Atmospheric Environment (v.44, #32)

Potential emissions reduction in road transport sector using biofuel in developing countries by A.M. Liaquat; M.A. Kalam; H.H. Masjuki; M.H. Jayed (3869-3877).
Use of biofuels as transport fuel has high prospect in developing countries as most of them are facing severe energy insecurity and have strong agricultural sector to support production of biofuels from energy crops. Rapid urbanization and economic growth of developing countries have spurred air pollution especially in road transport sector. The increasing demand of petroleum based fuels and their combustion in internal combustion (IC) engines have adverse effect on air quality, human health and global warming. Air pollution causes respiratory problems, adverse effects on pulmonary function, leading to increased sickness absenteeism and induces high health care service costs, premature birth and even mortality. Production of biofuels promises substantial improvement in air quality through reducing emission from biofuel operated automotives. Some of the developing countries have started biofuel production and utilization as transport fuel in local market. This paper critically reviews the facts and prospects of biofuel production and utilization in developing countries to reduce environmental pollution and petro dependency. Expansion of biofuel industries in developing countries can create more jobs and increase productivity by non-crop marginal lands and wastelands for energy crops plantation.Contribution of India and China in biofuel industry in production and utilization can dramatically change worldwide biofuel market and leap forward in carbon cut as their automotive market is rapidly increasing with a souring proportional rise of GHG emissions.
Keywords: Emission; Air pollution, health hazards; Environment; Biofuel; Developing countries;

Diesel particulate matter poses a threat to human health, and in particular nitrated polycyclic aromatic hydrocarbons (NPAHs) found within and on the surface of these particles. Although diesel particulate filters (DPFs) have been designed and implemented to reduce these and other harmful diesel emissions, the particle loaded filters may act as a reaction chamber for the enhanced production of NPAHs from the nitration of PAHs with NO2.Focus is on the investigation of the heterogeneous reactions that occur on soot particles by exposing laboratory produced pyrene- or benzo(a)pyrene-coated spark discharge soot particles to varying concentrations of NO2 and temperatures while following the formation of products over time. The sole nitration product that was observed throughout the experiments with pyrene-coated soot was 1-nitropyrene (1-NPYR), which increased linearly with reaction time for all NO2 concentrations chosen (0.11, 1.0, 2.0, 4.0 ppm, m m−1). Resulting 1-NPYR formation rate increased exponentially with [NO2]. Throughout the 3-h experiments less than 10% of pyrene has been converted to 1-NPYR and the partial reaction order with regard to [NO2] was estimated to 1.52. Benzo(a)pyrene (BaP) was more reactive than pyrene. After 3 h reaction time almost 80% of the BaP has been converted to 6-NBaP.Highest 1-NPYR concentrations on particles were detected at 373 K, and at higher temperatures a considerable decrease in particulate 1-NPYR was observed. A similar trend was observed in a DPF simulation system (PM-Kat®-like) with BaP-coated soot. In this case, highest 6-NBaP concentration on particles was detected at 423 K. Backed by corroborating results from separate gas/solid-phase partition experiments with 1-NPYR and 6-NBaP, it is likely that the newly formed 1-NPYR and 6-NBaP became transferred from particle to gas phase at higher temperatures. Results from this study confirm the presence of 1-NPYR and 6-NBaP in particulate and gas phase under conditions encountered in DPFs, especially when operated at low temperature situations of the aftertreatment system.
Keywords: Nitro-PAH formation; Nitrogen dioxide; Soot aerosol; Pyrene; Benzo[a]pyrene; Diesel particulate filter;

Respiration controls the unexpected seasonal pattern of carbon flux in an Asian tropical rain forest by Yiping Zhang; Zhenghong Tan; Qinghai Song; Guirui Yu; Xiaomin Sun (3886-3893).
Tropical rain forests play important roles in the global carbon cycle. We report a six-year eddy covariance carbon flux campaign in a primary tropical seasonal rain forest in southwest China. An unexpected seasonal pattern of net ecosystem carbon exchange was detected, with carbon lost during the rainy season and stored in the dry season. Strong seasonality of ecosystem respiration was suggested to primarily account for this seasonal pattern. The annual net uptake of CO2 by the forest varied from 0.98 to 2.35 metric tons of carbon per hectare between 2003 and 2008. 6-year averaged sink strength was 1.68 metric tons of carbon per hectare.
Keywords: Eddy covariance; Intensive leaf change; Carbon sink; Seasonal drought;

To understand the effect of water level on CH4 emissions from an invasive Spartina alterniflora coastal brackish marsh, we measured CH4 emissions from intermittently and permanently (5 cm water depth) inundated mesocosms with or without N fertilizer added at a rate of 2.7 g N m−2. Dissolved CH4 concentrations in porewater and vertically-profiled sediment redox potential were measured, as were aboveground biomass and stem density of S. alterniflora. Mean CH4 fluxes during the growing season in permanently inundated mesocosms without and with N fertilizer were 1.03 and 1.73 mg CH4 m−2  h−1, respectively, which were significantly higher than in the intermittently inundated mesocosms. This response indicates that prolonged submergence of sediment, up to a water depth of 5 cm, stimulated CH4 release. Inundation did not greatly affect aboveground biomass and stem density, but did significantly reduce redox potential in sediment, which in turn stimulated CH4 production and increased the CH4 concentration of porewater, resulting in higher CH4 emission in the mesocosm. Our data showed that the stimulatory effect of shallow, permanent inundation on CH4 emission in S. alterniflora marsh sediment was due primarily to an improved methanogenic environment rather than an increase in plant-derived substrates and/or the number of gas emission pathways through the plant’s aerenchymal system.
Keywords: Coastal brackish marsh; Intermittent inundation; N fertilization; Permanent inundation; Spartina alterniflora; Methane emission;

Estimating historical landfill quantities to predict methane emissions by Seán Lyons; Liam Murphy; Richard S.J. Tol (3901-3906).
There are no observations for methane emissions from landfill waste in Ireland. Methane emissions are imputed from waste data. There are intermittent data on waste sent to landfill. We compare two alternative ways to impute the missing waste “data” and evaluate the impact on methane emissions. We estimate Irish historical landfill quantities from 1960–2008 and Irish methane emissions from 1968–2006. A model is constructed in which waste generation is a function of income, price of waste disposal and, household economies of scale. A transformation ratio of waste to methane is also included in the methane emissions model. Our results contrast significantly with the Irish Environmental Protection Agency’s (EPA) figures due to the differences in the underlying assumptions. The EPA’s waste generation and methane emission figures are larger than our estimates from the early 1990s onwards. Projections of the distance to target show that the EPA overestimates the required policy effort.
Keywords: Methane emissions; Landfill; Modelling;

Comparison of SOC estimates and uncertainties from aerosol chemical composition and gas phase data in Atlanta by Jorge E. Pachon; Sivaraman Balachandran; Yongtao Hu; Rodney J. Weber; James A. Mulholland; Armistead G. Russell (3907-3914).
In the Southeastern US, organic carbon (OC) comprises about 30% of the PM2.5 mass. A large fraction of OC is estimated to be of secondary origin. Long-term estimates of SOC and uncertainties are necessary in the evaluation of air quality policy effectiveness and epidemiologic studies. Four methods to estimate secondary organic carbon (SOC) and respective uncertainties are compared utilizing PM2.5 chemical composition and gas phase data available in Atlanta from 1999 to 2007. The elemental carbon (EC) tracer and the regression methods, which rely on the use of tracer species of primary and secondary OC formation, provided intermediate estimates of SOC as 30% of OC. The other two methods, chemical mass balance (CMB) and positive matrix factorization (PMF) solve mass balance equations to estimate primary and secondary fractions based on source profiles and statistically-derived common factors, respectively. CMB had the highest estimate of SOC (46% of OC) while PMF led to the lowest (26% of OC). The comparison of SOC uncertainties, estimated based on propagation of errors, led to the regression method having the lowest uncertainty among the four methods. We compared the estimates with the water soluble fraction of the OC, which has been suggested as a surrogate of SOC when biomass burning is negligible, and found a similar trend with SOC estimates from the regression method. The regression method also showed the strongest correlation with daily SOC estimates from CMB using molecular markers. The regression method shows advantages over the other methods in the calculation of a long-term series of SOC estimates.
Keywords: SOC; WSOC; EC tracer; Regression; Uncertainty;

Occurrence of currently used pesticides in ambient air of Centre Region (France) by Clara Coscollà; Patrice Colin; Abderrazak Yahyaoui; Olivier Petrique; Vicent Yusà; Abdelwahid Mellouki; Agustin Pastor (3915-3925).
Ambient air samples were collected, from 2006 to 2008 at three rural and two urban sites in Centre Region (France) and analyzed for 56 currently used pesticides (CUPs), of which 41 were detected. The four CUPs most frequently detected were the herbicides trifluralin, acetochlor and pendimethalin and the fungicide chlorothalonil, which were found with frequencies ranging between 52 and 78%, and with average concentrations of 1.93, 1.32, 1.84 and 12.15 ng m−3, respectively. Among the detected pesticides, concentrations of eight fungicides (spiroxamine, fenpropimorph, cyprodinil, tolyfluanid, epoxiconazole, vinchlozolin, fluazinam, fludioxinil), two insecticides (propargite, ethoprophos), and one herbicide (oxyfluorfen) are, to our knowledge, reported for the first time in the literature.The majority of the CUPs showed a seasonal trend, with most of the detections and the highest concentrations occurring during the spring and early summer. The most important pesticides detected were related to arable crops and fruit orchards, the main cultures in this region, highlighting the fact that the main sources come from local applications. Minor differences were found in the profiles of pesticides within rural areas and between rural and urban areas.
Keywords: Pesticides; Air; Occurrence; Temporal variations;

Optimizing emission inventory for chemical transport models by using genetic algorithm by M.J. Li; D.S. Chen; S.Y. Cheng; F. Wang; Y. Li; Y. Zhou; J.L. Lang (3926-3934).
Air pollutant emission inventory is an important input parameter for chemical transport models (CTMs). Since great uncertainties exist in the emission inventory, further improvements and refinements are required. In this paper, genetic algorithm (GA), a global search and optimization method, was applied to optimize the emission inventory for the Models-3/Community Multiscale Air Quality (CMAQ) model. An emission optimizing system based on GA was developed and embedded to the CMAQ through the design of several core modules, which implemented the basic functions such as emission adjusting, GA population initializing, CMAQ results evaluating and GA operating. Hypothetical and real-data experiments were respectively performed to examine the validity of GA for emission calibrating. GA showed good performance in both experiments and was always able to find the global minimum. The emission optimizing system was then used to calibrate seasonal PM10 emission inventories of Beijing. Results revealed that PM10 emission in Beijing was underestimated in 2002, an average of 62.74% higher adjustment factor should be imposed on the original emission in target months of different seasons. With the calibrated emission inventories, CMAQ model errors were decreased by 6.46% on average in different seasons. It was concluded that GA was a promising search technique in calibrating emission inputs for CTMs.
Keywords: Genetic algorithm; Emission inventory; Chemical transport models; CMAQ;

Receptor modeling techniques like chemical mass balance are used to attribute pollution levels at a point to different sources. Here we analyze the composition of particulate matter and use the source profiles of sources prevalent in a region to estimate quantitative source contributions. In dispersion modeling on the other hand the emission rates of various sources together with meteorological conditions are used to determine the concentrations levels at a point or in a region. The predictions using these two approaches are often inconsistent. In this work these differences are attributed to errors in emission inventory. Here an algorithm for coupling receptor and dispersion models is proposed to reduce the differences of the two predictions and determine the emission rates accurately. The proposed combined approach helps reconcile the differences arising when the two approaches are used in a stand-alone mode. This work is based on assuming that the models are perfect and uses a model-to-model comparison to illustrate the concept.
Keywords: Receptor model; Dispersion model; Emission rates; Coupled model; Optimization;

A new analytical method was developed for the determination of formaldehyde in ambient air based on the use of a modified configuration of the Analyst® passive sampler. It consists of a polyethylene cylinder filled with appropriate reactive adsorbent and a special anti-turbulence net which works as an ozone scrubber.The performance of a diffusive sampler depends critically on the selection and use of a suitable adsorbent and on environmental factors, such as temperature, humidity and the interference of oxidant species. In this study two adsorbent types were investigated: 2,4-dinitrophenylhydrazine (2,4-DNPH) coated silica gel and Florisil® particles. Interference of ozone was removed by using a silver net upstream as an anti-turbulence device. The performance of this net was then compared with that of stainless steel. Furthermore, the aim of the work was the optimization of the adsorbent type and the study of the interference of ozone with particular attention placed on the effect of relative humidity and temperature.A dynamic system for generating a known concentration of the test gas (formaldehyde) in an appropriate exposure chamber was used to evaluate the performance of the passive sampler and to allow the calibration of the methodology. Inter-comparisons with a reference method, active sampling using 2,4-DNPH-silica gel coated cartridges, were also carried out. Results were in accordance with each other.Tests were planned using a statistical method based on Design of Experiment methodology. The operating conditions were chosen in order to obtain the best configuration of the passive device by evaluating the statistical significance of the different factors and their interactions by analysis of variance.Results showed that the best configuration was achieved using 2,4-DNPH Florisil® coated particles as an adsorbent and a silver anti-turbulence net as an ozone scrubber.With the aim of achieving further results in realistic conditions, some field experiments were also carried out.
Keywords: Carbonyl compounds; Formaldehyde; Passive samplers; Factorial design of experiment; ANOVA;

Characterization of fine primary biogenic organic aerosol in an urban area in the northeastern United States by Esther Coz; Begoña Artíñano; Lisa M. Clark; Mark Hernandez; Allen L. Robinson; Gary S. Casuccio; Traci L. Lersch; Spyros N. Pandis (3952-3962).
Scanning electron microscopy coupled to energy-dispersive x-ray spectroscopy (SEM/EDX) was used to quantify individual bioparticles in PM2.5 samples collected during the Pittsburgh Air Quality Study. Microscopy-based estimates of primary biogenic organic aerosol (PBOA) mass were compared to carbohydrate mass associated with PM2.5. Carbohydrates show substantial seasonal variations, with higher concentrations in the spring and the fall. During the summer, carbohydrates were about 30% of the estimated PBOA concentrations, but in the winter carbohydrate concentrations often greatly exceeded the PBOA mass estimate. Spores and insect detritus were the most abundant PBOA types in the summer samples, while winter samples were comprised predominantly of a mixture of microorganisms, insect and vegetative detritus. During the summer PBOA contributed on average 6.9 ± 5.4% by mass of the PM2.5 versus 3.3 ± 1.4% of the PM2.5 mass during the winter.
Keywords: Carbohydrates; Primary biogenic organic aerosols; SEM/EDX;

Exposure to particle number, surface area and PM concentrations in pizzerias by G. Buonanno; L. Morawska; L. Stabile; A. Viola (3963-3969).
The aim of this work was to quantify exposure to particles emitted by wood-fired ovens in pizzerias. Overall, 15 microenvironments were chosen and analyzed in a 14-month experimental campaign. Particle number concentration and distribution were measured simultaneously using a Condensation Particle Counter (CPC), a Scanning Mobility Particle Sizer (SMPS), an Aerodynamic Particle Sizer (APS). The surface area and mass distributions and concentrations, as well as the estimation of lung deposition surface area and PM1 were evaluated using the SMPS-APS system with dosimetric models, by taking into account the presence of aggregates on the basis of the Idealized Aggregate (IA) theory. The fraction of inhaled particles deposited in the respiratory system and different fractions of particulate matter were also measured by means of a Nanoparticle Surface Area Monitor (NSAM) and a photometer (DustTrak DRX), respectively. In this way, supplementary data were obtained during the monitoring of trends inside the pizzerias. We found that surface area and PM1 particle concentrations in pizzerias can be very high, especially when compared to other critical microenvironments, such as the transport hubs. During pizza cooking under normal ventilation conditions, concentrations were found up to 74, 70 and 23 times higher than background levels for number, surface area and PM1, respectively. A key parameter is the oven shape factor, defined as the ratio between the size of the face opening in respect to the diameter of the semicircular oven door, and particular attention must also be paid to hood efficiency.
Keywords: Particle exposure; Surface area concentration; Indoor aerosol; Particle number concentration; Pizzeria;

Aromatic hydrocarbons are important constituents of vehicle exhaust and of non-methane volatile organic compounds in ambient air in urban areas. It has recently been proposed that dealkylation is a significant pathway for the OH radical-initiated reactions, leading to the formation of phenolic compounds and/or oxepins (Noda, J., Volkamer, R., Molina, M.J., 2009. Dealkylation of alkylbenzenes: a significant pathway in the toluene, o-, m-, and p-xylene + OH reaction. Journal of Physical Chemistry A 113, 9658–9666.). We have investigated the formation of cresols from the reactions of OH radicals with m-xylene and p-cymene, and obtain upper limits of <1% for formation of each cresol isomer from OH +  m-xylene and <2% for formation of each cresol isomer from OH +  p-cymene. In addition, we have measured the formation yield of 4-methylacetophenone (the major product formed subsequent to H-atom abstraction from the CH(CH3)2 group) in the OH +  p-cymene reaction to be 14.8 ± 3.2%, and estimate that H-atom abstraction from the CH3 and CH(CH3)2 groups in p-cymene accounts for 20 ± 4% of the overall OH radical reaction. We also used a relative rate technique to measure the rate constant for the reaction of OH radicals with 4-methylacetophenone to be (4.50 ± 0.43) × 10−12  cm3 molecule−1  s−1 at 297 ± 2 K.
Keywords: Hydroxyl radical; m-Xylene; p-Cymene; 4-Methylacetophenone; Cresol; Abstraction;

We applied a multiple linear regression (MLR) model to study the correlations of total PM2.5 and its components with meteorological variables using an 11-year (1998–2008) observational record over the contiguous US. The data were deseasonalized and detrended to focus on synoptic-scale correlations. We find that daily variation in meteorology as described by the MLR can explain up to 50% of PM2.5 variability with temperature, relative humidity (RH), precipitation, and circulation all being important predictors. Temperature is positively correlated with sulfate, organic carbon (OC) and elemental carbon (EC) almost everywhere. The correlation of nitrate with temperature is negative in the Southeast but positive in California and the Great Plains. RH is positively correlated with sulfate and nitrate, but negatively with OC and EC. Precipitation is strongly negatively correlated with all PM2.5 components. We find that PM2.5 concentrations are on average 2.6 μg m−3 higher on stagnant vs. non-stagnant days. Our observed correlations provide a test for chemical transport models used to simulate the sensitivity of PM2.5 to climate change. They point to the importance of adequately representing the temperature dependence of agricultural, biogenic and wildfire emissions in these models.
Keywords: PM2.5; Climate change; Meteorology; Multiple linear regression; Stagnation;

A new inventory for two-wheel vehicle emissions in West Africa for 2002 by Eric-Michel Assamoi; Catherine Liousse (3985-3996).
Keywords: Black carbon; Primary organic carbon; Emission inventory; West Africa; Two-wheel vehicles and motorcycle-taxis;