Tomoaki Okuda

Polycyclic Aromatic Hydrocarbon (PAHs) and Hopanes in Stranded Tar-balls on the Coasts of Peninsular Malaysia: Applications of Biomarkers for Identifying Sources of Oil Pollution

Malaysian coasts are subjected to various threats of petroleum pollution including routine and accidental oil spill from tankers, spillage of crude oils from inland and off-shore oil fields, and run-off from land-based human activities. Due to its strategic location, the Straits of Malacca serves as a major shipping lane. This paper expands the utility of biomarker compounds, hopanes, in identifying the source of tar-balls stranded on Malaysian coasts. 20 tar-ball samples collected from the east and west coast were analyzed for hopanes and polycyclic aromatic hydrocarbons (PAHs). Four of the 13 tar-ball samples collected from the west coast of Peninsular Malaysia were identified as the Middle East crude oil (MECO) based on their biomarker signatures, suggesting tanker-derived sources significantly contributing the petroleum pollution in the Straits of Malacca. The tar-balls found on the east coast seem to originate from the offshore oil platforms in the South China Sea. The presence of South East Asian crude oil (SEACO) tar-balls on the west coast carry several plausible explanations. Some of the tar-balls could have been transported via sea currents from the east coast. The tankers carrying SEACO to other countries could have accidentally spilt the oil as well. Furthermore, discharge of tank washings and ballast water from the tankers were suggested based on the abundance in higher molecular weight n-alkanes and the absence of unresolved complex mixture (UCM) in the tar-ball samples. The other possibilities are that the tar-balls may have been originated from the Sumatran oil fields and spillage of domestic oil from oil refineries in Port Dickson and Malacca. The results of PAHs analysis suggest that all the tar-ball samples have undergone various extent of weathering through evaporation, dissolution and photooxidation.

Sulfate Aerosol as a Potential Transport Medium of Radiocesium from the Fukushima Nuclear Accident

To date, areas contaminated by radionuclides discharged from the Fukushima Dai-ichi nuclear power plant accident have been mapped in detail. However, size of the radionuclides and their mixing state with other aerosol components, which are critical in their removal from the atmosphere, have not yet been revealed. We measured activity size distributions of (134)Cs and (137)Cs in aerosols collected 47 days after the accident at Tsukuba, Japan, and found that the activity median aerodynamic diameters of (134)Cs and (137)Cs in the first sample (April 28-May 12) were 0.54 and 0.53 μm, respectively, and those in the second sample (May 12-26) were both 0.63 μm. The activity size distributions of these radiocesium were within the accumulation mode size range and almost overlapped with the mass size distribution of non-sea-salt sulfate aerosol. From the analysis of other aerosol components, we found that sulfate was the potential transport medium for these radionuclides, and resuspended soil particles that attached radionuclides were not the major airborne radioactive substances at the time of measurement. This explains the relatively similar activity sizes of radiocesium measured at various sites during the Chernobyl accident. Our results can serve as basic data for modeling the transport/deposition of radionuclides.

Source identification of Malaysian atmospheric polycyclic aromatic hydrocarbons nearby forest fires using molecular and isotopic compositions

We report measurements of molecular and carbon isotopic compositions of Malaysian atmospheric polycyclic aromatic hydrocarbons (PAHs) in smoke haze from the 1997 Indonesian forest fire. Comparison of the carbon isotopic compositions (δ13C) of individual PAHs from the smoke haze, with those from other PAHs sources (soot collected from gasoline and diesel vehicle muffler, woodburning smoke), enables us to discriminate among the diverse sources of atmospheric PAHs. Soot PAHs extracted from gasoline and diesel vehicles show heavy isotopic signatures with a large inter-species δ13C variation from −12.9‰ to −26.6‰, compared to soot PAHs extracted from woodburning smoke which are isotopically light, and have a small inter-species δ13C variation from −26.8‰ to −31.6‰. Values from −17.7‰ to −27.9‰ were obtained for the corresponding PAHs extracted from the smoke haze, indicating that they are derived mainly from automotive exhaust. Molecular and isotopic compositions of PAHs extracted from smoke haze were similar to those extracted from non-haze aerosol. Quantitative estimation shows that woodburning contribution to Malaysian atmospheric PAHs ranges from 25% to 35% with no relation to haze intensity, while automotive contribution ranges from 65% to 75%. These results suggest that the major contributor of PAHs in Malaysian air is automotive exhaust whether smoke haze is observed or not.

Trends in hazardous trace metal concentrations in aerosols collected in Beijing, China from 2001 to 2006

Daily observations of hazardous trace metal concentrations in aerosols in Beijing, China were made in the period from 2001 to 2006. We considered coal combustion as a major source of some anthropogenic metals by achieving a correlation analysis and by investigating enrichment factors and relative composition of metals. A possible extra source of some specific metals, such as Cu and Sb, was brake abrasion particles, however, we did not think the transport-related particle was a major source for the hazardous anthropogenic metals even though they could originate from vehicle exhaust and brake/tire abrasion particles. A time-trend model was used to describe temporal variations of chemical constituent concentrations during the five-year period. Several crustal elements, such as Al, Ti, V, Cr, Mn, Fe, and Co, did not show clear increases, with annual rates of change of -15.2% to 3.6%. On the other hand, serious increasing trends were noted from several hazardous trace metals. Cu, Zn, As, Cd, and Pb, which are derived mainly from anthropogenic sources, such as coal combustion, showed higher annual rate of change (4.9-19.8%, p<0.001) according to the regression model. In particular, the Cd and Pb concentrations increased remarkably. We hypothesize that the trend towards increasing concentrations of metals in the air reflects a change that has occurred in the process of burning coal, whereby the use of higher temperatures for coal combustion has resulted in increased emissions of these metals. The increasing use of low-rank coal may also explain the observed trends. In addition, nonferrous metal smelters are considered as a potential, albeit minor, reason for the increasing atmospheric concentrations of anthropogenic hazardous metals in Beijing city.

Seasonal Variations and Evidence for the Effectiveness of Pollution Controls on Water-Soluble Inorganic Species in Total Suspended Particulates and Fine Particulate Matter from Xi'an, China

Abstract Total suspended particulate (TSP) and particulate matter less than 2.5 μm in aerodynamic diameter (PM2.5) sam ples were collected over Xi’an for a 1-yr period to characterize the seasonal variations of water-soluble inorganic ions and to evaluate the effectiveness of the pollution policies and controls during the past 10 yr. Mass concentrations of five cations (sodium [Na+], potassium [K+], ammonium [NH4 +]], calcium [Ca2+], and magnesium [Mg2+) and four anions (fluoride [F−], chloride [Cl−], nitrate [NO3 −], and sulfate [SO4 2−]) were determined by ion chromatography. The yearly arithmetic-mean mass concentrations of the total measured water-soluble ions in TSP and PM2.5 were 83.9 ± 58.4 and 45 ± 34.3 μg∙m-3. The most abundant ions in TSP were SO4 2−, NO3 −, Ca2+, and NH4 +; whereas in PM2.5 the dominant ions were SO4 2−, NH4 +, and NO3 −. Most of the ions were more concentrated in the PM2.5 than in TSP, but two exceptions were Ca2+ and Mg2+. Comparisons of the molar ratios of Mg2+/Ca2+ in TSP indicated that fugitive dust was the main source for these two ions, and the influence of soil dust from outside of the city was most evident during dust storms. The mass concentrations of SO4 2−, NO3 −, NH4 +, and K+ in TSP were highest in winter and lowest in spring, but Ca2+ was much higher in spring than other seasons because of suspended mineral dust. In PM2.5, NO3 − and K+ also showed winter maxima, but SO4 2− and NH4 + were highest in summer. Calculations of ion equivalents showed that TSP samples were more alkaline than PM2.5, the latter being weakly acidic in winter and autumn. High sulfur and nitrogen oxidation ratios occurred in summer and autumn, and there was evidence for the formation of ammonium bisulfate in TSP, ammonium sulfate in PM2.5, and ammonium nitrate in both fractions. Comparisons with the results of prior studies indicate that pollution controls in Xi’an have reduced the levels of air pollution over the past 10 yr. The SO4 2− concentration during the heating season in 2006 was only about one-eighth of that in 1996, and NH4 + decreased to one-ninth of that in 1996. Seasonal variations in the NO3 −/SO4 2− ratio are different than the patterns observed 10 yr ago, suggesting that emission sources have changed, with those from motor vehicles becoming increasingly important.

Vertical distributions and δ13C isotopic compositions of PAHs in Chidorigafuchi Moat sediment, Japan

Abstract Compound-specific carbon isotope analysis and molecular composition analysis were performed on polycyclic aromatic hydrocarbons (PAHs) extracted from a dated 50 cm sediment core from the Chidorigafuchi Moat, Japan. δ 13 C values ranged from −23.0 to −26.9‰ for individual PAHs, and ranged from −24.0 to −25.5‰ for the weighted average of PAHs at different core depths. Whilst total PAH concentrations showed a distinct maximum at around the year 1960, δ 13 C values did not show a statistically significant feature in the corresponding section of the core. Indeed, there was little correlation ( r 2 =0.12, P =0.19) between ΣPAH and δ 13 C throughout the core. PAHs in surface sediment (ca 0–8 cm) were characterised by a significantly higher benzo(ghi)perylene to indeno(1,2,3-cd)pyrene ratio ( t -test, P δ 13 C values ( P

Thermodynamic behavior of stable carbon isotopic compositions of individual polycyclic aromatic hydrocarbons derived from automobiles

Concentrations, molecular compositions, and compound-specific stable carbon isotopic compositions ( i 13 C) of polycyclic aromatic hydrocarbons (PAHs) in gasoline exhaust particles (GEPs) and diesel exhaust particles (DEPs) were investigated in this study. i 13 C of PAHs in GEPs ranged from m 13.3 to m 26.8, and that in DEPs ranged from m 21.7 to m 26.3. The interspecies i 13 C variations in each sample were 5.3 - 2.2 in GEPs and 2.6 - 1.3 in DEPs. PAHs in GEPs show larger interspecies i 13 C variation than those in DEPs; hence, a degree of carbon isotopic fractionation during the conversion from fuel to PAH seems to be larger in gasoline engines than that in diesel engines. Pyrene series PAHs, which consist of only hexagonal rings, in almost all GEP samples show strong negative correlation between the H/C ratio and i 13 C whereas fluoranthene series PAHs, which contain a pentagonal ring, show less systematic isotopic behavior in GEP samples. A kinetic isotope effect in thermal cracking of organic macromolecules may be minor for PAH formation in vehicle engines. We suggest that the isotopic trend of pyrene series in GEPs can be explained by a thermodynamic isotope effect, and that disturbance from isotopic equilibrium may cause a weak correlation between the isotopic behavior and the H/C ratio among the interspecies PAHs.

Exploring CO pollution episodes observed at Rishiri Island by chemical weather simulations and AIRS satellite measurements: long-range transport of burning plumes and implications for emissions inventories.

The summer of 2003 was an active forest fire season in Siberia. Several events of elevated carbon monoxide (CO) were observed at Rishiri Island in northern Japan during an intensive field campaign in September 2003. A simulation with a global chemistry-transport model is able to reproduce the general features of the baseline levels and variability in the observed CO, and a source attribution for CO in the model suggests that the contribution from North Asia dominated, accounting for approximately 50% on average, with contributions of 7% from North America and 8% from Europe and 30% from oxidation of hydrocarbons. With consideration of recent emission estimates for East Asian fossil fuel and Siberian biomass burning sources, the model captures the timing and magnitude of the CO enhancements in two pollution episodes well (17 and 24 September). However, it significantly underestimates the amplitude during another episode (11–13 September), requiring additional CO emissions for this event. Daily satellite images from AIRS reveal CO plumes transported from western Siberia toward northern Japan. These results suggest that CO emissions from biomass burning in western Siberia in 2003 are likely underestimated in the inventory and further highlight large uncertainties in estimating trace gas emissions from boreal fires.

Sensitivity of diesel particulate material emissions and composition to blends of petroleum diesel and biodiesel fuel

A number of investigations have examined the impact of the use of biodiesel on the emissions of carbon dioxide and regulated emissions, but limited information exists on the chemical composition of particulate matter from diesel engines burning biodiesel blends. This study examines the composition of diesel particulate matter (DPM) emissions from a commercial agriculture tractor burning a range of biodiesel blends operating under a load that is controlled by a power take off (PTO) dynamometer. Ultra-low sulfur diesel (ULSD) fuel was blended with soybean and beef tallow based biodiesel to examine fuels containing 0% (B0), 25% (B25), 50% (B50), 75% (B75), and 100% (B100) biodiesel. Samples were then collected using a dilution source sampler to simulate atmospheric dilution. Diluted and aged exhaust was analyzed for particle mass and size distribution, PM2.5 particle mass, PM2.5 organic and elemental carbon, and speciated organic compounds. PM2.5 mass emissions rates for the B25, B50, and B75 soybean oil biodiesel mixtures had 20%–30% lower emissions than the petroleum diesel, but B100 emissions were about 40% higher than the petroleum diesel. The trends in mass emission rates with the increasing biodiesel content can be explained by a significant decrease in elemental carbon (EC) emissions across all blending ranges and increasing organic carbon (OC) emissions with pure biodiesel. Beef tallow biodiesel blends showed similar trends. Nevertheless, it is important to note that the study measurements are based on low dilution rates and the OC emissions changes may be affected by ambient temperature and different dilution conditions spanning micro-environments and atmospheric conditions. The results show that the use of biodiesel fuel for economic or climate change mitigation purposes can lead to reductions in PM emissions and a co-benefit of EC emission reductions. Detailed speciation of the OC emissions were also examined and are presented to understand the sensitivity of OC emissions with respect to biodiesel fuel blends. Copyright 2012 American Association for Aerosol Research

PM2.5-induced airway inflammation and hyperresponsiveness in NC/Nga mice

The allergic inflammatory effects of particulate matter (PM) 2.5, collected with the cyclone system in Yokohama city in Japan, were investigated in NC/Nga mice, which are hypersensitive to mite allergens. PM2.5 with alum was injected intraperitoneally for sensitization. Five days later, 200 μg of PM2.5 in 25 μL of saline was administered to mice intranasally five times for further sensitization. On the 11th day, PM2.5 was administered as a challenge. On the 12th day, mice were examined for airway hyperresponsiveness (AHR), the bronchoalveolar lavage fluid (BALF) cell count, mRNA expression of Th1, Th2 cytokines, and metallothioneins in lung tissue, and histopathology. PM2.5 increased AHR, total cell numbers including eosinophils in BALF, and mRNA levels of IL‐5, IL‐22, eotaxin, eotaxin 2, and metallothionein 3. In PM2.5‐induced lungs, inflammation was observed around the bronchus. These results demonstrate that PM2.5 alone, collected with the cyclone system in Yokohama city in Japan, induces asthma‐like airway inflammation.