Carbon In Atmospheric Aerosols Research Articles

Water-soluble brown carbon in atmospheric aerosols from the resource-dependent cities: Optical properties, chemical compositions and sources

As a vital type of light-absorbing aerosol, brown carbon (BrC) presents inherent associations with atmospheric photochemistry and climate change. However, the understanding of the chemical and optical properties of BrC is limited, especially in some resource-dependent cities with long heating periods in northwest China. This study showed that the annual average abundances of Water-soluble BrC (WS-BrC) were 9.33±7.42 and 8.69±6.29 µg/m3 in Baotou and Wuhai and the concentrations, absorption coefficient (Abs365), and mass absorption efficiency (MAE365) of WS-BrC presented significant seasonal patterns, with high values in the heating season and low values in the non-heating season; while showing opposite seasonal trends for the Absorption Ångström exponent (AAE300-400). Comparatively, the levels of WS-BrC in developing regions (such as cities in Asia) were higher than those in developed regions (such as cities in Europe and Australia), indicating the significant differences in energy consumption in these regions. By combining fluorescence excitation-emission matrix (EEM) spectra with the parallel factor (PARAFAC) model, humic-like (C1 and C2) and protein-like (C3) substances were identified, and accounted for 61.40%±4.66% and 38.6%±3.78% at Baotou, and 60.33%±6.29% and 39.67%±4.17% at Wuhai, respectively. The results of source apportionment suggested that the potential source regions of WS-BrC varied in heating vs. non-heating seasons and that the properties of WS-BrC significantly depended on primary emissions (e.g., combustion emissions) and secondary formation.

Interfacial Oxidative Oligomerization of Catechol.

The heterogeneous reaction between thin films of catechol exposed to O3(g) creates hydroxyl radicals (HO•) in situ, which in turn generate semiquinone radical intermediates in the path to form heavier polyhydroxylated biphenyl, terphenyl, and triphenylene products. Herein, the alteration of catechol aromatic surfaces and their chemical composition are studied during the heterogeneous oxidation of catechol films by O3(g) molar ratios ≥ 230 ppbv at variable relative humidity levels (0% ≤ RH ≤ 90%). Fourier transform infrared micro-spectroscopy, atomic force microscopy, electrospray ionization mass spectrometry, and reverse-phase liquid chromatography with UV–visible and mass spectrometry detection provide new physical insights into understanding the surface reaction. A Langmuir–Hinshelwood mechanism is accounted to report reaction rates, half-lives, and reactive uptake coefficients for the system under variable relative humidity levels. The reactions reported explain how the oligomerization of polyphenols proceeds at interfaces to contribute to the formation of brown organic carbon in atmospheric aerosols.

Water-soluble brown carbon in atmospheric aerosols along the transport pathway of Asian dust: Optical properties, chemical compositions, and potential sources

As an important type of light-absorbing aerosol, brown carbon (BrC) has the potential to affect the atmospheric photochemistry and Earth's energy budget. A comprehensive field campaign was carried out along the transport pathway of Asian dust during the spring of 2016, including a desert site (Erenhot), a rural site (Zhangbei), and an urban site (Jinan), in northern China. Optical properties, bulk chemical compositions, and potential sources of water-soluble brown carbon (WS-BrC) were investigated in atmospheric total suspended particulate (TSP) samples. Samples from Zhangbei had higher mass absorption efficiency at 365 nm (MAE365, 1.32 ± 0.34 m2 g−1) than those from Jinan (1.00 ± 0.23 m2 g−1) and Erenhot (0.84 ± 0.30 m2 g−1). Compere to the non-dust samples, elevated water-soluble organic carbon (WSOC) concentrations and MAE365 values of dust samples from Erenhot are related to the input of high molecular weight organic compounds and biogenic matter from the Gobi Desert, while lower values from Zhangbei and Jinan are attributed to the dilution effect caused by strong northwesterly winds. Based on fluorescence excitation–emission matrix spectra and parallel factor analysis, two humic-like (C1 and C2) and two protein-like (C3 and C4) substances were identified. Together, C1 and C2 accounted for ~64% of total fluorescence intensity at the highly polluted urban Jinan site; C3 represented ~45% at the rural Zhangbei site where local biomass burning affects; and C4 contributed ~24% in the desert region (Erenhot) due to dust-sourced biogenic substances. The relative absorptive forcing of WS-BrC compared to black carbon at 300–400 nm was about 31.3%, 13.9%, and 9.2% during non-dust periods at Erenhot, Zhangbei, and Jinan, respectively, highlighting that WS-BrC may significantly affect the radiative balance of Earth's climate system and should be included in radiative forcing models.

Atmospheric Processing of Nitrophenols and Nitrocresols From Biomass Burning Emissions

AbstractWe present the analysis of the atmospheric budget of nitrophenols and nitrocresols, a class of nitroaromatics that raise great ecosystem and health concerns due to their phytotoxic and genotoxic properties, during the spring wheat harvest season in Eastern China. Significant quantities with maximum concentrations over 100 pptv and distinct diurnal patterns that peak around midnight and maintain low levels throughout the day were observed, in coincidence with the extensive open crop residue burning activities conducted in the vicinity. An observationally constrained zero‐dimension box model was constructed to assess the relative importance of various production and removal pathways at play in determining the measured surface concentrations. The NO3‐initiated dark chemistry, in concert with meteorological variations predominantly dilution and entrainment, exerts major controls over the observed diurnal behaviors of nitrophenols and nitrocresols. Structural isomerism is predicted to have a significant impact on the multiphase partitioning and chemistry of nitrophenol isomers. Furthermore, simulations show that an appreciable amount of nitrophenols is present in the aerosol water, thereby representing an important source of water‐soluble brown carbon in atmospheric aerosols under the humid subtropical weather prevailing during the campaign. Sensitivity analysis performed on the model parameterizations of reaction schemes helps to further understand the chemistry underlying the diurnal cycles. Implementing NO‐dependent yields of cresols from toluene photooxidation improves the model predictions of nitrocresols at low NO ranges (<1 ppb), thereby underscoring the complexity of the peroxy radical reaction pathways from toluene photooxidation under atmospheric relevant conditions.

Fluorescence characteristics of water-soluble organic carbon in atmospheric aerosol☆.

Fluorescence spectroscopy is a commonly used technique to analyze dissolved organic matter in aquatic environments. Given the high sensitivity and non-destructive analysis, fluorescence has recently been used to study water-soluble organic carbon (WSOC) in atmospheric aerosols, which have substantial abundance, various sources and play an important role in climate change. Yet, current research on WSOC characterization is rather sparse and limited to a few isolated sites, making it challenging to draw fundamental and mechanistic conclusions. Here we presented a review of the fluorescence properties of atmospheric WSOC reported in various field and laboratory studies, to discuss the current advances and limitations of fluorescence applications. We highlighted that photochemical reactions and relevant aging processes have profound impacts on fluorescence properties of atmospheric WSOC, which were previously unnoticed for organic matter in aquatic environments. Furthermore, we discussed the differences in sources and chemical compositions of fluorescent components between the atmosphere and hydrosphere. We concluded that the commonly used fluorescence characteristics derived from aquatic environments may not be applicable as references for atmospheric WSOC. We emphasized that there is a need for more systematic studies on the fluorescence properties of atmospheric WSOC and to establish a more robust reference and dataset for fluorescence studies in atmosphere based on extensive source-specific experiments.

Investigation of the spatio-temporal heterogeneity and optical property of water-soluble organic carbon in atmospheric aerosol and snow over the Yulong Snow Mountain, southeastern Tibetan Plateau

Atmospheric aerosols are a branch of active research in recent decades. The deposition of light-absorbing substances on high-altitude glaciers causes substantial adverse impacts on the cryospheric environment, cryosphere-hydrology, and climate system. Although, the concentrations of water-soluble organic carbon (WSOC) in snow/ice on glaciers of Tibetan Plateau (TP) have been reported, their transfer processes and optical properties in the context of summer precipitation-atmosphere-snow-river water continuum are seldom studied. In this study, we have systematically examined some scientific issues associated with WSOC concentrations and light absorption properties of WSOC in various forms of samples from the Mt. Yulong region. Statistical results demonstrate that the spatial distribution of WSOC in the snow of Baishui glacier was heterogeneous. The average WSOC concentrations of each snowpit were significantly decreased, and its light-absorbing properties were significantly elevated with the time extension. Aerosol WSOC concentrations and light absorption have distinct spatial disparity and seasonal variation. Pre-monsoon and monsoon have the highest and lowest WSOC content, respectively. Whereas the light-absorbing properties present contrasting seasonal trends. Rivers of which runoff was supplied by glacier meltwater have significantly lower WSOC concentrations (e.g., 0.42 ± 0.03 mg L−1) compared with other forms of water bodies. Mass absorption cross-section of WSOC (MAC-WSOC) in multiple snow and meltwater samples was significantly different and type-dependent. Atmospheric aerosol has the lowest MAC-WSOC value among the four types of samples, which was likely associated with exhaust emissions from private vehicles and tour buses. Statistical results indicated that the average AAE330-400 values of various snow/ice samples are subequal. Snow of glaciers supplies a desirable platform for the deposition of gaseous materials which experienced long-range transport in high altitude zones. Biomass-burning emissions made an immense contribution to the WSOC deposition over the study area, as demonstrated by the distribution of active fire points. However, this preliminary study represents the first systematic investigation of WSOC deposition in southeastern TP. Further robust in-situ field investigations and laboratory measurements are urgently necessary to improve our understanding of the transfer process and optical property of WSOC.

Two-wavelength thermal–optical determination of light-absorbing carbon in atmospheric aerosols

Abstract. Thermal–optical analysis is widely adopted for the quantitative determination of total (TC), organic (OC), and elemental (EC) carbon in atmospheric aerosol sampled by suitable filters. Nevertheless, the methodology suffers from several uncertainties and artifacts such as the well-known issue of charring affecting the OC–EC separation. In the standard approach, the effect of the possible presence of brown carbon, BrC, in the sample is neglected. BrC is a fraction of OC, usually produced by biomass burning with a thermic behavior intermediate between OC and EC. BrC is optically active: it shows an increasing absorbance when the wavelength moves to the blue–UV region of the electromagnetic spectrum. Definitively, the thermal–optical characterization of carbonaceous aerosol should be reconsidered to address the possible BrC content in the sample under analysis. We introduce here a modified Sunset Lab Inc. EC–OC analyzer. Starting from a standard commercial instrument, the unit has been modified at the physics department of the University of Genoa (Italy), making possible the alternative use of the standard laser diode at λ=635 nm and of a new laser diode at λ=405 nm. In this way, the optical transmittance through the sample can be monitored at both wavelengths. Since at shorter wavelengths the BrC absorbance is higher, a better sensitivity to this species is gained. The modified instrument also gives the possibility to quantify the BrC concentration in the sample at both wavelengths. The new unit has been thoroughly tested, with both artificial and real-world aerosol samples: the first experiment, in conjunction with the multi-wavelength absorbance analyzer (MWAA; Massabò et al., 2013, 2015), resulted in the first direct determination of the BrC mass absorption coefficient (MAC) at λ=405 nm: MAC =23±1 m2 g−1.

Water-Soluble Brown Carbon in Atmospheric Aerosols from Godavari (Nepal), a Regional Representative of South Asia.

Brown carbon (BrC) has recently emerged as an important light-absorbing aerosol. This study provides interannual and seasonal variations in light absorption properties, chemical composition, and sources of water-soluble BrC (WS-BrC) based on PM10 samples collected in Godavari, Nepal, from April 2012 to May 2014. The mass absorption efficiency of WS-BrC at 365 nm (MAE365) shows a clear seasonal variability, with the highest MAE365 of 1.05 ± 0.21 m2 g-1 in premonsoon season and the lowest in monsoon season (0.59 ± 0.16 m2 g-1). The higher MAE365 values in nonmonsoon seasons are associated with fresh biomass burning emissions. This is further substantiated by a strong correlation ( r = 0.79, P < 0.01) between Abs365 (light absorption coefficient at 365 nm) and levoglucosan. We found, using fluorescence techniques, that humic-like and protein-like substances are the main chromophores in WS-BrC and responsible for 80.2 ± 4.1% and 19.8 ± 4.1% of the total fluorescence intensity, respectively. BrC contributes to 8.78 ± 3.74% of total light absorption over the 300-700 nm wavelength range. Considering the dominant contribution of biomass burning to BrC over Godavari, this study suggests that reduction in biomass burning emission may be a practical method for climate change mitigation in South Asia.

Characteristics of carbonaceous aerosols analyzed using a multiwavelength thermal/optical carbon analyzer: A case study in Lanzhou City

Characteristics of atmospheric carbonaceous aerosols in Lanzhou City from December 2014 to November 2015 are analyzed using a multiwavelength thermal/optical carbon analyzer. Results reveal that average concentrations of black carbon (BC) and organic carbon in atmospheric aerosols at Lanzhou are 6.7 and 25.4 µg m–3, respectively, showing obvious seasonality (higher in winter and lower in summer). This is consistent with findings in cities of northern China. Primary organic aerosols and secondary organic aerosols respectively account for approximately 60% and 17% of carbonaceous aerosols. No significant seasonality is found for secondary organic carbon, indicating that its potential sources do not vary significantly throughout the study period. The mass absorption cross-section (MAC632 nm) of BC is 7.1 m2 g−1, slightly higher than that of immediately emitted BC. MAC values of BC at different wavelengths vary drastically; they are higher for ultraviolet and visible light (8.5–10.2 m2 g–1) than for near-infrared light (4.9–5.7 m2 g–1). The aerosol absorption optical depth generally declines from the near-infrared to the near-ultraviolet region. The values are higher in winter than in summer, thus showing there are different contributions of BC deposition in different seasons. Brown carbon (BrC) has an Angstrom absorption exponent (AAE) value of approximately 2.75, which is similar to the AAE value of BrC generated by diesel combustion (2.3). The contribution of BrC to light absorption is as much as 34% at a wavelength of 635 nm. This study demonstrates that the multiwavelength thermal/optical carbon analyzer can quantify absorption properties of BrC in atmospheric aerosols. This can enhance understanding of carbonaceous aerosols and provide key parameters for simulations of climate models.

Pollution Characteristics of Organic Carbon and Elemental Carbon in Atmospheric Aerosols in Beibei District, Chongqing

To study the pollution characteristics of atmospheric carbon aerosols, aerosol samples were collected via a cascade impactor (Andersen) from March 2014 to February 2015 in Beibei District, Chongqing. Organic carbon (OC) and element carbon (EC) were detected using a DRI 2001A carbon analyzer. The results showed that the annual average concentrations of OC and EC in PM2.1 were (16.3±7.6) and (1.8±0.7), respectively, and (25.0±9.6), and (3.2±1.3) μg·m-3, respectively, in PM9.0. The concentrations of both OC and EC were higher in winter and spring than in summer and autumn for PM2.1, whereas, for PM9.0, the concentration of OC was higher in summer and spring than in winter and autumn and that of EC was higher in winter and spring than in summer and autumn. The particle size distributions of OC and EC for the study year were analyzed, and it was found that those of OC were bimodal, with peaks in the size ranges of 0.43-0.65 μm for fine particles and 4.7-5.8 μm for coarse particles, and those of EC were trimodal, with peaks in the size ranges of 0.43-0.65 μm for fine particles and 4.7-5.8 μm for coarse particles and a concurrent significant peak in the particle size range of 2.1-3.3 μm. In addition, the correlations between OC and EC were analyzed and the SOC in PM2.1 was estimated. It was found that the average concentration of SOC was (6.3±5.9) μg·m-3, which accounted for 33.5%±22.6% of the OC concentration in Beibei District. Furthermore, OC and EC were significantly correlated. Finally, the pollution sources of atmospheric aerosols in Beibei were analyzed, and it was found that the pollution in Beibei mainly came from the exhaust gas of gasoline vehicles, biomass combustion, and coal combustion.

Characteristics of Organic Carbon and Elemental Carbon in Atmospheric Aerosols in the Urban Area in Beibei, a Suburb of Chongqing

To investigate the pollutive characteristics of atmospheric carbonaceous aerosols in Beibei District, a suburb of Chongqing Municipal City, graded aerosol samples were continuously collected by cascade impactors over one year, from March 2014 to February 2015. Carbonaceous aerosols, including organic carbon (OC) and elemental carbon (EC), were detected by a DRI 2001A carbon analyzer. The results showed that the average annual concentrations of OC and EC in the PM2.1 were 16.3 ± 7.6 and 1.8 ± 0.7 µg m–3, and in the PM9.0 were 25.0 ± 9.6 and 3.2 ± 1.2 µg m–3, respectively. On the one hand, a more seasonal distribution of OC concentrations appeared in the PM2.1 (winter > spring > summer > autumn) than in the PM9.0 (winter ≈ spring ≈ summer > autumn); furthermore, whereas the OC significantly positively correlated with wind speed for both the PM2.1 (P spring > summer > autumn), and the EC in the PM2.1 significantly negatively correlated with temperature (P < 0.05). Additionally, both the OC and the EC were concentrated mainly in the fine particles (< 2.10 µm), and the size distributions of the OC in all four seasons displayed a bi-modal pattern that peaked in the size ranges of 0.43–0.65 µm (for fine particles) and 4.7–5.8 µm (for coarse particles), whereas the EC displayed a uni-modal pattern that peaked in the size range of 4.7–5.8 µm (for coarse particles). Furthermore, the correlations between the OC and the EC were analyzed, and the SOC (secondary organic carbon) in the PM2.1 was estimated using the primary OC/EC ratio. It was found that the OC highly significantly correlated with the EC (P < 0.01), with the average annual concentration of the SOC being 6.3 ± 5.9 µg m–3, which accounted for 33.5 ± 22.6% of the OC. Analyzing the sources of the pollutive atmospheric aerosol in Beibei further demonstrated that it mainly originated in biomass burning, gasoline-vehicle exhaust, and coal combustion.

Towards the isolation and estimation of elemental carbon in atmospheric aerosols using supercritical fluid extraction and thermo-optical analysis

Air-starved combustion of biomass and fossil fuels releases aerosols, including airborne carbonaceous particles, causing negative climatic and health effects. Radiocarbon analysis of the elemental carbon (EC) fraction can help apportion sources of its emission, which is greatly constrained by the challenges in isolation of EC from organic compounds in atmospheric aerosols. The isolation of EC using thermo-optical analysis is however biased by the presence of interfering compounds that undergo pyrolysis during the analysis. EC is considered insoluble in all acidic, basic, and organic solvents. Based on the property of insolubility, a sample preparation method using supercritical CO2 and methanol as co-solvent was developed to remove interfering organic compounds. The efficiency of the method was studied by varying the density of supercritical carbon dioxide by means of temperature and pressure and by varying the methanol content. Supercritical CO2 with 10% methanol by volume at a temperature of 60 °C, a pressure of 350 bar and 20 min static mode extraction were found to be the most suitable conditions for the removal of 59 ± 3% organic carbon, including compounds responsible for pyrolysis with 78 ± 16% EC recovery. The results indicate that the method has potential for the estimation and isolation of EC from OC for subsequent analysis methods and source apportionment studies.

Elemental and organic carbon in atmospheric aerosols over the northwestern coast of Kandalaksha Bay of the White Sea

This report presents data on the distribution of elemental and organic carbon in the surface layer of the atmosphere on the northwestern coast of Kandalaksha Bay of the White Sea for the years 2010–2012. Elemental carbon (EC) is the primary component of black carbon, which has made a considerable contribution to climate change in the Arctic region. The concentrations of EC are at the background level for the Arctic and are characterized by minor seasonal and annual variability. A significant source of EC is the western transfer from the direction of industrial regions of Northern Europe, including the gas flares of the oil fields in the North Sea. Forest fires during summer months are additional sources of EC.

Multi-wavelength optical determination of black and brown carbon in atmospheric aerosols

In this paper, a new way to apportion the absorption coefficient (babs) of carbonaceous atmospheric aerosols starting from a multi-wavelength optical analysis is shown. This methodology can disentangle and quantify the contribution to total absorption of equivalent black carbon (EBC) emitted by wood burning (EBCWB) and fossil fuel (EBCFF) as well as brown carbon (BrC) due to incomplete combustion. The method uses the information gathered at five different wavelengths in a renewed and upgraded version of the approach usually referred to as Aethalometer model. Moreover, we present the results of an apportionment study of carbonaceous aerosol sources performed in a rural area and in a coastal city, both located in the North-West of Italy. Results obtained by the proposed approach are validated against independent measurements of levoglucosan and radiocarbon. At the rural site the EBCWB and EBCFF relative contributions are about 40% and 60% in winter and 15% and 85% in summer, respectively. At the coastal urban site, EBCWB and EBCFF are about 15% and 85% during fall. The OC contribution to the wood burning source at the rural site results approximately 50% in winter and 10% in summer and about 15% at the coastal urban site in fall. The new methodology also provides a direct measurement of the absorption Ångström exponent of BrC (αBrC) which resulted αBrC = 3.95 ± 0.20.

Wide Ranged Measurement of Elemental Carbon in Atmospheric Aerosols using Spot Samples on the Tape Fillter mounted in Automated SPM Monitors

Wide Ranged Measurement of Elemental Carbon in Atmospheric Aerosols using Spot Samples on the Tape Fillter mounted in Automated SPM Monitors

Hygroscopic properties of Amazonian biomass burning and European background HULIS and investigation of their effects on surface tension with two models linking H-TDMA to CCNC data

Abstract. HUmic-LIke Substances (HULIS) have been identified as major contributors to the organic carbon in atmospheric aerosol. The term "HULIS" is used to describe the organic material found in aerosol particles that resembles the humic organic material in rivers and sea water and in soils. In this study, two sets of filter samples from atmospheric aerosols were collected at different sites. One set of samples was collected at the K-puszta rural site in Hungary, about 80 km SE of Budapest, and a second was collected at a site in Rondônia, Amazonia, Brazil, during the Large-Scale Biosphere-Atmosphere Experiment in Amazonia – Smoke Aerosols, Clouds, Rainfall and Climate (LBA-SMOCC) biomass burning season experiment. HULIS were extracted from the samples and their hygroscopic properties were studied using a Hygroscopicity Tandem Differential Mobility Analyzer (H-TDMA) at relative humidity (RH) &lt;100%, and a cloud condensation nucleus counter (CCNC) at RH &gt;100%. The H-TDMA measurements were carried out at a dry diameter of 100 nm and for RH ranging from 30 to 98%. At 90% RH the HULIS samples showed diameter growth factors between 1.04 and 1.07, reaching values of 1.4 at 98% RH. The cloud nucleating properties of the two sets of aerosol samples were analysed using two types of thermal static cloud condensation nucleus counters. Two different parameterization models were applied to investigate the potential effect of HULIS surface activity, both yielding similar results. For the K-puszta winter HULIS sample, the surface tension at the point of activation was estimated to be lowered by between 34% (47.7 mN/m) and 31% (50.3 mN/m) for dry sizes between 50 and 120 nm in comparison to pure water. A moderate lowering was also observed for the entire water soluble aerosol sample, including both organic and inorganic compounds, where the surface tension was decreased by between 2% (71.2 mN/m) and 13% (63.3 mN/m).

Comparison of analytical methods for Humic Like Substances (HULIS) measurements in atmospheric particles

Abstract. Humic-Like Substances (HULIS) are a major contributor to the organic carbon in atmospheric aerosol. It would be necessary to standardize an analytical method that could be easily and routinely used for HULIS measurements. We present one of the first comparisons of two of the main methods in use to extract HULIS, using I) a weak anion exchanger (DEAE) and II) the combination of two separation steps, one according to polarity (on C18) and the second according to acidity (with a strong anion exchanger SAX). The quantification is performed with a TOC analyzer, complemented by an investigation of the chemical structure of the extracted fractions by UV-Visible spectroscopy. The analytical performances of each method are determined and compared for humic substances standards. These methods are further applied to determine the water extractable HULIS (HULISWS) and the 0.1 M NaOH alkaline extractable HULIS (HULIS T) in atmospheric aerosol collected in an Alpine Valley during winter time. This comparison, although on a limited batch of samples shows that the simpler DEAE isolation procedure leads to higher recoveries and better reproducibility than the C18-SAX procedure, and might therefore be preferable.

Application of the Integrating Sphere Method to Separate the Contributions of Brown and Black Carbon in Atmospheric Aerosols

Until about a decade ago, black carbon (BC) was thought to be the only light absorbing substance in the atmospheric aerosol except for soil or desert dust In more recent years, light absorbing polymeric carbonaceous material was found in atmospheric aerosols. Absorption increases appreciably toward short wavelengths, so this fraction was called brown carbon. Because brown carbon is thermally rather refractory, it influences the split between organic carbon (OC) and elemental carbon (EC) in thermal methods and, through its light absorption characteristics, leads to overestimations of BC concentrations. The goal of the present study was to extend the integrating sphere method to correct the BC signal for the contribution of brown carbon and to obtain an estimate of brown carbon concentrations. Humic acid sodium salt was used as proxy for brown carbon. The extended method is first tested on mixtures of test substances and then applied to atmospheric samples collected during biomass smoke episodes (Easter bonfires) in Austria. The resulting concentrations of black and brown carbon are compared to EC obtained with a widely used thermal method, the Cachier method (Cachier et al. Tellus 1989, 41B, 379-390) and a thermal-optical method (Schmid et al. Atmos. Environ. 2001, 35, 2111-2121), as well as to concentrations of humic like substances (HULIS) and to biomass smoke POM (particulate organic matter). Both the thermal methods were found to overestimate BC on days with large contributions of woodsmoke, which agrees with the findings of the method intercomparison study by Reisinger et at. (Environ. Sci. Technol. 2008, 42, 884-889). During the days of the bonfires, the Cachier method gave EC concentrations that were higher by a factor of 3.8 than the BC concentrations, while the concentrations obtained with the thermal-optical method were higher by a factor of 2.6.

Elemental and organic carbon in atmospheric aerosols at downtown and suburban sites in Prague

Organic and elemental carbon (OC and EC) content in PM 10 was studied at two sites in Prague, which were located in a suburb and in the downtown. Similar overall average levels were found for both species and also for the PM 10 mass at the two sites (i.e., 5.5 and 4.8 μg/m 3 for OC, 0.74 and 0.80 μg/m 3 for EC, and 33 μg/m 3 and 37 μg/m 3 for the PM 10 mass at the suburb and downtown site, respectively), but substantial differences were observed between the two sites in some seasons and/or meteorological situations. Approximately three times higher values were found for OC in winter compared to summer, with a higher winter/summer ratio for the suburban site. The differences for EC were smaller, but still, compared to summer, more than two times higher EC levels were observed during autumn at the suburban site and 1.5 higher EC levels in winter and autumn at the downtown site. The lowest OC to EC ratios at the suburban site were 3.4, while they were around 1.3 for the downtown site. It was found that the origin of the air masses had a major impact on the observed PM 10 mass and OC levels, with largest concentrations noted for air masses recirculating over central Europe and arriving from southeastern Europe in winter. Trajectories coming from the west and northwest originating above the Atlantic Ocean and the Artic brought the cleanest air masses to the sites. For EC the largest difference between the two sites was observed for northwesterly winds during the non-heating season when the suburban site was upwind of Prague.

Quantification and radiocarbon source apportionment of black carbon in atmospheric aerosols using the CTO-375 method

To make progress towards linking the atmosphere and biogeosphere parts of the black carbon (BC) cycle, a chemothermal oxidation method (CTO-375), commonly applied for isolating BC from complex geomatrices such as soils, sediments and aquatic particles, was applied to investigate the BC also in atmospheric particles. Concentrations and 14C-based source apportionment of CTO-375 based BC was established for a reference aerosol (NIST RM-8785) and for wintertime aerosols collected in Stockholm and in a Swedish background area. The results were compared with thermal–optical (OC/EC) measurements. For NIST RM-8785, a good agreement was found between the BC CTO-375 concentration and the reported elemental carbon (EC) concentration measured by the “Speciation Trends Network—National Institute of Occupational Safety and Health” method (EC NIOSH) with BC CTO-375 of 0.054±0.002 g g −1 and EC NIOSH of 0.067±0.008 g g −1. In contrast, there was an average factor of ca. 20 difference between BC CTO-375 and EC NIOSH for the ambient Scandinavian wintertime aerosols, presumably reflecting a combination of BC CTO-375 isolating only the recalcitrant soot-BC portion of the BC continuum and the EC NIOSH metric inadvertently including some intrinsically non-pyrogenic organic matter. Isolation of BC CTO-375 with subsequent off-line radiocarbon analysis yielded fraction modern values (fM) for total organic carbon (TOC) of 0.93 (aerosols from a Swedish background area), and 0.58 (aerosols collected in Stockholm); whereas the fM for BC CTO-375 isolates were 1.08 (aerosols from a Swedish background area), and 0.87 (aerosols collected in Stockholm). This radiocarbon-based source apportionment suggests that contribution from biomass combustion to cold-season atmospheric BC CTO-375 in Stockholm was 70% and in the background area 88%.