scholarly journals Inter-comparison of elemental and organic carbon mass measurements from three North American national long-term monitoring networks at a co-located site

2019 ◽  
Vol 12 (8) ◽  
pp. 4543-4560 ◽  
Author(s):  
Tak W. Chan ◽  
Lin Huang ◽  
Kulbir Banwait ◽  
Wendy Zhang ◽  
Darrell Ernst ◽  
...  

Abstract. Carbonaceous aerosol is a major contributor to the total aerosol load and being monitored by diverse measurement approaches. Here, 10 years (2005–2015) of continuous carbonaceous aerosol measurements collected at the Centre of Atmospheric Research Experiments (CARE) in Egbert, Ontario, Canada, on quartz-fiber filters by three independent networks (Interagency Monitoring of Protected Visual Environments, IMPROVE; Canadian Air and Precipitation Monitoring Network, CAPMoN; and Canadian Aerosol Baseline Measurement, CABM) were compared. Specifically, the study evaluated how differences in sample collection and analysis affected the concentrations of total carbon (TC), organic carbon (OC), and elemental carbon (EC). Results show that different carbonaceous fractions measured by various networks were consistent and comparable in general among the three networks over the 10-year period, even with different sampling systems/frequencies, analytical protocols, and artifact corrections. The CAPMoN TC, OC, and EC obtained from the DRI model 2001 thermal–optical carbon analyzer following the IMPROVE-TOR protocol (denoted as DRI-TOR) method were lower than those determined from the IMPROVE_A TOR method by 17 %, 14 %, and 18 %, respectively. When using transmittance for charring correction, the corresponding carbonaceous fractions obtained from the Sunset-TOT were lower by as much as 30 %, 15 %, and 75 %, respectively. In comparison, the CABM TC, OC, and EC obtained from a thermal method, EnCan-Total-900 (ECT9), were higher than the corresponding fractions from IMPROVE_A TOR by 20 %–30 %, 0 %–15 %, and 60 %–80 %, respectively. Ambient OC and EC concentrations were found to increase when ambient temperature exceeded 10 ∘C. These increased ambient concentrations of OC during summer were possibly attributed to secondary organic aerosol (SOA) formation and forest fire emissions, while elevated EC concentrations were potentially influenced by forest fire emissions and increased vehicle emissions. Results also show that the pyrolyzed organic carbon (POC) obtained from the ECT9 protocol could provide additional information on SOA although more research is still needed.

2019 ◽  
Author(s):  
Tak W. Chan ◽  
Lin Huang ◽  
Kulbir Banwait ◽  
Wendy Zhang ◽  
Darrell Ernst ◽  
...  

Abstract. Carbonaceous aerosol is a major contributor to the total aerosol load and being monitored by diverse measurement approaches. Here, ten years of continuous carbonaceous aerosol measurements collected at the Centre of Atmospheric Research Experiments (CARE) in Egbert, Ontario, Canada on quartz filters by three independent networks (Interagency Monitoring of PROtected Visual Environments (IMPROVE), Canadian Air and Precipitation Monitoring Network (CAPMoN), and Canadian Aerosol Baseline Measurement (CABM)) were compared. Specifically, the study evaluated how differences in sample collection and analysis affected the yield of total carbon (TC), organic carbon (OC), and elemental carbon (EC). When all measurements were normalized with respect to concentration measured in a common reference year, OC measurements agreed to within 29–48 % and EC measurement to within 20 % amongst the different networks. Fitted with a sigmoid function, elevated OC and EC concentrations were found when ambient temperature exceeded 10 °C. These increased ambient concentrations of OC during summer were attributed to the secondary organic aerosol (SOA) formation and forest fire emissions, while elevated EC concentrations were attributed to forest fire emissions and increased vehicle emissions. The observations from this study suggest that carbonaceous aerosol measurements, especially EC, can be synchronized across networks if sample collection and analytical method in each network remain internally consistent. This study allows the generation of regional to continental-scale-harmonized concentration data sets for benchmarking of atmospheric chemical transport models that determine emission sources and sinks, and assess the effectiveness of government mitigation policies in improving air quality and reducing reliance on fossil fuel consumption.


2011 ◽  
Vol 11 (12) ◽  
pp. 5685-5700 ◽  
Author(s):  
S. Gilardoni ◽  
E. Vignati ◽  
F. Cavalli ◽  
J. P. Putaud ◽  
B. R. Larsen ◽  
...  

Abstract. The source contributions to carbonaceous PM2.5 aerosol were investigated at a European background site at the edge of the Po Valley, in Northern Italy, during the period January–December 2007. Carbonaceous aerosol was described as the sum of 8 source components: primary (1) and secondary (2) biomass burning organic carbon, biomass burning elemental carbon (3), primary (4) and secondary (5) fossil organic carbon, fossil fuel burning elemental carbon (6), primary (7) and secondary (8) biogenic organic carbon. The mass concentration of each component was quantified using a set of macro tracers (organic carbon OC, elemental carbon EC, and levoglucosan), micro tracers (arabitol and mannitol), and 14C measurements. This was the first time that 14C measurements covered a full annual cycle with daily resolution. This set of 6 tracers, together with assumed uncertainty ranges of the ratios of OC-to-EC, and the reference fraction of modern carbon in the 8 source categories, provides strong constraints to the source contributions to carbonaceous aerosol. The uncertainty of contributions was assessed with a Quasi-Monte Carlo (QMC) method accounting for the variability of OC and EC emission factors, the uncertainty of reference fractions of modern carbon, and the measurement uncertainty. During winter, biomass burning composed 64 % (±15 %) of the total carbon (TC) concentration, while in summer secondary biogenic OC accounted for 50 % (±16 %) of TC. The contribution of primary biogenic aerosol particles was negligible during the entire year. Moreover, aerosol associated with fossil sources represented 27 % (±16 %) and 41 % (±26 %) of TC in winter and summer, respectively. The contribution of secondary organic aerosol (SOA) to the organic mass (OM) was significant during the entire year. SOA accounted for 30 % (±16 %) and 85 % (±12 %) of OM during winter and summer, respectively. While the summer SOA was dominated by biogenic sources, winter SOA was mainly due to biomass burning and fossil sources. This indicates that the oxidation of semi-volatile and intermediate volatility organic compounds co-emitted with primary organics is a significant source of SOA, as suggested by recent model results and Aerosol Mass Spectrometer measurements. Comparison with previous global model simulations, indicates a strong underestimate of wintertime primary aerosol emissions in this region. The comparison of source apportionment results in different urban and rural areas showed that the sampling site was mainly affected by local aerosol sources during winter and regional air masses from the nearby Po Valley in summer. This observation was further confirmed by back-trajectory analysis applying the Potential Source Contribution Function method to identify potential source regions.


2010 ◽  
Vol 10 (12) ◽  
pp. 5223-5239 ◽  
Author(s):  
J. C. Chow ◽  
J. G. Watson ◽  
L.-W. A. Chen ◽  
J. Rice ◽  
N. H. Frank

Abstract. Field blanks (bQF) and backup filters (quartz-fiber behind quartz-fiber filter; QBQ) have been adopted by US long-term air quality monitoring networks to estimate PM2.5 organic carbon (OC) sampling artifacts. This study documents bQF and QBQ carbon levels for the: 1) Interagency Monitoring of Protected Visual Environments (IMPROVE); 2) Speciation Trends Network (STN; part of the Chemical Speciation Network [CSN]); and 3) Southeastern Aerosol Research and Characterization (SEARCH) networks and examines the similarities/differences associated with network-specific sampling protocols. A higher IMPROVE sample volume and smaller filter deposit area results in PM2.5 areal density (μg/cm2 on filter) 3–11 times those of STN/CSN and SEARCH samples for the same ambient PM2.5 concentrations, thus reducing the relative contribution of sampling artifacts from passive OC adsorption. A relatively short (1–15 min) passive exposure period of STN/CSN and SEARCH bQF OC (0.8–1 μg/cm2) underestimates positive and negative OC artifacts resulting from passive adsorption or evaporation of semi-volatile organic compounds on quartz-fiber filters. This is supported by low STN/CSN and SEARCH bQF levels and lack of temporal or spatial variability among the sites within the networks. With a much longer period, ~7 days of ambient passive exposure, average IMPROVE bQF and QBQ OC are comparable (2.4±0.5 and 3.1±0.8 μg/cm2, respectively) and more than twice levels found in the STN/CSN and SEARCH networks. Sampling artifacts in STN/CSN were estimated from collocated IMPROVE samples based on linear regression. At six of the eight collocated sites in this study, STN/CSN bQFs underestimated OC artifacts by 11–34%. Using a preceding organic denuder in the SEARCH network minimized passive adsorption on QBQ, but OC on QBQ may not be attributed entirely to the negative sampling artifact (e.g., evaporated or volatilized OC from the front filter deposits after sample collection).


2015 ◽  
Vol 8 (7) ◽  
pp. 2639-2648 ◽  
Author(s):  
Y. Cheng ◽  
K.-B. He

Abstract. A common approach for measuring the mass of organic carbon (OC) and elemental carbon (EC) in airborne particulate matter involves collection on a quartz fiber filter and subsequent thermal–optical analysis. Although having been widely used in aerosol studies and in PM2.5 (fine particulate matter) chemical speciation monitoring networks in particular, this measurement approach is prone to several types of artifacts, such as the positive sampling artifact caused by the adsorption of gaseous organic compounds onto the quartz filter, the negative sampling artifact due to the evaporation of OC from the collected particles and the analytical artifact in the thermal–optical determination of OC and EC (which is strongly associated with the transformation of OC into char OC and typically results in an underestimation of EC). The presence of these artifacts introduces substantial uncertainties to observational data on OC and EC and consequently limits our ability to evaluate OC and EC estimations in air quality models. In this study, the influence of sampling frequency on the measurement of OC and EC was investigated based on PM2.5 samples collected in Beijing, China. Our results suggest that the negative sampling artifact of a bare quartz filter could be remarkably enhanced due to the uptake of water vapor by the filter medium. We also demonstrate that increasing sampling duration does not necessarily reduce the impact of positive sampling artifact, although it will enhance the analytical artifact. Due to the effect of the analytical artifact, EC concentrations of 48 h averaged samples were about 15 % lower than results from 24 h averaged ones. In addition, it was found that with the increase of sampling duration, EC results exhibited a stronger dependence on the charring correction method and, meanwhile, optical attenuation (ATN) of EC (retrieved from the carbon analyzer) was more significantly biased by the shadowing effect. Results from this study will be useful for the design of China's PM2.5 chemical speciation monitoring network, which can be expected to be inaugurated in the near future.


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.


2016 ◽  
Author(s):  
Ulrike Dusek ◽  
Regina Hitzenberger ◽  
Anne Kasper-Giebl ◽  
Magdalena Kistler ◽  
Harro A. J. Meijer ◽  
...  

Abstract. We measured the radioactive carbon isotope 14C (radiocarbon) in various fractions of the carbonaceous aerosol sampled between February 2011 and March 2012 at the Cesar observatory in the Netherlands. Based on the radiocarbon content in total carbon (TC), organic carbon (OC), water insoluble organic carbon (WIOC), and elemental carbon (EC), we estimated the contribution of major sources to the carbonaceous aerosol. The main source categories were fossil fuel combustion, biomass burning and other contemporary carbon, which is mainly biogenic secondary organic aerosol material (SOA). A clear seasonal variation is seen in EC from biomass burning (ECBB), with lowest values in summer and highest values in winter, but ECBB is a minor fraction of EC in all seasons. WIOC from contemporary sources is highly correlated with ECBB, indicating that biomass burning is the dominant source of contemporary WIOC. This suggests that most biogenic SOA is water-soluble and that water insoluble carbon stems mainly from primary sources. Seasonal variations in other carbon fractions are less clear and hardly distinguishable from variations related to air mass history. Air masses originating from the ocean sector presumably contain little carbonaceous aerosol from outside the Netherlands, and during these conditions measured carbon concentrations reflect regional sources. In these situations absolute TC concentrations are usually rather low, around 1.5 μg m−3 and ECBB is always very low (~ 0.05 μg m−3), even in winter, indicating that biomass burning is not a strong source of carbonaceous aerosol in the Netherlands. In continental air masses, which usually arrive from the East or South and have spent several days over land, TC concentrations are on average by a factor of 3 higher. ECBB increases more strongly than TC to 0.2 μg m−3. Fossil EC and fossil WIOC, which are indicative of primary emissions, show a more moderate increase by a factor of 2.5 on average. An interesting case is fossil water soluble organic carbon (WSOC, calculated as OC-WIOC), which can be regarded as a proxy for SOA from fossil precursors. Fossil WSOC has low concentrations when regional sources are sampled and increases by more than a factor of 5 in continental air masses. A longer residence time of air masses over land seems to result in increased SOA concentrations from fossil origin.


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.


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.


2006 ◽  
Vol 6 (12) ◽  
pp. 4569-4576 ◽  
Author(s):  
K. F. Ho ◽  
S. C. Lee ◽  
J. J. Cao ◽  
Y. S. Li ◽  
J. C. Chow ◽  
...  

Abstract. To determine the levels and variations of carbonaceous aerosol in Hong Kong, PM2.5 and PM10 samples were collected by high volume (Hi-vol) samplers at three monitoring stations (representing middle-scale roadside, urban-, and regional-scale environments) during winter (November 2000 to February 2001) and summer (June 2001 to August 2001) periods. The highest concentrations of organic carbon (OC), elemental carbon (EC), and water-soluble organic carbon (WSOC) were found at the middle-scale roadside site with the lowest at the regional-scale site. The percentages of WSOC in total carbon at these sites were inversely correlated with their concentrations (i.e., the highest percentages of WSOC were observed at the regional-scale site). A high WSOC fraction may be associated with aged aerosol because of the secondary formation by photochemical oxidation of organic precursors of anthropogenic pollutants during transport. The annual average of isotope abundances (δ13C) of OC and EC were –26.9±0.5‰ and –25.6±0.1‰, respectively. There were no notable differences for seasonal distributions of carbon isotopic composition, consistent with motor vehicle emissions being the main source contributors of carbonaceous aerosol in Hong Kong. OC 13C abundances at the regional-scale site were higher than those at the middle-scale roadside and urban sites, consistent with secondary organic aerosols of biogenic origin.


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