8
Available online at www.sciencedirect.com Journal of Hazardous Materials 153 (2008) 1262–1269 Toxicity assessment of volatile organic compounds and polycyclic aromatic hydrocarbons in motorcycle exhaust Chang-Tang Chang a , Bor-Yann Chen b,a Department of Environmental Engineering, National I-Lan University, I-Lan, 260 Taiwan, ROC b Department of Chemical & Materials Engineering, National I-Lan University, I-Lan, 260 Taiwan, ROC Received 24 June 2007; received in revised form 4 September 2007; accepted 21 September 2007 Available online 29 September 2007 Abstract This study investigates the toxicity of various pollutant species from motorcycle exhaust via dose–response analysis and margin of safety using Escherichia coli DH5. The toxicity evaluation of the major components of motorcycle exhaust volatile organic compounds (VOCs), collected with impinger, and polycyclic aromatic hydrocarbons (PAHs), collected with filter and XAD-2, is essential to determine emission standards for motorcycles. The toxicity of benzene (B), toluene (T), ethyl benzene (E) and xylene (X) was selected for comparison as standard VOCs emitted from motorcycles. In addition, three types of reformulated gasoline (high oxygenate and high benzene content (No. 1), low oxygen and high benzene (No. 2), and low oxygen and low benzene (No. 3) were prepared to reveal combined toxicity of individual compositions. Motorcycle exhaust is significantly more toxic than BTEX due to the highly toxic VOCs generated from incomplete combustion. Overall toxicity evaluation showed that the toxicity, indicated as EC 50 , was approximately as follows: PAHs > two-stroke engines > four-stroke engines > BTEX. © 2007 Elsevier B.V. All rights reserved. Keywords: Dose–mortality curves; Volatile organic compounds; Polycyclic aromatic hydrocarbons; Escherichia coli 1. Introduction Due to marked rises in congested traffic of metropolitan Taiwan, significant increases in waste gas have the inevitable risks to impact public health. In the highly populated Taiwan, people frequently use motorcycle as a common means of metropolitan transportation due to their higher convenience and mobility. According to the Taiwan Ministry of Transportation and Communications (http://www.motc.gov.tw/) [1], there were 13.2 × 10 6 motorcycles officially reported in Taiwan before December 2006. The motorcycle density in Taiwan (ca. 452 vehicles per square kilometer) almost ranked first in the world. In some cities, the exhaust gas from motorcycles is apparently the primary source of mobile pollutants. The exhaust gas is presumed to be harmful to human health as it is known to contain a range of volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs) particulate matter and other chemicals [2]. Corresponding author. Tel.: +886 3 9357400x741; fax: +886 3 9357025. E-mail address: [email protected] (B.-Y. Chen). VOCs have been found to cause acute toxic effects (primar- ily neurological), cancer (such as leukemia), neurobehavioral effects and adverse effects on the kidney [3]. The major volatile components of motorcycle exhaust include benzene (B), toluene (T), ethyl benzene (E) and xylene (X) [4,5]. A portion of the absorbed benzene is excreted in exhaled air unmetabolized; how- ever, a large portion of the absorbed compound is metabolized to benzoic acid. This compound is conjugated with glycine in the liver and eventually excreted in urine as hippuric acid [6,7]. The acute health effects associated with exposure to benzene include dizziness, muscle weakness, confusion and incoordina- tion. These effects generally occur only a high concentrations and are not likely to be associated with motorcycle exhaust. The effects associated with exposure to benzene are similar to the physiological response following exposure to most organic solvents. With respect to chemicals, evidence for benzene leuke- mogenesis has been reported in both human populations [8,9] and in experimental animals [10]. In addition, ophthalmic effects of VOCs also have been noted; for instance, the injury of the optic nerves may have resulted from toluene as a metabolite [11]. Toluene has also been crim- inated as the cause of polyneuropathy in shoe factory workers 0304-3894/$ – see front matter © 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.jhazmat.2007.09.091

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  • Available online at www.sciencedirect.com

    Journal of Hazardous Materials 153 (2008) 12621269

    Toxicity assessment of volatile organic cooto

    ann

    n Uni-Lan

    er 20er 200

    Abstract

    This study exhaEscherichia rcycwith imping r andmotorcycles ne (Xfrom motorc natebenzene (No eal cexhaust is si ratedshowed that two- 2007 Elsevier B.V. All rights reserved.

    Keywords: Dosemortality curves; Volatile organic compounds; Polycyclic aromatic hydrocarbons; Escherichia coli

    1. Introdu

    Due toTaiwan, sigrisks to impeople fremetropolitamobility. Aand Commwere 13.2before De(ca. 452 vethe world.is apparenexhaust gais known(VOCs), pomatter and

    CorresponE-mail ad

    0304-3894/$doi:10.1016/jction

    marked rises in congested traffic of metropolitannificant increases in waste gas have the inevitable

    pact public health. In the highly populated Taiwan,quently use motorcycle as a common means ofn transportation due to their higher convenience andccording to the Taiwan Ministry of Transportationunications (http://www.motc.gov.tw/) [1], there

    106 motorcycles officially reported in Taiwancember 2006. The motorcycle density in Taiwanhicles per square kilometer) almost ranked first inIn some cities, the exhaust gas from motorcycles

    tly the primary source of mobile pollutants. Thes is presumed to be harmful to human health as itto contain a range of volatile organic compoundslycyclic aromatic hydrocarbons (PAHs) particulateother chemicals [2].

    ding author. Tel.: +886 3 9357400x741; fax: +886 3 9357025.dress: [email protected] (B.-Y. Chen).

    VOCs have been found to cause acute toxic effects (primar-ily neurological), cancer (such as leukemia), neurobehavioraleffects and adverse effects on the kidney [3]. The major volatilecomponents of motorcycle exhaust include benzene (B), toluene(T), ethyl benzene (E) and xylene (X) [4,5]. A portion of theabsorbed benzene is excreted in exhaled air unmetabolized; how-ever, a large portion of the absorbed compound is metabolizedto benzoic acid. This compound is conjugated with glycine inthe liver and eventually excreted in urine as hippuric acid [6,7].The acute health effects associated with exposure to benzeneinclude dizziness, muscle weakness, confusion and incoordina-tion. These effects generally occur only a high concentrationsand are not likely to be associated with motorcycle exhaust.The effects associated with exposure to benzene are similar tothe physiological response following exposure to most organicsolvents. With respect to chemicals, evidence for benzene leuke-mogenesis has been reported in both human populations [8,9]and in experimental animals [10].

    In addition, ophthalmic effects of VOCs also have been noted;for instance, the injury of the optic nerves may have resultedfrom toluene as a metabolite [11]. Toluene has also been crim-inated as the cause of polyneuropathy in shoe factory workers

    see front matter 2007 Elsevier B.V. All rights reserved..jhazmat.2007.09.091aromatic hydrocarbons in mChang-Tang Chang a, Bor-Y

    a Department of Environmental Engineering, National I-Lab Department of Chemical & Materials Engineering, National I

    Received 24 June 2007; received in revised form 4 SeptembAvailable online 29 Septemb

    investigates the toxicity of various pollutant species from motorcyclecoli DH5. The toxicity evaluation of the major components of motoer, and polycyclic aromatic hydrocarbons (PAHs), collected with filte. The toxicity of benzene (B), toluene (T), ethyl benzene (E) and xyleycles. In addition, three types of reformulated gasoline (high oxyge. 2), and low oxygen and low benzene (No. 3) were prepared to revgnificantly more toxic than BTEX due to the highly toxic VOCs genethe toxicity, indicated as EC50, was approximately as follows: PAHs >mpounds and polycyclicrcycle exhaustChen b,

    versity, I-Lan, 260 Taiwan, ROCUniversity, I-Lan, 260 Taiwan, ROC07; accepted 21 September 20077

    ust via doseresponse analysis and margin of safety usingle exhaust volatile organic compounds (VOCs), collectedXAD-2, is essential to determine emission standards for) was selected for comparison as standard VOCs emitted

    and high benzene content (No. 1), low oxygen and highombined toxicity of individual compositions. Motorcyclefrom incomplete combustion. Overall toxicity evaluation

    stroke engines > four-stroke engines > BTEX.

  • C.-T. Chang, B.-Y. Chen / Journal of Hazardous Materials 153 (2008) 12621269 1263

    [12]. Generally, toluene in vapor phase can be absorbed rapidlyfrom the lungs, and liquid toluene is taken up readily fromthe gastroiXylene is amembranescan be absThe euphoity is attracof sniffingter instancecase(s) [17are thus usin compariRegardingBTEX, thecategoriesAmong thetion reactiobenzene co

    Motorcybe toxic anmutation rethose of soupon conceeasy to be afetta et al. [and bladdeassociatedadducts) anexposed toPAHDNAide (B[a]PDlung cance

    Althougmotorcycleseriously dTherefore,determinatcrucial forcycle exha(e.g., Micrquantitativemethods arof assessmwe intentiomentally semicroorganVOCs andBTEX as swith econoopen policble alternatalso confirmwith costicity for gwere carrie(QA/QC).

    2. Materials and methods

    ested pollutants, engine and gasoline

    Challenge pollutantsjor compositions of motorcycle exhaust are BTEX (ben-), toluene (T), ethyl benzene (E) and xylene (X)). First, to

    bases for toxicity comparison, individual BTEX solventserially diluted with deionized water to obtain solutionserent concentrations. The VOCs analysis method was

    to use of gas chromatography (GC)-flame ionisationr (FID) to analyze concentration of species. The HNU

    le Gas Chromatography, model-311, with GC column0, 1.75% Bentonite 34, 6 in. 1/8 in. was used to ana-OCs composition. The sampling procedures composedparing and preheating the sampling system, connectingto-analysis system and combining the data-log system.mpligas ing thin thst ree, eth

    s wd PAlid Pples

    enginAD-s phat 1h twnd fi

    mpliwere

    . Thichroion pat 9

    was

    an d

    centr-stro

    nds

    tert-b

    ne

    nzeneeeelbenz

    imethntestinal tract, but poorly through the skin [13,14].powerful solvent, but is irritating to eyes, mucousand skin [15]. It can pass through intact skin or

    orbed from lungs and the gastrointestinal tract [16].ria that is a typical response to ethyl benzene toxic-tive to certain individuals who have made a practiceglue, paint thinner, or ethyl benzene itself, the lat-resulting in a schizophreniform psychosis in some

    ,18]. As BTEX are well-characterized pollutants, theyed as standard pollutants of petroleum hydrocarbonsson with other pollutants (e.g., motorcycle exhaust).toxic metabolites and/or suspected carcinogens inir metabolic transformations are divided into four

    oxidation, reduction, hydrolysis and conjugation.se, oxidation is the most common biotransforma-n mediated by microsomal enzymes. For example,nverts to phenol via hydroxylation.cle exhaust also contains PAHs which are known tod genotoxic. In addition, as Cerna [19] indicated thesponse of gaseous PAHs are more significant thanlid PAHs, and their toxicity are strongly dependentntration [20]. The reason is that the gaseous PAHs arebsorbed into blood than that of the solid PAHs. Bof-21] also demonstrated that cancer of the skin, lungsr can result from exposure to PAHs. PAHs have beenwith elevated levels of DNA adducts (e.g., AHDNAd p53 mutations in persons who smoke and/or arePAH in the either workplace or ambient air [22,23].adducts formed by the carcinogen B[a]P diol epox-E) have been strongly linked to an increased risk of

    r.

    h the concentration of highly toxic VOCs is low inexhausted waste gas, it might affect human health

    ue to long-term exposure and/or bioaccumulation.from the perspective of air pollution control, the

    ion of toxicity of VOCs and PAHs is extremelyhow to take actions of toxicity attenuation for motor-ust. As known, there are some standard methodsotox [24], Mutatox and Ames test) that can bely evaluated toxicity of pollutants. However, thesee not cost-effective to be a first screening protocolent upon suspected toxicants for public uses. Thus,nally selected a genetically defective and environ-nsitive strain Escherichia coli DH5 as a probingism [25] to reveal dosemortality relationships ofPAHs in motorcycle exhaust using well-known

    tandards for comparison. With this plausible methodmic feasibility, industrial sectors can adopt a morey toward diverse waste sources to consider possi-ives for reduction, reuse or recycling. Results wereed with literature data, revealing the practicability

    effectiveness as first screening assessment of tox-eneral use. Serial dilutionagar plating proceduresd out in duplicate for quality assurance and control

    2.1. T

    2.1.1.Ma

    zene (Bobtainwere s

    in diffrelateddetectoPortabSP-l20lyze Vof prethe auThe sawasteassessiVOCsThe tetoluen

    PAHsampleand so

    Samcycleand Xgaseoudrawnthrougticles agas safiltersiccatorwith dextractheated7.5 g)in a cle

    Table 1The conwith two

    Compou

    MethylBenzenen-HeptaTolueneEthylbep-Xylenm-XylenO-XylenIsopropy1,2,4-Trng volume was about 1 L for each run. However, thenjected to GC was only 300 mL for analysis. Beforee toxicity of VOCs, the concentrations of main toxice motorcycle were measured and shown in Table 1.sults shows that the main toxic VOCs are benzene,yl benzene and xylene.ere also extracted from the motorcycle exhaust. TheHs can be classified into two phases, gaseous PAHs

    AHs.of PAHs were taken from the exhaust gas of motor-e. Impactor sampling combined with quartz filter

    2 adsorbent was used to collect solid phase andase PAHs and carried out in triplicate. The air was0 L/min first through a 2.5m cutoff cyclone, theno 47-mm quartz filters (Whatman) that collected par-nally through two XAD-2 resins (Supleco Co.) for

    ng [26,27]. According to literatures [28,29], quartztreated after the humidity was removed in a des-

    e XAD-2 was cleaned by Soxhlet extraction firstlomethane (24 h) and then with methanol (24 h). Therocedure was repeated twice. The XAD-2 was then0 C to remove moisture. The cleaned XAD-2 (ca.packed in a glass resin (6 cm 1.5 cm I.D.) and keptessicator until sampling. The filters and XAD-2 were

    ation of main toxic VOCs components in the exhaust waste gaske engine

    No. 1 gasoline(ppm-v)

    No. 2 gasoline(ppm-v)

    No. 3 gasoline(ppm-v)

    utyl ether 14.4 14.2 13.6101.6 103.2 65.3

    14.1 15.1 13.477.1 86.5 66.869.0 68.3 58.653.3 56.4 58.413.2 14.3 13.612.9 12.0 12.5

    ene 1.2 1.1 1.5ylbenzene 1.6 1.8 1.3

  • 1264 C.-T. Chang, B.-Y. Chen / Journal of Hazardous Materials 153 (2008) 12621269

    analyzed with GCMS, Hp GCD. The instrumentation as wellas the analytical procedure was established and conducted asdescribed eR) containipurchased

    2.1.2. ChaThe tox

    assessed inreformulateand benzengasoline (hoxygen anand low beNote that aand benzencontent.

    2.1.3. ChaTo have

    cles in heaengine, twmodel engthe same afour-stroke

    2.2. Dose

    E. coliChang, Naan indicatoindicator stplate was pMiller, Difthe synchrotioning in tbroth was tculture wasphase (ca.culture wasile saline swith appropwas chosen

    2.3. Biotox

    Biotoxica modificaTo excludeall of the swere first s20 min) anized througconcentratichemicalswas postuldilutions o

    Table 2The composition of gasoline

    Volume %

    etailed chemical analysis of gasolineffinsutane 4.82entane 3.62exane 1.75eptane 0.51ctane 0.30

    11.00

    hed paraffinsutane 1.14entane 10.26ethylpentane 4.39ethylpentane 2.59

    -Dimethylbutane 1.83ethylhexane 1.39ethylhexane 1.39

    -Dimethylpentane 0.84-Dimethylpentane 0.93,4-Trimethylpentane 5.51,4-Trimethylpentane 3.04,3-Trimethylpentane 2.87,3-Trimethylpentane 0.33-Dimethylhexane 1.00-Dimethylhexane 0.84-Dimethylhexane 0.98ethylheptane 0.90ethylheptane 0.71ethyloctane 0.30ethyloctane 0.30

    ,5-Trimethylhexane 0.72

    42.26

    paraffinsthylcyclopentane 0.921,3-Dimethylcyclopentane 0.30thylcyclohexane 0.30

    1.52

    sutene-2 0.49ntene-2 0.64

    entene-2 0.33ethylpentene-l 0.48ethylpentene-2 0.78

    2.72

    aticszene 1.69

    uene 3.99ylbenzene 1.69ylene 1.89ylene 4.79ylene 1.46ethyl,3-ethylbenzene 1.30ethyl,4-ethylbenzene 1.31

    ,4-Trimethylbenzene 2.72

    20.84

    Oxygenate content (%) Benzene content (%)xygenate and benzene content of gasolinegasoline 3.0 1.0gasoline 1.0 1.0gasoline 1.0 0.5lsewhere [30,31]. A standard PAH mixture (Z-014G-ng 17 compounds in CH2Cl2/benzene (1:1 v/v) wasfrom Supleco company for quantitative analysis.

    llenge gasolinesicity of PAHs in different kinds of gasolines was also

    the exhaust waste gas since the characteristics ofd PAHs was dependent on the content of oxygene [24]. Three types of reformulated gasolines, No. 1igh oxygen and high benzene), No. 2 gasoline (lowd high benzene), and No. 3 gasoline (low oxygennzene) (Table 2) were intentionally used for study.ccording to US CARB [26], the content of oxygene above 1.8 and 0.8, respectively are defined as high

    llenge enginetoxicity figures for exhaust waste gas of motorcy-

    vy traffic for city dwellers, two kinds of motorcycleo-stroke (2T) and four-stroke (4T), were used asines for assessment. The ages of the two-stroke arend are 3 years old. The powers of two-stroke andengines are 1.5 and 5.0 horse power, respectively.

    mortality assessment

    DH5 (generously provided by Professor Jo-Shutional Cheng-Kung University, Taiwan) was used asr strain for biotoxicity assessment. A loopful of therain seed taken from an isolated colony in LB-streakrecultured in 50 mL Luria-Bertani medium (LB broth,co) for 12 h overnight at 37 C, 200 rpm. To ensurenous growth activity and maximum metabolic func-

    he same growth phase for bioassay, 5% (v/v) culturedhen inoculated to fresh sterile LB medium and a cellharvested at approximately mid-exponential growth

    4 h) for further toxicity assessment. The 1.0 mL cellthen serially diluted and well mixed with 9.0 mL ster-

    olution (SSS; NaCl 10.0 g L1) and only the diluentriate cell concentrations (ca. 150015,000 cells/mL)as the test seed (TS) for later uses.

    icity assessment

    ity assessment was specifically designated throughtion of doseresponse analysis [3239] as follows:

    the presence of unwanted bacterial contaminants,olutions for sampled chemicals (e.g., BTEX, PAHs)terilized via moist-heat method (121 C at 15 psi ford then tested materials (e.g., BTEX, PAHs) steril-h 0.2m sterile filter were added. Thus, the sampleon defined herein was the concentration of testedand their serial diluents well mixed with SSS. Itated that the sodium chloride solution used for serialf various solution was the toxicity-free control. To

    (a) The dn-Para

    n-Bn-Pn-Hn-Hn-O

    Total

    BrancIsobIsop2-M3-M2,32-M3-M2,32,42,22,32,32,22,42,52,33-M2-M2-M3-M2,2

    Total

    CycloMecis-Me

    Total

    Olefint-Bt-Pec-P2-M2-M

    Total

    AromBenTolEtho-Xm-Xp-X1-M1-M1,2

    Total

    (b) The oNo. 1No. 2No. 3

  • C.-T. Chang, B.-Y. Chen / Journal of Hazardous Materials 153 (2008) 12621269 1265

    exclude confounding interferences, phosphate buffered saline(PBS) solution, which is regularly used for biological assay,was not usbe formed dtoxicity tescriteria of mcentration. . ., 1/2n Ctested or itsresulted serfor use inseed (TS)count dilue1.0 mL frestoxicity-frethe control[34,35]. Stfollows: SPsampling, awere spreawould be amedium plcells in allat 37 C fomeration. Ostatisticallying proceduand controRSD can thcell count):

    Cells per lit

    To havedenoted as0 and 1 diretoxicity tosimply sugconcentratitoxicity). Ttoxicity ofThe concenin doserestoxicity (Tvide an obchemicals.less than thmore toxicdilution fachave zero

    2.4. Dose

    The con

    Y = A + B

    Schemunt m

    .5{

    (

    B and inttratise (%r furma

    latioC/V

    hal cTo

    espotrati.0, 3

    ults

    TEX

    toxncentration (ECx) administered to the bacterial populationvoke x% response (e.g., x = 50 as EC50). The EC0 andcan be defined as the maximum concentration to have

    ctable response (i.e., 0+%) and minimum concentratione 100% response, respectively. The discrepancy amongof effective concentrations at different levels (e.g., EC0,nd EC50) are response effect of each level. The highern be illustrated with lower toxicity of maximum concen-to have a detectable response. Whereas, the EC50 are theetectable response of the bacterial population. It is moreto use EC50 than to use EC20 as an indicator in regula-

    he target compounds over and under their EC100 obviouslyn extinction and survival of viable cells, respectively. ECxtatively provides a more clear indication for toxicity com-

    among chemicals; the smaller the ECx, the more toxiced here, since metallic phosphate precipitates mighturing serial dilution. The initial concentration C0 forts of all chemicals was appropriately chosen underaximal solubility. Serial-half dilution of initial con-

    C0 (i.e., 1/2 C0, 1/4 C0, 1/8 C0, 1/16 C0, 1/32 C0,0) was carried out by using 50 mL solution to bederived diluents mixed with 50 mL SSS. The 9.0 mLial diluents (RSD) were all placed in sterile test tubesquantification of viable cells afterwards. The test

    was then well mixed with RSD to form serial platents (SPCD) via serial dilution technique. Meanwhile,h TS mixed with 9.0 mL pure SSS was used as thee control. The numbers of viable DH5 in SPCD orwere estimated by the standard plate count method

    andard plate count in LB medium was carried out asCD were serially diluted with SSS immediately afternd then appropriate volumes (ca. 0.20 mL) of SPCDd onto agar Petri plates. Note that all cells in SPCDssumed metabolically viable and culturable on LB-ates due to fresh preparation of fast-growing E. colisteps. The LB-medium plates were then incubatedr ca. 1624 h to form observable colonies for enu-nly plates with between 30 and 300 colonies wereappropriate for counting. Serial dilutionagar plat-res were carried out in duplicate for quality assurance

    l (QA/QC). The microbial population in the originalen be calculated using the following formula (CC:

    er of broth (CC) = number of coloniesamount plated dilution factor

    (1)quantitative toxicity for comparison, CC0 was

    the CC at zero-toxicity control. The ratio CC/CC0 ofctly indicated complete inhibition and no inhibitorybacterial cell, respectively. The unity of this ratiogests that the present toxicity of this diluent at thison is nearly equal to the toxicity of SSS (i.e., zerohe toxicity of SSS can be used to indicate the mainair pollutants that many species were mixed together.tration range for the ratio jumped from 1.0 to 0.0ponse curves [37] is defined here as the thresholdT) range. The comparison on TT range could pro-

    vious diagram of toxicity ranking for various testedFor example, if the TT range for chemical A is muchat for chemical B, chemical A is inevitable muchthan chemical B and this indicated that much highertor must be carried out for chemical A in order to

    toxicity as same as control (SSS) (Fig. 1).

    response analysis

    version formulae for doseresponse analysis were

    log Z, (2)

    Fig. 1.plate co

    P = 0

    erf(x)

    wheretor) anconcen

    responan erro

    was no

    sion re1 VCthe lettively.doserconcen

    (e.g., 1

    3. Res

    3.1. B

    Thetive coto proEC100a deteto havranksEC20 aEC0 catration50% dstrictlytion. Tresult iquantiparisonatic of toxicity assessment (dosemortality relationships) usingethod.

    1 + erf( (Y 5)

    2

    )}, (3)

    2

    ) x0

    e2 d, (4)

    dA denoted the Hill slope (i.e., steepness or slope fac-ercept of doseresponse relation, Z and Y were metalon (mg/L) and probit unit, respectively; P was the

    ) corresponding to administered metal, erf(x) wasnction. It should be noted that the response variablelized to be located between 0 and 1. The conver-n between the probit unit and provoked responseCC0 was calculated. The VCC and VCC0 denote

    oncentration and initial lethal concentration, respec-consider the non-biased experimental design fornse analysis in log-normal distribution, pollutantons were approximately equally spaced on a log scale.16, 10, 31.6, 100, 316 mg/L).

    and discussion

    icity of a compound can be expressed by the effec-

  • 1266 C.-T. Chang, B.-Y. Chen / Journal of Hazardous Materials 153 (2008) 12621269

    Table 3Critical effective concentrations and related parameters of toxicity predicted from the probit model for BTEX

    EC0 (mg/L) EC20 (mg/L)Benzene 8.18 102 9.65 101Toluene 9.52 103 5.63 101Ethyl benzene 5.74 102 7.89Xylene 1.66 101 1.42

    the compound. As lower ECx clearly revealed higher toxic char-acteristics of pollutants in comparison, the toxicity ranking, inincreasing order, based upon EC20 and EC50 are listed as follows(Table 3; Fig. 2):

    EC0: toluene > ethyl benzene > benzene > xylene,EC20: toluene > benzene > xylene > ethyl benzene,EC50: benzene > xylene > toluene > ethyl benzene.

    Note that the difference in the ranking of ECx values was dueto diverse tolerance to the suspected toxic material to be tested.Moreover, the slope factor B of probit model for dosemortalitycurves (seeof a target chas a slopewere greatcharacterisorder, base

    Slope B:

    Note thresponse csusceptibilorganism.gests the smtolerance (FB for ethylto ethyl ben

    Fig. 2. Dose(curves) (line

    imum effecairbone eaused to esttially lethahttp://flora2doc for xylsame orderzene (5.46)US EPA (efor xylene)OM trendsethylbenze

    ely vuldnts (

    otornes

    Diffratud arn thncen

    Thealenrmorbenzlso snt thin Fasol

    No.(S),: No(S),: No(S),

    B(S) >Eqs. (2)(4)) is also another indicator to the toxicityompound. Note that a standard doseresponse curve

    factorBof unity. Since all slope factorsBof the curveser than unity, steeper curves thus indicate the toxictics of all cases. The toxicity ranking, in increasingd upon slope B is listed as follows (Table 3; Fig. 2):

    xylene > benzene > (1.0) > toluene > ethyl benzene.

    at if the slope B (e.g., less than unity) of the doseurve is shallow, there is considerable variation inity to that particular chemical within probing micro-The largest value (1.675) of slope B for xylene sug-allest tolerance range from EC0 to EC100 for toxicityig. 2). In contrast, the smallest value (0.73) of slope

    benzene simply implies the widest range of tolerancezene toxicity from the threshold dose (EC0) to a max-

    relativand copolluta

    3.2. Mgasoli

    3.2.1.Lite

    gen anrises iThe coFig. 3.naphthFurthesition,This aaugmeshownlated g

    EC0:PAHsEC20PAHsEC50PAHsSlopePAHsmortality curve of BTEX toxicity predicted from the probit models indicated EC50 values).

    These raincreasinglines. Thesince the mof No. 1 iserature [36EC50 (mg/L) Y=A + B log C3.64 Y= 4.183 + 1.456 log C5.07 Y = 4.380 + 0.880 log C

    111.78 Y = 3.506 + 0.730 log C4.50 Y = 3.907 + 1.675 log C

    t dose (EC100). As many chemicals do not becomesily, oral LD50 in acute dosemortality curve wasimate the quantity of chemical that would be poten-l for a human [36]. According to Taiwan EPA (e.g.,.epa.gov.tw/toxicweb/ToxicUC4/database/1330207.ene), oral LD50 (in g/kg) in rats were almost in theof magnitude (OM) (e.g., benzene (4.70), ethylben-, toluene (5.00), xylene (5.10 3.5)). According to.g., http://www.epa.gov/ttn/atw/hlthef/xylenes.html

    , air LD50 (in g/m3) in mice almost followed identical(e.g., benzene (32.0), toluene (33.2), xylene (27.6),

    ne (17.4)). Thus, this suggested that EC50 might beiable for parallel OM trends (except ethylbenzene)

    be used to define the margin of safety for suspectedsee afterwards).

    cycle exhaust using different reformulated

    erent reformulated oxygen and benzene gasolinere [15,3739] indicated that increases in the oxy-omatic hydrocarbon (HC) contents lead to markede concentrations of PAHs in motorcycle exhaust.tration of PAHs composition profiles were listed inhighest mass concentration of the main composition,e, is approximately ranged from 45 to 80g/Nm3.e, the highest toxic concentration of the main compo-o(a)pyrene, is roughly ranged from 20 to 30g/Nm3.uggested that increases in these contents might alsoe toxicity of motorcycle exhaust to be generated. Asig. 4 and Table 4, toxicity rankings of these reformu-ines (in increasing order) were shown as follows:

    1 PAHs(S) > No. 2 PAHs(S) > No. 3 PAHs(G) > No. 3

    . 1 PAHs(S) > No. 3 PAHs(G) > No. 2 PAHs(S) > No. 3

    . 1 PAHs(S) > No. 3 PAHs(G) > No. 2 PAHs(S) > No. 3

    : No. 3 PAHs(G) > No. 1 PAHs(S) > No. 21.0 > No. 3 PAHs(S).nkings in toxicity seemed to be in parallel with anorder in oxygen and benzene in reformulated gaso-rankings can be also verified with the data in Fig. 3ost toxic compound, benzo(a)pyrene, concentration

    larger than that of the other gasolines. In addition, lit-] indicated that PAHs may react with strong oxidative

  • C.-T. Chang, B.-Y. Chen / Journal of Hazardous Materials 153 (2008) 12621269 1267

    Fig. 3. The mengine.

    compoundsspecies. Mospecies prefrequency ttoxicity in

    3.2.2. MotTo Con

    in two-stroengine) weings (i.e., Eshowed thastraightforw

    osemortality curve of toxicity of motorcycle exhaust using No. 1, No.o. 3 gasolines.

    Table 4Critical effect

    No. 1 PAHs(SNo. 2 PAHs(SNo. 3 PAHs(SNo. 3 PAHs(G

    Table 5Critical effect

    Two-stroke enFour-stroke enain composition of PAHs in the motorcycle exhaust with two-stroke

    (e.g., O3, NOx) in air to form highly toxic pollutantreover, due to less mass transfer resistance, chemical

    Fig. 4. D2 and Nsent in gas phase would have a significantly highero collide with species for reaction, leading to a highergas phase for No. 3 PAHs [40,41].

    orcycle exhaust using different stroke enginessider evaluation upon practical cases, motorcycleske engine (2T engine) and four-stroke engine (4Tre used (Table 5 and Fig. 5). The toxicity rank-C0, EC20, EC50, slope B) of these two engines all

    t 2T engine > 4T engine. The reasons of this result areard. Compared to 4T engine, 2T engine is relatively

    Fig. 5. Dosemortality curve of toxicity of motorcycle exhaust using two-strokeand four-stroke engines.

    ive concentrations and related parameters of toxicity predicted from the probit model for different motorcycle exhaust using reformulated gasoline

    EC0 (mg/L) EC20 (mg/L) EC50 (mg/L) Y = A + B log C) 1.66 103 1.12 102 3.13 102 Y = 7.846 + 1.879 log C) 2.48 103 7.80 102 4.99 101 Y = 5.315 + 1.042 log C) 5.95 103 3.14 101 2.66 Y = 4.615 + 0.906 log C) 4.16 103 2.14 102 5.16 102 Y = 7.824 + 2.194 log C

    ive concentrations and related parameters of toxicity predicted from the probit model for motorcycle exhaust using 2T, 4T engines

    EC0 (mg/L) EC20 (mg/L) EC50 (mg/L) Y = A + B log Cgine 8.46 103 1.18 101 4.87 101 Y = 5.427 + 1.364 log Cgine 3.47 102 4.98 101 2.09 Y = 4.568 + 1.349 log C

  • 1268 C.-T. Chang, B.-Y. Chen / Journal of Hazardous Materials 153 (2008) 12621269

    Fig. 6. CompPAHs).

    inexpensivsame size.plete combof engine oengine evidcity even toThis couldage 4T enregulations

    3.3. Overa

    The ranous pollut(1.879) > x(1.364) > 43 PAHs(S)In additionNo. 1 PAH(0.487) > N3 PAHs(S(5.07) etis significalikely duecombustionapparentlyoverall toxtoxicity serPAHs (ca. 0(No. 3 PAH

    Reference

    [1] Taiwan Iand Comturers in

    [2] Lin, C.S., Study on the Influence of Oil and Engine Speed on Two-strokeMotorcycle Engine Exhaust Gases Toxicity, Masters Thesis, National SanYat-Sen University, 1997.

    dwar. KaoWas

    K. Jo,ociateor em

    F. Oets of tWilcznal ex. Infancell tyviron.Aksod. 8 (Rithileuke

    . Smting o. WaC emnage.. Ticcatalolko

    anicprin

    Fu, J.ir W

    Broww Yor. We570

    J. Tarcup. MCernCzec

    Armsosure

    viron.arison of toxicity potency for all tested pollutants (e.g., BTEX and

    e to generate larger power output than 4T engine in theHowever, the 2T engine has disadvantages of incom-ustion and less efficiency due to mixed combustionil and gasoline. According to EC50, compared to 2Tently using 4T engine at least reduced fourfold toxi-xicity tolerance (i.e., slope B) seems to be identical.explain why Taiwan EPA tended to strongly encour-gine in place of 2T engine for new environmental[42].

    ll toxicity comparison

    king of toxicity tolerance (slope B) for vari-ants are No. 3 PAHs(G) (2.194) > No. 1 PAHs(S)ylene (1.675) > benzene (1.456) > 2T engine

    [3] J. E[4] A.S

    Air[5] W.

    ass

    vap[6] W.

    ger[7] T.

    tio[8] P.F

    byEn

    [9] M.Me

    [10] K.in46.

    [11] C.Mcoa

    [12] R.AVOMa

    [13] B.Avia

    [14] P. Worgand

    [15] L.J. A

    [16] E.Ne

    [17] B.L569

    [18] M.Oc

    [19] M.the

    [20] B.expEnT engine (1.349) > No. 2 PAHs(S) (1.042) > 1.0 > No.(0.906) > toluene (0.880) > ethyl benzene (0.730)., the toxicity series based on EC50 (in mg/L) ares(S) (0.0313) > No. 3 PAHs(G)(0.0516) > 2T engineo. 2 PAHs(S) (0.499) > 4T engine (2.09) > No.

    )(2.60) > benzene (3.64) > xylene (4.50) > toluenehylbenzene (111.78). Obviously, motorcycle exhaustntly more toxic than typical VOCs (e.g., BTEX)to highly toxic VOCs generated from incomplete. EC50s also indicated that all the pollutants weremore toxic than BTEX. Regarding margin of safety,icity evaluation upon all pollutants showed that theies (EC50 in mg/L) was approximately as follows:.050.5) >2T, 4T engines (0.52) >BTEX (3.65.0)s(s) and ethylbenzene excluded) (Tables, Figs. 26).

    s

    ndustrial Development Bureau (TIDB), Ministry of Transportationmunication, Ministry of Economic Affairs, Direction of Manufac-Taiwan Area, 2005.

    [21] P. Boffetand enviCause C

    [22] L.E. SmTargetincarbons,

    [23] M. PelusDNA poAm. J. E

    [24] Chou, Cters The

    [25] B.Y. Chpal solid741746

    [26] US CARAmendm

    [27] S.S. Buecide conTechnol.

    [28] A. Sanuof pestic4951.

    [29] U.S. EnvMethodds, C.E.M. Kenyon, Air Toxics Risk Assess. (1991) 256307., Formation and removal reactions of hazardous air pollutants, J.

    te Manage. Assoc. 44 (1994) 683696.K.B. Song, Exposure to VOCs for individuals with occupationsd with potential exposure to motor vehicle exhaust and/or gasolineissions, Sci. Total Environ. 269 (2001) 2537.tingen, P.A. Neal, D.D. Donahue, The toxicity and potential dan-oluene, J. Am. Med. Assoc. 118 (1942) 579584.ok, G. Bieniek, Uniary hippuric acid concentration after occupa-posure to toluene, J. Ind. Med. 35 (1978) 330334.te, M.C. White, Benzene: epidemiologic observations of leukemiape and adverse health effects associated with low-level exposure,Health Perspect. 52 (1983) 7582.y, Benzene as a leukemogenic and carcinogenic agent, Am. J. Ind.1985) 920.dech, E.P. Cronkite, V.P. Bond, Advantages of the CBA mousemogenesis research, blood cells, Mol. Dis. 25 (1999) 38

    ith, W.E. Brown, Elimination of VOCs emissions from surfaceperations, J. Air Waste Manage. Assoc. 43 (1993) 10151021.dden, P.A. Scheff, J.E. Franke, L.M. Controy, Determination ofission rates and compositions for offset printing, J. Air WasteAssoc. 45 (1995) 547555.

    henor, M.A. Palazzolo, Destruction of volatile organic compoundsytic incineration, Environ. Prog. 16 (1997) 223243.ff, C.K. Wilkins, P.A. Clausen, K. Larsen, Comparison of volatile

    compounds from processed paper and toners from office copiersters, Indoor Air 10 (1999) 113123.Hao, D. He, K. He, Assessment of vehicular pollution in China,

    aste Manage. Assoc. 51 (2001) 658668.ning, Toxicity and Metabolism of Industrial Solvents, Elsevier,k, 1965, pp. 412462.isenberger, Toluene habituation, J. Occup. Med. 19 (1977).sh, Schizophreniform psychosis caused by sniffing toluene, J. Soc.

    ed. 29 (1979) 131133.a, Mutagenicity monitoring of airborne particulate matter PM10 inh Republic, Mutat. Res. 444 (1999) 373386.trong, E. Hutchinson, J. Unwin, T. Fletcher, Lung cancer risk afterto polycyclic aromatic hydrocarbons: a review and meta-analysis,Health Perspect. 112 (2004) 970978.ta, N. Jourenkova, P. Gustavsson, Cancer risk from occupationalronmental exposure to polycyclic aromatic hydrocarbons, Cancerontrol 8 (1997) 444472.ith, M.F. Denissenko, W.P. Bennett, H.Y. Li, S. Amin, M.S. Tang,g of lung cancer mutational hotspots by polycyclic aromatic hydro-J. Nat. Cancer Inst. 92 (2000) 803811.o, M. Ceppi, A. Munnia, R. Puntoni, S. Parodi, Analysis of 13 P-32-stlabeling studies on occupational cohorts exposed to air pollution,pidemiol. 153 (2001) 546582..Y., Study on the VOCs toxicity assessment using microtox, Mas-sis, National Cheng-Kung University, 2002.en, K.L. Lin, Biotoxicity assessment on reusability of munici-

    waste incinerator (MSWI) ash, J. Hazard. Mater. B136 (2006).B, South Coast Air Quality Management District, Proposedents to the CaRFG Property Limits, 1990.hler, I. Basu, R.A. Hites, A comparison of PAH, PCB, and pesti-centrations in air at two rural site on Lake Superior, Environ. Sci.35 (2001) 24172422.

    si, M. Millet, P. Mirabel, H. Wortham, Gas-particle partitioningides in atmospheric samples, Atmos. Environ. 33 (1999) 4941

    ironment Protection Agency, Modified Method 5 Sample Train,0010, 1986.

  • C.-T. Chang, B.-Y. Chen / Journal of Hazardous Materials 153 (2008) 12621269 1269

    [30] H. Garivait, C. Polprasert, K. Yoshizumi, L.B. Reutergardh, Airbornepolycyclic aromatic hydrocarbons (pah) in bangkok urban air. I. Character-ization and quantification, Polycyclic Aromat. Compd. 13 (1999) 313327.

    [31] M. Shimmo, T. Hyotylainen, K. Hartonen, M.-L. Riekkola, On-linecoupled supercritical fluid extractionliquid chromatographygaschromatographymass spectrometry for the analysis of organic acids, J.Microcol. Sep. 13 (2001) 202210.

    [32] M. Shimmo, H. Adler, T. Hyotylainen, K. Hartonen, M. Kulmala,M.-L. Riekkola, Analysis of particulate polycyclic aromatic hydrocarbonsby on-line coupled supercritical fluid extractionliquid chromatographygas chromatographymass spectrometry, Atmos. Environ. 36 (2002) 29852995.

    [33] B.Y. Chen, C.H. Wu, J.S. Chang, An Assessment of the toxicity of metalsto Pseudomonas aeruginosa PU21 (Rip64), Bioresour. Technol. 97 (2006)18801886.

    [34] B.Y. Chen, Toxicity assessment of aromatic amines to Pseudomonas lute-ola: chemostat pulse technique and doseresponse analysis, Proc. Biochem.41 (2006) 15291538.

    [35] B.Y. Chen, J.S. Chang, Phenol degradation and toxicity assessmentupon biostimulation to an indigenous Rhizobium Ralstonia taiwanensis,Biotechnol. Prog. 21 (2005) 10851092.

    [36] M.A. Ottobni, Chronic toxicity, in: The Dose Makes the Poison, 2nd ed.,ITP Company, New York, 1997, pp. 7990 (Chapter 8).

    [37] C. Ewards, Environmental Monitoring of Bacteria. Methods in Biotech-nology Some Problems Posed by Natural Environments for MonitoringMicroorganisms, vol. 1, Human Press, Totowa, NJ, USA, 1999, pp. 14(Chapter 1).

    [38] B.Y. Chen, K.L. Lin, Dosemortality assessment on municipal solid wasteincinerator (MSWI) ash, J. Hazard. Mater. A139 (2007) 1924.

    [39] E.W. Kaiser, W.O. Siegl, D.F. Cotton, R.W. Anderson, Effect of fuel struc-ture on emissions from spark-inited engine olefinic fuels, Environ. Sci.Technol. 27 (1993) 14401447.

    [40] P.J. Tsai, H.Y. Shieh, W.J. Lee, S.O. Lai, Characterization of PAHs in theatmosphere of carbon black manufacturing workplaces, J. Hazard. Mater.A91 (2002) 2542.

    [41] Y.S. El-Alawi, B.J. McConkey, D.G. Dixon, B.M. Greenberg, Measurementof short- and long-term toxicity of polycyclic aromatic hydrocarbons usingluminescent bacteria, Environ. Res. Sect. B: Ecotoxicol. Environ. Saf. 51(2002) 1221.

    [42] J. Friedrich, B. Diedrich, M. Uwe, E. Ulf, G. Rolf, M. Bernd, Emissionsof two- and four-stroke outboard engines. II. Impact on water quality, Wat.Res. 29 (1995) 19831987.

    Toxicity assessment of volatile organic compounds and polycyclic aromatic hydrocarbons in motorcycle exhaustIntroductionMaterials and methodsTested pollutants, engine and gasolineChallenge pollutantsChallenge gasolinesChallenge engine

    Dose-mortality assessmentBiotoxicity assessmentDose-response analysis

    Results and discussionBTEXMotorcycle exhaust using different reformulated gasolinesDifferent reformulated oxygen and benzene gasolineMotorcycle exhaust using different stroke engines

    Overall toxicity comparison

    References