direct-acting mutagenicity of diesel participate extract is unchanged by addition of neat aromatic...

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This article was downloaded by: [University of Reading] On: 22 December 2014, At: 09:35 Publisher: Taylor & Francis Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK JAPCA Publication details, including instructions for authors and subscription information: http://www.tandfonline.com/loi/uawm17 Direct-Acting Mutagenicity of Diesel Participate Extract Is Unchanged by Addition of Neat Aromatic Compounds to Diesel Fuel Trescott E. Jensen a , Willie Young a , James C. Ball a & Lois E. Freeman a a Ford Motor Company , Dearborn , Michigan , USA Published online: 08 Mar 2012. To cite this article: Trescott E. Jensen , Willie Young , James C. Ball & Lois E. Freeman (1988) Direct-Acting Mutagenicity of Diesel Participate Extract Is Unchanged by Addition of Neat Aromatic Compounds to Diesel Fuel, JAPCA, 38:1, 56-58, DOI: 10.1080/08940630.1988.10466354 To link to this article: http://dx.doi.org/10.1080/08940630.1988.10466354 PLEASE SCROLL DOWN FOR ARTICLE Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and should be independently verified with primary sources of information. Taylor and Francis shall not be liable for any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of the Content. This article may be used for research, teaching, and private study purposes. Any substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http:// www.tandfonline.com/page/terms-and-conditions

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Page 1: Direct-Acting Mutagenicity of Diesel Participate Extract Is Unchanged by Addition of Neat Aromatic Compounds to Diesel Fuel

This article was downloaded by: [University of Reading]On: 22 December 2014, At: 09:35Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number: 1072954 Registered office: MortimerHouse, 37-41 Mortimer Street, London W1T 3JH, UK

JAPCAPublication details, including instructions for authors and subscription information:http://www.tandfonline.com/loi/uawm17

Direct-Acting Mutagenicity of Diesel ParticipateExtract Is Unchanged by Addition of Neat AromaticCompounds to Diesel FuelTrescott E. Jensen a , Willie Young a , James C. Ball a & Lois E. Freeman aa Ford Motor Company , Dearborn , Michigan , USAPublished online: 08 Mar 2012.

To cite this article: Trescott E. Jensen , Willie Young , James C. Ball & Lois E. Freeman (1988) Direct-ActingMutagenicity of Diesel Participate Extract Is Unchanged by Addition of Neat Aromatic Compounds to Diesel Fuel, JAPCA,38:1, 56-58, DOI: 10.1080/08940630.1988.10466354

To link to this article: http://dx.doi.org/10.1080/08940630.1988.10466354

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) containedin the publications on our platform. However, Taylor & Francis, our agents, and our licensors make norepresentations or warranties whatsoever as to the accuracy, completeness, or suitability for any purposeof the Content. Any opinions and views expressed in this publication are the opinions and views of theauthors, and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should notbe relied upon and should be independently verified with primary sources of information. Taylor and Francisshall not be liable for any losses, actions, claims, proceedings, demands, costs, expenses, damages, andother liabilities whatsoever or howsoever caused arising directly or indirectly in connection with, in relationto or arising out of the use of the Content.

This article may be used for research, teaching, and private study purposes. Any substantial or systematicreproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in anyform to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://www.tandfonline.com/page/terms-and-conditions

Page 2: Direct-Acting Mutagenicity of Diesel Participate Extract Is Unchanged by Addition of Neat Aromatic Compounds to Diesel Fuel

Direct-Acting Mutagenicity of Diesel Participate Extract IsUnchanged by Addition of Neat Aromatic Compounds

to Diesel Fuel

Trescott E. Jensen, Willie Young, James C. Ball, and Lois E. FreemanFord Motor CompanyDearborn, Michigan

Diesel fuel available in the future maycontain more aromatic hydrocarbonmaterial than it does at the presenttime.1 Increasing the aromatic contentof diesel fuel, however, adversely af-fects the cetane number.3 In addition,the amount of benzo(a)pyrene [B(a)P],a known mutagen requiring S9 liver ho-mogenate for activation, present in die-sel exhaust emissions has been report-ed to be directly related to the aroma-t ic i ty of the fuel.2 T h e effect ofincreasing the aromaticity of diesel fuelon the direct-act ing mutagenici ty(without S9 activation) of diesel engineemissions is a question that needs to beanswered. The effect of aromatics inthe fuel on the direct-acting mutageni-city of emissions from four differentdiesel vehicles was studied by South-west Research Institute.3 Their dataindicated that an increase in fuel aro-maticity resulted in an increase in thedirect-acting mutagenicity of emis-sions for three of the four vehicles.Changing the aromaticity of one of thefuels, however, did not affect the di-rect-act ing mutagenici ty emissionrates for any of the four vehicles. Sincethe influence of aromaticity in fuel wasnot evidenced by all fuels in all vehi-cles, other factors must have influ-enced the direct-acting mutagenicityemission rate in these experiments.

Three groups have investigated theeffect of aromatics in diesel fuel onPAH in exhaust emissions. Simple aro-matics Cs-Ci4 added to fuel produced agreater increase in B(a)P in diesel ex-haust than did a fuel containing aheavy aromatic naphtha.4 The naphthacontaining fuel actually decreased theB(a)P in the emissions compared to thereference fuel. In another study, theamount of B(a)P found in the exhaustemissions of a light-duty diesel was not

well correlated with the PAH in thefuel.5 In one study, substantial concen-trations of PAH were added to dieselfuel and the direct-acting Ames assaymutagenicity of the engine emissionswere measured.6 The direct-acting mu-tagenicity did not increase with in-creasing concentrations of PAH. Insummary, these three studies suggestthat increasing the concentrations oflarge aromatic compounds (>Cu) indiesel fuel has no effect on the PAHconcentration in emissions from thesefuels.

While there appears to be no consis-tent evidence to suggest that an in-crease in the aromatic content (com-pounds > C14) of diesel fuel will have anadverse affect on the emission of muta-genic material the effect of adding alarge amount of a single aromatic com-pound (^Cu) is unknown. Compoundswere selected for this study, in part,because they are among the major aro-matic compounds present in diesel fueland because they are at a concentrationless than 1 percent. Fourteen aromaticcompounds were used in this study.

Table I. Direct-acting mutagenicity observed for standards and extracts ofparticulates produced from combustion of reference diesel fuel and fuel to which singlearomatic compounds had been added.

Injectornozzle

A

B

Sample formutagenicity

testing8

1-Nitropyrene2-NitrofluoreneControl A (reference fuel)n-Propylbenzenen-Butylbenzenesec-Butylbenzenetert-ButylbenzeneIsobutylbenzeneIsopropylbenzene1,3-DiisopropylbenzeneControl B (reference fuel)n-AmylbenzeneMesityleneDureneDiethylbenzene (mixture)TetralinNaphthalene2,4-Dimethylnaphthalene

Mutagenicity (revertants/Vg)

1

900120

3.3

3.33.43.23.7

for test groupb

2

1000100

3.43.0

3.93.85.1

3

1400120

4.5

6.55.17.0

4

1200120

3.5

4.76.25.54.6

Copyright 1988—APCA

a 1-Nitropyrene and 2-nitrofluorene were used for positive controls in the Ames assay.All other samples tested were extracts of particulates. Samples Sbtained with referencefuel and old injector nozzles, Control A, and new injector nozzles, Control B. Aromaticcompounds were added to reference fuel to 10% by volume.b Ames assays were done on four different days. Values were determined as the least-squares fit of the linear portion of the dose response curve. Mean ± S.D. of mutagenicityvalues for extracts (excluding controls) is 4.7 ± 1.2 revertants//xg (n = 15).

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Page 3: Direct-Acting Mutagenicity of Diesel Participate Extract Is Unchanged by Addition of Neat Aromatic Compounds to Diesel Fuel

These compounds were alkyl benzenesand naphthalenes (C9-C12) with nor-mal and branched alkyl substituents.Particulate samples were generated bya direct injection engine running onNo. 2 diesel fuel augmented withknown amounts of specific aromaticcompounds. The objective of this studywas to determine the relationship be-tween the addition of (10 percent byvolume) of a single aromatic compound(<Ci4) and the direct-acting Ames as-say mutagenicity (without S9 liver ho-mogenate) of methylene chloride ex-tracts of diesel engine particulate.

Experimental

A standard No. 2 reference fuel(Phillips Petroleum), with an aromaticcontent of 30.1 percent, was used. Thepercent aromatic content of an individ-ual compound in the diesel fuel wasincreased by the addition of the com-pound selected for compatibility withthe reference fuel and its minimal ex-pected effect on engine running condi-tions. The 14 aromatic compoundsused in this study were n-propylben-zene, n-butylbenzene, sec-butylben-zene, terf-butylbenzene, isobutylben-zene, isopropylbenzene, 1,3-diisopro-pylbenzene, diethylbenzene (a mixtureof isomers), n-amylbenzene, 1,3,5-tri-methylbenzene (mesitylene), 1,2,3,4-tetrahydronaphthalene (tetralin),1,2,3,4-tetramethylbenzene (durene),naphthalene, and 2,5-dimethylnaphth-alene. The amount of the aromaticcompound added to the fuel was about10 percent by volume.

The diesel engine was a prototypenaturally aspirated 1.3 L direct injec-tion (DI) engine. A mini-dilution tun-nel was set up as described elsewhere.7

Fuel injection timing for fuel with add-ed aromatics required minor adjust-ment (not more than 2°) to give thebest fuel efficiency. For this study, bestfuel efficiency and optimum enginerunning conditions were used in prefer-ence to fixed engine operating condi-tions. After steady state engine condi-tions were achieved (1500 rpm at 37BMEP), two filter samples were ob-tained for each fuel used. Samples werecollected for 10 minutes, except wherenoted. Reference fuel was used in theengine after each experimental fuel topurge the engine system. A change ofthe fuel injector nozzles was requiredduring the collection of the particulatesample sets because of deposit accumu-lation. Control A particulate was col-lected using the old injector nozzlesand Control B particulate using thenew injector nozzles. Control A andControl B samples were generated us-ing the same reference fuel. Particulatesamples were soxhlet extracted over-night in the dark using dichlorometh-ane. The extracting solvent was re-

Table II. Direct-acting mutagenicity emission rate calculated for diesel fuel to whichsingle aromatic compounds had been added.

Injectornozzle

set

A

B

Sample

ControlControlControlControln-Propylbenzenen-Butylbenzenesec-Butylbenzeneterfc-ButylbenzeneIsobutylbenzeneIsopropylbenzene

Mutagenicity^(revertants//xg)

1,3-DiisopropylbenzeneAvge ± S.D.

Controln-AmylbenzeneMesityleneDureneDiethylbenzenesTetralinNaphthalene2,4-Dimethyl-NaphthaleneAvge ± S.D.

a From Table I.

b Pol^illotQ.

3.33.44.53.53.03.33.43.23.73.93.8

3.5 ± 0.4

5.16.55.17.04.76.25.5

4.6> 5.7 ± 0.9

Mutagenicity X Extract weighta . . . (rev/Vg) (MJ)

Extractweight(nig)

4.654.654.654.653.485.423.865.085.094.104.79

4.55 ± 0.73

3.633.963.193.364.942.824.16

4.783.84 ± 0.81

— FiTnission rate

Emissionrateb

(rev/sec)

26263527173023C

27312730

26 ±5314327393842d

38

3737 ± 5

Collection time 600 sec (rev/sec)c Collection time was 570 sec.^Collection time was 420 sec.e Calculated excluding data for controls.

moved by evaporation and the extractdried under a stream of dry nitrogengas to constant mass. The Ames assay,without addition of S9 liver homoge-nate, was done as previously de-scribed.8-9 Positive controls were 2-ni-trofluorene and 1-nitropyrene. Due tothe number of extracts to be assayed,the samples were divided into fourgroups. The direct-acting mutagenicityof standard fuel A extract was selectedfor comparison of day-to-day Ames as-say variation and was included in eachof the four sets of samples. The direct-acting mutagenicities of extracts ofthese samples were approximately lin-ear over the range of 10-400 /ug/plate.Some of the dose response curves werenonlinear at high dose. The direct-act-ing mutagenicity of each extract wasdefined as the slope of the least-squares fit of the linear portion of thedose-response curve.

Results and Discussion

, Direct-acting mutagenicity valuesfor particle extracts obtained usingstandard reference fuel and fuel towhich had been added an aromaticcompound are shown in Table I. Themutagenicity for 2-nitrofluorene mea-sured in these experiments (average =114 ± 11 revertants/jug) fell within one

standard deviation of our historical av-erage (average = 134 ± 23 revertants/Hg, n = 48). The mutagenicity of 1-nitrdpyrene measured in these experi-ments was very similar to the historicalvalues obtained in this laboratory (av-erage = 1160 ± 260 revertants/jug, n =29). Table I presents the data in theorder that the particulate samples werecollected. The direct-acting mutageni-city appears to be more dependent onthe injector nozzles used than the com-position of the fuel. Table II gives thedirect-acting mutagenicity emissionrate for the aromatic compounds test-ed. The observed direct-acting muta-genicity emission rates of samples gen-erated using the old injector nozzles Awere lower than those of samples gen-erated using the new injector nozzles B.Considering the change from the re-spective reference and the variabilityof the mutagenicity emission rates, thedirect-acting mutagenicity of these fu-els were well within the variation ob-served for the Ames assay. Therefore,these data suggest that under the con-ditions of these experiments, there wasno detectable increase in direct-actingmutagenicity of particle extracts ormutagenicity emission rates, as a resultof the addition of these aromatic com-pounds to diesel fuel. In addition, thedata suggest that injector nozzle de-

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Page 4: Direct-Acting Mutagenicity of Diesel Participate Extract Is Unchanged by Addition of Neat Aromatic Compounds to Diesel Fuel

APCA NOTE-BOOK

tailed function alters the direct-actingmutagenicity emission rates. The rea-son for this dependence on these injec-tors has not been determined.

Conclusions

The addition of neat aromatic com-pounds containing less than fourteencarbon atoms, with a variety of struc-tures, to diesel fuel did not significant-ly alter the direct-acting mutagenicityof extracts of particles or the emissionrate. A mechanical factor, injectors, didaffect the direct-acting mutagenicity ofthe samples. The sensitivity of direct-acting mutagenicity to specific injec-tors should be investigated.

Acknowledgment

We are grateful for the helpful com-ments and encouragement of WilliamR. Pierson, Richard E. Baker, andGranger K. Chui.

References

1. W. R. Wade, C. M. Jones, "Current andFuture Light-Duty Diesel Engines and

Their Fuels," NPRA Annual Meeting,San Francisco, CA, AM-83-47,1983.

2. A. Candeli, G. Morozzi, M. A. Shapiro,"PAH Content of Exhaust Gases fromFuels with Different Aromatic Fraction,"in Mobile Source Emissions IncludingPolycyclic Organic Species, D. Rodia, M.Cpoke, R. K. Haroz, eds., D. Reidel Pub-lishing Co., Drodrecht, Germany, 1983,pp. 29-47.

3. L. Smith, "Study of the Effects of FuelComposition, and Injection and Combus-tion Systems Type and Adjustment onAmes Bioassay, Nitroaromatics andPAH Emissions from Light-Duty Die-sels," Coordinating Research Council,Atlanta, SWRI-7658,1985.

4. B. B. Bykowski, C. T. Hare, T. M. Baines,"Effects of a Narrow-cut No. 1 Fuel, andVariations in Its Properties on Light-duty Diesel Emissions," SAE paper811193,1981, pp. 37-64.

5. P. A. Gabele, R. Zweidinger, F. Black,"Passenger Car Exhaust Emission Pat-terns; Petroleum and Oil Shale DerivedDiesel Fuels," U.S. EPA, Research Tri-angle Park, NC, 1982, pp. 1-37.

6. T. R. Henderson, J. D. Sun, A. P. Li, R. L.Hanson, W. E. Bechtold, T. M. Harvey, J.Shabanowitz, D. F. Hunt, "GC/MS andMS/MS studies of diesel exhaust muta-genicity and emissions from chemicallydefined fuels," Environ. Sci. Technol. 18:428 (1984).

7. J. A, Harrington, R. A. Yetter, "Applica-tion of a Mini-Dilution Tube in theStudy of Fuel Effects on StratifiedCharge Engine Emissions and Combus-tion," SAE paper 811198,1981.

8. J. C. Ball, S. Foxall-VanAken, T. E. Jen-sen, "Mutagenicity studies of p-substi-

tuted benzyl derivatives in the Ames sal-monella plate-incorporation assay," Mu-tation Res. 138:145 (1984).

9. D. M. Maron, B. N. Ames, "Revisedmethods for the salmonella mutagenicitytest," Mutation Res. 113:173 (1983).

The authors are research scientistsof the Research Staff, Ford MotorCompany, P.O. Box 2053, Dearborn,MI 48121. Their departments are T.E. Jensen, Chemical Analysis Re-search; and W. Young and J. C. Ball,Chemistry Department. L. E. Free-man, formerly with Ford's Fuels andLubricants Department, is currentlywith General Motors Research, War-ren, MI 48090. This note manuscriptwas peer reviewed.

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