The limited understanding of black carbon (BC) aerosol emissions from incomplete combustion causes a poorly constrained anthropogenic climate warming that globally may be second only to CO2 and ...regionally, such as over East Asia, the dominant driver of climate change. The relative contribution to atmospheric BC from fossil fuel versus biomass combustion is important to constrain as fossil BC is a stronger climate forcer. The source apportionment is the underpinning for targeted mitigation actions. However, technology-based “bottom-up” emission inventories are inconclusive, largely due to uncertain BC emission factors from small-scale/household combustion and open burning. We use “top-down” radiocarbon measurements of atmospheric BC from five sites including three city sites and two regional sites to determine that fossil fuel combustion produces 80 ± 6% of the BC emitted from China. This source-diagnostic radiocarbon signal in the ambient aerosol over East Asia establishes a much larger role for fossil fuel combustion than suggested by all 15 BC emission inventory models, including one with monthly resolution. Our results suggest that current climate modeling should refine both BC emission strength and consider the stronger radiative absorption associated with fossil-fuel-derived BC. To mitigate near-term climate effects and improve air quality in East Asia, activities such as residential coal combustion and city traffic should be targeted.
Carbonaceous aerosols cause strong atmospheric heating and large surface cooling that is as important to South Asian climate forcing as greenhouse gases, yet the aerosol sources are poorly ...understood. Emission inventory models suggest that biofuel burning accounts for 50 to 90% of emissions, whereas the elemental composition of ambient aerosols points to fossil fuel combustion. We used radiocarbon measurements of winter monsoon aerosols from western India and the Indian Ocean to determine that biomass combustion produced two-thirds of the bulk carbonaceous aerosols, as well as one-half and two-thirds of two black carbon subfractions, respectively. These constraints show that both biomass combustion (such as residential cooking and agricultural burning) and fossil fuel combustion should be targeted to mitigate climate effects and improve air quality.
This paper reports the first study applying a triple-isotope approach for source apportionment of polycyclic aromatic hydrocarbons (PAHs). The 13C/12C, 14C/12C, and 2H/1H isotope ratios of PAHs were ...determined in forest soils from mountainous areas of the Czech Republic, European Union. Statistical modeling applying a Bayesian Markov chain Monte Carlo (MCMC) framework to the environmental triple isotope PAH data and an end-member PAH isotope database allowed comprehensive accounting of uncertainties and quantitative constraints on the PAH sources among biomass combustion, liquid fossil fuel combustion, and coal combustion at low and high temperatures. The results suggest that PAHs in this central European region had a clear predominance of coal combustion sources (75 ± 6%; uncertainties represent 1 SD), mainly coal pyrolysis at low temperature (∼650 °C; 61 ± 8%). Combustion of liquid fossil fuels and biomass represented 16 ± 3 and 9 ± 3% of the total PAH burden (∑PAH14), respectively. Although some soils were located close to potential PAH point sources, the source distribution was within a narrow range throughout the region. These observation-based top-down constraints on sources of environmental PAHs provide a reference for both improved bottom-up emission inventories and guidance for efforts to mitigate PAH emissions.
Fluvial discharge and coastal erosion of the permafrost-dominated East Siberian Arctic delivers large quantities of terrigenous organic carbon (Terr-OC) to marine waters. The composition and fate of ...the remobilized Terr-OC needs to be better constrained as it impacts the potential for a climate–carbon feedback. In the present study, the bulk isotope (δ13C and Δ14C) and macromolecular (lignin-derived phenols) composition of the cross-shelf exported organic carbon (OC) in different marine pools is evaluated. For this purpose, as part of the SWERUS-C3 expedition (July–September 2014), sediment organic carbon (SOC) as well as water column (from surface and near-bottom seawater) dissolved organic carbon (DOC) and particulate organic carbon (POC) samples were collected along the outer shelves of the Kara Sea, Laptev Sea and East Siberian Sea. The results show that the Lena River and the DOC may have a preferential role in the transport of Terr-OC to the outer shelf. DOC concentrations (740–3600 µg L−1) were 1 order of magnitude higher than POC (20–360 µg L−1), with higher concentrations towards the Lena River plume. The δ13C signatures in the three carbon pools varied from −23.9 ± 1.9 ‰ in the SOC, −26.1 ± 1.2 ‰ in the DOC and −27.1 ± 1.9 ‰ in the POC. The Δ14C values ranged between −395 ± 83 (SOC), −226 ± 92 (DOC) and −113 ± 122 ‰ (POC). These stable and radiocarbon isotopes were also different between the Laptev Sea and the East Siberian Sea. Both DOC and POC showed a depleted and younger trend off the Lena River plume. Further, the Pacific inflow and the sea-ice coverage, which works as a barrier preventing the input of “young” DOC and POC, seem to have a strong influence in these carbon pools, presenting older and more enriched δ13C signatures under the sea-ice extent. Lignin phenols exhibited higher OC-normalized concentrations in the SOC (0.10–2.34 mg g−1 OC) and DOC (0.08–2.40 mg g−1 OC) than in the POC (0.03–1.14 mg g−1 OC). The good relationship between lignin and Δ14C signatures in the DOC suggests that a significant fraction of the outer-shelf DOC comes from “young” Terr-OC. By contrast, the slightly negative correlation between lignin phenols and Δ14C signatures in POC, with higher lignin concentrations in older POC from near-bottom waters, may reflect the off-shelf transport of OC from remobilized permafrost in the nepheloid layer. Syringyl ∕ vanillyl and cinnamyl ∕ vannillyl phenol ratios presented distinct clustering between DOC, POC and SOC, implying that those pools may be carrying different Terr-OC of partially different origin. Moreover, 3,5-dihydroxybenzoic acid to vanillyl phenol ratios and p-coumaric acid to ferulic acid ratios, used as a diagenetic indicators, enhanced in POC and SOC, suggesting more degradation within these pools. Overall, the key contrast between enhanced lignin yields both in the youngest DOC and the oldest POC samples reflects a significant decoupling of terrestrial OC sources and pathways.
Black carbon (BC) aerosols impact climate and air quality. Since BC from fossil versus biomass combustion have different optical properties and different abilities to penetrate the lungs, it is ...important to better understand their relative contributions in strongly affected regions such as South Asia. This study reports the first year-round 14C-based source apportionment of elemental carbon (EC), the mass-based correspondent to BC, using as regional receptor sites the international Maldives Climate Observatory in Hanimaadhoo (MCOH) and the mountaintop observatory of the Indian Institute of Tropical Meteorology in Sinhagad, India (SINH). For the highly-polluted winter season (December-March), the fractional contribution to EC from biomass burning (fbio) was 53 5% (n = 6) at MCOH and 56 3% at SINH (n = 5). The fbio for the non-winter remainder was 53 11% (n = 6) at MCOH and 48 8% (n = 7) at SINH. This observation-based constraint on near-equal contributions from biomass burning and fossil fuel combustion at both sites compare with predictions from eight technology-based emission inventory (EI) models for India of (fbio)EI spanning 55-88%, suggesting that most current EI for Indian BC systematically under predict the relative contribution of fossil fuel combustion. A continued iterative testing of bottom-up EI with top-down observational source constraints has the potential to lead to reduced uncertainties regarding EC sources and emissions to the benefit of both models of climate and air quality as well as guide efficient policies to mitigate emissions.
Atmospheric Brown Clouds (ABC), regional‐scale haze events, are a significant concern for both human cardiopulmonary health and regional climate impacts. In order to effectively mitigate this ...pollution‐based phenomenon, it is imperative to understand the magnitude, scope and source of ABC in regions such as South Asia. Two sites in S. Asia were chosen for a 15‐month field campaign focused on isotope‐based source apportionment of carbonaceous aerosols in 2008–2009. Both the Maldives Climate Observatory in Hanimaadhoo (MCOH) and a mountaintop site in Sinhagad, India (SINH) act as regionally mixed receptor sites. Annual radiocarbon‐based source apportionment for soot elemental carbon (SEC) at MCOH and SINH revealed 73 ± 6% and 59 ± 5% contribution from biomass combustion, respectively (remainder from fossil fuel). The contributions from biogenic/biomass combustion to total organic carbon were similar between MCOH and SINH (69 ± 5% and 64 ± 5, respectively). The biomass combustion contribution for SEC in the current study, especially the results from MCOH, shows good agreement with published black carbon emissions inventories for India. Geographic source assessment, including clustered back trajectory analysis and carbon contribution by source region, indicated that the highest SEC/TOC loads originated from the W. Indian coastal margin, including the coastal city of Mumbai, India. The winter dry season 14C‐based source apportionment of the BC‐tracing SEC fraction for 2006, 2008, 2009 were not statistically different (p = 0.7) and point to a near‐constant two‐thirds contribution from biomass combustion practices, including wood and other biofuels as well as burning of agricultural crop residues.
Key Points
S. Asian soot elemental carbon was 59–73% biomass combustion
Year‐round biomass contribution to black carbon similar for 2006, 2008 and 2009
S. Asian total organic carbon was 64‐69% contemporary carbon
Urban-like plumes of gases and particulate matter originating from the South Asian region are frequently observed over the Indian Ocean, especially during the dry winter period. However, in addition ...to the strong sources on mainland South Asia, there are also local Maldivian emissions. The local contributions to the load of fine particulate matter (PM2.5) in the Maldivian capital Malé was assessed using the well-established Maldives Climate Observatory at Hanimaadhoo (MCOH) to represent local background, recording the long-range transported component for a full-year synoptic campaign at both sites in 2013. The year-round levels in both Malé and MCOH are strongly influenced by the seasonality of the monsoon cycle, including precipitation patterns and air-mass transport pathways, with lower levels during the wet summer season. The annual-average PM2.5 levels in Malé are higher (avg. 19μg/m3) than at MCOH (avg. 13μg/m3) with the difference being the largest during the summer, when local emissions play a larger role. The 24-h World Health Organization (WHO) PM2.5 health guideline was surpassed for the weeklong collections in 71% of the cases in Malé and in 74% of the cases for Hanimaadhoo. This study shows that in the dry/winter season 90±11% of PM2.5 levels in Malé could be from long-range transport with only 8±11% from local emissions while in the wet/monsoon season the relative contributions are about equal. The concentrations of organic carbon (OC) and elemental carbon (EC) showed similar seasonal patterns as bulk mass PM2.5. The relative contribution of total carbonaceous matter to bulk mass PM2.5 was 17% in Malé and 13% at MCOH, suggesting larger contributions from incomplete combustion practices in the Malé local region.
Figure: Monthly average variations of A. Organic carbon (OC), B. Elemental carbon (EC) and C. PM2.5 concentrations in Malé and MCOH. Vertical shaded bars indicates the transition periods (May and October). Display omitted
•Year-round average contribution to Malé PM2.5 is 30% local and 70% distant sources.•In dry season 90% of PM2.5 load is from distant sources.•The local Malé sources have higher carbonaceous content.
In this study the environmental fate of two novel trifluoromethoxy-substituted surfactants with respectively an ether or thioether linkage were investigated, of which the design aimed for less ...persistency and complete mineralization. Long-term microbial transformation studies under aerobic conditions in activated sludge-wastewater medium were performed for 126 days. A semi-closed experimental system with a trapping sorbent was selected to avoid losses of possible volatile transformation products (TPs). The changes in the concentration of the surfactants and their expected TPs were monitored by target analysis using liquid chromatography–tandem mass spectrometry. Significant decrease in the concentration of the surfactants was observed over the incubation period. The main detected TPs were short-chained carboxylic acids (CAs), including a CA with two fluorinated carbon atoms representing the last product prior to mineralization. High stability of these CAs and lack in the formation of inorganic fluoride over the incubation time was however observed. Consequently, unequivocal final mineralization of the investigated surfactants could not be confirmed. Regarding the mass balance, the total amount of detected substances achieved only 30–37% of the expected concentration at the end of the incubation time. The reason of the incomplete mass balance should be further investigated.
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•Fluorinated surfactants were designed and synthesized with the goal of mineralization.•Degradability was tested in aerobic activated sludge over 126 days.•Main transformation products were carboxylic acids with ≤3 fluorinated carbon atoms.•No mineralization was proved.
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