[Show abstract][Hide abstract] ABSTRACT: Black carbon (BC) and light-absorbing organic carbon (brown carbon, BrC) play key roles in warming the atmosphere, but the magnitude of their effects remains highly uncertain. Theoretical modelling and laboratory experiments demonstrate that coatings on BC can enhance BCâ ™ s light absorption, therefore many climate models simply assume enhanced BC absorption by a factor of â1/41.5. However, recent field observations show negligible absorption enhancement, implying models may overestimate BCâ ™ s warming. Here we report direct evidence of substantial field-measured BC absorption enhancement, with the magnitude strongly depending on BC coating amount. Increases in BC coating result from a combination of changing sources and photochemical aging processes. When the influence of BrC is accounted for, observationally constrained model calculations of the BC absorption enhancement can be reconciled with the observations. We conclude that the influence of coatings on BC absorption should be treated as a source and regionally specific parameter in climate models.
[Show abstract][Hide abstract] ABSTRACT: Aerosol source apportionment remains a critical challenge for understanding the transport and aging of
aerosols, as well as for developing successful air pollution mitigation strategies. The contributions of fossil and nonfossil sources to organic carbon (OC) and elemental carbon (EC) in carbonaceous aerosols can be quantified by measuring the radiocarbon (14C) content of each carbon fraction. However, the use of 14C in studying OC and EC has been limited by technical challenges related to the physical separation of the two fractions and small sample sizes. There is no common procedure for OC/EC 14C analysis, and uncertainty studies have largely focused on the precision of yields. Here, we quantified the uncertainty in 14C measurement of aerosols associated with the isolation and analysis of each carbon fraction with the Swiss_4S thermal–optical analysis (TOA) protocol. We used an OC/EC analyzer (Sunset Laboratory Inc., OR, USA) coupled to a vacuum line to separate the two components. Each fraction was thermally desorbed and converted to carbon dioxide (CO2) in pure oxygen (O2). On average, 91% of the evolving CO2 was then cryogenically trapped on the vacuum line, reduced to filamentous graphite, and measured for its 14C content via accelerator mass spectrometry (AMS). To test the accuracy of our setup, we quantified the total amount of extraneous carbon introduced during the TOA sample processing and graphitization as the sum of modern and fossil (14C-depleted) carbon introduced during the analysis of fossil reference materials (adipic acid for OC and coal for EC) and contemporary standards (oxalic acid for OC and rice char for EC) as a function of sample size. We further tested our methodology by analyzing five ambient airborne particulate matter (PM2:5) samples with a range of OC and EC concentrations and 14C contents in an interlaboratory comparison. The total modern and fossil carbon blanks of our setup were 0.8�0.4 and 0.67�0.34 μg C, respectively, based on multiple measurements of ultra-small samples. The extraction procedure (Swiss_4S protocol and cryo-trapping only) contributed 0.37�0.18 μg of modern carbon and 0.13�0.07 μg of fossil carbon to the total blank of our system, with consistent estimates obtained for the two laboratories. There was no difference in the background correction between the OC and EC fractions. Our setup allowed us to efficiently isolate and trap each carbon fraction with the Swiss_4S protocol and to perform 14C analysis of ultra-small OC and EC samples with high accuracy and low 14C blanks.
[Show abstract][Hide abstract] ABSTRACT: Radiocarbon (14C) measurements of both organic carbon (OC) and elemental carbon (EC) allow a more detailed source apportionment, leading to a full and unambiguous distinction and quantification of the contributions from non-fossil and fossil sources. A thermal-optical method with a commercial OC/EC analyzer to isolate water-insoluble OC (WIOC) and EC for their subsequent 14C measurement was applied for the first time to filtered precipitation samples collected at a costal site in Portugal and at a continental site in Switzerland. Our results show that WIOC in precipitation is dominated by non-fossil sources such as biogenic and biomass-burning emissions regardless of rain origins and seasons, whereas EC sources are shared by fossil-fuel combustion and biomass burning. In addition, monthly variation of WIOC in Switzerland was characterized by higher abundance in warm than in cold seasons, highlighting the importance of biogenic emissions to particulate carbon in rainwater. Samples with high particulate carbon concentrations in Portugal were found to be associated with increased biogenic input. Despite the importance of non-fossil sources, fossil emissions account for approximately 20% of particulate carbon in wet deposition for our study, which is in line with fossil contribution in bulk rainwater dissolved organic carbon as well as aerosol WIOC and EC estimated by the 14C approach from other studies.
[Show abstract][Hide abstract] ABSTRACT: A detailed characterization of air quality in Paris (France), a megacity of more than 10 million inhabitants, during two one month intensive campaigns and from additional one year observations, revealed that about 70% of the fine particulate matter (PM) at urban background is transported on average into the megacity from upwind regions. This dominant influence of regional sources was confirmed by in-situ measurements during short intensive and longer term campaigns, aerosol optical depth (AOD) measurements from ENVISAT, and modeling results from PMCAMx and CHIMERE. While advection of sulfate is well documented for other megacities, there was surprisingly high contribution from long-range transport for both nitrate and organic aerosol. The origin of organic PM was investigated by a comprehensive analysis of aerosol mass spectrometer (AMS), radiocarbon and tracer measurements during two intensive campaigns. Primary fossil fuel combustion emissions contributed less than 20% in winter and 40% in summer to carbonaceous fine PM, unexpectedly little for a megacity. Cooking activities and, during winter, residential wood burning are the major primary organic PM sources. This analysis suggests that the major part of secondary organic aerosol is of modern origin, i.e. from biogenic precursors and from wood burning. Black carbon concentrations are on the lower end of values encountered in megacities worldwide, but still represent an issue for air quality. These comparatively low air pollution levels are due to a combination of low emissions per inhabitant, flat terrain, and a meteorology that is in general not conducive to local pollution build-up. This revised picture of a megacity only controlling part of its own average and peak PM levels has important implications for air pollution regulation policies.
[Show abstract][Hide abstract] ABSTRACT: Field deployments of the Aerodyne Aerosol Mass Spectrometer (AMS) have significantly advanced real-time measurements and source apportionment of non-refractory particulate matter. However, the cost and complex maintenance requirements of the AMS make impractical its deployment at sufficient sites to determine regional characteristics. Furthermore, the negligible transmission efficiency of the AMS inlet for supermicron particles significantly limits the characterization of their chemical nature and contributing sources. In this study, we utilize the AMS to characterize the water-soluble organic fingerprint of ambient particles collected onto conventional quartz filters, which are routinely sampled at many air quality sites. The method was applied to 256 particulate matter (PM) filter samples (PM1, PM2.5, PM10) collected at 16 urban and rural sites during summer and winter. We show that the results obtained by the present technique compare well with those from co-located online measurements, e.g. AMS or Aerosol Chemical Speciation Monitor (ACSM). The bulk recoveries of organic aerosol (60–91 %) achieved using this technique, together with low detection limits (0.8 μg of organic aerosol on the analyzed filter fraction) allow its application to environmental samples. We will discuss the recovery variability of individual hydrocarbon, oxygen containing and other ions. The performance of such data in source apportionment is assessed in comparison to ACSM data. Recoveries of organic components related to different sources as traffic, wood burning and secondary organic aerosol are presented. This technique, while subjected to the limitations inherent to filter-based measurements (e.g. filter artifacts and limited time resolution) may be used to enhance the AMS capabilities in measuring size-fractionated, spatially-resolved long-term datasets.
[Show abstract][Hide abstract] ABSTRACT: Elemental carbon (EC) or black carbon (BC) in the atmosphere has a strong influence on both climate and human health. In this study, radiocarbon (14C) based source apportionment is used to distinguish between fossil fuel and biomass burning sources of EC isolated from aerosol filter samples collected in Beijing from June 2010 to May 2011. The 14C results demonstrate that EC is consistently dominated by fossil-fuel combustion throughout the whole year with a mean contribution of 79% ± 6% (ranging from 70% to 91%), though EC has a higher mean and peak concentrations in the cold season. The seasonal molecular pattern of hopanes (i.e. a class of organic markers mainly emitted during the combustion of different fossil fuels) indicates that traffic-related emissions are the most important fossil source in the warm period and coal combustion emissions are significantly increased in the cold season. By combining 14C based source apportionment results and picene (i.e. an organic marker for coal emissions) concentrations, relative contributions from coal and vehicle to EC in the cold period were estimated as 25±4% and 50±7%, respectively, whereas the coal combustion contribution was negligible or very small in the warm period.
[Show abstract][Hide abstract] ABSTRACT: AMS-14C applications often require the analysis of small samples. Such is the case of atmospheric aerosols where frequently only a small amount of sample is available. The ion beam physics group at the ETH, Zurich, has designed an Automated Graphitization Equipment (AGE III) for routine graphite production for AMS analysis from organic samples of approximately 1 mg. In this study, we explore the potential use of the AGE III for graphitization of particulate carbon collected in quartz filters. In order to test the methodology, samples of reference materials and blanks with different sizes were prepared in the AGE III and the graphite was analyzed in a MICADAS AMS (ETH) system. The graphite samples prepared in the AGE III showed recovery yields higher than 80% and reproducible 14C values for masses ranging from 50 to 300 μg. Also, reproducible radiocarbon values were obtained for aerosol filters of small sizes that had been graphitized in the AGE III. As a study case, the tested methodology was applied to PM10 samples collected in two urban cities in Mexico in order to compare the source apportionment of biomass and fossil fuel combustion. The obtained 14C data showed that carbonaceous aerosols from Mexico City have much lower biogenic signature than the smaller city of Cuernavaca.
Nuclear Instruments and Methods in Physics Research Section B Beam Interactions with Materials and Atoms 06/2015; 361. DOI:10.1016/j.nimb.2015.05.027 · 1.12 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: This paper reports on novel separation methods developed for the direct determination of 14C in organic carbon (OC) and elemental carbon (EC), two sub-fractions of total carbon (TC) of atmospheric air particulate matter. Until recently, separation of OC and EC has been performed off-line by manual and time-consuming techniques that relied on the collection of massive CO2 fractions. We present here two on-line hyphenated techniques between a Sunset OC/EC analyzer and a MICADAS (MIni radioCArbon DAting System) accelerator mass spectrometer (AMS) equipped with a gas ion source. The first implementation facilitates the direct measurement in the low sample size range (<10 μg C) with high throughput on a routine basis, while the second explores the potential for a continuous-flow real-time CO2 gas feed into the ion source. The performance achieved with reference materials and real atmospheric samples will be discussed to draw conclusions on the improvement offered in the field of 14C aerosol source apportionment.
Nuclear Instruments and Methods in Physics Research Section B Beam Interactions with Materials and Atoms 06/2015; 361. DOI:10.1016/j.nimb.2015.06.008 · 1.12 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Organic soils in peatlands store a great proportion of the global soil carbon pool and can lose carbon via the atmosphere due to degradation. In Germany, most of the greenhouse gas (GHG) emissions from organic soils are attributed to sites managed as grassland. Here, we investigated a land use gradient from near-natural wetland (NW) to an extensively managed (GE) to an intensively managed grassland site (GI), all formed in the same bog complex in northern Germany. Vertical depth profiles of δ13C, δ15N, ash content, C / N ratio and bulk density as well as radiocarbon ages were studied to identify peat degradation and to calculate carbon loss. At all sites, including the near-natural site, δ13C depth profiles indicate aerobic decomposition in the upper horizons. Depth profiles of δ15N differed significantly between sites with increasing δ15N values in the top soil layers paralleling an increase in land use intensity owing to differences in peat decomposition and fertilizer application. At both grassland sites, the ash content peaked within the first centimetres. In the near-natural site, ash contents were highest in 10–60 cm depth. The ash profiles, not only at the managed grassland sites, but also at the near-natural site indicate that all sites were influenced by anthropogenic activities either currently or in the past, most likely due to drainage. Based on the enrichment of ash content and changes in bulk density, we calculated the total carbon loss from the sites since the peatland was influenced by anthropogenic activities. Carbon loss at the sites increased in the following order: NW < GE < GI. Radiocarbon ages of peat in the topsoil of GE and GI were hundreds of years, indicating the loss of younger peat material. In contrast, peat in the first centimetres of the NW was only a few decades old, indicating recent peat growth. It is likely that the NW site accumulates carbon today but was perturbed by anthropogenic activities in the past. Together, all biogeochemical parameters indicate a degradation of peat due to (i) conversion to grassland with historical drainage and (ii) land use intensification.
[Show abstract][Hide abstract] ABSTRACT: Aerosol source apportionment remains a critical challenge for understanding the transport and aging of aerosols, as well as for developing successful air pollution mitigation strategies. The contributions of fossil and non-fossil sources to organic carbon (OC) and elemental carbon (EC) in carbonaceous aerosols can be quantified by measuring the radiocarbon (14C) content of each carbon fraction. However, the use of 14C in studying OC and EC has been limited by technical challenges related to the physical separation of the two fractions and small sample sizes. There is no common procedure for OC/EC 14C analysis, and uncertainty studies have largely focused on the precision of yields. Here, we quantified the uncertainty in 14C measurement of aerosols associated with the isolation and analysis of each carbon fraction with the Swiss_4S thermal-optical analysis (TOA) protocol. We used an OC/EC analyzer (Sunset Laboratory Inc., OR, USA) coupled to vacuum line to separate the two components. Each fraction was thermally desorbed and converted to carbon dioxide (CO2) in pure oxygen (O2). On average 91% of the evolving CO2 was then cryogenically trapped on the vacuum line, reduced to filamentous graphite, and measured for its 14C content via accelerator mass spectrometry (AMS). To test the accuracy of our set-up, we quantified the total amount of extraneous carbon introduced during the TOA sample processing and graphitization as the sum of modern and fossil (14C-depleted) carbon introduced during the analysis of fossil reference materials (adipic acid for OC and coal for EC) and contemporary standards (oxalic acid for OC and rice char for EC) as a function of sample size. We further tested our methodology by analyzing five ambient airborne particulate matter (PM2.5) samples with a range of OC and EC concentrations and 14C contents in an interlaboratory comparison. The total modern and fossil carbon blanks of our set-up were 0.8�0.4 and 0.67�0.34 μgC, respectively, based on multiple measurements of ultra-small samples. The Swiss_4S protocol and the cryo-trapping contributed 0.37�0.18 μg of modern carbon and 0.13�0.07 μg of fossil carbon to the estimated blanks, with consistent estimates obtained for the two laboratories. There was no difference in the background correction between the OC and EC fractions. Our set-up allowed us to e�ciently isolate and trap each carbon fraction with the Swiss_4S protocol and to perform 14C analysis of ultra-small OC and EC samples with high accuracy and low 14C blanks.
[Show abstract][Hide abstract] ABSTRACT: A fast and automatic method for radiocarbon analysis of aerosol samples is presented. This type of analysis requires high number of sample measurements of low carbon masses, but accepts precisions lower than for carbon dating analysis. The method is based on online Trapping CO2 and coupling an elemental analyzer with a MICADAS AMS by means of a gas interface. It gives similar results to a previously validated reference method for the same set of samples. This method is fast and automatic and typically provides uncertainties of 1.5-5% for representative aerosol samples. It proves to be robust and reliable and allows for overnight and unattended measurements. A constant and cross contamination correction is included, which indicates a constant contamination of 1.4 ± 0.2 μg C with 70 ± 7 pMC and a cross contamination of (0.2 ± 0.1)% from the previous sample. A Real-time online coupling version of the method was also investigated. It shows promising results for standard materials with slightly higher uncertainties than the Trapping online approach.
Nuclear Instruments and Methods in Physics Research Section B Beam Interactions with Materials and Atoms 04/2015; 111. DOI:10.1016/j.nimb.2015.03.051 · 1.12 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Determining the contribution of wood smoke to air pollution in large cities such as London is becoming increasingly important due to the changing nature of domestic heating in urban areas. During winter, biomass burning emissions have been identified as a major cause of exceedances of European air quality limits. The aim of this work was to quantify the contribution of biomass burning in London to concentrations of PM2:5 and determine whether local emissions or regional contributions were the main source of biomass smoke. To achieve this, a number of biomass burning chemical tracers were analysed at a site within central London and two sites in surrounding rural areas. Concentrations of levoglucosan, elemental carbon (EC), organic carbon (OC) and KC were generally well correlated across the three sites. At all the sites, biomass burning was found to be a source of OC and EC, with the largest contribution of EC from traffic emissions, while for OC the dominant fraction included contributions from secondary organic aerosols, primary biogenic and cooking sources. Source apportionment of the EC and OC was found to give reasonable estimation of the total carbon from non-fossil and fossil fuel sources based upon comparison with estimates derived from 14C analysis. Aethalometer-derived black carbon data were also apportioned into the contributions frombiomass burning and traffic and showed trends similar to those observed for EC. Mean wood smoke mass at the sites was estimated to range from 0.78 to 1.0 μgm3 during the campaign in January–February 2012. Measurements on a 160m tower in London suggested a similar ratio of brown to black carbon (reflecting wood burning and traffic respectively) in regional and London air.Peaks in the levoglucosan and KC concentrations were observed to coincide with low ambient temperature, consistent with domestic heating as a major contributing local source in London. Overall, the source of biomass smoke in London was concluded to be a background regional source overlaid by contributions from local domestic burning emissions. This could have implications when considering future emission control strategies during winter and may be the focus of future work in order to better determine the contributing local sources.
[Show abstract][Hide abstract] ABSTRACT: The recent warming of the global climate is well recognized. However, does a warmer climate also mean a moister climate? Does dry get drier and wet get wetter? There are important questions as they relate to changes in the water cycle and impacts the water resources as well as the frequency and intensity of storms and floods in the near future. In Europe, regional climate models do not show consistent and robust results for future hydroclimatic changes and how extreme events will evolve in response to future climate change.
[Show abstract][Hide abstract] ABSTRACT: During winter 2013, extremely high concentrations (i.e., 4-20 times higher than the World Health Organization guideline) of PM2.5 (particulate matter with an aerodynamic diameter < 2.5 mu m) mass concentrations (24 h samples) were found in four major cities in China including Xi'an, Beijing, Shanghai and Guangzhou. Statistical analysis of a combined data set from elemental carbon (EC), organic carbon (OC), C-14 and biomass-burning marker measurements using Latin hypercube sampling allowed a quantitative source apportionment of carbonaceous aerosols. Based on C-14 measurements of EC fractions (six samples each city), we found that fossil emissions from coal combustion and vehicle exhaust dominated EC with a mean contribution of 75 +/- 8% across all sites. The remaining 25 +/- 8% was exclusively attributed to biomass combustion, consistent with the measurements of biomass-burning markers such as anhydrosugars (levoglucosan and mannosan) and water-soluble potassium (K+). With a combination of the levoglucosan-to-mannosan and levoglucosan-to-K+ ratios, the major source of biomass burning in winter in China is suggested to be combustion of crop residues. The contribution of fossil sources to OC was highest in Beijing (58 +/- 5 %) and decreased from Shanghai (49 +/- 2 %) to Xi'an (38 +/- 3 %) and Guangzhou (35 +/- 7 %). Generally, a larger fraction of fossil OC was from secondary origins than primary sources for all sites. Nonfossil sources accounted on average for 55 +/- 10 and 48 +/- 9% of OC and total carbon (TC), respectively, which suggests that non-fossil emissions were very important contributors of urban carbonaceous aerosols in China. The primary biomassburning emissions accounted for 40 +/- 8, 48 +/- 18, 53 +/- 4 and 65 +/- 26% of non-fossil OC for Xi'an, Beijing, Shanghai and Guangzhou, respectively. Other non-fossil sources excluding primary biomass burning were mainly attributed to formation of secondary organic carbon (SOC) from non-fossil precursors such as biomass-burning emissions. For each site, we also compared samples from moderately to heavily polluted days according to particulate matter mass. Despite a significant increase of the absolute mass concentrations of primary emissions from both fossil and non-fossil sources during the heavily polluted events, their relative contribution to TC was even decreased, whereas the portion of SOC was consistently increased at all sites. This observation indicates that SOC was an important fraction in the increment of carbonaceous aerosols during the haze episode in China.
[Show abstract][Hide abstract] ABSTRACT: A review of the techniques concerning the Molecular Identification of Organic Compounds in the Atmosphere is presented. An organic compound is fully identified only if its molecular structure is entirely known, including its isomeric and spatial (stereo) configuration. The first type of problem is when organic compounds need to be inventoried for the purpose of establishing a budget. Generally, such budgets are required to gain insights into specific properties of the compounds, such as their optical properties for the global energy budget or their volatility for SOA precursors. In such cases, the organic compounds do not need to be individually identified, but only quantified on the basis of this common property.
Chemical Reviews 02/2015; 115(10). DOI:10.1021/cr5003485 · 46.57 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Four different parameterizations for the formation and evolution of secondary
organic aerosol (SOA) are evaluated using a 0-D box model representing the Los Angeles
Metropolitan Region during the CalNex 2010 field campaign. We constrain the model
predictions with measurements from several platforms and compare predictions with particle
and gas-phase observations from the CalNex Pasadena ground site. That site provides a
unique opportunity to study aerosol formation close to anthropogenic emission sources
[Show abstract][Hide abstract] ABSTRACT: While several studies have investigated winter-time air pollution with a wide range of concentration levels, hardly any results are available for longer time periods covering several winter-smog episodes at various locations; e.g., often only a few weeks from a single winter are investigated. Here, we present source apportionment results of winter-smog episodes from 16 air pollution monitoring stations across Switzerland from five consecutive winters. Radiocarbon (14C) analyses of the elemental (EC) and organic (OC) carbon fractions, as well as levoglucosan, major water-soluble ionic species and gas-phase pollutant measurements were used to characterize the different sources of PM10. The most important contributions to PM10 during winter-smog episodes in Switzerland were on average the secondary inorganic constituents (sum of nitrate, sulfate and ammonium = 41 ± 15%) followed by organic matter (OM) (34 ± 13%) and EC (5 ± 2%). The non-fossil fractions of OC (fNF,OC) ranged on average from 69 to 85 and 80 to 95% for stations north and south of the Alps, respectively, showing that traffic contributes on average only up to ~ 30% to OC. The non-fossil fraction of EC (fNF,EC), entirely attributable to primary wood burning, was on average 42 ± 13 and 49 ± 15% for north and south of the Alps, respectively. While a high correlation was observed between fossil EC and nitrogen oxides, both primarily emitted by traffic, these species did not significantly correlate with fossil OC (OCF), which seems to suggest that a considerable amount of OCF is secondary, from fossil precursors. Elevated fNF,EC and fNF,OC values and the high correlation of the latter with other wood burning markers, including levoglucosan and water soluble potassium (K+) indicate that residential wood burning is the major source of carbonaceous aerosols during winter-smog episodes in Switzerland. The inspection of the non-fossil OC and EC levels and the relation with levoglucosan and water-soluble K+ shows different ratios for stations north and south of the Alps (most likely because of differences in burning technologies) for these two regions in Switzerland.