Characterization of Polycyclic Aromatic Hydrocarbons from the

Abstract

Diesel fuels governed by U.S. regulations are based on the index of the total aromatic contents. Three diesel fuels, containing various fractions of light cycle oil (LCO) and various sulfur, total polyaromatic, and total aromatic contents, were used in a heavy-duty diesel engine (HDDE) under transient cycle test to assess the feasibility of using current indices in managing the emissions of polycyclic aromatic hydrocarbons (PAHs) from HDDE. The mean sulfur content in LCO is 20.8 times as much as that of premium diesel fuel (PDF). The mean total polyaromatic content in LCO is 28.7 times as much as that of PDF, and the mean total aromatic content in LCO is 2.53 times as much as that of PDF. The total polyaromatic hydrocarbon emission factors in the exhaust from the diesel engine, as determined using PDF L3.5 (3.5% LCO and 96.5% PDF), L7.5 (7.5% LCO and 92.5% PDF), and L15 (15% LCO and 85% PDF) were 14.3, 25.8, 44, and 101 mg L^?1, respectively. The total benzo(a)pyrene equivalent (BaP_eq) emission factors in the exhaust from PDF, L3.5, L7.5, and L15 were 0.0402, 0.121, 0.219, and 0.548 mg L^?1, respectively. Results indicated that using L3.5 instead of PDF will result in an 80.4% and a 201% increase of emission for total PAHs and total BaP_eq, respectively. The relationships between the total polyaromatic hydrocarbon emission factor and the two emission control indices, including fuel polyaromatic content and fuel aromatic content, suggest that both indices could be used feasibly to regulate total PAH emissions. These results strongly suggest that LCO used in the traveling diesel vehicles significantly influences PAH emissions.     

A new alternative fuel for reduction of polycyclic aromatic hydrocarbon and particulate matter emissions from diesel engines

This study investigated the emissions of polycyclic aromatic hydrocarbons (PAHs), carcinogenic potential of PAH and particulate matter (PM), brake-specific fuel consumption (BSFC), and power from diesel engines under transient cycle testing of six test fuels: premium diesel fuel (PDF), B100 (100% palm biodiesel), B20 (20% palm biodiesel + 80% PDF), BP9505 (95% paraffinic fuel + 5% palm biodiesel), BP8020 (80% paraffinic fuel + 20% palm biodiesel), and BP100 (100% paraffinic fuel; Table 1). Experimental results indicated that B100, BP9505, BP8020, and BP100 were much safer when stored than PDF. However, we must use additives so that B100 and BP100 will not gel as quickly in a cold zone. Using B100, BP9505, and BP8020 instead of PDF reduced PM, THC, and CO emissions dramatically but increased CO2 slightly because of more complete combustion. The CO2-increased fraction of BP9505 was the lowest among test blends. Furthermore, using B100, B20, BP9505, and BP8020 as alternative fuels reduced total PAHs and total benzo[a]pyrene equivalent concentration (total BaPeq) emissions significantly. BP9505 had the lowest decreased fractions of power and torque and increased fraction of BSFC. These experimental results implied that BP9505 is feasible for traveling diesel vehicles. Moreover, paraffinic fuel will likely be a new alternative fuel in the future. Using BP9505 instead of PDF decreased PM (22.8%), THC (13.4%), CO (25.3%), total PAHs (88.9%), and total BaPeq (88.1%) emissions significantly.     

Comparison of vehicle exhaust emissions from modified diesel fuels

Three diesel fuels, one oil sand-derived (OSD) diesel serving as base fuel, one cetane-enhanced base fuel, and one oxygenate [diethylene glycol dimethyl ether (DEDM)]-blended base fuel, were tested for their emission characterizations in vehicle exhaust on a light-duty diesel truck that reflects the engine technology of the 1994 North American standard. Both the cetane-enhanced and the oxygenate-blended fuels were able to reduce regulated [CO, particulate matter (PM), total hydrocarbon (THC)] and nonregulated [polyaromatic hydrocarbons (PAHs), carbonyls, and other volatile organic chemicals] emissions, except for nitrogen oxides (NO(x)), compared with the base fuel. Although burning a fuel that contains oxygen could conceivably yield more oxygenated compounds in emissions, the oxygenate-blended diesel fuel resulted in reduced emissions of formaldehyde along with hydrocarbons such as benzene, 1,3-butadiene, and PAHs. Reductions in nitro-PAH emissions have been observed in both the cetane-enhanced and oxygenated fuels. This further demonstrates the benefits of using a cetane enhancer and the oxygenated fuel component.     

Effect of fuel aromatic content on PAH emission from a heavy-duty diesel engine

Polycyclic aromatic hydrocarbons (PAHs) emission tests for a heavy-duty diesel engine fueled with blend base diesel fuel by adding batch fractions of poly-aromatic and mono-aromatic hydrocarbons, Fluorene and Toluene, respectively, were simulated to five steady-state modes by a DC-current dynamometer with fully automatic control system. The main objective of this study is to investigate the effect of total aromatic content and poly-aromatic content in diesel fuels on PAH emission from the HDD engine exhaust under these steady-state modes. The results of this study revealed that adding 3% and 5% (fuel vol%) Fluorene in the diesel fuel increases the amount of total-PAH emission by 2.6 and 5.7 times, respectively and increases the amount of Fluorene emission by 52.9 and 152 times, respectively, than no additives. However, there was no significant variation of PAH emission by adding 10% (vol%) of Toluene. To regulate the content of poly-aromatic content in diesel fuel, in contrast to the total aromatic content, will be more suitable for the management of PAH emission.     

A New Alternative Fuel for Reduction of Polycyclic Aromatic Hydrocarbon and Particulate Matter Emissions from Diesel Engines

Abstract

This study investigated the emissions of polycyclic aromatic hydrocarbons (PAHs), carcinogenic potential of PAH and particulate matter (PM), brake-specific fuel consumption (BSFC), and power from diesel engines under transient cycle testing of six test fuels: premium diesel fuel (PDF), B100 (100% palm biodiesel), B20 (20% palm biodiesel + 80% PDF), BP9505 (95% paraffinic fuel + 5% palm biodiesel), BP8020 (80% paraffinic fuel + 20% palm biodiesel), and BP100 (100% paraffinic fuel; Table 1). Experimental results indicated that B100, BP9505, BP8020, and BP100 were much safer when stored than PDF. However, we must use additives so that B100 and BP100 will not gel as quickly in a cold zone. Using B100, BP9505, and BP8020 instead of PDF reduced PM, THC, and CO emissions dramatically but increased CO₂ slightly because of more complete combustion. The CO₂-increased fraction of BP9505 was the lowest among test blends. Furthermore, using B100, B20, BP9505, and BP8020 as alternative fuels reduced total PAHs and total benzo[a]pyrene equivalent concentration (total BaP_eq) emissions significantly. BP9505 had the lowest decreased fractions of power and torque and increased fraction of BSFC. These experimental results implied that BP9505 is feasible for traveling diesel vehicles. Moreover, paraffinic fuel will likely be a new alternative fuel in the future. Using BP9505 instead of PDF decreased PM (22.8%), THC (13.4%), CO (25.3%), total PAHs (88.9%), and total BaP_eq (88.1%) emissions significantly.     

Polycyclic aromatic hydrocarbon exhaust emissions from different reformulated diesel fuels and engine operating conditions

The study of light-duty diesel engine exhaust emissions is important due to their impact on atmospheric chemistry and air pollution. In this study, both the gas and the particulate phase of fuel exhaust were analyzed to investigate the effects of diesel reformulation and engine operating parameters. The research was focused on polycyclic aromatic hydrocarbon (PAH) compounds on particulate phase due to their high toxicity. These were analyzed using a gas chromatography–mass spectrometry (GC–MS) methodology.Although PAH profiles changed for diesel fuels with low-sulfur content and different percentages of aromatic hydrocarbons (5–25%), no significant differences for total PAH concentrations were detected. However, rape oil methyl ester biodiesel showed a greater number of PAH compounds, but in lower concentrations (close to 50%) than the reformulated diesel fuels. In addition, four engine operating conditions were evaluated, and the results showed that, during cold start, higher concentrations were observed for high molecular weight PAHs than during idling cycle and that the acceleration cycles provided higher concentrations than the steady-state conditions. Correlations between particulate PAHs and gas phase products were also observed.The emission of PAH compounds from the incomplete combustion of diesel fuel depended greatly on the source of the fuel and the driving patterns.     

Study of Miller timing on exhaust emissions of a hydrotreated vegetable oil (HVO)-fueled diesel engine

The effect of intake valve closure (IVC) timing by utilizing Miller cycle and start of injection (SOI) on particulate matter (PM), particle number, and nitrogen oxide (NO_x) emissions was studied with a hydrotreated vegetable oil (HVO)-fueled nonroad diesel engine. HVO-fueled engine emissions, including aldehyde and polyaromatic hydrocarbon (PAH) emissions, were also compared with those emitted with fossil EN590 diesel fuel. At the engine standard settings, particle number and NO_x emissions decreased at all the studied load points (50%, 75%, and 100%) when the fuel was changed from EN590 to HVO. Adjusting IVC timing enabled a substantial decrease in NO_x emission and combined with SOI timing adjustment somewhat smaller decrease in both NO_x and particle emissions at IVC??50 and??70 °CA points. The HVO fuel decreased PAH emissions mainly due to the absence of aromatics. Aldehyde emissions were lower with the HVO fuel with medium (50%) load. At higher loads (75% and 100%), aldehyde emissions were slightly higher with the HVO fuel. However, the aldehyde emission levels were quite low, so no clear conclusions on the effect of fuel can be made. Overall, the study indicates that paraffinic HVO fuels are suitable for emission reduction with valve and injection timing adjustment and thus provide possibilities for engine manufacturers to meet the strictening emission limits.

Implications: NO_x and particle emissions are dominant emissions of diesel engines and vehicles. New, biobased paraffinic fuels and modern engine technologies have been reported to lower both of these emissions. In this study, even further reductions were achieved with engine valve adjustment combined with novel hydrotreated vegetable oil (HVO) diesel fuel. This study shows that new paraffinic fuels offer further possibilities to reduce engine exhaust emissions to meet the future emission limits.

Supplementary Materials: Supplementary materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association for a complete list of analysed PAH compounds.     

Simulation of atmospheric PAH emissions from diesel engines

Simulation of atmospheric PAH emissions in a typical European passenger car diesel engine at steady conditions or under a certification cycle is made using in-house software. It is based on neural fitting of experimental data from eight different fuels tested under five operating steady conditions (reproducing modes of the European transient urban/extraurban certification cycle). The software allows the determination of PAH emissions as a function of the fuel composition parameters (aromatic content, cetane index, gross heat power, nitrogen and sulphur content) and operation conditions (torque and engine speed). The mathematical model reproduces experimental data with a maximum error of 20%. This tool is very useful, since changes in parameters can be made without experimental cost and the trend in modifications in PAH emissions is immediately obvious.     

Reducing carbonyl emissions from a heavy-duty diesel engine at US transient cycle test by use of paraffinic/biodiesel blends

Formaldehyde and acetaldehyde are toxic carcinogens so their reductions in diesel-engine emissions are desirable. This study investigated emissions of carbonyl compounds (CBCs) from an HDDE (heavy-duty diesel engine) at US transient cycle test, using five test fuels: premium diesel fuel (D100), P100 (100% palm-biodiesel), P20 (20% palm-biodiesel + 80% premium diesel fuel), PF80P20 (80% paraffinic fuel + 20% palm-biodiesel), and PF95P05 (95% paraffinic fuel + 5% palm-biodiesel). Experimental results indicate that formaldehyde was the major carbonyl in the exhaust, accounting for 70.1–76.2% of total CBC concentrations for all test fuels. In comparison with D100 (172 mg BHP^?1 h^?1), the reductions of formaldehyde and acetaldehyde emission factor for P100, P20, PF80P20, and PF95P05 were (?16.8%, ?61.8%), (?10.0%, ?39.0%), (21.3%, 1.10%), and (31.1%, 19.5%), respectively. Using P100 and P20 instead of D100 in the HDDE increased CBC concentrations by 14.5% and 3.28%, respectively, but using PF80P20 and PF95P05 significantly reduced CBC concentrations by 30.3% and 23.7%, respectively. Using P100 and P20 instead of D100 (2867 ton yr^?1) in the HDDE increased CBC emissions by 240 and 224 ton yr^?1, respectively, but using PF80P20, and PF95P05 instead of D100 in the HDDE decreased CBC emissions by 711 and 899 ton yr^?1, respectively. The above results indicate that the wide usage of paraffinic–palmbiodiesel blends as alternative fuels could protect the environment.     

Effect of fuel composition and engine operating conditions on polycyclic aromatic hydrocarbon emissions from a fleet of heavy-duty diesel buses

Emissions from 12 in-service heavy-duty buses powered by low- (LSD) and ultra low-sulfur (ULSD) diesel fuels were measured with the aim to characterize the profile of polycyclic aromatic hydrocarbons (PAHs) in the exhaust and to identify the effect of different types of fuels on the emissions. To mimic on-road conditions as much as possible, sampling was conducted on a chassis dynamometer at four driving modes, namely: mode 7 or idle (0% power), mode 11 (25% power), mode 10 (50% power) and mode 8 (100% power). Irrespective of the type of fuel used, naphthalene, acenaphthene, acenaphthylene, anthracene, phenanthrene, fluorene, fluoranthene and pyrene were found to be the dominant PAHs in the exhaust emissions of the buses. However, the PAH composition in the exhausts of ULSD buses were up to 91±6% less than those in the LSD buses. In particular, three- and four-ringed PAHs were more abundant in the later than in the former. Lowering of fuel sulfur content not only reduced PAH emission, but also decreased the benzo(a)pyrene equivalent (BAP_eq) and hence the toxicity of the exhaust. Result from multicriteria decision-making and multivariate data analysis techniques showed that the use of ULSD afforded cleaner exhaust compositions and emissions with characteristics that are distinct from those obtained by the use of LSD.     

Emissions of PCDD/Fs, PCBs, and PAHs from legacy on-road heavy-duty diesel engines

Exhaust emissions of seventeen 2,3,7,8-substituted polychlorinated dibenzo-p-dioxin/furan (PCDD/F) congeners, tetra-octa PCDD/F homologues, 12 WHO 2005 polychlorinated biphenyl (PCB) congeners, mono-nona chlorinated biphenyl homologues, and 19 polycyclic aromatic hydrocarbons (PAHs) from three legacy diesel engines were investigated. The three engines tested were a 1985 model year GM 6.2 J-series engine, a 1987 model year Detroit Diesel Corporation 6V92 engine, and a 1993 model year Cummins L10 engine. Results were compared to United States’ mobile source inventory for on-road diesel engines, as well as historic and modern diesel engine emission values. The test fuel contained chlorine at 9.8 ppm which is 1.5 orders of magnitude above what is found in current diesel fuel and 3900 ppm sulfur to simulate fuels that would have been available when these engines were produced. Results indicate PCDD/F emissions of 13.1, 7.1, and 13.6 pg International Toxic Equivalency (I-TEQ) L⁻¹ fuel consumed for the three engines respectively, where non-detects are equal to zero. This compares with a United States’ mobile source on-road diesel engine inventory value of 946 pg I-TEQ L⁻¹ fuel consumed and 1.28 pg I-TEQ L⁻¹ fuel consumed for modern engines equipped with a catalyzed diesel particle filter and urea selective catalytic reduction. PCB emissions are 2 orders of magnitude greater than modern diesel engines. PAH results are representative of engines from this era based on historical values and are 3-4 orders of magnitude greater than modern diesel engines.     

A fuel-based assessment of off-road diesel engine emissions

The use of diesel engines in off-road applications is a significant source of nitrogen oxides (NOx) and particulate matter (PM10). Such off-road applications include railroad locomotives, marine vessels, and equipment used for agriculture, construction, logging, and mining. Emissions from these sources are only beginning to be controlled. Due to the large number of these engines and their wide range of applications, total activity and emissions from these sources are uncertain. A method for estimating the emissions from off-road diesel engines based on the quantity of diesel fuel consumed is presented. Emission factors are normalized by fuel consumption, and total activity is estimated by the total fuel consumed. Total exhaust emissions from off-road diesel equipment (excluding locomotives and marine vessels) in the United States during 1996 have been estimated to be 1.2 x 10(9) kg NOx and 1.2 x 10(8) kg PM10. Emissions estimates published by the U.S. Environmental Protection Agency are 2.3 times higher for both NOx and exhaust PM10 emissions than estimates based directly on fuel consumption. These emissions estimates disagree mainly due to differences in activity estimates, rather than to differences in the emission factors. All current emission inventories for off-road engines are uncertain because of the limited in-use emissions testing that has been performed on these engines. Regional- and state-level breakdowns in diesel fuel consumption by off-road mobile sources are also presented. Taken together with on-road measurements of diesel engine emissions, results of this study suggest that in 1996, off-road diesel equipment (including agriculture, construction, logging, and mining equipment, but not locomotives or marine vessels) was responsible for 10% of mobile source NOx emissions nationally, whereas on-road diesel vehicles contributed 33%.     

Reducing emissions of carbonyl compounds and regulated harmful matters from a heavy-duty diesel engine fueled with paraffinic/biodiesel blends at one low load steady-state condition

This study investigated the emissions of carbonyl compounds (CBCs) and regulated harmful matters (traditional pollutants) from an HDDE (heavy-duty diesel engine) at one low load steady-state condition, 24.5% of the max load (40 km h^?1), using five test fuels: premium diesel fuel (D100), P100 (100% palm-biodiesel), P20 (20% palm-biodiesel + 80% premium diesel fuel), PF80P20 (80% paraffinic fuel + 20% palm-biodiesel), and PF95P05 (95% paraffinic fuel + 5% palm-biodiesel). Experimental results indicate that formaldehyde was the major carbonyl in the exhaust, accounting for 70.3–75.4% of total CBC concentrations for all test fuels. Using P100 and P20 instead of D100 in the HDDE increased CBC concentrations by 9.74% and 2.89%, respectively. However, using PF80P20 and PF95P05 as alternative fuels significantly reduced CBC concentrations by 30.3% and 24.2%, respectively. Using PF95P05 instead of D100 decreased CBCs by 30.3%, PM by 11.1%, THC by 39.0%, CO by 34.0%, NOx by 24.3%, and CO₂ by 7.60%. The wide usage of paraffinic–palmbiodiesel blends as alternative fuels could protect the environment. However, it should be noted that only one engine operated at one low load steady-state condition was investigated.     

Effects of diesel/biodiesel blends on regulated and unregulated pollutants from a passenger vehicle operated over the European and the Athens driving cycles

This paper presents the regulated and unregulated exhaust emissions of a diesel passenger vehicle, operated with low sulphur automotive diesel and soy methyl ester blends. Emission and fuel consumption measurements were conducted under real driving conditions (Athens Driving Cycle, ADC) and compared with those of a modified New European Driving Cycle (NEDC) using a chassis dynamometer. A Euro II compliant diesel vehicle was used in this study, equipped with an indirect injection diesel engine, fuelled with diesel fuel and biodiesel blends at proportions of 5, 10, and 20% respectively. Unregulated emissions of 11 polycyclic aromatic hydrocarbons (PAHs), 5 nitro-PAHs, 13 carbonyl compounds (CBCs) and the soluble organic fraction (SOF) of the particulate matter were measured. Qualitative hydrocarbon analysis was also performed on the SOF. Regulated emissions of NO_x, CO, HC, CO₂, and PM were also measured over the two test cycles. It was established that some of the emissions measured over the (hot-start) NEDC differed from the real-world cycle. Significant differences were also observed in the vehicle's fuel consumption between the two test cycles. The addition of biodiesel reduced the regulated emissions of CO, HC and PM, while an increase in NO_x was observed over the ADC. Carbonyl emissions, PAHs and nitro-PAHs were reduced with the addition of biodiesel over both driving cycles.     

Bioethanol-gasoline fuel blends: exhaust emissions and morphological characterization of particulate from a moped engine

This study was aimed at evaluating the effects of gasoline-ethanol blends on the exhaust emissions in a catalyst-equipped four-stroke moped engine. The ethanol was blended with unleaded gasoline in at percentages (10, 15, and 20% v/v). The regulated pollutants and the particulate matter emissions were evaluated over the European ECE R47 driving cycle on the chassis dynamometer bench. Particulate matter was characterized in terms of total mass collected on filters and total number ofparticles in the range 7 nm-10 microm measured by electrical low-pressure impactor (ELPI). In addition, particle-phase polycyclic aromatic hydrocarbons (PAHs) emissions were evaluated to assess the health impact of the emitted particulate. Finally, an accurate morphological analysis was performed on the particulate by high-resolution transmission electron microscope (TEM) equipped with a digital image-processing/data-acquisition system. In general, CO emission reductions of 60-70% were obtained with 15 and 20% v/v ethanol blends, while the ethanol use did not reduce hydrocarbon (HC) and NOx emissions. No evident effect of ethanol on the particulate mass emissions and associated PAHs emissions was observed. Twenty-one PAHs were quantified in the particulate phase with emissions ranging from 26 to 35 microg/km and benzo[a]pyrene equivalent (BaPeq) emission factors from 2.2 to 4.1 microg/km. Both particulate matter and associated PAHs with higher carcinogenic risk were mainly emitted in the submicrometer size range (<0.1 microm). On the basis of the TEM observations, no relevant effect of the ethanol use on the particulate morphology was evidenced, showing aggregates composed ofprimary particles with mean diameters in the range 17.5-32.5 nm.     

Emissions of PCDD/Fs,PCBs, and PAHs from legacy on-road heavy-duty diesel engines

Exhaust emissions of seventeen 2,3,7,8-substituted polychlorinated dibenzo-p-dioxin/furan (PCDD/F) congeners, tetra–octa PCDD/F homologues, 12 WHO 2005 polychlorinated biphenyl (PCB) congeners, mono–nona chlorinated biphenyl homologues, and 19 polycyclic aromatic hydrocarbons (PAHs) from three legacy diesel engines were investigated. The three engines tested were a 1985 model year GM 6.2 J-series engine, a 1987 model year Detroit Diesel Corporation 6V92 engine, and a 1993 model year Cummins L10 engine. Results were compared to United States’ mobile source inventory for on-road diesel engines, as well as historic and modern diesel engine emission values. The test fuel contained chlorine at 9.8 ppm which is 1.5 orders of magnitude above what is found in current diesel fuel and 3900 ppm sulfur to simulate fuels that would have been available when these engines were produced. Results indicate PCDD/F emissions of 13.1, 7.1, and 13.6 pg International Toxic Equivalency (I-TEQ) L⁻¹ fuel consumed for the three engines respectively, where non-detects are equal to zero. This compares with a United States’ mobile source on-road diesel engine inventory value of 946 pg I-TEQ L⁻¹ fuel consumed and 1.28 pg I-TEQ L⁻¹ fuel consumed for modern engines equipped with a catalyzed diesel particle filter and urea selective catalytic reduction. PCB emissions are 2 orders of magnitude greater than modern diesel engines. PAH results are representative of engines from this era based on historical values and are 3–4 orders of magnitude greater than modern diesel engines.     

The effect of diesel fuel sulfur content on particulate matter emissions for a nonroad diesel generator

The effect of sulfur content on diesel particulate matter (DPM) emissions was studied using a diesel generator (Generac Model SD080, rated at 80 kW) as the emission source to simulate nonroad diesel emissions. A load simulator was used to apply loads to the generator at 0, 25, 50, and 75 kW, respectively. Three diesel fuels containing 500, 2100, and 3700 ppm sulfur by weight were selected as generator fuels. The U.S. Environmental Protection Agency sampling Method 5 "Determination of Particulate Matter Emissions from Stationary Sources" together with Method 1A "Sample and Velocity Traverses for Stationary Sources with Small Stacks or Ducts" was adopted as a reference method for measurement of the exhaust gas flow rate and DPM mass concentration. The effects of various parameters on DPM concentration have been studied, such as fuel sulfur contents, engine loads, and fuel usage rates. The increase of average DPM concentrations from 3.9 mg/Nm3 (n cubic meter) at 0 kW to 36.8 mg/Nm3 at 75 kW is strongly correlated with the increase of applied loads and sulfur content in the diesel fuel, whereas the fuel consumption rates are only a function of applied loads. An empirical correlation for estimating DPM concentration is obtained when fuel sulfur content and engine loads are known for these types of generators: Y = Zm(alphaX + beta), where Y is the DPM concentration, mg/m3, Z is the fuel sulfur content, ppm(w) (limited to 500-3700 ppm(w)), X is the applied load, kW, m is the constant, 0.407, alpha and beta are the numerical coefficients, 0.0118 +/- 0.0028 (95% confidence interval) and 0.4535 +/- 0.1288 (95% confidence interval), respectively.     

Emissions of polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs from heavy-duty diesel vehicles with DPF and SCR

In total, 24 polycyclic aromatic hydrocarbons (PAHs) in both gas and particle phases and 35 nitro-PAHs in particle phase were analyzed in the exhaust from heavy-duty diesel vehicles equipped with after-treatment for particulate matter (PM) and NO_X control. The test vehicles were carried out using a chassis dynamometer under highway cruise, transient Urban Dynamometer Driving Schedule (UDDS), and idle operation. The after-treatment efficiently abated more than 90% of the total PAHs. Indeed, the particle-bound PAHs were reduced by >99%, and the gaseous PAHs were removed at various extents depending on the type of after-treatment and the test cycles. The PAHs in gas phase dominated the total PAH (gas + particle phases) emissions for all the test vehicles and for all cycles; that is, 99% of the two-ring and 98% of the three-ring and 97% of the four-ring and 95% of the carcinogenic PAHs were in the gas-phase after a diesel particle filter (DPF) and not bound to the very small amount of particulate matter left after a DPF. Consequently, an evaluation of the toxicity of DPF exhaust must include this volatile fraction and cannot be based on the particle fraction only. The selective catalytic reduction (SCR) did not appear to promote nitration of the PAHs in general, although there might be some selective nitration of phenanthrene. Importantly the after-treatmtent reduced the equivalent B[a]P (B[a]Peq) emissions by >95%, suggesting a substantial health benefit.

Implications: This study demonstrated that after-treatments, including diesel particulate filters (DPF), diesel oxidation catalysts (DOC), and selective catalytic reduction (SCR), significantly reduce the emissions of PAHs from heavy-duty diesel engines. The gas-phase PAHs dominate the total PAH (gas + particle phases) emissions from heavy-duty diesel vehicles retrofitted with various DPFs and not bound to the very small amount of particulate matter left after a DPF. Consequently, an evaluation of the toxicity of DPF exhaust must also include this volatile fraction and cannot be based on the particle fraction only.

Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association.     

Emission profile of 18 carbonyl compounds,CO, CO2, and NOx emitted by a diesel engine fuelled with diesel and ternary blends containing diesel,ethanol and biodiesel or vegetable oils

The impact of vehicular emissions on air depends, among other factors, on the composition of fuel and the technology used to build the engines. The reduction of vehicular emissions requires changes in the fuel composition, and improving the technologies used in the manufacturing of engines and for the after-treatment of gases. In general, improvements to diesel engines have targeted not only emission reductions, but also reductions in fuel consumption. However, changes in the fuel composition have been shown to be a more rapid and effective alternative to reduce pollution. Some factors should been taken into consideration when searching for an alternative fuel to be used in diesel engines, such as emissions, fuel stability, availability and its distribution, as well as its effects on the engine durability. In this work, 45 fuel blends were prepared and their stability was evaluated. The following mixtures (v/v/v) were stable for the 90-day period and were used in the emission study: diesel/ethanol – 90/10%, diesel/ethanol/soybean biodiesel – 80/15/5%, diesel/ethanol/castor biodiesel – 80/15/5%, diesel/ethanol/residual biodiesel – 80/15/5%, diesel/ethanol/soybean oil – 90/7/3%, and diesel/ethanol/castor oil – 90/7/3%. The diesel/ethanol fuel showed higher reduction of NO_x emission at a lower load (2 kW) when compared with pure diesel. The other fuels showed a decrease of NO_x emissions in the ranges of 6.9–75% and 4–85% at 1800 rpm and 2000 rpm, respectively. The combustion efficiencies of the diesel can be enhanced by the addition of the oxygenate fuels, like ethanol and biodiesel/vegetable oil, resulting in a more complete combustion in terms of NO_x emission. In the case of CO₂ the decreases were in the ranges of 5–24% and 4–6% at 1800 rpm and 2000 rpm, respectively. Meanwhile, no differences were observed in CO emission. The carbonyl compounds (CC) studied were formaldehyde, acetaldehyde, propionaldehyde, acrolein, acetone, crotonaldehyde, butyraldehyde, butanone, benzaldehyde, isovaleraldehyde, valeraldehyde, o-toluenaldehyde, m-toluenaldehyde, p-toluenaldehyde, hexaldehyde, octaldehyde, 2,5-dimethylbenzaldehyde, and decaldehyde. Among them, formaldehyde, acetaldehyde, acetone, and propionaldehyde showed the highest emission concentrations. When ternary blend contains vegetable oil, there is a strong tendency to increase the emissions of the high weight CC and decrease the emissions of the low weight CC. The highest concentration of acrolein was observed when the fuel contains diesel, ethanol and biodiesel. With the exception of NO_x, the use of ternary blended fuels resulted on the increase in the emission rates of the studied compounds.     

Environmental Progress and Problems: A Chemical Industry Perspective

From 1995 to 2004, in Genoa, Italy, daily concentrations of twelve polycyclic aromatic hydrocarbons (PAHs) were measured in particulate phase (PM10), around a coke oven plant in operation from the 1950s and closed in 2002. The study permitted to identify the coke oven as the main PAH source in Genoa, causing constant exceeding of benzo(a)pyrene (BaP) air quality target (1.0 ng/m3) in the urban area till 1,900 meters distance downwind the plant. For this reason the plant was closed. Distance and daily hours downwind the coke plant were the main sources of variability of toxic BaP equivalent (BaPeq) concentrations and equations that best fitted these variables were experimentally obtained. During full plant activity, annual average BaPeq concentrations, measured in the three sampling sites aligned downwind to the summer prevalent winds, were: 85 ng/m3 at 40 m (site 2, industrial area), 13.2 ng/m3 at 300 m (site 3, residential area) and 5.6 ng/m3 at 575 m (site 4, residential area).

Soon after the coke oven's closure (February 2002) BaPeq concentrations (annual average) measured in residential area, decreased drastically: 0.2 ng/m3 at site 3, 0.4 ng/m3 at site 4. Comparing 1998 and 2003 data, BaPeq concentrations decreased 97.6% in site 3 and 92.8% in site 4.

Samples collected at site 3, during the longest downwind conditions, provided a reliable PAH profile of fugitive coke oven emissions. This profile was significantly different from the PAH profile, contemporary found at site 5, near the traffic flow.

This study demonstrates that risk assessment based only on distance of residences from a coke plant can be heavily inaccurate and confirmed that seasonal variability of BaPeq concentrations and high variability of fugitive emissions of PAHs during coke oven activities require at least one year of frequent and constant monitoring (10-15 samples each month).

Implications: Around a coking plant, polycyclic aromatic hydrocarbons (PAHs), concentrations depend mainly on downwind hours and distance. Equations that best fit these variables were experimentally calculated. Fugitive emissions of an old coke oven did not comply with the threshold BAP air concentration proposed by the World Health Organization (WHO), up to 1,900 m distance. The study identified the PAH profile of fugitive emissions of a coke oven, statistically different from the profile of traffic emissions. During its activity, in the Genoa residential area, 575 m away from the plant, 92.8% of found PAHs was due to coke oven emission only.