scholarly journals Source Apportionment of Aerosols by 14C Measurements in Different Carbonaceous Particle Fractions

Radiocarbon ◽  
2004 ◽  
Vol 46 (1) ◽  
pp. 475-484 ◽  
Author(s):  
S Szidat ◽  
T M Jenk ◽  
H W Gäggeler ◽  
H-A Synal ◽  
R Fisseha ◽  
...  

Radiocarbon enables a distinction between contemporary and fossil carbon, which can be used for the apportionment of biogenic and anthropogenic sources in environmental studies. In order to apply this approach to carbonaceous atmospheric aerosols, it is necessary to adapt pretreatment procedures to the requirements of 14C measurements. In this work, we followed an approach in which total carbon (TC) is subdivided into fractions of different chemical and physical properties. 14C data of ambient aerosols from Zürich (Switzerland) are presented for the 2 sub-fractions of TC, organic carbon (OC) and elemental carbon (EC). Furthermore, OC is separated into water-insoluble OC (WINSOC) and water-soluble OC (WSOC). Results demonstrate the importance to differentiate between these fractions for 14C-deduced source apportionment, as the contributions can range between both extremes, nearly exclusively biogenic and anthropogenic.

2011 ◽  
Vol 11 (22) ◽  
pp. 11387-11400 ◽  
Author(s):  
J. Genberg ◽  
M. Hyder ◽  
K. Stenström ◽  
R. Bergström ◽  
D. Simpson ◽  
...  

Abstract. A one-year study was performed at the Vavihill background station in southern Sweden to estimate the anthropogenic contribution to the carbonaceous aerosol. Weekly samples of the particulate matter PM10 were collected on quartz filters, and the amounts of organic carbon, elemental carbon, radiocarbon (14C) and levoglucosan were measured. This approach enabled source apportionment of the total carbon in the PM10 fraction using the concentration ratios of the sources. The sources considered in this study were emissions from the combustion of fossil fuels and biomass, as well as biogenic sources. During the summer, the carbonaceous aerosol mass was dominated by compounds of biogenic origin (80%), which are associated with biogenic primary and secondary organic aerosols. During the winter months, biomass combustion (32%) and fossil fuel combustion (28%) were the main contributors to the carbonaceous aerosol. Elemental carbon concentrations in winter were about twice as large as during summer, and can be attributed to biomass combustion, probably from domestic wood burning. The contribution of fossil fuels to elemental carbon was stable throughout the year, although the fossil contribution to organic carbon increased during the winter. Thus, the organic aerosol originated mainly from natural sources during the summer and from anthropogenic sources during the winter. The result of this source apportionment was compared with results from the EMEP MSC-W chemical transport model. The model and measurements were generally consistent for total atmospheric organic carbon, however, the contribution of the sources varied substantially. E.g. the biomass burning contributions of OC were underestimated by the model by a factor of 2.2 compared to the measurements.


2011 ◽  
Vol 11 (5) ◽  
pp. 13575-13616 ◽  
Author(s):  
J. Genberg ◽  
M. Hyder ◽  
K. Stenström ◽  
R. Bergström ◽  
D. Simpson ◽  
...  

Abstract. A one-year study was performed at the Vavihill background station in southern Sweden to estimate the anthropogenic contribution to the carbonaceous aerosol. Weekly samples of the particulate matter PM10 were collected on quartz filters, and the amounts of organic carbon, elemental carbon, radiocarbon (14C) and levoglucosan were measured. This approach enabled source apportionment of the total carbon in the PM10 fraction using the concentration ratios of the sources. The sources considered in this study were emissions from the combustion of fossil fuels and biomass, as well as biogenic sources. During the summer, the carbonaceous aerosol mass was dominated by compounds of biogenic origin (82 %), which are associated with biogenic primary and secondary organic aerosols. During the winter months, biomass combustion (38 %) and fossil fuel combustion (33 %) were the main contributors to the carbonaceous aerosol. Elemental carbon concentrations in winter were about twice as large as during summer, and can be attributed to biomass combustion, probably from domestic wood burning. The contribution of fossil fuels to elemental carbon was stable throughout the year, although the fossil contribution to organic carbon increased during the winter. Thus, the organic aerosol originated mainly from natural sources during the summer and from anthropogenic sources during the winter. The result of this source apportionment was compared with results from the EMEP model. The model and measurements were generally consistent for total atmospheric organic carbon, however, the contribution of the sources varied substantially. E.g. the biomass burning contributions of OC were underestimated by the model by a factor of 8.2 compared to the measurements.


2015 ◽  
Vol 15 (23) ◽  
pp. 34949-34979 ◽  
Author(s):  
J. Liu ◽  
J. Li ◽  
D. Liu ◽  
P. Ding ◽  
C. Shen ◽  
...  

Abstract. Fine carbonaceous aerosols (CAs) is the key factor influencing the currently filthy air in megacities of China, yet seldom study simultaneously focuses on the origins of different CAs species using specific and powerful source tracers. Here, we present a detailed source apportionment for various CAs fractions, including organic carbon (OC), water-soluble OC (WSOC), water-insoluble OC (WIOC), elemental carbon (EC) and secondary OC (SOC) in the largest cities of North (Beijing, BJ) and South China (Guangzhou, GZ), respectively, using the measurements of radiocarbon and anhydrosugars. Results show that non-fossil fuel sources such as biomass burning and biogenic emission make a significant contribution to the total CAs in Chinese megacities: 56 ± 4 % in BJ and 46 ± 5 % in GZ, respectively. The relative contributions of primary fossil carbon from coal and liquid petroleum combustions, primary non-fossil carbon and secondary organic carbon (SOC) to total carbon are 19, 28 and 54 % in BJ, and 40, 15 and 46 % in GZ, respectively. Non-fossil fuel sources account for 52 % in BJ and 71 % in GZ of SOC, respectively. These results suggest that biomass burning has a greater influence on regional particulate air pollution in North China than in South China. We observed an unabridged haze bloom–decay process in South China, which illustrates that both primary and secondary matter from fossil sources played a key role in the blooming phase of the pollution episode, while haze phase is predominantly driven by fossil-derived secondary organic matter and nitrate.


2016 ◽  
Vol 16 (5) ◽  
pp. 2985-2996 ◽  
Author(s):  
Junwen Liu ◽  
Jun Li ◽  
Di Liu ◽  
Ping Ding ◽  
Chengde Shen ◽  
...  

Abstract. Fine carbonaceous aerosols (CAs) is the key factor influencing the currently filthy air in megacities in China, yet few studies simultaneously focus on the origins of different CAs species using specific and powerful source tracers. Here, we present a detailed source apportionment for various CAs fractions, including organic carbon (OC), water-soluble OC (WSOC), water-insoluble OC (WIOC), elemental carbon (EC) and secondary OC (SOC) in the largest cities of North (Beijing, BJ) and South China (Guangzhou, GZ), using the measurements of radiocarbon and anhydrosugars. Results show that non-fossil fuel sources such as biomass burning and biogenic emission make a significant contribution to the total CAs in Chinese megacities: 56 ± 4 in BJ and 46 ± 5 % in GZ, respectively. The relative contributions of primary fossil carbon from coal and liquid petroleum combustions, primary non-fossil carbon and secondary organic carbon (SOC) to total carbon are 19, 28 and 54 % in BJ, and 40, 15 and 46 % in GZ, respectively. Non-fossil fuel sources account for 52 in BJ and 71 % in GZ of SOC, respectively. These results suggest that biomass burning has a greater influence on regional particulate air pollution in North China than in South China. We observed an unabridged haze bloom-decay process in South China, which illustrates that both primary and secondary matter from fossil sources played a key role in the blooming phase of the pollution episode, while haze phase is predominantly driven by fossil-derived secondary organic matter and nitrate.


Author(s):  
Xiaoyao Ma ◽  
Zhenghui Xiao ◽  
Lizhi He ◽  
Zongbo Shi ◽  
Yunjiang Cao ◽  
...  

Xiangtan, South China, is characterized by year-round high relative humidity and very low wind speeds. To assess levels of PM2.5, daily samples were collected from 2016 to 2017 at two urban sites. The mass concentrations of PM2.5 were in the range of 30–217 µg/m3, with the highest concentrations in winter and the lowest in spring. Major water-soluble ions (WSIIs) and total carbon (TC) accounted for 58–59% and 21–24% of the PM2.5 mass, respectively. Secondary inorganic ions (SO42−, NO3−, and NH4+) dominated the WSIIs and accounted for 73% and 74% at the two sites. The concentrations of K, Fe, Al, Sb, Ca, Zn, Mg, Pb, Ba, As, and Mn in the PM2.5 at the two sites were higher than 40 ng/m3, and decreased in the order of winter > autumn > spring. Enrichment factor analysis indicates that Co, Cu, Zn, As, Se, Cd, Sb, Tl, and Pb mainly originates from anthropogenic sources. Source apportionment analysis showed that secondary inorganic aerosols, vehicle exhaust, coal combustion and secondary aerosols, fugitive dust, industrial emissions, steel industry are the major sources of PM2.5, contributing 25–27%, 21–22%, 19–21%, 16–18%, 6–9%, and 8–9% to PM2.5 mass.


2009 ◽  
Vol 9 (5) ◽  
pp. 1521-1535 ◽  
Author(s):  
S. Szidat ◽  
M. Ruff ◽  
N. Perron ◽  
L. Wacker ◽  
H.-A. Synal ◽  
...  

Abstract. Particulate matter was collected at an urban site in Göteborg (Sweden) in February/March 2005 and in June/July 2006. Additional samples were collected at a rural site for the winter period. Total carbon (TC) concentrations were 2.1–3.6 μg m−3, 1.8–1.9 μg m−3, and 2.2–3.0 μg m−3 for urban/winter, rural/winter, and urban/summer conditions, respectively. Elemental carbon (EC), organic carbon (OC), water-insoluble OC (WINSOC), and water-soluble OC (WSOC) were analyzed for 14C in order to distinguish fossil from non-fossil emissions. As wood burning is the single major source of non-fossil EC, its contribution can be quantified directly. For non-fossil OC, the wood-burning fraction was determined independently by levoglucosan and 14C analysis and combined using Latin-hypercube sampling (LHS). For the winter period, the relative contribution of EC from wood burning to the total EC was >3 times higher at the rural site compared to the urban site, whereas the absolute concentrations of EC from wood burning were elevated only moderately at the rural compared to the urban site. Thus, the urban site is substantially more influenced by fossil EC emissions. For summer, biogenic emissions dominated OC concentrations most likely due to secondary organic aerosol (SOA) formation. During both seasons, a more pronounced fossil signal was observed for Göteborg than has previously been reported for Zurich, Switzerland. Analysis of air mass origin using back trajectories suggests that the fossil impact was larger when local sources dominated, whereas long-range transport caused an enhanced non-fossil signal. In comparison to other European locations, concentrations of levoglucosan and other monosaccharide anhydrides were low for the urban and the rural site in the area of Göteborg during winter.


2021 ◽  
Author(s):  
Peng Yao ◽  
Haiyan Ni ◽  
Norbertas Kairys ◽  
Lu Yang ◽  
Ru-Jin Huang ◽  
...  

<p>Isotopic source apportionment is commonly used to gain insight into sources and atmospheric processing of carbonaceous aerosols. Since elemental carbon (EC) is chemically stable, it is possible to apportion the main sources of EC (coal/biomass burning and traffic emissions) using a dual <sup>14</sup>C-<sup>13</sup>C isotope approach. However, dual-isotope source apportionment crucially relies on accurate knowledge of the <sup>13</sup>C source signatures, which are seldom measured directly for EC. In this work, we present extensive measurements of organic carbon (OC) and EC <sup>13</sup>C signatures for relevant sources in China. The EC <sup>13</sup>C source signatures are provided first time using the optical split point in a thermal-optical analyzer to isolate EC, which can greatly reduce the influence of pyrolyzed organic carbon (pOC). A series of sensitivity studies (pOC/EC separation) were conducted to investigate the reliability of our method and its relation to other EC isolation methods. Meanwhile, we summarized and compared the literature <sup>13</sup>C signatures in detail of raw source materials, total carbon (TC) and EC using a variety of thermal methods. Finally, we recommend composite EC <sup>13</sup>C source signatures with uncertainties and detailed application conditions. There are two points worth noting. First, the traffic <sup>13</sup>C signatures of raw materials and EC are separated into three groups according to geographical distribution. Second, the EC <sup>13</sup>C signature of C4 plant combustion can be influenced greatly if pOC and EC are not well separated, so the thermal-optical method is necessary. Using these EC <sup>13</sup>C source signatures in an exemplary dual-isotope source apportionment study shows improvement in precision. In addition, some interesting distinct and repeatable patterns were discovered in <sup>13</sup>C source signatures of semi-volatile, low-volatile, and non-volatile primary OC fractions.</p>


2013 ◽  
Vol 13 (20) ◽  
pp. 10325-10338 ◽  
Author(s):  
S. L. Mkoma ◽  
K. Kawamura ◽  
P. Q. Fu

Abstract. Atmospheric aerosol samples of PM2.5 and PM10 were collected at a rural site in Tanzania, East Africa, in 2011 during wet and dry seasons and were analysed for carbonaceous components, levoglucosan, mannosan and water-soluble inorganic ions. The contributions of biomass/biofuel burning to the organic carbon (OC) and particulate matter (PM) mass were estimated to be 46–52% and 87–13%, respectively. The mean mass concentrations of PM2.5 and PM10 were 28 ± 6 μg m−3 and 47 ± 8 μg m−3 in wet season, and 39 ± 10 μg m−3 and 61 ± 19 μg m−3 in dry season, respectively. Total carbon (TC) accounted for 16–19% of the PM2.5 mass and 13–15% of the PM10 mass. On average, 86 to 89% of TC in PM2.5 and 87 to 90% of TC in PM10 was OC, of which 67–72% and 63% was found to be water-soluble organic carbon (WSOC) in PM2.5 and PM10, respectively. We found that concentrations of levoglucosan and mannosan (specific organic tracers of pyrolysis of cellulose) well correlated with non-sea-salt potassium (nss-K+) (r2 = 0.56–0.75), OC (r2 = 0.75–0.96) and WSOC (r2 = 0.52–0.78). The K+ / OC ratios varied from 0.06 to 0.36 in PM2.5 and from 0.03 to 0.36 in PM10 with slightly higher ratios in dry season. Mean percent ratios of levoglucosan and mannosan to OC were found to be 3–4% for PM2.5 and PM10 in both seasons. We found lower levoglucosan / K+ ratios and higher K+ / EC (elemental carbon) ratios in the biomass-burning aerosols from Tanzania than those reported from other regions. This feature is consistent with the high levels of potassium reported in the soils of Morogoro, Tanzania, suggesting an importance of direct emission of potassium by soil resuspension although K+ is present mostly in fine particles. It is also likely that biomass burning of vegetation of Tanzania emits high levels of potassium that may be enriched in plant tissues. The present study demonstrates that emissions from mixed biomass- and biofuel-burning activities largely influence the air quality in Tanzania.


2012 ◽  
Vol 12 (22) ◽  
pp. 10841-10856 ◽  
Author(s):  
Y. L. Zhang ◽  
N. Perron ◽  
V. G. Ciobanu ◽  
P. Zotter ◽  
M. C. Minguillón ◽  
...  

Abstract. Radiocarbon (14C) measurements of elemental carbon (EC) and organic carbon (OC) separately (as opposed to only total carbon, TC) allow an unambiguous quantification of their non-fossil and fossil sources and represent an improvement in carbonaceous aerosol source apportionment. Isolation of OC and EC for accurate 14C determination requires complete removal of interfering fractions with maximum recovery. The optimal strategy for 14C-based source apportionment of carbonaceous aerosols should follow an approach to subdivide TC into different carbonaceous aerosol fractions for individual 14C analyses, as these fractions may differ in their origins. To evaluate the extent of positive and negative artefacts during OC and EC separation, we performed sample preparation with a commercial Thermo-Optical OC/EC Analyser (TOA) by monitoring the optical properties of the sample during the thermal treatments. Extensive attention has been devoted to the set-up of TOA conditions, in particular, heating program and choice of carrier gas. Based on different types of carbonaceous aerosols samples, an optimised TOA protocol (Swiss_4S) with four steps is developed to minimise the charring of OC, the premature combustion of EC and thus artefacts of 14C-based source apportionment of EC. For the isolation of EC for 14C analysis, the water-extraction treatment on the filter prior to any thermal treatment is an essential prerequisite for subsequent radiocarbon measurements; otherwise the non-fossil contribution may be overestimated due to the positive bias from charring. The Swiss_4S protocol involves the following consecutive four steps (S1, S2, S3 and S4): (1) S1 in pure oxygen (O2) at 375 °C for separation of OC for untreated filters and water-insoluble organic carbon (WINSOC) for water-extracted filters; (2) S2 in O2 at 475 °C followed by (3) S3 in helium (He) at 650 °C, aiming at complete OC removal before EC isolation and leading to better consistency with thermal-optical protocols like EUSAAR_2, compared to pure oxygen methods; and (4) S4 in O2 at 760 °C for recovery of the remaining EC. WINSOC was found to have a significantly higher fossil contribution than the water-soluble OC (WSOC). Moreover, the experimental results demonstrate the lower refractivity of wood-burning EC compared to fossil EC and the difficulty of clearly isolating EC without premature evolution. Hence, simplified techniques of EC isolation for 14C analysis are prone to a substantial bias and generally tend towards an overestimation of fossil sources. To obtain the comprehensive picture of the sources of carbonaceous aerosols, the Swiss_4S protocol is not only implemented to measure OC and EC fractions, but also WINSOC as well as a continuum of refractory OC and non-refractory EC for 14C source apportionment. In addition, WSOC can be determined by subtraction of the water-soluble fraction of TC from untreated TC. Last, we recommend that 14C results of EC should in general be reported together with the EC recovery.


2012 ◽  
Vol 12 (7) ◽  
pp. 17657-17702 ◽  
Author(s):  
Y. L. Zhang ◽  
N. Perron ◽  
V. G. Ciobanu ◽  
P. Zotter ◽  
M. C. Minguillón ◽  
...  

Abstract. Radiocarbon (14C) measurements of elemental carbon (EC) and organic carbon (OC) separately (as opposed to only total carbon, TC) allow an unambiguous quantification of their non-fossil and fossil sources and represent an improvement in carbonaceous aerosol source apportionment. Isolation of OC and EC for accurate 14C determination requires complete removal of interfering fractions with maximum recovery. To evaluate the extent of positive and negative artefacts during OC and EC separation, we performed sample preparation with a commercial Thermo-Optical OC/EC Analyser (TOA) by monitoring the optical properties of the sample during the thermal treatments. Extensive attention has been devoted to the set-up of TOA conditions, in particular, heating program and choice of carrier gas. Based on different types of carbonaceous aerosols samples, an optimised TOA protocol (Swiss_4S) with four steps is developed to minimise the charring of OC, the premature combustion of EC and thus artefacts of 14C-based source apportionment of EC. For the isolation of EC for 14C analysis, the water-extraction treatment on the filter prior to any thermal treatment is an essential prerequisite for subsequent radiocarbon; otherwise the non-fossil contribution may be overestimated due to the positive bias from charring. The Swiss_4S protocol involves the following consecutive four steps (S1, S2, S3 and S4): (1) S1 in pure oxygen (O2) at 375 °C for separation of OC for untreated filters, and water-insoluble organic carbon (WINSOC) for water-extracted filters; (2) S2 in O2 at 475 °C, followed by (3) S3 in helium (He) at 650 °C, aiming at complete OC removal before EC isolation and leading to better consistency with thermal-optical protocols like EUSAAR_2, compared to pure oxygen methods; and (4) S4 in O2 at 760 °C for recovery of the remaining EC. WINSOC was found to have a significantly higher fossil contribution than the water-soluble OC (WSOC). Moreover, the experimental results demonstrate the lower refractivity of wood-burning EC compared to fossil EC and the difficulty of clearly isolating EC without premature evolution. Hence, simplified techniques of EC isolation for 14C analysis are prone to a substantial bias and generally tend towards an underestimation of the non-fossil sources. Consequently, the optimal strategy for 14C-based source apportionment of carbonaceous aerosols should follow an approach to subdivide TC into different carbonaceous aerosol fractions for individual 14C analyses, as these fractions differ in their origins. To obtain the comprehensive picture of the sources of carbonaceous aerosols, the Swiss_4S protocol is not only implemented to measure OC and EC fractions, but also WINSOC as well as a continuum of refractory OC and non-refractory EC for 14C source apportionment. In addition, WSOC can be determined by subtraction of the water-soluble fraction of TC from untreated TC. Last, we recommend that 14C results of EC should in general be reported together with the EC recovery.


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