use d t o collec t particu lat e 1 s normall yabou t 10-2 0 t o 1 , A1 rt o Exhaust
. I n practice , th e actua l dilutio n rati o 1 s usuall ydetermine d by th e Incomin g exhaus t temperatur e an d th e amoun t o fai r require d t o achiev e a 125° F (52°C ) o rlowe rfilte rtempera ture . Th e tim e t o collec t a desire d mas s o fparticulat e i s als o a facto r1 n selectin g th e dilutio n ratio
. Reference s 9 an d 1 0 discus s thes e Interactions
. Normally , th e C0 2 level s o fth e ra

wexhaus t an d dilute d exhaust , correcte d fo rC0 2 i n th e Incomin g air , ar e use d t o calculat e dilutio n rati o i n steady-stat e tests . Mas s flo wmeasurements ar e usuall yuse d i n transien t test s t o determin e th e dilution
. Th e dilutio n rati o ca n als o b e determine d fro m th e concentratio n o fN0 Xi n th e ra

wan d dilute d exhaust
. 3
. Tunne l Backgroun d - Tunne l backgroun d an d conditionin g ca n affec t th e level s o fsom e specifi chydrocarbo n specie s suc h a s PAH
. Th e tunne l backgroun d 1 s normall yno t a majo r facto rI n tota l particulat e an d SO F measurement s I fsom e simpl e precaution s ar e taken
. Tunne l blank s shoul d be periodicall yru n bydrawin g dilutio n ai rthroug h th e filte r fo ra n equivalen t perio d o ftim e as tha t use d fo rsampling
. Backgroun d level s shoul d be wel l unde rI Xo fth e tota l mas s expecte d t o b e collected
. O n start-u p o fa test , engin e

- exhaus t condition s (e.g. , temperature , FI D emissions ) shoul d b e stabilized* 1 1 ' 1 2 * befor e Introducin g th e exhaus t Int o th e tunnel
. Ai ronl yshoul d b e ru n throug h th e tunne l durin g engin e warm-up . Aminimu m o f2 0 minute s a t th e desire d dilutio n rati o shoul d b e allowe d fo rtunne l equilibratio n befor e collectin g samples
. I fth e samplin g poin t follow s a hig h hydrocarbo n emission s poin t (e.g. , Lo wIdl e o rligh t loa d conditions) , a 15-minut e hig h loa d burnou t o fth e ex haus t syste m ma

yb e desirabl e prio rt o settin g th e engin e tes t condition
.P.1 6
•22 - 4
. Particulat e Collectio n - Particulat e collectio n methodolog y fo rtransien t test s i s define d i n th e USEP Aprocedures' 8 '
. Fo rsteady-stat e measurements , th e methodolog yca n b e con siderabl ydifferen t dependin g o n th e typ e o fdilutio n tunne l used (13,14)

. Th e procedure s use d ar e usuall ythos e tha t hav e bee n develope d byth e researcher
. Th e particulat e characterizatio n method s discusse d i n th e followin g sectio n d o no t depen d o n ho

wth e sampl e was collected
. However , severa l precautionar yitem s tha t wil l improv e reproduci bilit yi n a laborator yar e a s follows : (a ) Utiliz e Pallfle xTX40HI20W Wfilters
. (Filte rsize s fro m 47m

m t o 102m

m ar e commonl yused. ) (b ) Handl e th e filte ra t al l time s usin g tweezer s o r forceps
. Avoi d usin g finger s o n th e filter s o ran y devic e tha t ma

ytea rparticle s fro m th e filter
. (c ) Conditio n th e filte rb yallowin g i t t o equilibrat e i n a constan t temperatur e an d humidit yenvironmen t fo r16-2 4 hour s prio rt o collectio n o fth e sample
. Afte r sampling , th e filter s shoul d b e conditione d i n th e sam e environmen t prio rt o weighing
. Roo m temperature s shoul d no t var ymor

e tha n 20°+3° C durin g conditioning
. Th e humidity , durin g conditioning , shoul d b e betwee n 30 % an d 70

% an d b e controlle d t o a rang e o f+ 10 * - (d ) The filte rshal l b e weighe d t o th e neares t 0.0 1 m g jus t prio rt o use . (e ) Monito rth e A P acros s th e filte rdurin g sampling
. A A P greate rtha n 1 3 cmH g i s excessiv e an d th e termina tio n o fth e tes t shoul d be considered
. I n no cas e shoul d th e A P excee d 2 5 cmHg
. (f ) I t i s preferabl e t o collec t a s larg e a sampl e i n as shor t a tim e a s possible
. Sampl e time s o f2 0 - 40 minute s ar e common . The mas s pe rfilte ra

s liste d ar e minimum s desired :

Filte rSize , Minimu m Mas s m m m g 4 7 1 7 0 2 90 3. 5 102 5 

### A t ligh t particulat e load s longe r collectio ntime s ma y b e required .•23 - (g ) Filte rfac e velocitie s o f10-2 0 c m pe rsecon d ar e suggested . (h ) Tw o o rthre e blan k

filter s fro m eac h lo t o ffilter s shoul d be chose n a t rando m an d the n subjecte d t o th e SOF an d sulfat e analyse s describe d i n Sectio n III . Normall yth e value s fo rSOF o n thes e blank s wil l be les s tha n 0. 1 m

g an d sulfate s shoul d b e belowdetectio n limits . ( i ) Tw o blan k filter s fro m eac h lo t o ffilter s shoul d be selecte d a t rando m an d store d i n th e constan t tem peratur e an d humidit ychambe ro rroom . Eac h da yth e filter s ca n be weighe d an d recorded . Additiona l filter s loade d wit h standar d particulat e (NB S ST D Referenc e Materia l 1650 ) o rsulfuri c ad d ma yb e mor e sensitiv e t o changes . Th e weigh t ca n be compare d t o previou s day' s value s an d ca n serv e as a n Indicato ro f th e performanc e o fth e environmenta l chamber .
B . MEASUREMEN

TO F TOTA L PARTICULAT

E MAS S 1 . Afte rth e sampl e i s obtaine d a s pe rSectio n III.1A-4 , plac e th e filte ri n th e constan t temperatur e an d humidit y chambe ro rroo m an d allo wt o equilibrat e 1 n th e dar k o r unde ryello wligh t fo r16-2 4 hours . A s a n option , se e th e followin g sectio n (III.1B-2) . 2 . Plac e th e filte r1 n a vacuu m desiccato rsaturate d wit h NH 4 0 H fo ron e hour . A

s a n option , evacuat e th e desiccato rwit h a wate raspirato ro rvacuu m pump (approximatel y2 0 m m vacuum ) an d allo wammoni a gas t o lea k int o th e desiccato runti l i t 1 s a t atmospheri c pressure . Le t th e filte rsi t 1 n th e ammoni a atmospher e fo r1 5 minutes , an d displac e th e ammoni a fro m th e desiccato rwit h air . Plac e th e filte r1 n th e constan t humidit ychambe rfo r16-2 4 hours . I fth e NHJO H procedur e 1 s used , th e combine d wate rcorrec tio n 1 n Sectio n III.2- E does no t appl ysinc e wate ri s remove d durin g th e equilibration . Thi s metho d I s usefu l 1 n handlin g sample s containin g hig h sulfat e levels . I t stabilize s th e weigh t a t abou t on e mol e o fwate rpe rmol e o f sulfate* 15 * . 3 . Remov

e th e filter s fro m thei rcontainer s wit h filte rforcep s and weig h t o th e neares t 0.0 1 mg. Recor d th e weight .P.1 8



## SECTIO N

III. 2
SOLVENT EXTRACTABL E FRACTION S (SEF )

### •27 -

III. 2 SOLVEN T EXTRACTABL E FRACTION S (SEF )
A . SCOP E Th e method

s o fcollectio n o fa particulat e sampl e fro m ligh t duty diese l vehicle s an d heav ydut ydiese l engine s ar e specifie d b y USEP A procedures* 8 ' . Thes e sample

s are collecte d directl yfro m diese l exhaus t o rfro m dilutio n tunnel s usin g specifi c engin e operatin g an d samplin g procedure s an d ar e compose d o fvariou s subfractlon s describe d 1 n th e nex t section . Thes

e fraction s ar e o fInteres t 1 n evaluatin g healt h effect s Issue s an d effect s o f engineerin g o rtechnolog ychanges i n th e engin e systems . Par ticulat e sample s ca n b e obtaine d a t transien t o rsteady-stat e condition s dependin g o n th e purpos

e o fth e test . SE F fraction s discussed include , SOF , TOE, Sulfat e and Combine d Water . B . EXTRACTIO

N O F SO F - Thi s fractio n 1 s obtaine d b yextractio n wit h dichloromethan e (see note o n pag e 17) . 1 . Procedur

e (a ) Carryou t al l operation s unde r"yello wlight " an d mini miz e exposur

e t o sunlight . Otherwise , kee p th e sample

s I n th e dark . (b ) Fol d th e filte r1 n halves , and finall yquarter s and/o r eight s wit h th e particulat e t o th e Inside . Bend ove r th e to p o fth e filte rbefor e th e fina l fold . Us e th e filte rforcep s an

d wea rglove s and avoi d tearin g fiber s fro m th e filter . Carr you t th e filte rfoldin g o n a clean , plat e glas s surface . Plac e th e filter s i n th e Soxhle t extracto rwit h th e poin t o fth e fol d toward s th e bas e o fth e extractor . (c ) Assembl e th e Soxhle t apparatu s as Illustrate d i n Figure 7 . Fo r47 m m filter s a micr o Soxhle t uni t equipped wit h a 3

0 m l fla t bottome

d flas k 1 s used . Pu t 20 m l o fdichloromethan e I n th e flask . Wra p th e flas k an d Soxhle t uni t i n aluminu m foil . Star t th e wate r flowin g throug h th e condenser . Large rflask s and con denser s ma yb e require d fo rlarg e filters .P.2 0

•29 - NOTE : The toluene:ethano l solven t ma yals o remov

e som e o fth e sulfates . Therefore , sulfat e analysi s shoul d not b e conducte

d o n filter s afte ra TO

E extraction . D . DETERMINATIO

N O F SULFAT E The filte rfro m th e SO F determinatio n ma

yb e used t o determin e sulfate s o ra separat e filte rma yb e used . I fenoug h TP M ha s bee n collecte d fo ra

n accurat e analysis , sufficien t sulfat e wil l hav e bee n collected . Basically , th e procedur e Involve s extrac tio n o fth e wate rsolubl e sulfate s an d analysi s b yio n chroma tography . Instrumen t operatin g procedure s ar e supplie d b yth e manufacturer (17) . 1 . Plac e th e filte r1 n a 4 oz . Teflo n capped bottl e an d ad d 2 0 m l o fa n aqueous solutio n tha t 1 s 0.003 mola r1 n NaHCO o and 0.0024 mola r1 n Na 2 C0 3 . Distilled , deionize d wate rshoul d b e used . Som

e olde runit s usin g olde rcolum n technolog yma y us e a 60/4 0 Isopropy l alcohol/wate rsolutio n fo rextraction . 2 . Shak

e bottle s vigorousl yo rplac e th e bottle s i n a sonica tio n bat h wit h l-1nc h o fwate ri n th e bottom . Shak e o r sonicat e unti l th e filte rbreak s u p o rfo r1 0 minutes . 3 . Filte rth e sampl e throug h a 0.4 5 v m filte ro

n a Lue rfitte d syring e filter . 4 . Calibrat e a n 1o n chromatograp h wit h a standar d potassiu m sulfat e solutio n t o obtai n a calibratio n curve . 5 . Injec t th e filte rsampl e directl yInt o th e 1o n chromatograp h o rdilut e wit h th e eluen t i fsulfat e concentration s ar e to o high . 6. . Compar

e th e respons

e fro m th e filte rsampl e t o th e calibra tio n curve . 7 . Calculat e th e m g o fsulfat e on th e filte ran d relat e th e result s t o th e volume o fexhaust sampled .P.2 1



## SECTIO N

I V
NITRATEDPOLYCYCLI C AROMATI C HYDROCARBON SP.2 2


### -33 - IV . NITRATE DPOLYCYCLI C AROMATI C HYDROCARBON S
A . SCOP E Thi s procedur

e define s th e syste m an d analytica l metho

d fo rth e measuremen t o fnitrate d polycycli c aromati c hydrocarbon s i n diese l particulat e sample s b ythei rconversio n t o amine s an d detectio n b

yfluorescence . B . BACKGROUN

D Th e determinatio n o fN0 2 PA H compound

s describe d i n thi s procedur e i s based on a n analytica l method develope d b yS . Tejad a a t th e U.S . EPA-RT

P laboratory' 21 . Th e method wa s Initiall ydeveloped fo rth e analysi s o f1-nitropyren e (1-NOP ) and i s currentl yundergoin g cooperativ e round-robi n testing . Th e method 1 s a n HPL C metho d an d use s a Pt/R h catalys t t o convert th e N0 2 PA H t o amine

s on column . Th e amine s ar e the n analyze d usin g fluorescenc e detection . C . DEFINITIONS/ABBREVIATIONS 

### N0 2 

### PA H —Nitrate d Polycycli c Aromati c Hydrocarbon s 1-NO P —l-N1tropyren e HPL C —Hig hPerformanc e Liqui d Chromatograp h Pt/R h—Platinum/Rhodiu m D . EXPERIMENTA

L EQUIPMEN

T HPL C —Variou s unit s ar e available . Column s —1 . Pt/R h catalys t coate d on 5 in n Sperlsor b 5A Y alumina. * (Availabl e fro m Johnson-Mattey , Inc. , Malvern , PA) . Tw

o columns (typica l 5 c m x4. 6 mm

) ar e required .

* CAUTIO N - Methano l mus

t b e flushe d fro m th e colum n wit h wate revery tim e an end fittin g 1 s removed . (The catalys t ha s bee n observed t o flam e spontaneousl ywhe n allowe d t o dryi n ai rafte rus e o fan MeO

H ric h aqueous solution. )P.2 3
-35 - 4 . The flo wrat e o fth e mobil e phase i s se t a t 1 ml/mi n wit h th e firs t solven t (77 % MeOH/23

% water) . 5 . Followin g th e elutio n o fth e desire d reduce d N02 PAH , e.g. , 1-NO P elute s a t about 3

0 minutes afte rinjection , th e sol ven t flo wi s changed t o pum p #2 an d 100

% MeO H i s used t o clea n th e columns . Afte rabout 2 0 minutes , th e colum n flo w i s switche d back

t o pum p # 1 an d th e columns are equilibrate d fo r20 minutes prio rt o injectio n o fth e nex t sample . (Se

e cautio n i n Sectio n IV-D. ) 6 . Sample

s ar e quantifie d agains t standard s obtaine d fro m th e Nationa l Burea u o fStandards (20) . The NB S standard s ca n als o b e incorporate d a

s interna l standards . G . PRECISIO

N AN D ACCURAC

Y(Round-Robi n i n Progress) Estimate d +20

% o rbetter . H . ALTERNAT

E COLUM N CONFIGURATIO

N I fInterferenc e o rpeak separatio n problem s d o occur , th e colum n syste m ca n b

e modifie d as describe d b yTejada (21 \

Tejada' s colum n syste m 1 s mor e complicate d bu t doe s eliminat e th e overla p o fsom e peaks . 

### I . ALTERNAT E METHO D A gas chromatograph y(GC ) method utilizin g a n electio n captur e detecto r(ECD

) wa s developed b

yA.D . Little , Inc . unde rcontrac t fo rCRC-APRA

C CAPE-30 . Th e metho d 1 s reporte d i n th e I1terature (22) . Th e method ha s bee n used b

ysom e CC P members . However , theydi d replac e th e splitles s Injectio n o fth e sampl e wit h on-colum n Injectio n o fth e sampl e t o obtai n bette rresults .P.2 4



## SECTIO N

V
POLYCYCLI C AROMATI C HYDROCARBON SP.2 5


### •39 -
V . POLYCYCLI C AROMATI C HYDROCARBON S

A . SCOP E Thi s procedur e define s th e syste m an d analytica l metho d fo rth e measuremen t o fpolycycli c aromati c hydrocarbon s i n diese l par ticulat e sample s byhig h performanc e liqui d chromatography . B . BACKGROUN

D Th e analysi s o fPA

H compound s 1 n diese l exhaus t an d N0 2 PA H com pound s hav e receive d considerabl e attentio n relativ e t o th e healt h issue s associate d wit h diese l particulate . Tw o method s ar e discusse d i n thi s section . Th e firs t metho d evolve d a s a resul t o fcooperativ e effort s o fth e CCP . However , th e metho d i s manpowe rintensive , requirin g som e 10-1 2 HPL C run s t o analyz e eac h sample . Th e metho d use s a norma l phas e chromatographi c extrac t cleanu p followe d b ya n analysi s usin g revers e phas e column s an d fluorescenc e detectio n fo rquantification . Th e com pound s analyze d ar e foun d i n Tabl e IV . Th e metho d developmen t wa s conducte d unde ra CR C contract* 2 3 ' an d a round-robi n wa s conducte d b yth e CCP (24) . Th e secon d metho d require s onl ya silic a ge l cleanu p followe d b ya n HPL C separation . I t i s adequat e fo rroutin e screenin g o fsample s bu t 1 s no t a s compre hensiv e a s Metho d No . 1 . C . DEFINITIONS/ABBREVIATION S CC P - Chemica l Characterizatio n Panel , CRC-APRA C CAPI-1-6 4 In-Hous e Grou p PA H - Polycycli c aromati c hydrocarbons-fuse d rin g aromati c compound s N02 PA H - Nitrate d PA H AC N - Acetonitril e v/ v- Volume/volum e SO F - Dichloromethan e extractabl e fractio n TO E - Toluene:ethano l extractabl e fractio n VOC - Vapo rphas e organi c compound s HPL C - Hig h performanc e liqui d chromatograp hP.2 6
•41 - PROCEDURE

S Th e analysi s o fPA H compound s i n diese l particulat e usuall y involve s a n extractio n t o remov e th e organi cfractio n containin g th e PAH' s fro m th e particulat e o rcollectio n media
. Th e extrac t undergoe s a separatio n procedur e t o isolat e th e PA H compounds
. Thi s i s followe d b ychromatographi canalysi s o fth e PAH
. Th e larg e numbe ro fcompound s i n diese l extract s mak e th e precis e an d accurat e analysi s o fth e PA H difficul t unles s ther e i s prio r cleanu p o fth e sample
. Two method s ar e describe d i n thi s report . Metho d 1 involve s a mor e complicate d preparatio n an d analysi s o fth e PA H b yrin g size
. Th e fraction s ar e analyze d b yHPL C usin g specifi ccondi tion s fo reac h fraction
. Considerabl e tim e an d effor t ar e require d t o analyz e PA H bythi s metho d bu t excellen t accuracyan d precisio n ar e obtained
. Th e secon d method , Metho d 2 , require s les s effort
. I t involve s cleanu p o fth e sampl e usin g ope n colum n silic a ge l chromatograph y prio rt o analysi s b yrevers e phase HPLC
.P.2 7
-43 - METHO D 1
Thi s metho d wa

s develope d b yth e CRC (23 ) an d evaluate d i n a round robi n byth e CCP (24)

. Th e metho d ma yb e furthe rmodifie d as a resul t o fa secon d round-robi n currentl yi n progress , bu t majo rchange s ar e unlikely
. Aschemati csummarizin g th e metho d i s foun d i n Figur e 10
. Thi s metho d i s applicabl e t o SOF, TOE , an d VO C samples
. Ste p 1 - Extrac t Preparatio n § Followin g th e extractio n o fth e SOF , TOE , o rVOC , th e extract s ar e reduce d 1 n volum e t o abou t 1 m l b yevaporatio n o fth e solven t usin g a gentl e strea m o fclea n nitroge n i n th e Kuderna-Danis h evaporato ra t 65°C
. The solven t leve l i s adjusted , i frequired , t o abou t 1 m l jus t prio rt o makin g a solven t exchang e t o heptane
. (Isooctan e ca n b e use d i fextrac t solubilit yproblem s ar e ob served. ) I n th e cas e o fTO E fractions , a solven t exchang e t o dichloromethan e mus t b e conducte d prio rt o th e heptan e exchange
. •I n th e heptan e exchang e ad d 2 m l o fheptan e an d evaporat e th e sampl e unde ra gentl e strea m o fnitroge n t o les s tha n 0. 5 ml
. Add an additiona l 3 m l o fheptan e an d concentrat e th e sampl e t o a fina l volum e o fexactl y1 ml
. The extrac t 1 n heptan e (5 0 pl ) i s fractionate d usin g th e norma l phas e Bondapa k column
. (Note : Smal l extrac t samples , les s tha n 4 mg , o rsample s containin g lo w PA H concentration s ma

yrequir e furthe rconcentratin g o fth e hep tan e solutio n t o obtai n adequat e sample s fro m th e fractionatio n i n th e nex t step . Thi s ca n bette rb e evaluate d afte rconductin g Ste p 2. ) Ste p 2 - Extrac t Fractionatio n t The heptan e solutio n (5 0 ul ) 1 s fractionate d usin g norma l phas e HPL C o n th e 7. 5 m

m x30 c

m Bondapa k

amlnosllan e column
. Th e eluan t 1 s hexan e a t a flo wrat e o f3 ml/min
. Th e elutin g com pound s ar e monitore d usin g a U V detecto ra t a wavelengt h o f254 nm . Thre e fraction s ar e collecte d as the yelut e fro m th e colum n a t approximatel y0-1 1 minutes , 11-2 1 minute s an d 21-4 0 minutes
. Atypica l separatio n 1 s foun d 1 n Figur e 11
. Fractio n 1 contain s PA H wit h 3 ring s o rless , Fractio n 2 contain s 4-rin g compounds , an d Fractio n 3 contain s th e PA H wit h 5 o rmor e rings
. Th e col lectio n time s ma

yvar yslightl ydependin g o n experimenta l factors , e.g. , colum n differences , sampl e composition , etc . I t 1 s Important , therefore , t o periodicall yru n a PA H standard
. Th e actua l collectio n time s ca n b e determine d b

yanalyzin g a standar d solutio n containin g bot h Fluo ran d Chrysene
. The collectio n tim e fo rFractio n 2 begin s jus t prio rt o th e elutio n o fFluo ran d end s jus t afte rth e elutio n o fChrysene
. Th e NB S standard 125 ' con tain s bot h fluoranthen e an d chrysene , an d ca n b e use d t o estab lis h actua l collectio n times
.P.2 8
•44 - METHO D 1 - (Continued ) 

### Th e flo w rate s shoul dbe checke dvolumetricall y t o accuratel y establis hth e retentio nvolum e i nth e HPL

C syste mfromth e U

V detecto r t o th e collectio npoint . Following th e completio no f th e fractionatio no

f th e extract , th e colum nshoul dbe backflushed . Us e alinea r

gradien t

t o 100 % dichloromethan e a t

arat e o f 10 % per minute . Thi s i s followe db y arevers e gradien t

bac k t o 100 % hexan e an dequilibratio no

f th e colum nfo r 1 5 minute s a t

100 % hexane . Periodi c regeneratio nof th e colum

nma y b e require di f

signifi
can t change s i nth e profil e o r retentio ntime s occur . Flushin g th e colum nfo r on e hou r wit hTH Fma y b e required* 26 

### ' 27 

### ' . Ste p 3 - FractionAnalysi s
• Th e thre e fraction s collecte dar e concentrate dt o 5- 8 m l a t ambien t temperature usin g agentl e streamo f cleannitrogen . Th

e sample s ar e the ntransferre dt o 1 0 m l concentrato r

tube s an

d reduce di nvolum

e t o 2 ml . Avolum

e of 1 m l AC Ni s addedalon g wit hsufficien t

dichloromethan e t o mak e amiscibl e solution . Th e solutio ni s reduce di nvolum e t o abou t

0. 5 m l unde r nitrogen . AC Ni s addedt o Fraction s 1 an d2 t o brin g thei r

volum e t o exactl y 2. 0 ml . Fractio n3 shoul dbe a t exactl y 0. 5 ml . (Note : I f sample s ar e no t

use dimmediately , som

e readjustment

o f volumes wit hAC Nma y b e required. ) tTh e thre e fraction s ar e analyze dusin g singl e colum nrevers e phas e HPL C an dselectiv e fluorescenc e detection . Th e specifi c condition s ar e describe di nTable s V , VI , an dVII . • Al l thre e separation s o f th e fraction s ar e performe do nth e 4. 6 m mx 25 c mVyda c five-micro nreverse-phas e colum nusin g a

n acetonitrile/wate r

gradient . Initia l condition s ar e reestab
lishe di neac hcas e b

y usin g arevers e phas e gradien t o f 5 % pe r minut e unti l th e initia l condition s ar e attained . Th e systemi s allowe dt o reequilibrat e fo r 1 5 minute s prio r

t o th e injectio no

f th e next sample . Additiona l detail s o

nth e methodca

nbe foundi nReference s 23 , 24 , an d26 .P.2 9

-45 - METHO D 2
Thi s metho d wa

s on e utilize d b

ytw o o fth e participant s o fth e CC P an d wa s submitte d t o th e grou p fo rconsideratio n i n 1980 (28)

. Th e method , whic h i s summarize d i n Figur e 12 , wa s use d i n th e round-robi n an d ha s bee n compare d betwee n laboratories
. Typica l trace s ar e show n o n Figur e 13
. Simila rprocedure s hav e bee n use d b

ypane l members* 5 ' 29 '
. Repeatabilit ywithi n th e laborator yi s normall yaroun d 10 % r.s.d
. I t i s presente d as a convenien t metho d fo ranalyzin g larg e number s o f sample s an d ca n b

e automate d fo rroutin e analysis
. The separatio n o f certai n compounds suc h a s Ba Aan d Be

P i s no t clea n bu t th e procedur e i s usefu l i n screenin g samples
. Metho d 1 i s th e preferre d metho d whe n precisio n an d accurac yo fal l 1 1 compounds ar e o fconcern . Ste p 1 - Extrac t Preparatio n o Th e extrac t fro m th e SO F o rVO C ar e transferre d t o a Khuderna Danls h evaporativ e concentrato rflas k alon g wit h rinsing s o fth e flasks
. Th e Kuderna-Danls h unit s alon g wit h th e M1cro-Snyde r condenso rar e place d I n a n aluminu m heate rbloc k a t 40-45°C
. The sample s ar e blow n down t o a 1 m l volum e wit h a gentl e strea m o f clean , dr ynitrogen
. (TOE extract s hav e t o underg o a solven t exchang e t o dichloromethan e prio rt o undergoin g Ste p 1. ) Th e sample s ca n b

e store d 1 n 1-m l vial s 1 n th e freeze runti l suffi cien t sample s ar e obtained
. (Si xsample s ca n b e processe d manuall yi n an eight-hou rday , o rsom e tw o doze n ca n b

e ru n o n an automati cprocesse rovernite. ) o The extract s ar e fractionate d byope n silic a ge l colum n chroma tograph yt o remov

e Interferin g oxidize d material
. Th e s1 1 le a ge l column s ca n b e purchase d o rprepare d a s follows : Asmal l amoun t o fOttaw a (white ) san d I s place d I n th e botto m o fan ope n 1-c m colum n an d 1 0 cco fchromatographi cgrad e silic a ge l (60-23 0 mesh ) added
. The ge l shoul d b e activate d overnit e a t 175°C
. The colum n shoul d b e lightl ytappe d t o insur e a reasonabl ytigh t colum n bed an d a smal l amoun t o fOttaw a san d 1 s place d o n to p o f th e column
. Th e colum n 1 s rinse d wit h 2 5 m l o fhexane
. I fth e column s ar e no t goin g t o b e use d Immediately , the yshoul d b e kep t we t b yclosin g of fth e stopcoc k o fth e chromatographi ccolum n a s th e hexan e leve l jus t reache s th e to p o fth e san d laye ro n to p o f th e column
. o T o clea n u p th e extract , eac h 1-m l sampl e I s place d o n it s ow n colum n bypipett e transfe ran d tw o rinsing s o fth e Kuderna-Danls h evaporato rtub e o rvia l ar e als o adde d t o th e column
. A s th e extrac t enter s th e column , i t i s followe d b y25 m l o fhexan e an d the n by2

5 m l o fdichloromethane
. ALLelutin g liquid s ar e col lecte d i n on e 10 0 m l beaker
. Whe n th e las t o fth e solvent s ha s drained , abou t hal fo fth e mixtur e 1 s poure d int o th e evaporato r tub e an d concentrate d dow n t o 2- 3 ml
. Th e remainde ro fth e mixtur e alon g wit h tw o dichloromethan e rinsing s o fth e beake rar eP.3 0 -46 - METHOD2 - (Continued ) adde d and blow n dow n unde r nitroge n a t 40-45°C . I f th e origina l extrac t weigh t wa s greate r than 4 mg , th e sample s ar e blow n dow n t o a fina l volum e o f 1 ml . I f th e extrac t weigh t wa s les s than 4 mg , th e fina l volum e i s 0. 5 ml . Next , transfe r th e sampl e t o a 10-m l volumetri c flas k alon g wit h tw o washing s o f th e sampl e container . Blo wdow n wit hnitroge n t o 1 m l (> 4 m g sample ) o r 0.2-0. 3 m l (< 4 m g sample ) an d brin g th e volum e u

p t o 1 0 m l wit hacetonitrile . Sampl e i s transferre d t o a 1 0 m l via l an d store d i n th e freeze r unti l read yfo r HPL C analysis . Ste p2 - Sampl e Analysi s
•AZorbaxOD

S colum n (4. 6 m

m x25 cm ) i s use d fo rth e analysis
. A shor t (4. 6 m

m x5 cm ) micro-Porasi l C-1 8 colum n i s use d a s a precolum n t o prolon g th e lif e o fth e Zorbaxcolumn
. t Th e NB

S PA H standard' 2 1 ' i s use d t o calibrat e th e system . One millilite ro fth e NB

S standar d i s dilute d t o 1 0 mi s wit h acetoni trile
. Thi s i s furthe rdilute d 1:1 0 wit h acetonitrile
. Te n microliter s o fthi s solutio n i s injecte d fo rth e calibration
. The HPL C operatin g condition s are :

Flow= 1. 0 ml/min
. Solven t = ACN/Water
. Initia l % AC N = 74 % Fina l %AC

N = 86 % Tim e = 4

0 minute s (Waters 660 programe rsolven t Curve #7 ) Colum n = ZorbaxODS , 4. 6 m m x25 c m wit h C 1 8 u-Porasi l precolum n Fluorescenc e Detecto rCondition s = Ex/E m 280/38 9 t Solvent s ar e degasse d fo ra t leas t on e hou ra t approximatel y150 m m H g vacuum . Th e solvent s ar e maintaine d unde ra heliu m blanke t durin g us e b ybubblin g heliu m throug h th e solvent s a t a slo w rate . •Injectio n volume s o fsample s var ydependin g o n th e fina l tota l volum e o fsampl e an d th e milligram s o fextrac t i n th e sample
. A 20-y l injectio n i s a good startin g point
. •Th e solven t progra m i s ru n i n 40 minute s an d the n th e fina l conditio n i s hel d fo r20 minutes
. Thi s i s followe d bya rapi d retur n t o th e origina l condition s an d a 10-minut e equilibriu m dela ybefor e injectin g th e nex t sample
. Tota l ru n tim e fro m injectio n t o injectio n i s 7 0 minutes
.P.3 1



# REFERENCE SP.3 2
-49 -
REFERENCE

S

1 . Perez , J.M. , Lipari , F . an d Seizinger , D.E. , "Cooperativ e Devel opmen t o fAnalytica l Method s fo rDiese l Emission s an d Particu lates, " SA

E Pape rNo . 840413 , Detroit , MI , Marc h 1984 . 2 . Tejada , S. , CRC-APRA C CAPI-1-6 4 Chemica l Characterizatio n o f Diese l Exhaus t Emission s Worksho p II , Dearborn , MI , Marc h 1985 . 3 . Tejada , S.B. , "Evaluatio n i fSilic a Ge l Cartridge s Coate d I n Sit u wit h Acidifie d 2,4-D1nitrophenylhydrazin e fo rSamplin g Aldehyde s an d Ketone s 1 n A1r, " Intern . J . Environ. , Anal . Chem. , Vol . 26 , pp . 167-185 , 1986 . 4 . Perez , J.M. , "Chemica l Characterizatio n o fDiese l Exhaus t - A Repor t o fCooperativ e Studie s o fAnalytica l Methods, " Preprin t No . 83-48.5 , 76t h Annua l APC A Meeting , Atlanta , GA , Jun e 1983 . 5 . Wall , J.C . an d Hoekman , SX , "Fue l Compositio n Effect s o n Heavy Dut yDiese l Particulat e Emissions, " SAE Pape rNo . 841364 , Baltimore , MD , Octobe r1984 . 6 . "Methylen e Chlorid e Facin g Regulation, " Chemica l an d Engineerin g News , p . 17 , Marc h 17 , 1986 . 7 . SAE Recommende d Practices , Societ yo fAutomotiv e Engineers , 40 0 Commonwealt h Drive , Warrendale , P A 15096 . 8 . U S EP A Heavy-Dut yDiese l Transien t Test , Cod e o fFedera l Regula tions , Titl e 40 , Par t 86 , Subpar t N . 9 . Lipkea , W.H. , Johnson , J.H. , an d Vuk , C.T. , "Th e Physica l an d Chemica l Characte ro fDiese l Particulat e Emission s - Measuremen t Technique s an d Fundamenta l Considerations, " SA E Pape rNo . 7801 8 (SP-430) , 1978 . 10 . MacDonald , J.S. , Plee , S.L. , D'Arcy , J.B. , an d Schrek , R.M. , "Experimenta l Measurement s o fth e Independen t Effect s o fDilutio n Rati o an d Filte rTemperatur e o n Diese l Exhaus t Particulat e Samples, " SA

E Pape rNo . 800185 , Detroit , MI , Februar y1980 .

u 11 . Eisenberg , W.J. , "Developmen t o fa Metho d fo rth e Analysi s o f Polycycli c Aromati c Hydrocarbon s 1 n Diese l Exhaus t Emissions , Fina l Repor t b

yI I TResearc h Institut e t o th e Coordinatin g Researc h Council , Inc. , Atlanta , GA , Octobe r1983 . 12 . Williams , R.L. , Perez , J.M. , an d Griffing , M.E. , " A Revie wo f Samplin g Conditio n Effect s o n Polynuclea rAromati c Hydrocarbon s (PNA ) fro m Heavy-Dut yDiese l Engines, " SA E Pape rNo . 852081 , Tulsa , OK , Octobe r1985 .P.3 3
-50 - REFERENCE

S - (Continued )
13 . Coordinatin g Researc h Council , Inc. , "Informationa l Repor t o n th e Measuremen

t o fDiese l Particulat e Emissions, " CR C Repor t No. 522 , Jun e 1982 . 14 . MacDonald , J.S. , Barsic , N.J. , Gross , G.P. , Shahed , S.M. , an d Johnson , J.H. , "Statu s o fDiese l Particulat e Measuremen t Methods, " SA

E Pape rNo. 840345 , Detroit , MI , March 1984 . 15 . Seizinger , D.E. , Privat e Communicatio n t o th e Chemica l Charac terizatio n Pane l o fth e CRC-APRA C Program Group o

n Compositio n o f Diese l Exhaust , 1981 . 16 . Shimpl , S.A. an d Yu , M. , "Determinatio n o fa Reliabl e an d Effi cien t Diese l Particulat e Hydrocarbo n Extractio n Process, " SA E Pape rNo

. 811183 , Tulsa , OK

, Octobe r1981 . 17 . DIONEX

" Model s 10/1 4 Io n Chromatograp h Operatio n and Maintenance Manuel , DIONE

XCorporation , Sunnyvale , CA , Januar y1979 . 18 . Schuetzle , D

. an d Perez , J.M. , "

A CR C Cooperativ e Compariso n o f Extractio n an

d HPL C Technique

s fo rDiese l Particulat e Emissions, " Preprin t No. 81-56.4 , 74t h Annual APC A Meeting , Philadelphia , PA , Jun e 1982 . 19 . Hare , C.T. , "Supplementa l Stud yo fFue l Propert yan d Injectio n and Combustio n System Typ e Effect s o

n Emission s fro m Light-Dut y Diesels, " Fina l Repor t b ySouthwes t Researc h Institut e t o CRCAPRA C CAPE-32-8

0 Projec t Group , Coordinatin g Researc h Council , Inc. , Atlanta , GA

, Novembe

r1985 . 20 . Standar d Materials , SR M #1650 , Nationa l Burea u o fStandards , Washington , D. C . 21 . Tejada , S.B. , Zweidinger , R.B. , an d Sigsby , J.E. , Jr. , "Fluores cenc e Detecto rand Identificatio n o fN1tro-Der1vat1ve s o fPoly nuclea rAromati c Hydrocarbon s b yOn-Colum n Catalyti c Reductio n t o Aromati c Amines, " Anal . Chem. , pp . 1827-1834 , Jul y1986 . 22 . Menzles , K.T. , e t al , "Developmen t o fa Routin e Techniqu e fo r Analysi s o fa Nitro-PA H I n Diese l Particulat e Extract, " Fina l Repor t b

yA . D . Little , Inc . t o CRC-APRA C CAPE-30-8 1 Projec t Group , Coordinatin g Researc h Council , Inc. , Atlanta , Georgia , Februar y1985 . 23 . Elsenberg , W.C , "Developmen t o fa Metho d fo rth e Analysi s o f Polycycli c Aromati c Hydrocarbon s I n Diese l Exhaus t Emissions, " Fina l Report b

yII TResearc h Institut e t o CRC-APRA C CAPE-30-8 1 Projec t Group , Coordinatin g Researc h Council , Inc. , Atlanta , GA , Octobe r1983 .P.3 4
-51 - REFERENCE

S - (Continued )
24
. Eisenberg , W.C , Schuetzle , D. , an d Williams , R.L. , "Cooperativ e Evaluatio n o fMethod s fo rth e Analysi s o fPA H i n Extract s fro m Diese l Particulat e Emissions, " SA E Pape rNo
. 840414 , Detroit , MI , March 1984
. 25
. Standar d Materials , Priorit yPollutan t PAH , SR M #1647 , Nationa l Burea u o fStandards , Washington , D
. C
. 26
. Eisenberg , W.C
. an d Cunningham , D.L.B. , "Analysi s o fPA H i n Diese l Emission s Usin g HPLC : AMetho d Developmen t Study, " Presente d a t th e Eight h Internationa l Symposiu m o n Polynuclea r Aromati cHydrocarbons , Columbus , OH , Octobe r1983
. 27
. Warner , I. , Karlesky , D. , an d Skelly , D.C , "Reactivatio n o fa n Amin o Bonde

d Phas e Liqui d Chromatographi cColumn, " Anal
. Chem. , 53:2146 , 1981
. 28
. Coordinatin g Researc h Council , Inc. , "Informationa l Report o n th e Measuremen t an d Characterizatio n o fDiese l Exhaust Emissions, " CR C Repor t No
. 517 , Decembe r1980
. 29
. Swarin , S.J
. an d Williams , R.L. , "Polynuclea rAromati cHydro carbons : Chemistr yan d Biologica l Effects, " Bjorseth , A
. an d Dennis , A.J. , editors , Battell e Press , Columbus , Ohio , 1980
.P.3 5



### TABLE S AN D 

### FIGURE STABL E I PHYSICAL PROPERTIE S O F CARBONY L COMPOUND S DNP H Derivativ e Aldehyd e o r Keton e Formaldehyd e Acetaldehyd e Aceton e Propionaldehyd e Acrolei n n-Butyraldehyd e Isobutyraldehyd e Methylethy l keton e Crotonaldehyd e n-Valeraldehyd e I so-Valeraldehyd e Caproaldehyd e Enanthaldehyd e Benzaldehyd e p-Tolualdehyd e IU C Name Methana l Ethana l 2-Propanon e Propana l Propena l Butana l 2-Methylpropana l 2-Butanone trans-2-Butena l Pentana l 3-Methylbutana l Hexana i Heptana l Benzenecarbona l 4-Methylbenzene
carbona l Chemica l Formul a CH 2 0 CH 3 CH 0 CH3COCH 3 CH 3 CH 2 CH 0 CH 2 :CHCH 0 CH 3 (CH 2 ) 2 CH O CH 3 CH(CH 3 )CH O CH 3 C0CH 2 CH 3 CH 3 CH:CHCH 0 CH 3 (CH) 3 CH 0 (CH 3 ) 2 CHCH 2 CH 0 CH 3 (CH 2 ) 4 CH 0 CH 3 (CH 2 ) 5 CH 0 C 6 H 5 CH 0 CH 3 C 6 H 4 CH 0 Molecula r

Weigh t 30.0 3 44.0 5 58.0 8 58.0 8 56.0 7 72.1 0 72.1 1 72.1 1 70.0 9 86.1 3 86.1 3 100.1 6 114.1 8 106.1 3 120.1 4 Melting

Pt. , ° C -9 2 -12 1 

### -9 5 -8 1 -87. 7 

### -9 9 -65. 9 

### -8 4 -7 4 -9 2 -5 1 -5 6 -4 5 -2 6

— Mol . Wt .

210.1 5 224.1 8 238.2 1 238.2 1 236.2 0 252.2 3 252.2 3 252.2 3 250.2 1 266.2 6 266.2 6 279.2 8 294.3 1 286.2 5 300.2 7 Meltin g

Pt. , ° C 16 7 

### 16 7 12 8 15 6 16 5 12 2 18 2

— 

### 19 0 10 6

— 

### 10 4

— 

### 23 7 19 4 Densit y

0.81 5 0.78 3 0.79 2 0.80 7 0.84 1 0.81 7 0.79 4 0.80 5 0.85 8 0.82 0 0.80 5 0.83 3 0.85 0 1.0 5 1.0 2 Re l Re t

Time 0.45 3 0.57 4 0.71 4 0.79 5 0.69 9 ,

O l

_ _ 1 0.91 1

— 0.87 0

—

— 1.2 3

— 1.0 0

—TABL E I I STORAG E STABILIT Y (ng/yL ) SAMPL E NO .

Formaldehyd e Acetaldehyd e Acrolei n Aceton e Propionald . Crotonald . Isobutryald . Benzald . Hexana i ORIG .
23. 0 3.9 8 1.0 3 0.8 5 0.8 6 0.5 2 0.5 8 0.3 1 0.1 9 

### 1

A
22. 0 3.8 2 0.1 6 0.8 3 0.8 2 0.4 2 0.5 8 0.2 9 0.1 4

A= 

### B
22. 7 3.9 7 0.2 1 0.8 9 0.8 4 0.4 7 0.5 8 0.3 1 0.1 0
6 week s ORIG .

23. 6 4.1 6 0.9 4 0.9 0 0.9 1 0.5 2 0.6 1 0.3 2 0.1 5

B = 

### 2 A
22. 0 3.8 6 0.1 7 0.8 9 0.8 3 0.3 2 0.8 5 0.2 7 0.1 2

2 month s 

### B

22. 3 3.8 1 0.2 0 0.8 7 0.8 4 0.3 0 0.7 4 0.3 0 0.1 0


### N D ORIG .
14. 1 2.3 0 0.7 7 0.5 6 0.4 7 0.4 2 0.3 4 0.0 9 0.0 7

= No t 

### 3

A
13. 5 2.0 8 O.l l 0.5 6 0.4 3 0.1 4 0.4 2 

### N D N D

Detecte d 

### B

13. 8 2.0 6 0.1 4 0.5 7 0.4 7 0.1 2 0.3 5 

### N D N D ORIG .
14. 1 2.2 4 0.6 7 0.5 4 0.4 7 0.3 0 0.3 2 

### N D N D 

### 4 A
13. 3 2.0 1 0.1 2 0.5 3 0.4 4 0.1 4 0.3 3 

### N D N D 

### B
13. 5 1.9 6 0.0 9 0.5 2 0.4 5 0.1 2 0.4 2 

### N D N D I

i n iP.3 8


### •57 -

TABL E II I COMPARISON

O F SO F AN DVACUU

M REMOVAL O F ORGANI C FRACTION

Sampl e Size , m g
9.9 0 10. 2 7.7 7 7.7 7 SOF ,

W t . %
36. 4 43. 4

— 46. 1 Vacuu m Temperat u 200° F 275° F 

### re * 350° F Wt . Loss , %
38. 6

- - 22. 0 48. 6 41. 4

48. 2 39. 5

" " 44. 0

49. 2

— 51. 0



### * Al l sample s wer e unde r 15 " vacuu m (A15 " Hg ) fo r 6 hours .•58 - P.3 9

TABL E I V
HUJTUIU^ ^

P2tAJQNDAPAjU!H^ ^

Fluoren e Anthracen e Phenanthracen e Fluoranthen e Pyren e BenzU.anthracen e Chrysen e Benzo[k]fluoranthen e Benz[a]pyren e Benzo[b]fluoranthen e Benzo[g,h,i]perylen e Elution Time , min . 6.8 7 9.3 6 9.7 2 12.4 5 12.2 7 17.6 1 17.8 5 21.4 5 22.4 1 23.0 4 31.2 6 

### Relativ e

Elutio n TimeiJliO

j 0.5 5 0.7 5 0.7 8 1.0 0 0.9 8 1.4 1 1.4 3 1.7 0 1.8 0 1.8 5 2.5 1 Fractio n

Collectio n Time s Fractio n1 0-1 1 min .

Fraction2 11-2 1 min .

Fraction3 21-4 0 min .P.4 0
-59 -

TABL E V HIG H PERFORMANC E LIQUI D CHROMATOGRAPH Y O F POLYCYCLI C AROMATI C HYDROCARBONS : FRACTIO N l 1



### PA H Fluoren e Phenanthren e Anthracen e Retentio n

Time , min . 16.5 0 18.8 5 20.9 2 Fluorescenc e

Wavelength , n

m Excitatio n 26 0 

### 26 0 26 0 Emission 0

37 0 

### 37 0 37 0 Detectio n

Limit , ng 2 3.6 7 0.9 3 0.5 0

1
. HPL C elutio n conditions : 4. 6 m m x25. 0 c

m Vyda c5 micro n reverse-phas e column ; linea rgradient , acetonitrile/wate r(50/50 , V/V ) t o acetonitrile/wate r(70/30 , V/V ) i n 3 0 min
. the n t o 100 % acetonitril e I n 1 0 min. , followe d by1 0 min
. a t 100 % acetoni trile
. Th e syste m was returne d t o initia l condition s usin g a revers e gradien t o f5%/min
. fo r1 0 min
. an d equilibrate d a t initia l condition s fo r1 5 min. ; flow : 1. 0 ml/min. , detecto r range : 1. 0 (minimu m range : 0.01) ; injectio n volume : 1 5 ul
. 2
. Th e detectio n Umi t was define d a s th e on-colum n amoun t o f compoun d tha t woul d giv e a pea k tha t was 5 time s th e baselin e nois e unde rthes e instrumenta l conditions
. 3
. Adetecto rwit h a 37 0 n m emissio n cut-of ffilte rwa s used
.P.4 1


### -60 -

TABL E V I HIGHPERFORMANC E LIQUI DCHROMATOGRAPHY O F POLYCYCLI C AROMATI C HYDROCARBONS : FRACTION 2 1

Fluorescence Retentio n Wavelength , n m „ Detection , 

### PA H Fluoranthen e Pyren e Benz[a]anthracen e Chrysen e Time , min . 10.5 0 11.9 7 17.4 0 18.7 2 Excitatio n

26 0 

### 26 0 28 0 26 0 Emission J

37 0 

### 37 0 38 9 37 0 Limit , n

g 1.2 2 2.2 6 0.5 1 0.5 9

1 . HPL C elutio n conditions : 4. 6 m m x25. 0 c

m Vyda c 5 micro n reverse-phas e column ; isocrati c elution , acetonitrile/wate r (70/30 , V/V) fo r1 5 min. , the n a linea rgradien t t o 100 % acetoni tril e i n 1 5 m1n. , followe d b y1 5 min . a t 100

% acetonitrile . Th

e syste m Wa

s returne d t o initia l condition s usin g a 1 0 min . gradien t followe d b ya n equilibratio n perio d o f1 5 min. ; flow : 1.0 ml/m1n. ; detecto rrange : 1.0 (minimu m range : 0.01) ; injec tio n volume : 30 yl . 2 . The'detectio n limi t wa s define d a

s th e on-colum n amoun t o f compound tha t woul d giv e a pea k tha t wa

s 5 time s th e baselin e nois e unde rthes e instrumenta l conditions . 3 . A detecto rwit h a 37 0 and 38 9 n m emissio n cut-of ffilte rwa s use d i n thes e analyses .P.4 2


### •61 -

TABL E VI I HIG HPERFORMANC E LIQUI DCHROMATOGRAPH Y O F POLYCYCLI C AROMATI C HYDROCARBONS : FRACTIO N 3 1



### Fluorescenc e Retentio nWavelength , n mDetection , 

### PA H Benzo[b]fluoranthen e Benzo[k]fluoranthen e Benzo[a]pyren e Benzo[g,h,i]perylen e Time , min . 32.3 4 34.1 1 35.7 3 40.8 2 Excitatio n

28 0 

### 280 28 0 280 Emission* 1

38 9 

### 38 9 38 9 38 9 Limit , n

g 0.2 9 0.2 3 0.2 9 1.7 1



### 1 . HPL C elutio nconditions : 4. 6 m mx25. 0 c mVyda c 5 micro n reverse-phas e column ; linea r gradient , acetonitrile/wate r (50/50 , V/V ) t o acetonitril e i n 4 0 min. , followe db y2 0 min . a t 100 % acetonitrile . Th e syste mwa s returne dt o initia l condition s fo r 1 5 m1n. ; flow : 1. 0 ml/min. ; detecto r range : 1. 0 (minimu mrange : 0.01) ; injectio nvolume : 3 0 pl . 2 . Th e detectio nlimi t wa s define da s th e on-colum namoun t o f compoun dtha t woul dgiv e a pea k tha t wa s 5 time s th e baselin e nois e unde r thes e instrumenta l conditions . 3 . Adetecto r wit ha 38 9 n memissio ncut-of f filte r wa s used .P.4 3


### -62 - FIGUR E 1 SAMPLIN GCAR T (SCHEMATI C DIAGRAM )

FILTER S (A S REQUIRED )

.SOLENOI O ON-OF F

DRY-GA S

METE R TEM P READ O 

# hBm-j i fflbr*- c GAS VOLUM E EMERGENCYPOWE RP.4 4

•63 -



### FIGUR E 2 

## CARBONY L ANALYSI S METHO O

PREPARATION

* 

# I SAMPUN G HPLC ANALYSIS " TIM S (MIN ) STAR T 0 

## a 9 1 5 2 0 3 0 STOP

8 9 1 5 2 0 30 3 5 

# I 

# I

FLO WRAT E (MUMIN ) 0. 7 1.0 1.0 1.0 1. 0 2. 0 

# 1

SOLVEN T— GRADIENTCON C (VO L %) 87ACN/33 H, 0 67ACNJ3 3 H, 0 G RA O IEN TT O 8 5 AC N GRADIENTT

O 10 0 AC N 10 0 AC N REVERSE GRA0IEN T T O 67 ACN/23 H, 0 •ONP H SOLUTION S STANOARO

S ••HPL C —4. 8 mm x25 c m colum n —

5M Zorfia xOOS ; 60

0 PS I (initial) : UV-36 5 nm ; sensitivit

y0. 2 AUF

SP.4 5
-64 - 

### 1X 1 LU£ £ c u T 3 C U > > T 3 C O - C >,T 3 O J O J

- o £< U C O 0 1 " O 

### LL- O 0 ) 0

> -C ' >>" 0 0 » T 3 " O > > 0 ) " O " O Jl£i-T3 r>>-_ : O J " O O J >,> > -oa><0>><U.--0J"O>," O j=_ = n--o_._c-.oj-o>,.::> , i . a > ci.r - >, . 4)"Di- rai r " O " O •< - Q

J C « +•

> " O i — r —( 0 QJ- O O

J r —i — 0J__OC3i —<-<03"Or-" O (

_<_r —O •<- OJ Q <

0 > i . r

—r —( O r — XE - M O - M --.- M I N I O ) O <

_+ - ( O Q . E Q

J J . O J O O O C Oi- H XQ.- M zouuui-i.intiiA a i < u a ; o Q-.<<<Q.(J)HC.M > Q.. C
_c o



# 1 O ( A 

# i i 9 e s 

## aFIGUR E 4 250 FORMALDEHYD E STABILIT Y

_g > o . E a t <a
• U i Q > - I U J SAMPL E 1 200

15 0 i c\ t n i

10 0 

### tc 

## o 5 0 

## 1 1 6 2 4

HOUR S 32 4 0 48

### -f i 

### a. 

### E 

# I -i o U U

8 0


### e o

4 0

2 0 - \

^

^
_ 

# 1 FIGUR E 5

ACROLEI N STABILIT

Y



# 1 1 ^



# 1 1 SA K



# 1 I c n •

1 6 24 32 ELAPSE D TIM E —HOUR S 40 4 8

i -500 , FIGUR E 6 TOTA L ALDEHYD E STABIUT Y Engin e Operatio n Conditio n No . 1

• 2 400 | o. E 

### S 3 U J 

## o > - i U J 300 1 • i

2 200 1 No . 2

100« 1 6 ELAPSE D TIM E 24 HOUR S 32 4 0



### fcP.4 9 

### -68 - FIGURE 7 - SOXHLE T-

* * • o C O C\ J X o CV J a : o > -69 - FIGUR E 8 MAS S O F BOUND H- 0 PE

R GRA M H 2 S0 4 I N A N AQUEOU

S SOLUTIO N VERSUS RELATIV E HUMIDIT Y(25°C )

7

6

5

4
3
2
1
0 

# - j

~ / 

# I

-jiT^ i . 9


## J J 5

0 

## 1 1 1 0 2 0 4 0 6 0 8 0 10 0

Relativ e Humidity , % P.5 0

-P.5 1
-70 - FIGUR E 9 SCHEMATI C O F NITROPYREN E ANALYSI S SYSTE M

Solven t Reservoi r 77 : Methano l 23Z Wate r .i---- > 

# I Flo w 1. 1 mi/mi n 

# I

[Pum p J Solven t Reservoi r 100 2 Methano l

Reductio nCatalys t 3 inc h x4. 6 m

n packe d wit h groun d u p 3-way catalys t 70 mesh Fo rremova l o f

oxyge n 

# r D

r*. Septum-les s N ' Injecto r Analytica l Colum

n ZorbaxOD

S Colum n 2 3 c m* 4. 6 m

m 

# i

Analytica l Colua n ZorbaxOO

S Colum n 1 5 c m* 4. 6 m

m Reductio nCatalys t

3 inc h x4, 6
_ a packe d wit h ground-u p 3-wa y catalyst , 70 mesh

Waste Fluorescenc eDetecto r 36 0 n mexcitatio n 43 0 n memissio nfo r 1-nitropyren eP.5 2


### -71 - FIGUR E 1 0 HPL C PA HMETHO DNO . 1

FRACTION 1 ( 3 ORLES S RINGS ) DIESE L PARTICULAT E

EXTRACTION

KUDERNA-DANIS H (SOLVEN T EXCHANGE )

EXTRAC T FRACTIONATION (BONDAPA KNH,) *

FRACTION 2 ( 4 RINGS )

SOLVEN T EXCHANG E AND SAMPL E CONCENTRATION FRACTION 3 ( 5 ORMOR E RINGS )

VYDAC 5 pm

COLUM N SEPARATION

SE E TABL E V SE E TABL E V I SE E TABL E VI I

* Se e Figur e 11 .FIGUR E 1 1 HPL C METHO D SUMMAR

Y- FRACTIONATIO

N O F TH E DIESE L EXTRAC

T

STEP 1

FRACTIO N - FRACTIONATIO N UVDETECTIO N BONDAPAC KNH 2

i
STE P 2 VYDA C 5 COLUM N —FLUORESCENC E DETECTIO N FRACTIO N I FLUOREN E

ANTRACEN E PHENANTHEN E FRACTIO N I I FLUORANTHEN E PYREN E BENZ(A)ANTHRACEN E CHRYSEN E FRACTIO N II I BENZO(B)FLUORANTHEN E

BENZO(K)FLUORANTHEN E BENZO(A)PYREN E BENZO(GHI)PERYLEN E SEPARATIO N CHECKE D USIN G NB S SR M #164 7 (1 6 PA H STANDARDS)P.5 4 

### •73 -

FIGUR E 1 2
HPL C PA HMETHO DNO . 2

DIESE L PARTICULAT E

EXTRACTION

- MECL 2



### SILICA GE L SEPARATION HEXANE/MECL 2



### SAMPL E CONCENTRATE D T O1-m l (KUDERNA-DANIS H -

)



### SOLVEN T EXCHANG E (ACN )

- 

### HPLC-FLUORESCENC E EX/EM = 280/38 9 ZORBA XOD SP.5 5


### -74 - FIGUR E 1 3 TYPICAL HPL C TRACE S - METHO O2

A . PAHSTANDAR D.01' N



## r-mr

9 . JIESE L ENGIN E

PARTICULAT E EXTRAC T <SOP >

•~^h — ^ 

# W :