P. 1


# OAR Box 1846 Prepped byOllie Stewart



### Document

Number: 

# 72 ) ll-J-1 5 Docket Number: 

# A-90-0 7

Printed 11/18/20087:30:17

AM Sheet 72 of 93

### A -30-0 0 H-J - J5 " 

# CR C Repor

t No
. 55 1 i> ' r f_'.? ^ 

# \Ar' 

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

Carbonyls/Aldehyde s Particulate Characterizatio n Sulfate s PAH/N0

2 

# PA H
August 198

7

COORDINATIN G RESEARC H COUNCIL, INC . 21 9 PERIMETE R CENTE R PARKWAY , ATLANTA , GEORGI A3034 6P. 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, THE APPROPRIAT

E COMMITTE E O F TH E COORDINATIN G RESEARC H COUNCIL , INC . HA S NO TINVESTIGATE D O R CONSIDERE D PATENT S WHICH . MA YAPPL YT O THE SUBJEC

TMAHER . PROSPECTIVE USER S OFTH E REPOR TAR E RESPONSIBL E FO R PROTECTIN G THEM SELVE S AGAINS TLIABILIT

YFOR INFRINGEMEN TO F PATENTS . Prepare db

y th e Chemica l Characterizatio nPane l

o f th e CR C Program

Grou ponCompositio 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

* . . T
1 t TABL E O F CONTENT S Pag 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 NIII. l - 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 N111. 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 NIV

- NITRATE D POLYCYCLI C AROMATI C HYDROCARBON S A . Scope... . 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 . Equipment . 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 - Hig hPerformanc e Liqui d Chromatographyo f Polycycli c Aromati c Hydrocarbons : Fractio n 1 5 9 Tabl e V I - 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 Mixture... . 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 H? 0 Pe r Gra mH0SO 4 i n a n A Q ueou 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 X A- Membership : Chemica l Characterizatio n Pane l o f th e

CR C Diese l Exhaus t Compositio n Grou p A- 1

• n -P. 6

• . . f



## SECTIO NI INTRODUCTIONP. 7 -3 -

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 byth 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 base d 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 was 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 NO2PA

H metho d ha s evolve d primaril yas 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

i . . '



## SECTIO NI I

HIG H PERFORMANC E LIQUI D CHROMATOGRAPHI C (HPLC ) DINITROPHENYLHYDRAZIN E (DNPH ) METHO D FO R CARBONY L COMPOUNDSP. 9

I I . HIG H PERFORMANCE LIQUI D CHROMATOGRAPHI C (HPLC ) DINITRO PHENYLHYDRAZIN E (DNPH ) METHOD FOR CARBONY L COMPOUND

S

A
. SCOP

E Th e procedure incorporate s an improve d 2,4-dinitrophenylhydrazin e metho d i n whic h C j t o C g carbony l compound s ar e collecte d by bubblin g diese l exhaus t o rdilute d diese l exhaus t throug h a n 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 ^ 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 be 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

• 8 - Aldehyd e Standard s - Individua l aldehyde s fo rstandar d preparatio n shoul d b e bes t availabl e grade
. 2,4-DNP H Derivative s - Metho d o fpreparatio n discusse d i n late rsection
. 2
. Equipmen t HPL C wit hU

V detectio n(36 5 nm) . Variou s unit s ar e avail able . 5 uZorba xOD S 4. 6 m

m x25. 0 cm

HPL C column , DuPon t Inst . Co . Midge t Impinger s (Light-Dut y Diesels ) o r 10 0 m L Glas s Impin ger s (Heavy-Dut y

Diesels) . Flowmeter , pum

pan dmete r - - require dfo r sampl e collectio n (Figur e 1) . L C syringe s a s required . Meltin g Poin t Apparatus . 3 . 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 nin2 N HCL . Th e derivative s ar e filtered , washe dwit h2 N HC l an dHoO , 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 the standard s shoul dals o be checke dfo r purit y

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

6.25vmole/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 usedt o prepar e a 1. 6 mole/m L DNP Habsorbin g solutio ni nth e bubblers . Fiv e drop s o f IN HC10 4 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

formali nsolutio nb y titration . Standar dderivativ e solution s ar e prepare db y injectin g 2. 0 t o 2 0 y L o f th e aldehyd e solutio nint o a septu m seale dvia l containin g th e derivatizin g reagent . Weighin g soli dDNP Hhydra zone s an

ddissolvin g them

inacetonitril e canals o be use dt o prepar e standar dderivatives . D . SAMPL E COLLECTIO N 1 . Samplin qSystem - Th e samplin g system canvary

dependin g o

n th e sourc e o f aldehydes . On e system , Figur e 1 , wa s designe d t o sampl e dilute dexhaus t from variou s siz e dilutio ntunnel s o r heate dTeflo nRbag s containin g dilute dexhaust . Fo r samplin g directl y

fro m undilute dexhaus t stream s a shor t (approximatel y

2 meter s X0.63 5 c m O.D. ) stainles s stee l lin e shoul db e adde dt o allo w som e coolin g o f th e exhaus t prio r t o enterin g th e Teflo ncoate dheate dline . 2 . Samplin g - A

1.6ymole/m L DNP Hsolutio ni s usedfo r emissio n testing . Thi s i s obtaine db y dilutin g th e stoc ksolutio na s indicate dabov e o r th e solutio nca nb e prepare db y dis solvin g abou t 3 1 mg o f purifie dDNP Hin10 0 mL o f acetoni trile . Fo r eac hlight-dut y diese l (LDD ) sampl e t o b e taken , th e impinger s ar e prepare db y addin g 1 0 m L o f th e DNP Hsolutio n an d2 drop s (approximatel y 10 0 yL ) o f th e I

N HC10 4 t o eac h impinger . Sampler s ar e connecte dinserie s an dplace dina

n ic e bath . Fo r samplin g heavy-dut y diesel s (HDD) , 2 0 m l o f th e DNP Hsolutio nwit h4 drop s IN HC10 4 ar e adde dt o eac h impinger . Sampl e flo w throug hth e bubbler s i s maintaine da t 1/ 2 L/mi nfo r LD Dan d2- 4 L/mi nHDD . Normall y 10-3 0 L o f exhaus t (100-30 0 L a t 9: 1 dilutio nratio ) i s adequat e t o obtai nsufficien t sampl e fo r a reliabl e analysi s dependin g o nth e typ e o f emissio nsource . Th e lowe r th e sourc e con centratio nth e mor e sampl e tha t i s require dfo r goodquanti tativ e results . A s a guideline , aldehyd e level s fro m LDD<HDD<H Dgasolin e engines . Sample s shoul dbe analyze dimmediatel y o r refrigerate dunti l used . E . SAMPL E ANALYSI S 1 . Analysi s Procedur e - Sample s shoul dbe analyze da s soona s possible , preferabl y withi na fe w

hours , t o minimiz e th e losse s o f certai nspecies . Th e procedur e fo r analysi s i s showninFigur e 2 . Followin g a nacceptabl e HPL C blank , th e calibratio nstandard s ar e run .P.1 2
-10 -

Anexampl e o f a nHPL C trac e fo r th e standard s i s show ni n Figur e 3 . I t shoul db e emphasize dtha t th e appearanc e ma y var y dependin g o nth e HPL C syste m utilized . However , th e relativ e retentio ntime s o f th e peak s shoul dclosel y agre e wit hthos e showninTabl e I . I f not , retentio ntime s shoul d be redetermine dusin g a se t o f standards . Th e tim e require d from injectio nt o th e appearanc e o f th e interna l standard , benzaldehyde , i s considere dt o b e 1.0 . Th e time s fo r al l othe r peak s t o elut e ar e normalize dt o it . I f a nautomate d ' system

i s utilized , the sample s canbe sequence drunnin g a standar dchec ka t th e en do f th e serie s o r ever y 4- 6 sample s dependin g onth e numbe r o f sample s t o be analyzed . 2 . Sampl e Stabilit y - Th e stabilit y

o f sample s indicate s tha t losse s o f individua l aldehydes , wit hth e th e exceptio no f acrolein , ar e onl y

abou t 1 0 percen t in2 4 hours . Experimen tall y determine dlosse s fo r formaldehyde , acrolei nan dtota l aldehyde s ar e show ni nFigure s 4 , 5 , an d6 . Th e acrolei n losse s a s demonstrate donFigur e 5 ar e concentratio ndepen dent . Highe r concentration s approac h35 % los s in2 4 hours . Fortunately , thi s specie s i s normall y a mino r componen t o f the tota l aldehydes . Tota l aldehyd e losse s ar e 1 0 percen t o r less . Typically , samplin g an danalysi s i s complete d withi n2 4 hours . Storag e stabilit y beyond2 4 hour s i s show n o nTabl e II . Th e dat a sho w tha t losse s i ntota l aldehyde s withi na

neigh t wee kperiodwer e les s than5 percent . Thi s i s primaril y

du e t o acrolei nan

dcrotonaldehyd e degradation .

F . PRECISION

AN DACCURAC 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)
. Th e 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 b e 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 , was a s 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 b e 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 hour s afte rcollection , a precisio n an d accurac yo f1 0 percen t r.s.d
. o rbette rshoul d b e 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 cedures utilizin g DNPH-coate d silic a cartridge s fo rsamplin g and analyzin g carbony l compounds i n engin e exhaust . S.B . Tejada' s (EPA-RTP) metho d wa s 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 . On e 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 product o facrolei n i n air . A secon 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 and th e metho

d fo rpreparin g cartridge s hav e been publishe d i n th e literature* 3 5
.P.1 4



# SECTIO N

II I
DIESE L PARTICULAT E CHARACTERIZATIO NP.1 5


### -15 -

III . DIESE L PARTICULAT E CHARACTERIZATIO N

A . PURPOS E Thes e procedure s ar e intende d fo r us e i n th e collectio n an d characterizatio n o f particulat e emission s fro mdiese l engines . The yma yb e use d a s a guid e towar d standar d practice s s o tha t result s fro mvariou s source s ma yb e compare d wit hsom e degre e o f accuracy . I t shoul d b e kep t i n min d tha t th e procedure s tha t follo wma yb e subjec t t o chang e t o keep pac e wit hexperienc e and technica l advances . Th e procedure s cove r A ) Tota l Particulat e Mass , B ) Solven t Extractabl e Fractions , C ) Sulfate s an d Combine d Water , D ) PA

H an d N0 2 

### PAH .
B . SUMMARY I n th e procedure s described , th e particulate s ar e collecte d o n preweighed , Teflon R

### coated , glas s fibe r filters . Th e tota l particulat e mas s 1 s determine d b yweighin g th e filter s befor e and afte r use . Th e filter s ar e extracte d wit hdlchloromethan e i n a Soxhle t unit , drie d an d weighe d agai n t o giv e th e mas s o f th e solubl e organi c fraction . Th e filte r i s nex t extracte d wit ha wate r solutio n b

yagitatio n an

d th e sulfat e i s determine d b yio n exchang e chromatography . Th e mas s o f soli d materia l i n th e particulat e i s determine d b ysubtractin g th e mas s o f sulfat e and solubl e organi c fractio n fro mth e tota l particulat e matter . PA H an d NOoPA H analyse s ar e conducte d o n th e solubl e organi c frac
tion , variation s o f thes e procedure s ar e i n us e dependin g o n th e objective s o f th e test (1)


### . Th e NOoPA H procedur e i s foun d i n Sectio n IV . Th e PA H metho d i s found i n Sectio n V

alon g wit ha shor t PA H analysi s versio n usefu l fo r screenin g samples . Avacuu msublimatio n metho d usefu l i n measurin g Residua l Carbonaceou s Particulat e o n a numbe r o f sample s simultaneousl yi s describe d i n Sectio n III.2B(i) . Th e mas s rat e o f eac hcomponen t i s calculate d b ydividin g th e mas s o f th e componen t collecte d byth e cubi c meter s o f exhaus t sampled , th e kilowatt-hour s o f wor k done , th e distanc e traveled , o r o n a specifi c fue l consumptio n basis . Th e particulat e emis

sio n result s ca n b e expresse d i n mas s unit s o f gram s pe r cubi c mete r o f exhaust , gram s pe r kilowatt-hour , gram s pe r mile , o r gram s pe r kilogramo f fue l consumed .P.1 6 

### 16- C . DEFINITIONS/ABBREVIATION S Total Particulat e Mas s (TPM ) - Particulat e collecte d o n a Teflo n coate d glas s fibe rfilte ra t temperature s betwee n 52° C and 45°C . Solven t Extractabl e Fractio n (SEF ) - Thi s fractio n contain s th e materia l tha t ca n b e extracte d fro m th e tota l particulat e mas s b yvariou s solvent s and contain s bot h organi c solven t and inorgani c solven t extracts . Solubl e Organi c Fractio n (SOF ) - Th e solven t extractabl e fractio n o ftota l particulat e mas s remove d b

ySoxhle t extractio n usin g d 1 chloromethan e (see note , page 17) . Tota l Organi c Extrac t (TOE ) - Th e fractio n o fth e tota l partlcu lat e mas s remove d bySoxhle t extractio n usin g a toluene:ethano l binar ysolven t (32:6 8 wt/wt , B. P t 76.7°C ) system . Wate rSolubl e Sulfate s (Sulfates ) - The majo rextractabl e inor gani c fractio n i n th e particulat e sampl e i s th e wate r solubl e sulfat e fraction . Thes e ar e those sulfate s remove d b yagitatio n o fth e particulat e sampl e i n a wate rsolutio n an d analyze d directl yb yio n chromatography . Th e wate r solutio n contain s 60/4 0 isopropyl/wate ralcohol , o rnewe r io n chromatograp h procedure s use onl yth e chromatographi c eluan t fo rth e extractio n solution . Combined Wate r(Water ) - Thi s 1 s wate rtha t i s chemicall ycombine d wit h sulfuri c ad d and metalli c sulfate s i n th e par ticulat e material . I t amount s t o abou t 1.3 time s th e mas s o fmeasure

d sulfat e (1 ' 2 » 3 ) whe n th e TP

M i s equilibrate d a t 50 Xrelativ e humidit ya t 20°C . Residua l Carbonaceou s Particulat e (RCP) - Thi s fractio n 1 s th e calculate d particulat e remainin g afte rremova l o fth e tota l organi c extrac t fraction , sulfates , and combine d water . Th

e residua l "carbon " fractio n ma ycontai n a smal l amoun t o f sulfu rand metals :

RCP=TP M - TO E - SULFATE

S - WATER

.P.1 7

1 — •'• • -17 -

D . EXPERIMENTA L 1 . Reagent s - Solvent s shoul db e hig hpurity , distille di n glas s o r equivalent : 

### a . b . c . d . Dichloromethan e (Methylen e Chloride ) NOTE : Shoul donl y

b e use di na laborator y hoo dwit h adequat e ventilation (6) . Toluen e Ethano l Distilled , deionize dwate r 2 . Equipmen t - Bes t Sourc e Availabl e 

### a .

b . c . d . e . f . gh . i . j . k . Filter s - Pallfle xTX40HI20W W o r equivalent , 47mm t o 10 2 m m diamete r (T60A2 0 filter s ar e als o used . However , highe r extractabl e level s ar e obtaine dfrom T60A2 0 blan k filter s thanTX40HI20W W filters . I f T60A2 0 filter s ar e used , batche s shoul db e checke dfo r extractables. ) Filte r holder * Pum pan dmeterin g system * Timer * Millipor e Filte r cassette s o r Petr i dishe s Soxhle t Extracto r wit hboilin g flas kan dreflu xcon dense r Microbalanc e capabl e o f readin g t o + 0.0 1 m g Constan t temperatur e an dhumidit y

chambe r o r roo

m Rotar y evaporato r Kuderna-Danis hEvaporato r Yellow lightin g fo r roo

m (n o wavelength s below

50 0 nm ) 1 . Filte rForceps m. Ultrasoni c bat h

* Component

s o fparticulat e collectio n syste m whic h ma yvar ywit h respec t t o individua l syste m design .P.1 8



### SECTIO NIII. l
TOTA L PARTICULAT E MASSP.1 9
•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 be collec te d i 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 Procedur e J1003 (7 ) ar e guideline s fo rengine operation
. Fo rtransien t tests , th e USEP Aprocedures ^

ca n b e use d a

s a guideline
. Dilutio n Rati o - Th e dilutio n rati o use d t o collec t particu lat e i s normall yabou t 10-2 0 t o 1 , Ai rt o Exhaust
. I n practice , th e actua l dilutio n rati o i 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 ri 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 rawexhaus t an d dilute d exhaust , correcte d fo rCO 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 i 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 b

ydrawin 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 b e wel l unde rI S o 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 1 befor e introducin g th e exhaus t int o th e tunnel
. A1 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.2 0
•22-
4 . Particulat e Collectio n Particulat e collectio n methodology lefine d i n th e USEP

A procedures* 5 ' . fo rtransien t test s i s define d i n th e USEP A p i Fo rsteady-stat e measurements , th e methodologycan 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 used ar e usuall ythos e tha t hav e bee n develope d b yth e researcher . Th e particulat e characterizatio n methods discusse d i n th e followin g sectio n do no t depen d o n ho wth e sampl e wa

s 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 on 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 and 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 not varymor e tha n 20°+3° C durin g conditioning . Th e humidity , durin g conditioning , shoul d b e betwee n 30 % and 70

S and b e controlle d t o a rang e o f+102 . (d ) Th e filte rshal l b

e weighed 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 excessive and th e termina tio n o fth e tes t shoul d b e considered . I n no cas e shoul d th e A P exceed 2 5 cmHg. (f ) I t i s preferabl e t o collec t as larg e a sampl e i n as shor t a tim e as possible . Sampl e time s o f20 - 40 minute s ar e common. Th e mas s pe rfilte ra

s liste d ar e minimums desired :

Filte rSize , Minimu m Mas s m m m g 47 1 7 0 2 9 0 3. 5 102 5 

### At ligh t particulat e load s longe r collectio ntime s ma y b e required .P.2 1
•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 b

e chose n a t rando m an d the n subjecte d t o th e SO F an d sulfat e analyse s describe d i n Sectio n III . Normall yth e value s fo rSO F on thes e blank s wil l b e les s tha n 0. 1 m

g and sulfate s shoul d b e belo wdetectio n limits . (1 ) Tw o blan k filter s fro m eac h lo t o ffilter s shoul d b e 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 b

e weighe d an d recorded . Additiona l filter s loaded wit h standar d particulat e (NB S ST D Reference Materia l 1650 ) o rsulfuri c ad d ma yb e mor e sensitiv e t o changes . The weigh t ca n b e compare d t o previou s day' s value s and can serve a s a n indicato ro f th e performance 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 i n th e dar k o r unde ryello wligh t fo r16-2 4 hours . A s a n option , see th e followin g sectio n (III.1B-2) . Plac e th e filte ri n a vacuum desiccato rsaturate d wit h NH4O H fo ron e hour . A

s an option , evacuate th e desiccato rwit h a wate raspirato ro rvacuum pum p (approximatel y2

0 m m vacuum

) and allo wammoni

a ga s t o lea k

int o th e desiccato runti l i t i s a t atmospheri c pressure . Le t th e filte rsi t i n th e ammoni a atmospher

e fo r1 5 minutes , and displac e th e ammoni a fro m th e desiccato rwit h air . Plac e th e filte ri n th e constan t humidit ychamberfo r16-2 4 hours . I fth e NH4O

H procedur

e i s used , th e combine d wate rcorrec tio n i 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 i 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* 155
. 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.2 2


### -24 -
4 . Th e differenc e inweigh t betwee nthe firs t weighin g o f the filte r an

dthe weighin g instep3 i s th e TPM , i f ammoniatio n i s no t used . I f th e ammoniatio ni s used , th e weigh t adde d b y the additio no f tw o mol e equivalen t weight s o f NH 4 fo r eac hmol e o f sulfat e mus t be subtracte dfro m the TP M mass . 5 . Fo r long term

storag e the filte r i s returne dt o the cassett e o r Petr i dish , wrappe dinaluminu m foi l andstore di na freeze r a t -20°C . Whe nth e filte r i s remove dfro m th e freeze r i t shoul db e re-equilibrate dfo r 2 4 hour s andre weighe dt o se e i f an

y losse s inTP M

occurre ddurin g storage . I f losse s excee d1 0 wt . % o f th e TP M

o r 2 0 wt . %

o f th e SOF , discar dthe values .P.2 3



## SECTIO N

III . 2
SOLVENT EXTRACTABL E FRACTION S (SEF )P.2 4


### •27 -

III. 2 SOLVEN T EXTRACTABL E FRACTION S (SEF )

A . SCOP E Th e method s o f collectio n o f a particulat e sampl e fro m ligh t dut y diese l vehicle s an d heav ydut ydiese l engine s ar e specifie d b y USEP Aprocedures* 8 

### ' . Thes e sample s ar e collecte d directl yfro m diese l exhaus t o r fro mdilutio n tunnel s usin g specifi c engin e operatin g an d samplin g procedure s an d ar e compose d o f variou s subfraction s describe d i n th e nex t section . Thes e fraction s ar e o f interes t i n evaluatin g healt heffect s issue s an d effect s o f engineerin g o r technolog ychange s i n th e engin e systems . Par ticulat e sample s ca n b e obtaine d a t transien t o r steady-stat e condition s dependin g o n th e purpos e o f th e test . SE F fraction s discusse d include , SOF , TOE , Sulfat e an d Combine d Water .
B . EXTRACTIO NO F SO F - Thi s fractio n i s obtaine d byextractio n wit h dichloromethan e (se e not e o n pag e 17) . 1 . Procedur e (a ) Carryou t al l operation s unde r"yello wlight " an d mini mize exposur

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

s i n th e dark . (b ) Fol d th e filte ri 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 and wea rglove s and avoi d tearin g fiber s fro m th e filter . Carr you t th e filte rfoldin g on 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 a s illustrate d i n Figur e 7 . Fo r4

7 m m filter s a micr o Soxhle t uni t equipped wit h a 3

0 m l fla t bottomed flas k i 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 5 

### -28 - (d ) Star t th e ho t plat e o r plac e th e Soxhle t unit s in constan t temperatur e bat handallo w th e solven t t o begi ncycling throughthe apparatus . Adjus t the tem peratur e s o tha t the solven t cycle s throughthe extrac tio ncel l abou t ever y 5-1 0 minutes . Extrac t fo r a t leas t four hours . Cycl e tim e o f th e extractor s ma y vary . A

tota l o f 4 0 cycle s shoul dbe useda s a guideline . (e ) Tur nof f th e heat , o r remov e fro m bath , andallo w

th e solven t t o stopboiling . (f ) Disassembl e the Soxhle t apparatu s an dcarefull y

remov e the filte r wit hfilte r forceps . Plac e the filte r o na cleanwatc hglas s o r Petr i dis han dallow the dichloro methan e t o evaporat e ina fum e hood . Avoi dtearin g fiber s fro m

th e filter . Afte r 3 0 minute s a t roo m temperatur e the filte r canbe covere do r placedbac kin the plasti c cassett e an dreturnedt o the constan t tem peratur e andhumidit y chamber . Remov e th e cove r and le t th e filte r equilibrat e fo r 1 6 t o 2 4 hours . (g ) Th e filte r i s the nremove dfro m It s containe r and reweighe do

nthe micro-balanc e t o the neares t 0.0 1 mg . (h ) Th e los s o f weigh t afte r thi s extractioni s the SOF . (i ) Vacuu m

sublimatio n1 s a possibl e alternativ e t o thi s metho di f the SO F i s no t requiredfo r furthe r analyses . Th e filter s ar e hel dina vacuu m ovena t 200° C an

d15 - 3 0 in . Hg pressur e o r less . Afte r 1 6 hour s carefull y releas e the vacuu

m an dremov e the filters . Th e filter s ar e thenallowe dt o coo l an dar e placedinthe weighin g roo m t o equilibrat e fo r 1 6 t o 2 4 hours . Dat a t o sup por t thi s have beenreported* 16 

### ' . Dat a foun dinTabl e II I Indicat e shorte r time s ca nb e used . Additiona l stud y o f thi s option1 s needed . A disadvantag e o f the vacuu m sublimatio ntechniqu e i s tha t th e fractio nevaporate di s los t andcanno t b e furthe r analyzed .
C . EXTRACTIO

N O F TO E Thi s fractioncontain s the mor e pola r organic s an di s extracte d usin g a toluene:ethano l binar y solven t (32:6 8 wt/wt , B . P t 76.7°C) . Th e fractio ncontain s materia l tha t i s no t remove db y MeCl 2 

### andi s equa l t o th e SO F plu s th e additiona l material . Dependin g onth e purpos e o f th e extractio nth e entir e fractio n canb e remove di

non e step , bypassing the SOF extraction .P.2 6


### •29 -
NOTE : Th e toluene:ethano l solven t ma y als o remov e som e o f th e sulfates . Therefore , sulfat e analysi s shoul dno t be conducte don filter s afte r a TO E extraction .
D . DETERMINATION

O F SULFAT E Th e filte r fro m

th e SO F determinatio nma y b e use dt o determin e sulfate s o r a separat e filte r ma y b e used . I f enoug hTP M ha s bee ncollecte dfo r anaccurat e analysis , sufficien t sulfat e wil l have beencollected . Basically , the procedur e involve s extrac tio no f th e wate r solubl e sulfate s an danalysi s by io nchroma tography . Instrumen t operatin g procedure s ar e supplie db y th e manufacturer* 17 

### ' . 1 . Plac e th e filte r i na 4 oz . Teflo ncappe dbottl e andad d2 0 ml o f a naqueou s solutio ntha t i s 0.00 3 mola r inNaHCO o an d 0.002 4 mola r inNa 2 

### C0 3 

### . Distilled , deionize dwate r shoul d be used . Som e olde r unit s using olde r colum ntechnology

ma y us e a 60/4 0 isopropy l alcohol/wate r solutio nfo r extraction . Shak e bottle s vigorousl y o r plac e th e bottle s ina sonica tio nbat hwit h1-inc ho f wate r i nth e bottom . Shak e o r sonicat e unti l the filte r break s u po r fo r 1 0 minutes . 3 . Filte r th e sampl e througha 0.4 5 y m filte r ona Lue r fitte d syring e filter . 4 . Calibrat e a nio nchromatograp hwit ha standar dpotassiu m sulfat e solutio nt o obtai na calibratio ncurve . 5 . Injec t the filte r sampl e directl y int o th e io

nchromatograp h o r dilut e wit hthe eluen t i f sulfat e concentration s ar e to o high . 6 . Compar e th e respons e fro m th e filte r sampl e t o th e calibra tioncurve . 7 . Calculat e th e m g o f sulfat e o nth e filte r an drelat e th e result s t o th e volum e o f exhaus t sampled .P.2 7 •30- E . COMBINE

D WATE R 1 . Th e preferre d metho

d i s t o equilibrat e i n th e weighin g roo m a t 50 1 humidit yand subtrac t 1.3 time s th e weigh t o fsulfat e fro m th e TPM . A

n alternat e metho d i s foun d i n followin g sectio n 2 an d 3 . Correction s fo rothe rhumiditie s ca n b e determine d fro m Figur e 8 . 2 . A n optio n i s t o plac e th e filte r(i n it s containe rwit h th e to p removed ) int o a desiccato rcontainin g Dr1er1t e fo r1 6 hours , remov

e and weig h rapidly . Subtrac t thi s weigh t and a 1-mol e weigh t o fwate requivalen t time s th e mole s o fsulfat e fro m th e gros s weigh t obtaine d fo rth e TPM . 3 . I fth e ammoniatio n method , III.IB-2 , i s used , subtrac t a weigh t equa l t o 0. 2 o fth e sulfat e fro m th e TP M t o correc t fo rth e adde

d ammonia . (Th e stoichiometr ysuggests 2 mole s o fammonia pe rmol e o fsulfate , however , experimenta l dat a [Referenc e 15 ] Indicat e onl yabou t a 2 0 wt. % increas e i s obtained. )
F . REPEATABILIT

Y Th e precisio n o fth e measuremen t o fTPM , SOF , TO E an d sulfat e wil l depend upo

n th e tota l mas

s o feac h componen

t collecte d wit h highe rmasses producin g bette rprecision . A CR C round-robi n interlaborator yprogra m ha s establishe d a relativ e standar d deviatio n o f+15

% fo ra minimu m sampl e o f1 m g fo rSO

F and TOE

. Fo rsample s o f1 0 m g an d larger , precisio n withi n a laborator y shoul d b

e +10 % o rless . A round-robi n wa s conducte d an d th e result s reported* 18 ' . Precisio n o fth e sulfat e measurement ha s not been establishe d bu t i t 1 s expecte d t o b

e +5 % o rbetter .P.2 8



## SECTIO N

I V
NITRATEDPOLYCYCLI C AROMATI C HYDROCARBON SP.2 9


### -33 - IV . NITRATE DPOLYCYCLI C AROMATI C HYDROCARBONS

A . SCOP E Thi s procedur

e define s th e syste m and 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 base d on a n analytica l method develope d b yS . Tejad a a t th e U.S . EPA-RTP laboratory* 2 ' . 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 i s an HPL C metho d and 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 —1-Nitropyren 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 are available . Column s —1 . Pt/R h catalys t coate d on 5 ym Sperisor b 5A Y alumina. * (Availabl e fro m Johnson-Mattey , Inc. , Malvern , PA) . Tw

o column s (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 i s removed . (The catalys t ha s been 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.3 0

-34 -
2 . Zorba xOD S (2 5 cm x4. 6 m m ID ) DuPon t Company , Wilmington , Delawar e 3 . Zorba xOD S (1 5 c m x4. 6 m m ID ) Fluorescenc e Detecto r — 36 0 n m excitation ; 43 0 n

m emissio n A schemati c o f th e system i s show

ninFigur e 9 .
E . SOLVENT S Methano l (MeOH ) - Us e distille dinglas s qualit y o r equivalent . Dlchloromethan e (MeCl 2 ) - Us e distille di nglas s qualit y o r equivalent . (Se e not e onpag e 17. ) Distilled , deionize dwate r

F . PROCEDUR E The N0

2 PA H d o not fluoresc e bu t can b e converte d o

n colum n i n th e HPL C t o amines whic h d

o fluoresce . Thi s metho d i s currentl yon

e o ftw o bein g evaluate d b yth e CCP. Th e metho d wa s recentl y utilize d i n th e CRC-APRA C CAPE-33-8 0 Projec t conducte d b y SwRI* 19 ' . 1 . Th e syste m utilize s tw o shor t reductio n catalys t columns . Th e firs t on

e remove

s oxygen containin g compound s fro m th e solvent . Th

e secon d catalys t convert s th e NOoPA H t o fluor escen t NH 2 PAH . Th e HPL C ove n i s se t a t 80° C fo rth e columns . 2 . Tw o 5 - m Zorba

xOD S analytica l column s ar e als o used . Th e firs t colum n separate s an yNH 2 PA H presen t i n th e extrac t fro m th e N0

2 PA H befor e the yente rth e reductio n catalyst . Th e second analytica l colum n furthe rseparate s th e reduced N0 2 PA H fro m othe rInterferin g compound s i n th e extract . 3 . Th e appropriat e extrac t o rSEF fractio n i s dissolve d i n a 50:5 0 mixtur e o fMeCl 2 an d MeOH . Th e actua l volum e o f solven t use d depend s on th e N0 2 PAH level s expected . Ini tiall yus

e 1 m l o feac h solven t and dilut e appropriately .P.3 1 •35-
4 . Th e 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 N0 2 PAH , e.g. , 1-NO P elute s a t abou t 3 0 minute s afte rinjection , th e sol ven t flo wi s change d t o pum p #2 an d 100

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

t o pum p # 1 and th e column s ar e equilibrate d fo r2 0 minute s 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 . PRECISION 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 a

s describe d b

yTejada* 21 ' . Tejada' s colum n syste m i 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 i s reporte d i n th e literature* 2 2 ' . Th e metho d 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-colura n injectio n o fth e sampl e t o obtai n bette rresults .P.3 2



## SECTIO N

V
POLYCYCLI C AROMATI C HYDROCARBON S•39 -
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 b yhig h performanc e liqui d chromatography .
B . BACKGROUND Th e analysi s o fPA H compound s i 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 . Two 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 CRC contract* 2 3 ' an d a round-robi n wa s conducte d b yth e CCP* 2 4 ' . 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 i s no t a s compre hensiv e a s Metho d No . 1 .
C . DEFINITIONS/ABBREVIATION S CCP - 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 N0 2 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.3 4 -40 -


### PA HCompounds : Fl Ph Ant h Fluo r P y Ba A Ch BbF Bk F Ba P B(g,h,i ) - Be P Fluoren e

Phenanthren e Anthracen e Fluoranthen e Pyren e Benz(a)Anthracen e Chrysen e Benzo(b)Fluoranthen e Benzo(k)Fluoranthen e Benz(a)Pyren e Benzo(g,h,i)Perylen e Benz(e)Pyren e
D . EQUIPMEN

T HPL C - Hig h performanc e liqui d chromatograph . Sto p flo wcapa bilit yi s preferre d bu t i s not required . Variou s instrument s ar e available . U VDetecto r- Wavelengt h = 25 4 n m (use d fo rfractionatio n o f extrac t i n Metho

d 1) . Bondapa k

NH 2 Colum n - Norma l phas e aminosilan e semipreparativ e column , 7. 5 m

m x30 cm . Vyda c 5 Micro n Colum n - Reverse d phas e analytica l column , 4. 6 m m x2 5 cm . Fluorescenc e Detecto r- Wavelengt h capabilit ya s show n i n Table s V , VI , an d VII . Evaporato r- Kuderna-Danis h evaporato rwit h a Micro-Snyde rcon densor . E . SOLVENT

S 

### Distille dinGlas s o r equivalen t quality :

Hexan e
. Isooctan e Dichloromethan e (MeCl 2 

### ) Acetonitril e (ACN ) Tetrahydrofura n(THF ) Al l solvent s shoul db e degasse dimmediatel y prio r t o use .P.3 5 •41 - F
. 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 bychromatographi 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
. Tw o 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 byrin 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 b ythi s metho d bu t excellen t accurac yan d precisio n ar e obtained
. The 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 phas e HPLC
.P.3 6


### -43 - METHOD1
Thi s metho d wa s develope d byth e CRC* 2 3 

### ' an d evaluate d i n a round
robi n b yth e CCP* 24 

### ' . Th e metho d ma ybe furthe r modifie d a s a resul t o f a second round-robi n currentl yi n progress , bu t major change s ar e unlikely . Aschemati c summarizin g th e metho d i s found i n Figur e 10 . Thi s metho d i s applicabl e t o SOF , TOE , an d VO C samples . Ste p1 - Extrac t Preparation

• Followin g th e extractio n o f th e SOF , TOE , o r VOC , th e extract s ar e reduce d i n volum e t o abou t 1 m l b yevaporatio n o f th e solven t usin g a gentl e strea mo f clea n nitroge n i n th e Kuderna-Danis h evaporato r a t 65°C . Th e solven t leve l i s adjusted , i f required , t o abou t 1 m l jus t prio r t o makin g a solven t exchang e t o heptane . (Isooctan e ca n b e use d i f extrac t solubilit yproblem s ar e ob
served. ) I n th e cas e o f TO E fractions , a solven t exchang e t o dichloromethan e mus t be conducte d prio r t o th e heptan e exchange .
• I n th e heptan e exchang e ad d 2 m l o f heptan e an d evaporat e th e sampl e unde r a gentl e strea mo f nitroge n t o les s tha n 0. 5 ml . Add a n additiona l 3 m l o f heptan e an d concentrat e th e sampl e t o a fina l volum e o f exactl y1 ml . Th e extrac t i n heptan e (5 0 yl ) 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 r sample s containin g lo w PA H concentration s ma yrequir e furthe r concentratin g o f th e hep
tan e solutio n t o obtai n adequat e sample s fro mth e fractionatio n i n th e nex t step . Thi s ca n bette r b e evaluate d afte r conductin g Ste p 2. ) Ste p2 - Extrac t Fractionation

• Th e heptan e solutio n (5 0 yl ) i s fractionate d usin g norma l phas e HPL C o n th e 7. 5 m m

x3 0 c mBondapa k aminosilan e column . Th e eluan t 1 s hexan e a t a flo wrat e o f 3 ml/min . Th e elutin g com pound s ar e monitore d usin g a U V detecto r a t a wavelengt ho f 25 4 nm . Thre e fraction s ar e collecte d a s the yelut e fro mth e column a t approximatel y0-1 1 minutes , 11-2 1 minute s an d 21-4 0 minutes . Atypica l separatio n i s found i n Figur e 11 . Fractio n 1 contain s PAH wit h3 ring s o r less , Fractio n 2 contain s 4-ring compounds , an d Fractio n 3 contain s th e PA H wit h5 o r mor 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 i 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 hFluo r and Chrysene . Th e collectio n tim e fo r Fractio n 2 begin s jus t prio r t o th e elutio n o f Fluo r an d end s jus t afte r th e elutio n o f Chrysene . Th e NB S standard* 25 

### ' con tain s bot hfluoranthen e an d chrysene , an d ca n b e use d t o estab
lis hactua l collectio n times .P.3 7


### -44 - METHOD1 - (Continued )
Th e flo wrate s shoul d b e checke d volumetricall yt o accuratel y establis hth e retentio n volum e i n th e HPL C syste mfro mth e U V detecto r t o th e collectio n point . Followin g th e completio n o f th e fractionatio n o f th e extract , th e colum n shoul d b e backflushed . Us e a linea r gradien t t o 100 % dichloromethan e a t a rat e o f 10 % pe r minute . Thi s i s followe d b y a revers e gradien t bac k t o 100 % hexan e an d equilibratio n o f th e column fo r 1 5 minute s a t 100 % hexane . Periodi c regeneratio n o f th e colum n ma yb e require d i f signifi

can t change s i n th e profil e o r retentio n time s occur . Flushin g th e column fo r on e hou r wit hTH F ma yb e required* 26,27 

### ' .
Step3 - FractionAnalysi s

• Th e thre e fraction s collecte d ar e concentrate d t o 5- 8 m l a t ambien t temperatur e usin g a gentl e streamo f clea n nitrogen . Th e sample s ar e the n transferre d t o 1 0 m l concentrato r tube s an d reduce d i n volum e t o 2 ml . Avolum e of 1 m l AC Ni s adde d alon g wit hsufficien t dichloromethan e t o mak e a miscibl e solution . Th e solutio n i s reduce d i n volum e t o abou t 0. 5 m l unde r nitrogen . AC Ni s adde d t o Fraction s 1 an d 2 t o brin g thei r volum e t o exactl y2. 0 ml . Fractio n 3 shoul d b e a t exactl y0. 5 ml . (Note : I f sample s ar e no t use d immediately , som e readjustmen t o f volume s wit hACNma yb e required. ) t Th e thre e fraction s ar e analyze d usin g singl e colum n revers e phas e HPL C an d selectiv e fluorescenc e detection . Th e specifi c condition s ar e describe d i n Table s V , VI , an d VII .
• Al l thre e separation s o f th e fraction s ar e performe d o n th e 4. 6 m mx2 5 c mVyda c five-micro n reverse-phas e colum n usin g a n acetonitrile/wate r gradient . Initia l condition s ar e reestab
lishe d 1 n eac hcas e byusin g a revers 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 syste mi s allowe d t o reequlHbrat e fo r 1 5 minute s prio r t o th e injectio n o f th e nex t sample . Additiona l detail s o n th e metho d ca n b e foun d i n Reference s 23 , 24 , an d 26 .P.3 8


### -45 - METHOD2
Thi s metho d wa s on e utilize d b ytw o o f th e participant s o f th e CC P an d wa s submitte d t o th e group fo r consideratio n i n 1980* 28 

### ' . Th e method , whic hi s summarize d i n Figur e 12 , wa s use d i n th e round-robi n and ha s bee n compare d betwee n laboratories . Typica l trace s ar e show n o n Figur e 13 . Simila r procedure s hav e bee n use d b ypane l members* 5 

### ' 29 

### ' . Repeatabilit ywithi n th e laborator yi s normall yaround 10 % r.s.d . I t i s presente d a s a convenien t metho d fo r analyzin g larg e number s o f sample s an

d ca n b e automate d fo r routin e analysis . Th e separatio n o f certai n compound s suc ha 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 f al l 1 1 compound s ar e o f concern . Ste p1 - Extrac t Preparation o Th e extrac t fro mth e SO F o r VO C ar e transferre d t o a Khuderna
Danis hevaporativ e concentrato r flas k alon g wit hrinsing s o f th e flasks . Th e Kuderna-Danis hunit s alon g wit hth e Micro-Snyde r condenso r ar e place d i n a n aluminu mheate r bloc k a t 40-45°C . Th e sample s ar e blow n dow n t o a 1 m l volum e wit ha gentl e strea mo f clean , dr ynitrogen . (TO E extract s hav e t o underg o a solven t exchang e t o dichloromethan e prio r t o undergoin g Ste p 1. ) Th e sample s ca n b e store d i n 1-ml vial s i n th e freeze r unti l suffi

cien t sample s ar e obtained . (Si xsample s ca n b e processe d manuall yi n a n eight-hou r day , o r som e tw o doze n ca n b e run o n a n automati c processe r overnite. ) o Th e extract s ar e fractionate d b yope n silic a ge l column chroma
tograph yt o remov e interferrin g oxidize d material . Th e silic a ge l column s ca n b e purchase d o r prepare d a s follows : Asmal l amoun t o f Ottaw a (white ) san d i s place d i n th e botto mo f a n ope n 1-cmcolumn and 1 0 c c o f chromatographi c grad e silic a ge l (60-23 0 mesh ) added . Th e ge l shoul d b e activate d overnit e a t 175°C . Th e colum n shoul d b e lightl ytappe d t o insur e a reasonabl ytigh t column be d an

d a smal l amoun t o f Ottaw a san d i s place d o n to p o f th e column . Th e colum n i s rinse d wit h2 5 m l o f hexane . I f th 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 f th e stopcoc k o f th e chromatographi c column a s th e hexan e leve l jus t reache s th e top o f th e san d laye r o n to p o f th e column . o T o clea n up th e extract , eac h1-m l sampl e i s place d o n it s ow n column b ypipett e transfe r an

d tw o rinsing s o f th e Kuderna-Danis h evaporato r tub e o r via 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 y2 5 m l o f hexan e an

d the n b y2 5 m l o f dichloromethane . AL L elutin g liquid s ar e col
lecte d i n on e 10 0 m l beaker . Whe n th e las t o f th e solvent s ha s drained , abou t hal f o f th e mixtur e i 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 r o f th e mixtur e alon g wit htw o dichloromethan e rinsing s o f th e beake r ar eP.3 9
•46 - METHO D 2 - (Continued ) adde d an d blow n down unde rnitroge n a t 40-45°C
. I fth e origina l extrac t weigh t wa

s greate rtha n 4 mg , th e sample s ar e blow n down t o a fina l volum e o f1 ml
. I fth e extrac t weigh t wa s les s tha n 4 mg , th e fina l volum e i s 0. 5 ml
. Next , transfe rth e sampl e t o a 10-m l volumetri cflas k alon g wit h tw o washing s o fth e sampl e container
. Blowdown wit h nitroge n t o 1 m l (> 4 m

g sample ) o r0.2-0. 3 m l (< 4 m g sample ) an d brin g th e volum e u p t o 1 0 m l wit h acetonitrile
. Sampl e i s transferre d t o a 1 0 m l via l an d store d i n th e freeze runti l read yfo rHPL C analysis
. Ste p 2 - Sampl e Analysi s
•AZorbaxOD

S colum n (4. 6 m

m x2 5 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
.
•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
. Th e 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 (Water s 660 programe rsolven t Curve #7 ) Colum n = ZorbaxODS , 4. 6 m m x2 5 c m wit h C 1 8 li-Porasi l precolum n Fluorescenc e Detecto rCondition s = Ex/E m 280/38 9

•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-u l injectio n i s a good startin g point
.
•Th e solven t progra m i s ru n i n 4 0 minute s an d the n th e fina l conditio n i s hel d fo r2 0 minutes
. Thi s i s followe d b ya 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.4 0



## REFERENCE S' * *

1 .

2 . 3 .
4 . 5 . 6 . 7 . 8 . 9 . P.4 1 .— ——' -49 -
REFERENCE

S
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 . 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 . Tejada , S.B. , "Evaluatio n i fSilic a Ge l Cartridge s Coate d I n Sit u wit h Acidifie d 2,4-Dinitrophenylhydrazin e fo rSamplin g Aldehyde s an d Ketone s i n A1r, " Intern . J . Environ. , Anal . Chem. , Vol . 26 , pp . 167-185 , 1986 . 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 . Wall , J.C . an d Hoekman , SX , "Fue l Compositio n Effect s o n Heavy Dut yDiese l Particulat e Emissions, " SA E Pape rNo . 841364 , Baltimore , MD , Octobe r1984 . "Methylen e Chlorid e Facin g Regulation, " Chemica l an d Engineerin g News , p . 17 , Marc h 17 , 1986 . SA E Recommende

d Practices , Societ yo fAutomotiv e Engineers , 40 0 Commonwealt h Drive , Warrendale , P A 15096 . 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 . 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 . 11 . Elsenberg , W.J. , "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 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.4 2 -50 - REFERENCE

S - (Continued )
13
. 14
. 15
. 16
. 17
. 18
.
19
.

20
. 21
.
22
.

23
. Coordinatin g Researc h Council , Inc. , "Informationa l Report o n th e Measuremen t o fDiese l Particulat e Emissions, " CR C Report No
. 522 , Jun e 1982
. 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 , Marc h 1984
. Seizinger , D.E. , Privat e Communicatio n t o th e Chemica l Charac terizatio n Pane l o fth e CRC-APRA C Progra m Grou p o n Compositio n o f Diese l Exhaust , 1981
. Shimpi , 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
. DI0NEX

R Model s 10/1 4 Io n Chromatograp h Operatio n an d Maintenanc e Manuel , DIONE

XCorporation , Sunnyvale , CA, January1979
. Schuetzle , D
. an d Perez , J.M. , "ACR 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 Annua l APC AMeeting , Philadelphia , PA , Jun e 1982
. Hare , C.T. , "Supplementa l Stud yo fFue l Propert yan d Injectio n an d Combustio n Syste m 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
. Standar d Materials , SR M #1650 , Nationa l Burea u o fStandards , Washington , D
. C
. Tejada , S.B. , Zweidinger , R.B. , an d Sigsby , J.E. , Jr. , "Fluores cenc e Detecto ran d Identificatio n o fN1tro-Derivat1ve s o fPoly nuclea rAromati cHydrocarbon s byOn-Colum n Catalyti cReductio n t o Aromati cAmines, " Anal
. Chem. , pp . 1827-1834 , Jul y1986
. Menzies , K.T. , e t al , "Developmen t o fa Routin e Techniqu e fo r Analysi s o fa N1tro-PA H 1 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 , February1985
. Elsenberg , W.C , "Developmen t o fa Metho d fo rth e Analysi s o f Polycycli cAromati cHydrocarbon s i n Diese l Exhaus t Emissions, " Fina l Repor t 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.4 3
-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 , Marc h 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 Phase 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 Exhaus t Emissions, " CR C Report 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.4 4



### TABLE S AN D 

### FIGURE SAldehyd e o r Keton e Formaldehyd e Acetaldehyd e Aceton e Propionaldehyd e Acrolei n n-Butyraldehyd e Isobutyraldehyd e Methy l ethy l keton e Crotonaldehyd e n-Valeraldehyd e Iso-Valeraldehyd e Caproaldehyd e Enanthaldehyd e Benzaldehyd e p-Tolualdehyd e IU C Nam e Methana l Ethana l 2-Propanon e Propana l Propena l Butana l 2-Methylpropana l 2-Butanon e trans-2-Butena l Pentana l 3-Methylbutana l Hexana l Heptana l Benzenecarbona l 4-Methy1benzene
carbona l TABL E I

PHYSICA L PROPERTIE S OF CARBONY L COMPOUND S
Chemica l Molecula r Formul a Weigh t CH 2 0 30.0 3 CH 3 CH 0 44.0 5 CH3COCH 3 58.0 8 CH 3 CH 2 CH 0 58.0 8 CH 2 :CHCH 0 56.0 7 CH 3 (CH 2 ) 2 CH 0 72.1 0 CH 3 CH(CH 3 )CH 0 72.1 1 CH 3 C0CH 2 CH 3 72.1 1 CH 3 CH:CHCH 0 70.0 9 CH 3 (CH) 3 CH 0 86.1 3 (CH 3 ) 2 CHCH 2 CH 0 86.1 3 CH 3 (CH 2 ) 4 CH 0 100.1 6 CH 3 (CH 2 ) 5 CH 0 114.1 8 C 6 H 5 CH 0 106.1 3 CH 3 C 6 H 4 CH 0 120.1 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 b 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 DNP H Derivativ e

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 ,

t n t n 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 l 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 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

N D= No t 

### 3

A

13. 5 2.0 8 0.1 1 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 c n i

### -57 -

TABL E II I COMPARISON

O F SO F AN DVACUU

M REMOVAL O F ORGANI C FRACTION

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

W t . %
36. 4 43. 4
46. 1 VacuumTemperat 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.4 8

TABL E 

### I V
ELUTION O F POLYCYCLI C AROMATI C HYDROCARBON S



### PA H Fluoren e Anthracen e Phenanthracen e Fluoranthen e Pyren e Benz[a]anthracen e Chrysen e Benzo[k]fluoranthen e Benz[a]pyren e Benzo[b]fluoranthen e Benzo[g,h,i]perylen e O N A BONDAPA

KNH 2

Elutio n 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 COLUM

N
Relativ e Elutio n Time , min . 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 n 1 0-1 1 min .

Fractio n 2 11-2 1 mi n

Fractio n 3 21-4 0 mi nP.4 9 •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 0 370 370 Detectio n

Limit , nq z 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 30 min
. the n t o 100 % acetonitril e i n 1 0 min. , followe d b y1 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 yl
. 2
. Th e detectio n limi t was define d as 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.5 0
-60 -

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

PAH Fluoranthen e Pyren e Benz[a]anthracen e Chrysen e Retentio n Time , min . 10.5 0 11.9 7 17.4 0 18.7 2 Fluorescenc e

Wavelength , n

m Excitatio n 

### 26 0 26 0 28 0 26 0 Emission 0



### 37 0 37 0 38 9 370 Detectio n

Limit , n g 1.2 2 2.2 6 0.5 1 0.5 9

2
. 3
. HPL

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

m Vyda c5 micro n reverse-phas e column ; isocrati celution , 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 min. , followe d b y1 5 min
. a t 100

% acetonitrile
. The syste m was 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/min. ; detecto rrange : 1.0 (minimu m range : 0.01) ; injec tio n volume : 3

0 yl
. Th e detectio n limi 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
. Adetecto rwit h a 370 an d 389 n m emissio n cut-of ffilte rwa s use d i n thes e analyses
.P.5 1

•61 -

TABL E VI I HIG H PERFORMANCE LIQUI D CHROMATOGRAPH Y O F POLYCYCLI C AROMATI C HYDROCARBONS : FRACTIO N 3 1

Fluorescence Retentio n Wavelength , n m Detection , 

### 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 

### 28 0 28 0 28 0 Emission 0

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 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 acetonitril e i n 40 min. , followe d b y20 min
. a t 100 % acetonitrile
. Th e syste m wa s returne d t o initia l condition s fo r 1 5 min. ; flow : 1.0 ml/min. ; detecto rrange : 1.0 (minimu m range : 0.01) ; injectio n volume : 3 0 yl
. 2
. Th e detectio n limi t was define d as 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 389 n m emissio n cut-of ffilte rwa s used
.P.5 2 

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

FILTER S (A S REQUIRED )

.SOLENOI D ON-OF F

IMPINGER S

DRYING * TUB E

FLOWMETE R PUM P DRY-GA S METE R TEM P READ O ThlTlft l i T"*"

VOLUM E EMERGENC YPOWE RP.5 3 

### -63 -



### FIGUR E 2 

## CARBONY L ANALYSI S METHO D

PREPARATION ' SAMPLIN G HPLC ANALYSIS "
TIM E (MIN ) STAR T 0 

## a 9 1 5 2 0 0 0 STO P

8 9 1 5 20 3 0 3 5 

# I

FLO WRAT E (ML/MIN ) 0. 7 1.0 1.0 1.0 1. 0 1 0 SOLVENT—

GRAOIENTCON C (VO L % ) 67ACN/33 H, 0 67ACN/33 H, 0 GRAOIENTT

O 8 5 AC N GRAOIENTT

O 10 0 AC N 10 0 AC N REVERS E GRAOIENT T O 6 7 ACN/23 H, 0 •ONP H SOLUTION S STANOARO

S "HPL C —4. 8 mm x25 c m colum n —

5M ZortaxOOS ; 60

0 PS I (initial) ; UV-36 5 ntrr, sensitivit

y02 AUF SFIGUR E 3 

# CHROMOTOGRA M O F TH E STANDAR D DNPH-ALDEHYD E MIXTUR E

Relativ e Absorbanc

e 1
. 2
. 3
. 4
. 5
. 6
. 7
. 8
. 9
. 10
. 11
. 12
. 13
. 14
. 15
. DNP H Formaldehyd e Acetaldehyd e Acrolei n Aceton e Propionaldehyd e Crotonaldehyd e Iso-butyraldehyd e Benzaldehyd e Iso-valera l dehyd e Valera l dehyd e p-Tolualdehyd e Hexa l dehyd e Heptaldehyd e Octa l dehyd e i cn -P . i



### 1 0 1 2 1 4 Tim e (min )


## feFIGUR E 4
25 0 FORMALDEHYD E STABILIT Y

20 0 j_ Q . E C O c o
U J 15 0 Q SAMPL E 1

I U J cn i

CC O 10 0 •- - »

5 0

1 6 2 4 HOUR S 3 2 4 0 4 8100 

# r FIGUR E 5 ACROLEI N STABILIT

Y

SAMPL E 1
i CTt I

1 6 24 32 4 0 ELAPSE D TIM E - HOUR S 4850 0 FIGUR E 6 TOTA L ALDEHYD E STABILIT Y Engin e Operatio n Conditio n No . 1
-2 2 40 0 Q . 

## E a t c o
UJ 

### 5 30 0 I UJ 

## a i o- > I

P 200 NO . 2

10 0 1 6 ELAPSE D TIM E 2 4

HOUR S 32 4 0P.5 8 

### -68
- FIGUR E 7 - SOXHLE TP.5 9 

### -69 - FIGURE 8 MAS S O F BOUNDH 2 

### 0 PE

RGRA M H 2 

### S0 4 

### I N A N AQUEOU S SOLUTIO

N VERSU S RELATIV

E HUMIDITY(25°C )



### o cn CM 

### o CM X



### 2 0 4 0 6 0 8 0 10 0 Relativ e Humidity , %P.6 0 

### -70 - FIGUR E 9 SCHEMATI C O F NITROPYREN E ANALYSI S SYSTEM

Solven t Reservoi r 77 1 Methano l 23 2 Wate r T Flow 1. 1 tni/min 

# I

(Pum p] (Pum

pj J

«| l M Solven t

Reservoi r 100 2 Methano l

Reductio nCatalys t 3 Inc hx 4. 6 m

m packe dwit hground
u p 3-wa y catalyst , 7 0 mes h Fo r remova l o f

oxyge n 

# i Septum-les s

Inj ecco r Analytica l Column Zorba x OD

S Column 2 5 c m* 4. 6 ram 

# I Reductio nCatalys t 3 inc h* 4. 6 ~a —f Jpacke dwit hground-u p 3-wa y catalyst , 7 0 mes h

Analytica l Column Zorba x OD

S Column 1 5 c mx 4. 6 m

m

Wast e Fluorescenc e Detecto r 36 0 n mexcitatio n 43 0 n memissio nfo r 1-nitropyren eP.6 1

: A J * 

### -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

l 2 

### ] (BONDAPA KNHo) *

FRACTION 2 ( 4 RINGS )

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

VYDAC 5 y

m COLUM N SEPARATION

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

Se e Figur e 11 .FIGURE 1 1 HPL C METHO D SUMMAR

Y- FRACTIONATION O F THE DIESE L EXTRAC T

STEP 1

FRACTIO N - i 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 )

-». ,V 1 — J

A« • « * « u # -73 -

FIGUR E 1 2

HPL C PA H METHOD NO . 2

DIESE L PARTICULAT E

EXTRACTIO N - MECL2

SILIC A GE L SEPARATIO N HEXANE/MECL 2

SAMPLE CONCENTRATE D T O 1-m l (KUDERNA-DANIS H

SOLVENTEXCHANG E (ACN )

HPLC-FLUORESCENC E EX/E M = 280/38 9 ZORBA XOD S P.6 3

)

### -74 - FIGUR E 1 3 TYPICA L HPL C TRACE S - METHO D2

A . PAH STANDARDSOL' N



## T-m r

3 . MESC L ENCIN E ^ARTICULAT E EXTRAC T isory

&-" 

## .*vK~~ . 

# W