Comparative effects of oxygenates-gasoline blended fuels on the exhaust emissions in gasoline-powered vehicles.

This study aimed to investigate the comparative effects of oxygenates such as ethanol (EA), methyl tertiary-butyl ether (MTBE), and ethyl tertiary butyl ether (ETBE) by fixing the oxygen contents as 0.82 wt% 1.65 wt%, and 2.74 wt% of the fuels on the regulated (CO, NMHC and NOx) and unregulated (formaldehyde, acetaldehyde and BTEX) exhaust emissions in gasoline-powered vehicles. The most widely used type of vehicles (light-duty, medium-duty, heavy-duty) in Korea were tested on a chassis dynamometer under the CVS-75 Cycle. When EA, MTBE and ETBE percentage increased, the CO and NMHC concentration decreased. The NOx emission decreased at 1.65 wt% and 2.74 wt% oxygen content of MTBE and ETBE. The emissions of CO decreased by 0.363 g/km, 0.266 g/km and 0.356 g/km for light-duty vehicle when EA, MTBE and ETBE oxygenates blending ratio increased. Increased EA, MTBE and ETBE oxygenates blending ratio demonstrated no specific reducing effect on CO emissions from low-mileage vehicle, but NMHC emissions decreased by 0.011 g/km (medium-duty), 0.015 g/km (light-duty) and 0.018 g/km (heavy-duty). More CO was emitted from MTBE among three oxygenates at same oxygen content. The emitted concentrations of NMHC from three oxygenates at same oxygen content were almost similar, but reduced NOx emissions from EA (10%) to MTBE (20.4%) and ETBE (23.6%) were observed at 2.74 wt% oxygen content. Reducing effect on CO emissions was order of EA > ETBE > MTBE. Formaldehyde emissions increased up to 54.3% as MTBE ratio increased. When oxygen content of ETBE, EA, and MTBE increased from 0.82 wt% to 2.74 wt%, the acetaldehyde emissions increased up to 177.4%, 39.5% and 31.0%, respectively. There was significant formaldehyde concentration difference between high emission vehicle type (light-duty and medium-duty) and low emission vehicle type (heavy-duty and low-mileage) for three oxygenates. Reduction effect of MTBE and ETBE on BTEX was the order of toluene > benzene > ethylbenzene > xylene, and MTBE showed more reduction effect than ETBE at same oxygen content.

Characterizations of organic compounds in diesel exhaust particulates.

To characterize how the speed and load of a medium-duty diesel engine affected the organic compounds in diesel particle matter (PM) below 1 µm, four driving conditions were examined. At all four driving conditions, concentration of identifiable organic compounds in PM ultrafine (34-94 nm) and accumulation (94-1000 nm) modes ranged from 2.9 to 5.7 µg/m(3) and 9.5 to 16.4 µg/m(3), respectively. As a function of driving conditions, the non-oxygen-containing organics exhibited a reversed concentration trend to the oxygen-containing organics. The identified organic compounds were classified into eleven classes: alkanes, alkenes, alkynes, aromatic hydrocarbons, carboxylic acids, esters, ketones, alcohols, ethers, nitrogen-containing compounds, and sulfur-containing compounds. At all driving conditions, alkane class consistently showed the highest concentration (8.3 to 18.0 µg/m(3)) followed by carboxylic acid, esters, ketones and alcohols. Twelve polycyclic aromatic hydrocarbons (PAHs) were identified with a total concentration ranging from 37.9 to 174.8 ng/m(3). In addition, nine nitrogen-containing polycyclic aromatic compounds (NPACs) were identified with a total concentration ranging from 7.0 to 10.3 ng/m(3). The most abundant PAH (phenanthrene) and NPACs (7,8-benzoquinoline and 3-nitrophenanthrene) comprise a similar molecular (3 aromatic-ring) structure under the highest engine speed and engine load.

Composition and size distribution of metals in diesel exhaust particulates.

This study characterizes the size distribution and composition of metals in diesel exhaust particulates (DEPs) emitting from four driving conditions. We quantified 17 metals in DEPs (34-1000 nm) with a total concentration ranging from 5.4-7.0 microg/m(3). Depending on driving conditions, ultrafine (<100 nm) and accumulation-mode DEPs carried up to 41% and 75% of the quantified metals, respectively. The size distribution of individual metals consistently indicates that under a medium (60%) engine load, more than three fourths of quantified metals partitioned in accumulation-mode DEPs, indicating prominent heterogeneous condensation. Enhancing the engine load up to 100% significantly increased metals in ultrafine DEPs around 1.8 times, particularly in DEP < 66 nm, suggesting enhanced metal nucleation. Under the maximum engine load, metals and elemental carbon showed an opposite trend in size distribution, providing tailpipe evidence that metals may catalyze oxidation of DEPs during combustion. Among the identified metals, Fe (2.3-3.9 microg/m(3)) was most abundant contributing to more than 43% of quantified metals, followed by Li, V, and Pb. Although As and Cd together contributed to less than 2% of the total quantified metals in DEP (<1 microm), their concentrations peaked in ultrafine DEPs under the maximum engine load, indicating that a decrease in engine loads can reduce amounts and toxicity of ultrafine DEPs.

Effects of driving conditions on diesel exhaust particulates.

Four driving conditions were examined to characterize how speeds and loads of a medium-duty diesel engine affect resultant diesel exhaust particulates (DEPs) in terms of number concentrations (< or =400 nm), size distribution, persistent free radicals, elemental carbon (EC), and organic carbon (OC). At the medium engine load (60%), DEPs surged in number concentrations at around 40-70 nm, whereas DEPs from the full engine load (100%) showed a distinctive bimodal distribution with a large population of 30-50 nm and 100-400 nm. Under the full engine load, engine speeds insignificantly affected resultant DEP number concentrations. When the engine load decreased from 100% to the medium level (60%), DEPs of ultrafine size and 100-400 nm decreased at least 1.4 times (from 5.6 x 10(8) to 4 x 10(8) #/cm3) and more than 3 times (from 2.7 x 10(8) to 0.8 x 10(8) #/cm3), respectively. The same reduction in the engine load significantly decreased persistent free radicals in DEPs up to approximately 30 times (from 123 x 10(16) to 4 x 10(16) #spin/g). Decreasing the engine load from 100 to 60% also concurrently reduced both EC and OC in total DEPs around 2 times, from 27.3 to 13.9 mg/m3, and from 17.6 to 9.2 mg/m3, respectively. For DEPs smaller than 1 microm, under the full engine load, EC and OC consistently peaked at 170-330 nm under an engine speed of 1800 rpm or 94-170 nm under an engine speed of 3000 rpm, reflecting processes of nucleation, cluster-cluster agglomeration, and condensation. Decreasing the engine load from 100 to 60% reduced EC and OC in DEPs (smaller than 1 microm) at least 3 times (0.6 to 0.2 mg/m3) and 2 times (0.4 to 0.2 mg/m3), respectively. Taken together, decreasing the full engine load to a medium (60%) level effectively reduced the number concentrations (< or =400 nm), persistent free radicals, EC, and OC of total DEPs, as well as the concentration of EC and OC in ultrafine and accumulation-mode DEPs.

Induction of nuclear factor-kappaB activation through TAK1 and NIK by diesel exhaust particles in L2 cell lines.

Diesel exhaust particles (DEPs) are known to induce allergic responses in airway epithelial cells, such as the production of various cytokines via nuclear factor-kappa B (NF-kappaB). However, the intracellular signal transduction pathways underlying this phenomenon have not been fully examined. This study showed that DEP induced NF-kappaB activity via transforming growth factor-beta activated kinase 1 (TAK1) and NF-kappaB-inducing kinase (NIK) in L2 rat lung epithelial cells. DEP induced the NF-kB dependent reporter activity approximately two- to three-fold in L2 cells. However, this effect was abolished by the expression of the dominant negative forms of TAK1 or NIK. Furthermore, it was shown that DEP induced TAK1 phosphorylation in the L2 cells. These results suggest that TAK1 and NIK are important mediators of DEP-induced NF-kappaB activation.