Fine Organic Carbon Research Articles

Source apportionment of fine organic carbon at an urban site of Beijing using a chemical mass balance model

Abstract. Fine particles were sampled from 9 November to 11 December 2016 and 22 May to 24 June 2017 as part of the Atmospheric Pollution and Human Health in a Chinese Megacity (APHH-China) field campaigns in urban Beijing, China. Inorganic ions, trace elements, organic carbon (OC), elemental carbon (EC), and organic compounds, including biomarkers, hopanes, polycyclic aromatic hydrocarbons (PAHs), n-alkanes, and fatty acids, were determined for source apportionment in this study. Carbonaceous components contributed on average 47.2 % and 35.2 % of total reconstructed PM2.5 during the winter and summer campaigns, respectively. Secondary inorganic ions (sulfate, nitrate, ammonium; SNA) accounted for 35.0 % and 45.2 % of total PM2.5 in winter and summer. Other components including inorganic ions (K+, Na+, Cl−), geological minerals, and trace metals only contributed 13.2 % and 12.4 % of PM2.5 during the winter and summer campaigns. Fine OC was explained by seven primary sources (industrial and residential coal burning, biomass burning, gasoline and diesel vehicles, cooking, and vegetative detritus) based on a chemical mass balance (CMB) receptor model. It explained an average of 75.7 % and 56.1 % of fine OC in winter and summer, respectively. Other (unexplained) OC was compared with the secondary OC (SOC) estimated by the EC-tracer method, with correlation coefficients (R2) of 0.58 and 0.73 and slopes of 1.16 and 0.80 in winter and summer, respectively. This suggests that the unexplained OC by the CMB model was mostly associated with SOC. PM2.5 apportioned by the CMB model showed that the SNA and secondary organic matter were the two highest contributors to PM2.5. After these, coal combustion and biomass burning were also significant sources of PM2.5 in winter. The CMB results were also compared with results from the positive matrix factorization (PMF) analysis of co-located aerosol mass spectrometer (AMS) data. The CMB model was found to resolve more primary organic aerosol (OA) sources than AMS-PMF, but the latter could apportion secondary OA sources. The AMS-PMF results for major components, such as coal combustion OC and oxidized OC, correlated well with the results from the CMB model. However, discrepancies and poor agreements were found for other OC sources, such as biomass burning and cooking, some of which were not identified in AMS-PMF factors.

Source apportionment of fine organic carbon (OC) using receptor modelling at a rural site of Beijing: Insight into seasonal and diurnal variation of source contributions

This study was designed to investigate the seasonal characteristics and apportion the sources of organic carbon during non-haze days (<75 μg m−3) and haze (≥75 μg m−3) events at Pinggu, a rural Beijing site. Time-resolved concentrations of carbonaceous aerosols and organic molecular tracers were measured during the winter of 2016 and summer 2017, and a Chemical Mass Balance (CMB) model was applied to estimate the average source contributions. The concentration of OC in winter is comparable with previous studies, but relatively low during the summer. The CMB model apportioned seven separate primary sources, which explained on average 73.8% on haze days and 81.2% on non-haze days of the organic carbon in winter, including vegetative detritus, biomass burning, gasoline vehicles, diesel vehicles, industrial coal combustion, residential coal combustion and cooking. A slightly lower percentage of OC was apportioned in the summer campaign with 64.5% and 78.7% accounted for. The other unapportioned OC is considered to consist of secondary organic carbon (SOC). During haze episodes in winter, coal combustion and SOC were the dominant sources of organic carbon with 23.3% and 26.2%, respectively, followed by biomass burning emissions (20%), whereas in summer, industrial coal combustion and SOC were important contributors. Diurnal contribution cycles for coal combustion and biomass burning OC showed a peak at 6–9 pm, suggesting domestic heating and cooking were the main sources of organic aerosols in this rural area. Backward trajectory analysis showed that high OC concentrations were measured when the air mass was from the south, suggesting that the organic aerosols in Pinggu were affected by both local emissions and regional transport from central Beijing and Hebei province during haze episodes. The source apportionment by CMB is compared with the results of a Positive Matrix Factorization (PMF) analysis of ACSM data for non-refractory PM1, showing generally good agreement.

Cover crops in the Southeastern region of Buenos Aires, Argentina: effects on organic matter physical fractions and nutrient availability

In the Southeastern region of Buenos Aires province, soybean monoculture has led to a decline in soil organic matter (SOM) levels in soil, mostly the labile fractions. The reduction of SOM has a negative impact on the soil environment. Cover crops (CC) constitute an alternative to maintain or improve SOM levels. The aim of this study was to determine the effect of oat as CC on (a) the SOM dynamics and (b) the availability of macro- and micronutrients in a representative soil of the Southeastern region of Buenos Aires province. Total organic carbon (TOC) and nitrogen (TON), as well as their labile and mineral-associated fractions, and macro- and micronutrient availability were determined. The treatments were soybean monoculture with and without oat as cover crop. The increases in SOC and TON were 22.7% and 11%, respectively, when CC was included to the soybean monoculture. These increases were observed mostly in the labile fractions, with increases of 61.3 and 38.7% for the particulate coarse organic carbon (PCOf) and particulate fine organic carbon (PCOf), respectively, and 79.2% for the particulate coarse organic nitrogen (NOPg). Regarding the nutrients, an increase of 47.6% was observed in manganese (Mn) in the first 5 cm of soil depth, and a decrease in phosphorous (P) availability in the same soil layer due to its consumption and retention by CC. It can be conclude that CC presented a surface soil effect on the dynamic of SOM, increasing C, N, and available Mn contents, but decreasing soil P availability.

Chemical characteristics and source apportionment of fine particulate organic carbon in Hong Kong during high particulate matter episodes in winter 2003

PM2.5 samples were collected at six general stations and one roadside station in Hong Kong in two periods of high particulate matter (PM) in 2003 (27 October–4 November and 30 November–13 December). The highest PM2.5 reached 216μgm−3 during the first high PM period and 113μgm−3 during the second high PM period. Analysis of synoptic weather conditions identified individual sampling days under dominant influence of one of three types of air masses, that is, local, regional and long‐range transported (LRT) air masses. Roadside samples were discussed separately due to heavy influences from vehicular emissions. This research examines source apportionment of fine organic carbon (OC) and contribution of secondary organic aerosol on high PM days under different synoptic conditions. Six primary OC (POC) sources (vehicle exhaust, biomass burning, cooking, cigarette smoke, vegetative detritus, and coal combustion) were identified on the basis of characteristic organic tracers. Individual POC source contributions were estimated using chemical mass balance model. In the roadside and the local samples, OC was dominated by the primary sources, accounting for more than 74% of OC. In the samples influenced by regional and LRT air masses, secondary OC (SOC), which was approximated to be the difference between the total measured OC and the apportioned POC, contributed more than 54% of fine OC. SOC was highly correlated with water‐soluble organic carbon and sulfate, consistent with its secondary nature.

Characterization, sources and redox activity of fine and coarse particulate matter in Milan, Italy

Abstract The correlation between health effects and exposure to particulate matter (PM) has been of primary concern to public health organizations. An emerging hypothesis is that many of the biological effects derive from the ability of PM to generate reactive oxygen species (ROS) within affected cells. Milan, one of the largest and most polluted urban areas in Europe, is afflicted with high particle levels. To characterize its ambient PM, fine and coarse PM (PM2.5 and PM2.5–10, respectively) samples were collected on a weekly basis for a year-long period. Samples were analyzed for their chemical properties and ROS-activity. A molecular marker chemical mass balance (MM-CMB) model was also applied to apportion primary and secondary sources to fine organic carbon (OC) and PM. Findings revealed that PM2.5 is a major contributor to ambient particle levels in Milan, averaging 34.5 ± 19.4 μg m−3 throughout the year. Specifically, secondary inorganic ions and organic matter were the most dominant fine PM species contributing to 36 ± 7.1% and 34 ± 6.3% of its mass on a yearly-based average, respectively. Highest PM2.5 concentrations occurred during December–February and were mainly attributed to poor atmospheric dispersion. On the other hand, PM2.5–10 exhibited an annual average of 6.79 ± 1.67 μg m−3, with crustal elements prevailing. Source apportionment results showed that wood-smoke and secondary organic aerosol sources contribute to 4.6 ± 2.6% and 9.8 ± 11% of fine OC on a yearly-based average, respectively. The remaining OC is likely associated with petroleum-derived material that is not adequately represented by existing source profiles used in this study. Lastly, ROS-activity measurements indicated that PM2.5-induced redox activity expressed per m3 of air volume is greatest during January (837 μg Zymosan equivalents m−3) and February (920 μg Zymosan equivalents m−3). Conversely, intrinsic (per PM mass) ROS-activity peaked in July (22,587 μg Zymosan equivalents mg−1 PM) and August (25,161 μg Zymosan equivalents mg−1 PM), suggesting the influence of specific components on oxidant properties of PM. A correlation analysis between ROS-activity and select PM chemical components showed that Ni, Cr, Cu and water-soluble OC are strongly associated with ROS.

Sedimentation and burial of organic and inorganic temperature proxies in the Mozambique Channel, SW Indian Ocean

Paleoceanographic studies strongly rely on proxies to reconstruct past environmental conditions. However, several factors influence the reliability of these proxies, particularly during sedimentation and burial. In this study, we measured both inorganic (δ 18O and Mg/Ca on three species of planktonic foraminifera ( Globigerinoides ruber, Globigerinoides trilobus and Neogloboquadrina dutertrei) and organic ( U 37 k ′ and TEX 86) sea surface temperature (SST) proxies on core top sediment taken from an east-west transect across the Mozambique Channel. We contrast our findings with previously published modern time-series temperature proxy data from a sediment trap moored in the mid-channel. The coretop sediment was analyzed for 14C, 210Pb and excess (xs) 234Th. While 234Th xs data indicate a flux of fresh particulate matter to the bottom sediment, radiocarbon dating shows that the core top sediments are composed of material that is on average about 1000 years old. The fine organic carbon is consistently (even though only slightly) younger than the coarser foraminiferal calcite, which is likely caused by preferential downcore mixing of the fine fraction. Besides vertical mixing by bioturbation, stable lead isotope ratios from the time-series particle fluxes indicate episodic lateral transport of old particles from the shelf to the deep Mozambique Channel as an additional source of pre-aged material in core tops. Core top temperature proxies show warmer values close to the channel flanks while colder values are found in the mid-channel. These could be associated with higher maximum summer temperatures in modern coastal waters in contrast to the mid-channel. Additionally, we find an offset in all foraminiferal proxies between core top samples and time-series data that corresponds to 1–3 °C, which probably reflects climate variability over the past ∼2000 years. However, this temperature difference is not observed in the organic proxies U 37 k ′ and TEX 86, which may result from current transport of unconsolidated organic matter that can homogenize the organic proxy signal prior to burial.

Speciation of ambient fine organic carbon particles and source apportionment of PM2.5 in Indian cities

Fine particle organic carbon in Delhi, Mumbai, Kolkata, and Chandigarh is speciated to quantify sources contributing to fine particle pollution. Gas chromatography/mass spectrometry of 29 particle‐phase organic compounds, including n‐alkanes, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, and levoglucosan along with quantification of silicon, aluminum, and elemental carbon are used in a molecular‐marker based source apportionment model to quantify the primary source contributions to the PM2.5 mass concentrations for four seasons in three sites and for the summer in Chandigarh. Five primary sources are identified and quantified: diesel engine exhaust, gasoline engine exhaust, road dust, coal combustion, and biomass combustion. Important trends in the seasonal and spatial patterns of the impact of these five sources are observed. On average, primary emissions from fossil fuel combustion (coal, diesel, and gasoline) are responsible for about 25–33% of PM2.5 mass in Delhi, 21–36% in Mumbai, 37–57% in Kolkata, and 28% in Chandigarh. These figures can be compared to the biomass combustion contributions to ambient PM2.5 of 7–20% for Delhi, 7–20% for Mumbai, 13–18% for Kolkata, and 8% for Chandigarh. These measurements provide important information about the seasonal and spatial distribution of fine particle phase organic compounds in Indian cities as well as quantifying source contributions leading to the fine particle air pollution in those cities.

Composition and sources of carbonaceous aerosols at three contrasting sites in Hong Kong

A significant fraction of the fine particulate matter in Hong Kong is made up of organic carbon. In order to quantitatively assess the contributions of various sources to carbonaceous aerosol in Hong Kong, a chemical mass balance (CMB) receptor model in combination with organic tracers was employed. Organic tracers including n‐alkanes, polycyclic aromatic hydrocarbons (PAHs), steranes, hopanes, resin acids, cholesterol, levoglucosan, and picene in PM2.5 collected from three air monitoring sites located at roadside, urban, and rural areas in Hong Kong are quantified using gas chromatography‐mass spectrometry (GC/MS) in the present study. Analyses of some overlapping species from two separate laboratories will be compared for the first time. Spatial and seasonal source contributions to organic carbon (OC) in PM2.5 from up to nine air pollution sources are assessed, including diesel engine exhaust, gasoline engine exhaust, meat cooking, cigarette smoke, biomass burning, road dust, vegetative detritus, coal combustion, and natural gas combustion. Diesel engine exhaust dominated fine organic carbon in Hong Kong (57 ± 13% at urban sites and 25 ± 2% at the rural site). Other sources that play an important role are meat cooking and biomass burning, which can account for as much as 14% of fine organic carbon. The primary sources identified by this technique explained 49%, 79%, and 94% of the measured fine organic carbon mass concentration at the rural, the urban, and the roadside sites, respectively. The unexplained fine OC is likely due to secondary organic aerosol formation.

Characterization of nanoparticles of organic carbon (NOC) produced in rich premixed flames by differential mobility analysis

Differential mobility analysis (DMA) is used to measure on-line the size distributions of inception particles in atmospheric pressure premixed ethylene air flames ranging from C/O = 0.61 to 0.69, just at the onset of soot formation. DMA is also used, in combination with electrospray, to measure the size distributions of suspended flame products captured in water samples. The DMA systems used for this work employ detectors sensitive to the full range of molecular clusters/nanoparticles in gas-to-particle conversion processes (as small as about 1 nm) and they have much larger sheath gas flow rates than is typically used to reduce losses and peak broadening by diffusion. The measured size distributions show that the first particles observed in flames have a size of 2 nm, consistent with previous in situ measurements by light scattering and extinction (LSE) and the off-line measurements of material captured in water samples from the same flames. For richer flames, the quantity of the 2 nm particles measured increases, and the width of its size distribution shifts asymmetrically toward larger sizes. A numerical coagulation model assuming size-dependent coagulation efficiency predicts well the experimentally measured size distributions in the flames examined. Similarly, the slightly larger size distributions measured by atomic force microscopy of inception particles deposited on surfaces can also be attributed to the size-dependent coagulation/adhesion efficiency. The results imply that the smaller nanoparticles formed in combustion processes have a longer lifetime than those larger than 6–7 nm and may play an important role in the formation of fine organic carbon particulate in the atmosphere.

Seasonal trends in PM2.5 source contributions in Beijing, China

The 24-h PM2.5 samples (particles with an aerodynamic diameter of 2.5 μm or less) were taken at 6-day intervals at five urban and rural sites simultaneously in Beijing, China for 1 month in each quarter of calendar year 2000. Samples at each site were combined into a monthly composite for the organic tracer analysis by GC/MS (gas chromatography/mass spectrometry). Compared to the data obtained from other metropolitan cities in the US, the PM2.5 mass and fine organic carbon (OC) concentrations in Beijing were much higher with an annual average of 101 and 20.9 μg m^(−3), respectively. Over one hundred organic compounds including unique tracers for important sources were quantified in PM2.5 in Beijing. Source apportionment of fine OC was conducted using chemical mass balance receptor model (CMB) in combination with particle-phase organic compounds as fitting tracers. Carbonaceous aerosols and major ions (sulfate, nitrate and ammonium) constituted 69% of PM2.5 mass on average. The major sources of PM2.5 mass in Beijing averaged over five sites on an annual basis were determined as dust (20%), secondary sulfate (17%), secondary nitrate (10%), coal combustion (7%), diesel and gasoline exhaust (7%), secondary ammonium (6%), biomass aerosol (6%), cigarette smoke (1%), and vegetative detritus (1%). The lowest PM2.5 mass concentration was found in January (60.9 μg m^(−3)), but the contribution of carbonaceous aerosol to PM2.5 mass was maximal during this season, accounting for 57% of the mass. During cold heating season, the contributions from coal combustion and biomass aerosol to PM2.5 mass increased, accounting for 20.9% of fine particle mass in October and 24.5% in January. The contribution of the biomass aerosols peaked in the fall. In April 2000, the impact of dust storms was so significant that dust alone constituted 36% of PM2.5 mass. On average, the model resolved 88% of the sources of the PM2.5 mass concentrations in Beijing.

Source apportionment of PM2.5 in the Southeastern United States using solvent-extractable organic compounds as tracers.

A chemical mass balance (CMB) receptor model using particle-phase organic compounds as tracers is applied to apportion the primary source contributions to fine particulate matter and fine particulate organic carbon concentrations in the southeastern United States to determine the seasonal variability of these concentrations. Source contributions to particles with aerodynamic diameter < or =2.5 microm (PM2.5) collected from four urban and four rural/suburban sites in AL, FL, GA, and MS during April, July, and October 1999 and January 2000 are calculated and presented. Organic compounds in monthly composite samples at each site are identified and quantified by gas chromatography/mass spectrometry and are used as molecular markers in the CMB model. The major contributors to identified PM2.5 organic carbon concentrations at these sites in the southeastern United States include wood combustion (25-66%), diesel exhaust (14-30%), meat cooking (5-12%), and gasoline-powered motor vehicle exhaust (0-10%), as well as smaller but statistically significant contributions from natural gas combustion, paved road dust, and vegetative detritus. The primary sources determined in the present study when added to secondary aerosol formation account for on average 89% of PM2.5 mass concentrations, with the major contributors to PM2.5 mass as secondary sulfate (30+/-6%), wood combustion (15+/-12%), diesel exhaust (16+/-7%), secondary ammonium (8+/-2%), secondary nitrate (4+/-3%), meat cooking (3+/-2%), gasoline-powered motor vehicle exhaust (2+/-2%), and road dust (2+/-2%). Distinct seasonality is observed in source contributions, including higher contributions from wood combustion during the colder months of October and January. In addition, higher percentages of unexplained fine organic carbon concentrations are observed in July, which are likely due to an increase in secondary organic aerosol formation during the summer season.

Sources of fine organic aerosol. 1. Charbroilers and meat cooking operations

Meat cooking operations are a major source of organic aerosol emissions to the urban atmosphere, comprising up to 21 % of the primary fine organic carbon particle emissions in the Los Angeles area. In the present study, the chemical composition of meat smoke aerosol is examined by high-resolution gas chromatography and gas chromatography/ mass spectrometry. The objective is to search for molecular markers that will confirm the presence of meat smoke aerosol in urban atmospheric samples. More than 75 organic compounds are quantified, including the series of the n-alkanes, n-alkanoic acids, n-alkenoic acids, dicarboxylic acids, n-alkanals, n-alkenals, n-alkanones, n-alkanols, furans, lactones, amides, nitriles, polycyclic aromatic hydrocarbons, steroids, and pesticide residues. Prominent among the compounds emitted are n-hexadecanoic acid (i.e., palmitic acid), n-octadecanoic acid (i.e., stearic acid), cis-9-octadecenoic acid (i.e., oleic acid), nonanal, 2-octadecanal, 2-octadecanol, and cholesterol. Although cholesterol can be emitted from other sources, cholesterol concentrations measured in the West Los Angeles atmospheric aerosol are consistent with the cholesterol mass emission rates determined from meat cooking source tests.