| 1. |
- Aeppli, Christoph, et al.
(author)
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Chlorine Isotope Effects and Composition of Naturally Produced Organochlorines from Chloroperoxidases, Flavin-Dependent Halogenases, and in Forest Soil
- 2013
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In: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 47:13, s. 6864-6871
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Journal article (peer-reviewed)abstract
- The use of stable chlorine isotopic signatures (delta Cl-37) of organochlorine compounds has been suggested as a tool to determine both their origins and transformations in the environment. Here we investigated the delta Cl-37 fractionation of two important pathways for enzymatic natural halogenation: chlorination by chloroperoxidase (CPO) and flavin-dependent halogenases (FDH). Phenolic products of CPO were highly Cl-37 depleted (delta Cl-37 = -12.6 +/- 0.9 parts per thousand); significantly more depleted than all known industrially produced organochlorine compounds (delta Cl-37 = -7 to +6 parts per thousand). In contrast, four FDH products did not exhibit any observable isotopic shifts (delta Cl-37 = -0.3 +/- 0.6 parts per thousand). We attributed the different isotopic effect to the distinctly different chlorination mechanisms employed by the two enzymes. Furthermore, the delta Cl-37 in bulk organochlorines extracted from boreal forest soils were only slightly depleted in Cl-37 relative to inorganic Cl. In contrast to previous suggestions that CPO plays a key role in production of soil organochlorines, this observation points to the additional involvement of either other chlorination pathways, or that dechlorination of naturally produced organochlorines can neutralize delta Cl-37 shifts caused by CPO chlorination. Overall, this study demonstrates that chlorine isotopic signatures are highly useful to understand sources and cycling of organochlorines in nature. Furthermore, this study presents delta Cl-37 values of FDH products as well of bulk organochlorines extracted from pristine forest soil for the first time.
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| 2. |
- Aeppli, Christoph, et al.
(author)
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Direct compound-specific stable chlorine isotope analysis of organic compounds with quadrupole GC/MS using standard isotope bracketing
- 2010
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In: Analytical Chemistry. - Columbus, OH : American Chemical Society. - 0003-2700 .- 1520-6882. ; 82:1, s. 420-426
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Journal article (peer-reviewed)abstract
- A method has been developed for the direct determination of the stable chlorine isotope composition (delta(37)Cl) of organochlorines that eliminates sample preparation, achieves precision comparable to earlier techniques while improving the sensitivity, and makes use of benchtop gas chromatography-quadrupole mass spectrometry instruments (GCqMS). The method is based on the use of multiple injections (n = 8-10) of the sample, bracketed by a molecularly identical isotopic standard with known delta(37)Cl, determined using off-line thermal ionization mass spectrometry (TIMS). Mass traces of two isotopologues differing by one chlorine isotope were used to calculate delta(37)Cl values. Optimization of mass spectrometry and peak integration parameters as well as method validation was achieved using tetrachloroethene (PCE), p,p'-dichlorodiphenyltrichloroethane (DDT), and pentachlorophenol (PCP), spanning a delta(37)Cl range of -5.5 to +3.2 per thousand vs SMOC. Injecting 1.6-1100 pmol resulted in standard deviations (1sigma) of 0.6-1.3 per thousand, and the delta(37)Cl results agreed with values independently measured with TIMS. The method was tested by determining the Rayleigh fractionation during evaporation of pure liquid PCE, resulting in a chlorine isotopic enrichment factor of epsilon(Cl) = -1.1 +/- 0.4 per thousand. Furthermore, position-specific delta(37)Cl analysis based on analysis of DDT mass fragments was evaluated. The GCqMS-delta(37)Cl method offers a simplified yet sensitive approach for compound-specific chlorine isotope analysis.
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| 3. |
- Aeppli, Christoph, et al.
(author)
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Use of Cl and C Isotopic Fractionation to Identify Degradation and Sources of Polychlorinated Phenols : Mechanistic Study and Field Application
- 2013
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In: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 47:2, s. 790-797
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Journal article (peer-reviewed)abstract
- The widespread use of chlorinated phenols (CPs) as a wood preservative has led to numerous contaminated sawmill sites. However, it remains challenging to assess the extent of in situ degradation of CPs. We evaluated the use of compound-specific chlorine and carbon isotope analysis (Cl- and C-CSLA) to assess CP biotransformation. In a laboratory system, we measured isotopic fractionation during oxidative 2,4,6-trichlorophenol dechlorination by representative soil enzymes (C. fumago chloroperoxidase, horseradish peroxidase, and laccase from T. versicolor). Using a mathematical model, the validity of the Rayleigh approach to evaluate apparent kinetic isotope effects (AKIE) was confirmed. A small but significant Cl-AKIE of 1.0022 +/- 0.0006 was observed for all three enzymes, consistent with a reaction pathway via a cationic radical species. For carbon, a slight inverse isotope effect was observed (C-AKIE = 0.9945 +/- 0.0019). This fractionation behavior is clearly distinguishable from reported reductive dechlorination mechanisms. Based on these results we then assessed degradation and apportioned different types of technical CP mixtures used at two former sawmill sites. To our knowledge, this is the first study that makes use of two-element CSIA to study sources and transformation of CPs in the environment.
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| 4. |
- Alling, Vanja, et al.
(author)
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Degradation of terrestrial organic carbon, primary production and out-gassing of CO2 in the Laptev and East Siberian Seas as inferred from delta C-13 values of DIC
- 2012
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In: Geochimica Et Cosmochimica Acta. - : Elsevier BV. - 0016-7037 .- 1872-9533. ; 95, s. 143-159
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Journal article (peer-reviewed)abstract
- The cycling of carbon on the Arctic shelves, including outgassing of CO2 to the atmosphere, is not clearly understood. Degradation of terrestrial organic carbon (OCter) has recently been shown to be pronounced over the East Siberian Arctic Shelf (ESAS), i.e. the Laptev and East Siberian Seas, producing dissolved inorganic carbon (DIC). To further explore the processes affecting DIC, an extensive suite of shelf water samples were collected during the summer of 2008, and assessed for the stable carbon isotopic composition of DIC (delta C-13(DIC)). The delta C-13(DIC) values varied between -7.2 parts per thousand to +1.6 parts per thousand and strongly deviated from the compositions expected from only mixing between river water and seawater. Model calculations suggest that the major processes causing these deviations from conservative mixing were addition of (DIC) by degradation of OCter, removal of DIC during primary production, and outgassing of CO2. All waters below the halocline in the ESAS had delta C-13(DIC) values that appear to reflect mixing of river water and seawater combined with additions of on average 70 +/- 20 mu M of DIC, originating from degradation of OCter in the coastal water column. This is of the same magnitude as the recently reported deficits of DOCter and POCter for the same waters. The surface waters in the East Siberian Sea had higher delta C-13(DIC) values and lower DIC concentrations than expected from conservative mixing, consistent with additions of DIC from degradation of OCter and outgassing of CO2. The outgassing of CO2 was equal to loss of 123 +/- 50 mu M DIC. Depleted delta C-13(POC) values of -29 parts per thousand to -32 parts per thousand in the mid to outer shelf regions are consistent with POC from phytoplankton production. The low delta C-13(POC) values are likely due to low delta C-13(DIC) of precursor DIC, which is due to degradation of OCter, rather than reflecting terrestrial input compositions. Overall, the delta C-13(DIC) values confirm recent suggestions of substantial degradation of OCter over the ESAS, and further show that a large part of the CO2 produced from degradation has been outgassed to the atmosphere. (C) 2012 Elsevier Ltd. All rights reserved.
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| 5. |
- Alling, Vanja, et al.
(author)
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Non-conservative behavior of dissolved organic carbon across the Laptev and East Siberian Seas
- 2010
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In: Global Biogeochemical Cycles. - 0886-6236 .- 1944-9224. ; 24, s. GB4033-
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Journal article (peer-reviewed)abstract
- Climate change is expected to have a strong effect on the Eastern Siberian Arctic Shelf (ESAS) region, which includes 40% of the Arctic shelves and comprises the Laptev and East Siberian seas. The largest organic carbon pool, the dissolved organic carbon (DOC), may change significantly due to changes in both riverine inputs and transformation rates; however, the present DOC inventories and transformation patterns are poorly understood. Using samples from the International Siberian Shelf Study 2008, this study examines for the first time DOC removal in Arctic shelf waters with residence times that range from months to years. Removals of up to 10%–20% were found in the Lena River estuary, consistent with earlier studies in this area, where surface waters were shown to have a residence time of approximately 2 months. In contrast, the DOC concentrations showed a strong nonconservative pattern in areas with freshwater residence times of several years. The average losses of DOC were estimated to be 30%–50% during mixing along the shelf, corresponding to a first-order removal rate constant of 0.3 yr−1. These data provide the first observational evidence for losses of DOC in the Arctic shelf seas, and the calculated DOC deficit reflects DOC losses that are higher than recent model estimates for the region. Overall, a large proportion of riverine DOC is removed from the surface waters across the Arctic shelves. Such significant losses must be included in models of the carbon cycle for the Arctic Ocean, especially since the breakdown of terrestrial DOC to CO2 in Arctic shelf seas may constitute a positive feedback mechanism for Arctic climate warming. These data also provide a baseline for considering the effects of future changes in carbon fluxes, as the vast northern carbon-rich permafrost areas draining into the Arctic are affected by global warming.
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| 6. |
- Andersson, August, et al.
(author)
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(14)C-Based source assessment of soot aerosols in Stockholm and the Swedish EMEP-Aspvreten regional background site
- 2011
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In: Atmospheric Environment. - : Elsevier BV. - 1352-2310 .- 1873-2844. ; 45:1, s. 215-222
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Journal article (peer-reviewed)abstract
- Combustion-derived soot or black carbon (BC) in the atmosphere has a strong influence on both climate and human health. In order to propose effective mitigation strategies for BC emissions it is of importance to investigate geographical distributions and seasonal variations of BC emission sources. Here, a radiocarbon methodology is used to distinguish between fossil fuel and biomass burning sources of soot carbon (SC). SC is isolated for subsequent off-line (14)C quantification with the chemothermal oxidation method at 375 degrees C (CTO-375 method), which reflects a recalcitrant portion of the BC continuum known to minimize inadvertent inclusion of any non-pyrogenic organic matter. Monitored wind directions largely excluded impact from the Stockholm metropolitan region at the EMEP-Aspvreten rural station 70 km to the south-west. Nevertheless, the Stockholm city and the rural stations yielded similar relative source contributions with fraction biomass (f(biomass)) for fall and winter periods in the range of one-third to half. Large temporal variations in (14)C-based source apportionment was noted for both the 6 week fall and the 4 month winter observations. The f(biomass) appeared to be related to the SC concentration suggesting that periods of elevated BC levels may be caused by increased wood fuel combustion. These results for the largest metropolitan area in Scandinavia combine with other recent (14)C-based studies of combustion-derived aerosol fractions to suggest that biofuel combustion is contributing a large portion of the BC load to the northern European atmosphere.
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| 7. |
- Andersson, August, et al.
(author)
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Regionally-Varying Combustion Sources of the January 2013 Severe Haze Events over Eastern China
- 2015
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In: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 49:4, s. 2038-2043
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Journal article (peer-reviewed)abstract
- Thick haze plagued northeastern China in January 2013, strongly affecting both regional climate and human respiratory health. Here, we present dual carbon isotope constrained (Delta C-14 and delta C-13) source apportionment for combustion-derived black carbon aerosol (BC) for three key hotspot regions (megacities): North China Plain (NCP, Beijing), the Yangtze River Delta (YRD, Shanghai), and the Pearl River Delta (PRD, Guangzhou) for January 2013. BC, here quantified as elemental carbon (EC), is one of the most health-detrimental components of PM2.5 and a strong climate warming agent. The results show that these severe haze events were equally affected (similar to 30%) by biomass combustion in all three regions, whereas the sources of the dominant fossil fuel component was dramatically different between north and south. In the NCP region, coal combustion accounted for 66% (46-74%, 95% C.I.) of the EC, whereas, in the YRD and PRD regions, liquid fossil fuel combustion (e.g., traffic) stood for 46% (18-66%) and 58% (38-68%), respectively. Taken together, these findings suggest the need for a regionally-specific description of BC sources in climate models and regionally-tailored mitigation to combat severe air pollution events in East Asia.
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| 8. |
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| 9. |
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| 10. |
- Andersson, Per S., et al.
(author)
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The importance of colloids for the behavior of uranium isotopes in the low-salinity zone of a stable estuary
- 2001
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In: Geochimica et Cosmochimica Acta. - 0016-7037 .- 1872-9533. ; 65:1, s. 13-25
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Journal article (peer-reviewed)abstract
- Particle-mediated removal processes of U isotopes were investigated during spring flood discharge in the low-salinity zone (LSZ, up to 3 practical salinity units [psu]) of a stable estuary. A shipboard ultrafiltration cross-flow filtration (CFF) technique was used to separate particles (>0.2 μm) and colloids (between 3000 daltons (3 kD) and 0.2 μm) from ultrafiltered water (<3 kD) containing "dissolved" species. Sediment traps were used to collect sinking material. Concentration of Fe and organic C, which are indicators of the major U carrier phases, were used to interpret the behavior of 234U-238U during estuarine mixing. Colloids dominated the river water transport of U, carrying ≈90% of the U. On entering the estuary, colloids accounted for the dominant fraction of U to about a salinity of 1 psu, but only a minor fraction (<5%) at 3 psu. A substantial fraction of the total U is removed at <1 psu by Fe-organic rich colloids that aggregate and sink during initial estuarine mixing in the Kalix River estuary. In contrast, at salinities >1 psu, there is a general correlation between U and salinity in all filtered fractions. The 234U/238U ratios in different filtered fractions and sinking particles were generally indistinguishable at each station and showed enrichment in 234U, compared with secular equilibrium (δ234U = 266-567). This clearly shows that all size fractions are dominated by nondetrital U. Consideration of U isotope systematics across the estuary reveals that substantial U exchange must occur involving larger particles at least to 1 psu and involving colloids at least to ≈1.5 psu. Further exchange at higher salinities may also occur, as the proportion of U on colloids decreases with increasing salinity. This may be due to decreasing colloid concentration and increasing stabilization of uranyl carbonate complexes during mixing in the estuary. The results show that although U is a soluble element that shows generally conservative mixing in estuaries, removal occurs in the very low salinity zone, and this zone represents a significant sink of U. Variation in composition and concentration of colloidal particles between different estuaries might thus be an important factor for determining the varying behavior of U between estuaries.
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| 11. |
- Andersson, Per S., et al.
(author)
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The isotopic composition of Nd in a boreal river : a reflection of selective weathering and colloidal transport
- 2001
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In: Geochimica et Cosmochimica Acta. - 0016-7037 .- 1872-9533. ; 65:4, s. 521-527
-
Journal article (peer-reviewed)abstract
- In this study the Nd concentrations (CNd) from 18 months of weekly sampling of filtered water (<0.45 μm) in the Kalix River, northern Sweden, are reported with εNd(0) and 147Sm/144Nd ratios determined in samples representing major flow events as well as maxima and minima in CNd. The CNd varies by a factor of ten, between 200 pmol/L to 2100 pmol/L, and there is a strong relation between high discharge and high CNd. The Nd in the Kalix River is mainly transported on particles (>90%), dominated by a colloidal phase primarily composed of organic C and Fe. The εNd(0) and 147Sm/144Nd only vary within a narrow range, -27.1 to -24.8 and 0.103 to 0.110 respectively, with no obvious relationship to CNd and discharge. The εNd(0) and 147Sm/144Nd in the river water is significantly lower than in the unweathered till and average bedrock in the catchment and show a closer resemblance with the isotopic characteristics found in humic substances and plant material. These data show that the isotopic composition of Nd exported from a large boreal drainage basin does not directly reflect that of the bulk bedrock in the catchment. The isotopic composition is controlled by selective weathering and the Nd transport is dominated by organic colloidal particles.
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| 12. |
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| 13. |
- Berg, H, et al.
(author)
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Structural aspects of lithium insertion in transition metal oxide electrodes
- 1998
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In: JOURNAL OF APPLIED CRYSTALLOGRAPHY. - 0021-8898. ; 31, s. 103-105
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Journal article (peer-reviewed)abstract
- There is a considerable lack of detailed information on the structure of lithiated phases of popular-consensus positive electrode materials for lithium/polymer and lithium-ion/polymer batteries. Having illustrated this phenomenon for the specific cases o
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| 14. |
- Bergstrom, Örjan, et al.
(author)
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A neutron diffraction cell for studying lithium-insertion processes in electrode materials
- 1998
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In: JOURNAL OF APPLIED CRYSTALLOGRAPHY. - 0021-8898. ; 31, s. 823-825
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Journal article (other academic/artistic)abstract
- An electrochemical cell has been constructed for in situ neutron diffraction studies of lithium-insertion/extraction processes in electrode materials for Li-ion batteries. Its key components are a Pyrex tube, gold plated on its inside, which functions as
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| 15. |
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| 16. |
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| 17. |
- Bergstrom, Örjan, et al.
(author)
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Electrochemically lithiated vanadium oxide, Li3V6O13
- 1998
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In: ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS. - 0108-2701. ; 54, s. 1204-1206
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Journal article (other academic/artistic)abstract
- Single crystals of V6O13 Were grown by chemical vapour transport (CVT) and subsequently electrochemically lithiated. The title compound, trilithium hexavanadium tridecaoxide, was the phase formed during electrochemical lithiation at 2.45 V versus Li/Li+.
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| 18. |
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| 19. |
- Bergström, Örjan, et al.
(author)
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Electrochemically lithiated vanadium oxide Li2V6O13
- 1997
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In: Acta Crystallographica C. ; 53, s. 528-
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Journal article (peer-reviewed)abstract
- Single crystals of V6O13 were grown by chemical vapour transport and then electrochemically lithiated, The title compound, dilithium hexavanadium tridecaoxide, was the first phase formed during electrochemical lithiation at 2.65 V Versus Li/Li+. The Li2V
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| 20. |
- Bikkina, Srinivas, et al.
(author)
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Air quality in megacity Delhi affected by countryside biomass burning
- 2019
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In: Nature Sustainability. - : Springer Science and Business Media LLC. - 2398-9629. ; 2:3, s. 200-205
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Journal article (peer-reviewed)abstract
- South Asian megacities are strong sources of regional air pollution. Delhi is a key hotspot of health-and climate-impacting black carbon (BC) emissions, affecting environmental sustainability in densely populated northern India. Effective mitigation of BC impact is hampered by highly uncertain emission source estimates. Here, we use dual-carbon isotope fingerprints (delta C-13/Delta C-14) of BC to constrain the seasonal source variability in Delhi. These measurements show that lower BC concentrations in summer are predominantly from fossil fuel sources (similar to 83%). However, large-scale open burning of post-harvest crop residue/wood in nearby rural regions is contributing to severe haze pollution in Delhi during winter and autumn (similar to 42 +/- 17%). Hence, the common conception that megacities affect their surroundings is here amended or seasonally reversed. Therefore, to combat the severe air pollution problems in Delhi and the environmental quality of northern India, current urban efforts need to be complemented with countryside regional mitigation.
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| 21. |
- Bikkina, Srinivas, et al.
(author)
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Carbon isotope-constrained seasonality of carbonaceous aerosol sources from an urban location (Kanpur) in the Indo-Gangetic Plain
- 2017
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In: Journal of Geophysical Research - Atmospheres. - 2169-897X .- 2169-8996. ; 122:9, s. 4903-4923
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Journal article (peer-reviewed)abstract
- The Indo-Gangetic Plain (IGP) in northern India, Pakistan, and Bangladesh is a major source of carbonaceous aerosols in South Asia. However, poorly constrained seasonality of their sources over the IGP leads to large uncertainty in climate and health effects. Here we present a first data set for year-round radiocarbon (C-14) and stable carbon (C-13)-based source apportionment of total carbon (TC) in ambient PM10 (n = 17) collected from an urban site (Kanpur: 26.5 degrees N, 80.3 degrees E) in the IGP during January 2007 to January 2008. The year-round C-14-based fraction biomass (f(bio-TC)) estimate at Kanpur averages 777% and emphasizes an impact of biomass burning emissions (BBEs). The highest f(bio-TC) (%) is observed in fall season (October-November, 856%) followed by winter (December-February, 804%) and spring (March-May, 758%), while lowest values are found in summer (June-September, 69 +/- 2%). Since biomass/coal combustion and vehicular emissions mostly contribute to carbonaceous aerosols over the IGP, we predict C-13(TC) (C-13(pred)) over Kanpur using known C-13 source signatures and the measured C-14 value of each sample. The seasonal variability of C-13(obs)-C-13(pred) versus C-14(TC) together with air mass back trajectories and Moderate Resolution Imaging Spectroradiometer fire count data reveal that carbonaceous aerosols in winter/fall are significantly influenced by atmospheric aging (downwind transport of crop residue burning/wood combustion emissions in the northern IGP), while local sources (wheat residue combustion/vehicular emissions) dominate in spring/summer. Given the large temporal and seasonal variability in sources and emission strength of TC over the IGP, C-14-based constraints are, thus, crucial for reducing their uncertainties in carbonaceous aerosol budgets in climate models.
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| 22. |
- Bikkina, Srinivas, et al.
(author)
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Dual carbon isotope characterization of total organic carbon in wintertime carbonaceous aerosols from northern India
- 2016
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In: Journal of Geophysical Research - Atmospheres. - 2169-897X .- 2169-8996. ; 121:9, s. 4797-4809
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Journal article (peer-reviewed)abstract
- Large-scale emissions of carbonaceous aerosols (CA) from South Asia impact both regional climate and air quality, yet their sources are not well constrained. Here we use source-diagnostic stable and radiocarbon isotopes (delta C-13 and Delta C-14) to characterize CA sources at a semiurban site (Hisar: 29.2 degrees N, 75.2 degrees E) in the NW Indo-Gangetic Plain (IGP) and a remote high-altitude location in the Himalayan foothills (Manora Peak: 29.4 degrees N, 79.5 degrees E, 1950 m above sea level) in northern India during winter. The Delta C-14 of total aerosol organic carbon (TOC) varied from -178% to -63% at Hisar and from -198% to -1% at Manora Peak. The absence of significant differences in the C-14-based fraction biomass of TOC between Hisar (0.81 +/- 0.03) and Manora Peak (0.82 +/- 0.07) reveals that biomass burning/biogenic emissions (BBEs) are the dominant sources of CA at both sites. Combining this information with d13C, other chemical tracers (K+/OC and SO42-/EC) and air mass back trajectory analyses indicate similar source regions in the IGP (e.g., Punjab and Haryana). These results highlight that CA from BBEs in the IGP are not only confined to the atmospheric boundary layer but also extend to higher elevations of the troposphere, where the synoptic-scale circulations could substantially influence their abundances both to the Himalayas and over the downwind oceanic regions such as the Indian Ocean. Given the vast emissions of CA from postharvest crop residue combustion practices in the IGP during early Northeast Monsoon, this information is important for both improved process and model understanding of climate and health effects, as well as in guiding policy decision aiming at reducing emissions.
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| 23. |
- Bischoff, Juliane, et al.
(author)
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Source, transport and fate of soil organic matter inferred from microbial biomarker lipids on the East Siberian Arctic Shelf
- 2016
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In: Biogeosciences. - : Copernicus GmbH. - 1726-4170 .- 1726-4189. ; 13:17, s. 4899-4914
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Journal article (peer-reviewed)abstract
- The Siberian Arctic contains a globally significant pool of organic carbon (OC) vulnerable to enhanced warming and subsequent release by both fluvial and coastal erosion processes. However, the rate of release, its behaviour in the Arctic Ocean and vulnerability to remineralisation is poorly understood. Here we combine new measurements of microbial biohopanoids including adenosylhopane, a lipid associated with soil microbial communities, with published glycerol dialkyl glycerol tetraethers (GDGTs) and bulk delta C-13 measurements to improve knowledge of the fate of OC transported to the East Siberian Arctic Shelf (ESAS). The microbial hopanoid-based soil OC proxy R'(soil) ranges from 0.0 to 0.8 across the ESAS, with highest values nearshore and decreases offshore. Across the shelf R'(soil) displays a negative linear correlation with bulk delta C-13 measurements (r(2) = -0.73, p = < 0 : 001). When compared to the GDGT-based OC proxy, the branched and isoprenoid tetraether (BIT) index, a decoupled (non-linear) behaviour on the shelf was observed, particularly in the Buor-Khaya Bay, where the R'(soil) shows limited variation, whereas the BIT index shows a rapid decline moving away from the Lena River outflow channels. This reflects a balance between delivery and removal of OC from different sources. The good correlation between the hopanoid and bulk terrestrial signal suggests a broad range of hopanoid sources, both fluvial and via coastal erosion, whilst GDGTs appear to be primarily sourced via fluvial transport. Analysis of ice complex deposits (ICDs) revealed an average R'(soil) of 0.5 for the Lena Delta, equivalent to that of the Buor-Khaya Bay sediments, whilst ICDs from further east showed higher values (0.6-0.85). Although R'(soil) correlates more closely with bulk OC than the BIT, our understanding of the endmembers of this system is clearly still incomplete, with variations between the different East Siberian Arctic regions potentially reflecting differences in environmental conditions (e.g. temperature, pH), but other physiological controls on microbial bacteriohopanepolyol (BHP) production under psychrophilic conditions are as yet unknown.
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| 24. |
- Bosch, Carme, et al.
(author)
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Source Apportionment of Polycyclic Aromatic Hydrocarbons in Central European Soils with Compound-Specific Triple Isotopes (delta C-13, Delta C-14, and delta H-2)
- 2015
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In: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 49:13, s. 7657-7665
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Journal article (peer-reviewed)abstract
- This paper reports the first study applying a triple-isotope approach for source apportionment of polycyclic aromatic hydrocarbons (PAHs). The C-13/C-12, and H-2/H-1 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 PAR data and an end-member PAR isotope database allowed comprehensive accounting of uncertainties and quantitative constraints on the PAR 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 (similar to 650 degrees C; 61 +/- 8%). Combustion of liquid fossil fuels and biomass represented 16 +/- 3 and 9 + 3% of the total PAR burden (Sigma PAH(14)), respectively. Although some soils were located close to potential PAR point sources, the source distribution was within a narrow range throughout the region. These observation-based top-down constraints on sources of environmental PARS provide a reference for both improved bottom-up emission inventories and guidance for efforts to mitigate PAR emissions.
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| 25. |
- Bosch, Carme, et al.
(author)
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Source-diagnostic dual-isotope composition and optical properties of water-soluble organic carbon and elemental carbon in the South Asian outflow intercepted over the Indian Ocean
- 2014
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In: Journal of Geophysical Research - Atmospheres. - 2169-897X .- 2169-8996. ; 119:20, s. 11743-11759
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Journal article (peer-reviewed)abstract
- The dual carbon isotope signatures and optical properties of carbonaceous aerosols have been investigated simultaneously for the first time in the South Asian outflow during an intensive campaign at the Maldives Climate Observatory on Hanimaadhoo (MCOH) (February and March 2012). As one component of the Cloud Aerosol Radiative Forcing Dynamics Experiment, this paper reports on the sources and the atmospheric processing of elemental carbon (EC) and water-soluble organic carbon (WSOC) as examined by a dual carbon isotope approach. The radiocarbon (C-14) data show that WSOC has a significantly higher biomass/biogenic contribution (865%) compared to EC (594%). The more C-13-enriched signature of MCOH-WSOC (-20.80.7) compared to MCOH-EC (-25.8 +/- 0.3 parts per thousand) and megacity Delhi WSOC (-24.1 +/- 0.9 parts per thousand) suggests that WSOC is significantly more affected by aging during long-range transport than EC. The C-13-C-14 signal suggests that the wintertime WSOC intercepted over the Indian Ocean largely represents aged primary biomass burning aerosols. Since light-absorbing organic carbon aerosols (Brown Carbon (BrC)) have recently been identified as potential contributors to positive radiative forcing, optical properties of WSOC were also investigated. The mass absorption cross section of WSOC (MAC(365)) was 0.5 +/- 0.2 m(2)g(-1) which is lower than what has been observed at near-source sites, indicating a net decrease of WSOC light-absorption character during long-range transport. Near-surface WSOC at MCOH accounted for similar to 1% of the total direct solar absorbance relative to EC, which is lower than the BrC absorption inferred from solar spectral observations of ambient aerosols, suggesting that a significant portion of BrC might be included in the water-insoluble portion of organic aerosols.
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| 26. |
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| 27. |
- Bröder, Lisa, et al.
(author)
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Bounding cross-shelf transport time and degradation in Siberian-Arctic land-ocean carbon transfer
- 2018
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In: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 9
-
Journal article (peer-reviewed)abstract
- The burial of terrestrial organic carbon (terrOC) in marine sediments contributes to the regulation of atmospheric CO2 on geological timescales and may mitigate positive feedback to present-day climate warming. However, the fate of terrOC in marine settings is debated, with uncertainties regarding its degradation during transport. Here, we employ compound-specific radiocarbon analyses of terrestrial biomarkers to determine cross-shelf transport times. For the World's largest marginal sea, the East Siberian Arctic shelf, transport requires 3600 +/- 300 years for the 600 km from the Lena River to the Laptev Sea shelf edge. TerrOC was reduced by similar to 85% during transit resulting in a degradation rate constant of 2.4 +/- 0.6 kyr(-1). Hence, terrOC degradation during cross-shelf transport constitutes a carbon source to the atmosphere over millennial time. For the contemporary carbon cycle on the other hand, slow terrOC degradation brings considerable attenuation of the decadal-centennial permafrost carbon-climate feedback caused by global warming.
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| 28. |
- Bröder, Lisa, et al.
(author)
-
Fate of terrigenous organic matter across the Laptev Sea from the mouth of the Lena River to the deep sea of the Arctic interior
- 2016
-
In: Biogeosciences. - : Copernicus GmbH. - 1726-4170 .- 1726-4189. ; 13:17, s. 5003-5019
-
Journal article (peer-reviewed)abstract
- Ongoing global warming in high latitudes may cause an increasing supply of permafrost-derived organic carbon through both river discharge and coastal erosion to the Arctic shelves. Mobilized permafrost carbon can be either buried in sediments, transported to the deep sea or degraded to CO2 and outgassed, potentially constituting a positive feedback to climate change. This study aims to assess the fate of terrigenous organic carbon (TerrOC) in the Arctic marine environment by exploring how it changes in concentration, composition and degradation status across the wide Laptev Sea shelf. We analyzed a suite of terrestrial biomarkers as well as source-diagnostic bulk carbon isotopes (delta C-13, Delta C-14) in surface sediments from a Laptev Sea transect spanning more than 800 km from the Lena River mouth (< 10m water depth) across the shelf to the slope and rise (2000-3000m water depth). These data provide a broad view on different TerrOC pools and their behavior during cross-shelf transport. The concentrations of lignin phenols, cutin acids and high-molecular-weight (HMW) wax lipids (tracers of vascular plants) decrease by 89-99% along the transect. Molecular-based degradation proxies for TerrOC (e.g., the carbon preference index of HMW lipids, the HMW acids / alkanes ratio and the acid / aldehyde ratio of lignin phenols) display a trend to more degraded TerrOC with increasing distance from the coast. We infer that the degree of degradation of permafrost-derived TerrOC is a function of the time spent under oxic conditions during protracted cross-shelf transport. Future work should therefore seek to constrain cross-shelf transport times in order to compute a TerrOC degradation rate and thereby help to quantify potential carbon-climate feedbacks.
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| 29. |
- Bröder, Lisa, et al.
(author)
-
Historical records of organic matter supply and degradation status in the East Siberian Sea
- 2016
-
In: Organic Geochemistry. - : Elsevier BV. - 0146-6380 .- 1873-5290. ; 91, s. 16-30
-
Journal article (peer-reviewed)abstract
- Destabilization and degradation of permafrost carbon in the Arctic regions could constitute a positive feedback to climate change. A better understanding of its fate upon discharge to the Arctic shelf is therefore needed. In this study, bulk carbon isotopes as well as terrigenous and marine biomarkers were used to construct two centennial records in the East Siberian Sea. Differences in topsoil and Pleistocene Ice Complex Deposit permafrost concentrations, modeled using delta C-13 and Delta C-14, were larger between inner and outer shelf than the changes over time. Similarly, lignin-derived phenol and cutin acid concentrations differed by a factor of ten between the two stations, but did not change significantly over time, consistent with the dual-carbon isotope model. High molecular weight (HMW) n-alkane and n-alkanoic acid concentrations displayed a smaller difference between the two stations (factor of 3-6). By contrast, the fraction for marine OC drastically decreased during burial with a half-life of 19-27 years. Vegetation and degradation proxies suggested supply of highly degraded gymnosperm wood tissues. Lipid Carbon Preference Index (CPI) values indicated more extensively degraded HMW n-alkanes on the outer shelf with no change over time, whereas n-alkanoic acids appeared to be less degraded toward the core top with no large differences between the stations. Taken together, our results show larger across-shelf changes than down-core trends. Further investigation is required to establish whether the observed spatial differences are due to different sources for the two depositional settings or, alternatively, a consequence of hydrodynamic sorting combined with selective degradation during cross-shelf transport.
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| 30. |
- Bröder, Lisa-Marie, 1985-
(author)
-
Transport, degradation and burial of organic matter released from permafrost to the East Siberian Arctic Shelf
- 2016
-
Doctoral thesis (other academic/artistic)abstract
- Permafrost soils in the Arctic store large quantities of organic matter, roughly twice the amount of carbon that was present in the atmosphere before the industrial revolution. This freeze-locked carbon pool is susceptible to thawing caused by amplified global warming at high latitudes. The remobilization of old permafrost carbon facilitates its degradation to carbon dioxide and methane, thereby providing a positive feedback to climate change.Accelerating coastal erosion in addition to projected rising river discharge with enhancing sediment loads are anticipated to transport increasing amounts of land-derived organic carbon (OC) to the Arctic Ocean. On its shallow continental shelves, this material may be remineralized in the water column or in the sediments, transported without being altered off shelf towards the deep sea of the Arctic Interior or buried in marine sediments and hence sequestered from the contemporary carbon cycle. The fate of terrigenous material in the marine environment, though offering potentially important mechanisms to either strengthen or attenuate the permafrost-carbon climate feedback, is so far insufficiently understood.In this doctoral thesis, sediments from the wide East Siberian Arctic Shelf, the world’s largest shelf-sea system, were used to investigate some of the key processes for OC cycling. A range of bulk sediment properties, carbon isotopes and molecular markers were employed to elucidate the relative importance of different organic matter sources, the role of cross-shelf transport and the relevance of degradation during transport and after burial.Overall, OC released from thawing permafrost constitutes a significant proportion of the sedimentary organic matter on the East Siberian Arctic Shelf. Two sediment cores from the inner and outer East Siberian Sea recorded no substantial changes in source material or clear trends in degradation status for the last century. With increasing distance from the coast, however, strong gradients were detected towards lower concentrations of increasingly reworked land-derived OC. The time spent during cross-shelf transport was consequently found to exert first-order control on degradation. Compound-specific radiocarbon dating on terrigenous biomarkers revealed a net transport time of ~4 000 years across the 600 km wide Laptev Sea shelf, yielding degradation rate constants for bulk terrigenous OC and specific biomarkers on the order of 2-4 kyr-1.From these results, the carbon flux released by degradation of terrigenous OC in surface sediments was estimated to be ~1.7 Gg yr-1, several orders of magnitude lower than what had been quantified earlier for dissolved and particulate OC in the water column. Lower oxygen availability and close associations with the mineral matrix may protect sedimentary OC from remineralization and thereby weaken the permafrost-carbon feedback to present climate change.
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| 31. |
- Bröder, Lisa, et al.
(author)
-
Quantifying Degradative Loss of Terrigenous Organic Carbon in Surface Sediments Across the Laptev and East Siberian Sea
- 2019
-
In: Global Biogeochemical Cycles. - 0886-6236 .- 1944-9224. ; 33:1, s. 85-99
-
Journal article (peer-reviewed)abstract
- Ongoing permafrost thaw in the Arctic may remobilize large amounts of old organic matter. Upon transport to the Siberian shelf seas, this material may be degraded and released to the atmosphere, exported off-shelf, or buried in the sediments. While our understanding of the fate of permafrost-derived organic matter in shelf waters is improving, poor constraints remain regarding degradation in sediments. Here we use an extensive data set of organic carbon concentrations and isotopes (n=109) to inventory terrigenous organic carbon (terrOC) in surficial sediments of the Laptev and East Siberian Seas (LS + ESS). Of these similar to 2.7 Tg terrOC about 55% appear resistant to degradation on a millennial timescale. A first-order degradation rate constant of 1.5 kyr(-1) is derived by combining a previously established relationship between water depth and cross-shelf sediment-terrOC transport time with mineral-associated terrOC loadings. This yields a terrOC degradation flux of similar to 1.7Gg/year from surficial sediments during cross-shelf transport, which is orders of magnitude lower than earlier estimates for degradation fluxes of dissolved and particulate terrOC in the water column of the LS + ESS. The difference is mainly due to the low degradation rate constant of sedimentary terrOC, likely caused by a combination of factors: (i) the lower availability of oxygen in the sediments compared to fully oxygenated waters, (ii) the stabilizing role of terrOC-mineral associations, and (iii) the higher proportion of material that is intrinsically recalcitrant due to its chemical/molecular structure in sediments. Sequestration of permafrost-released terrOC in shelf sediments may thereby attenuate the otherwise expected permafrost carbon-climate feedback. Plain language summary Frozen soils in the Arctic contain large amounts of old organic matter. With ongoing climate change this previously freeze-locked carbon storage becomes vulnerable to transport and decay. Upon delivery to the shallow nearshore seas, it may either be directly degraded to carbon dioxide or methane and thereby fuel further warming or get buried and stored in sediments on the sea floor. Our understanding of the fate of carbon released from permafrost soils is increasing, yet uncertainties remain regarding its degradation in the sediment. Here we constrain how much land-derived organic carbon is deposited in the top layer of the sediment (the part that is prone to transport and exposed to oxygen-stimulated degradation) in the Laptev and East Siberian Seas. We find that more than half of this stock likely resists degradation, while the rest decays relatively slowly. Therefore, the amount of carbon released annually from degradation in surface sediments is much smaller than what was found to be emitted from overlying waters in earlier studies. We suspect that this difference is caused by a combination of mechanisms hindering degradation in sediments and thus conclude that the burial of land-derived carbon may help to dampen the climate impact of thawing permafrost.
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| 32. |
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| 33. |
- Budhavant, Krishnakant, et al.
(author)
-
Anthropogenic fine aerosols dominate the wintertime regime over the northern Indian Ocean
- 2018
-
In: Tellus. Series B, Chemical and physical meteorology. - : Stockholm University Press. - 0280-6509 .- 1600-0889. ; 70
-
Journal article (peer-reviewed)abstract
- This study presents and evaluates the most comprehensive set to date of chemical, physical and optical properties of aerosols in the outflow from South Asia covering a full winter (Nov. 2014 - March 2015), here intercepted at the Indian Ocean receptor site of the Maldives Climate Observatory in Hanimaadhoo (MCOH). Cluster analysis of air-mass back trajectories for MCOH, combined with AOD and meteorological data, demonstrate that the wintertime northern Indian Ocean is strongly influenced by aerosols transported from source regions with three major wind regimes, originating from the Indo-Gangetic Plain (IGP), the Bay of Bengal (BoB) and the Arabian Sea (AS). As much as 97 +/- 3% of elemental carbon (EC) in the PM10 was also found in the fine mode (PM2.5). Other mainly anthropogenic constituents such as organic carbon (OC), non-sea-salt (nss) -K+, nss-SO42- and NH4+ were also predominantly in the fine mode (70-95%), particularly in the air masses from IGP. The combination at this large-footprint receptor observatory of consistently low OC/EC ratio (2.0 +/- 0.5), strong linear relationships between EC and OC as well as between nss-K+ and both OC and EC, suggest a predominance of primary sources, with a large biomass burning contribution. The particle number-size distributions for the air masses from IGP and BoB exhibited clear bimodal shapes within the fine fraction with distinct accumulation (0.1m0.03. Taken together, the aerosol pollution over the northern Indian Ocean in the dry season is dominated by a well-mixed long-range transported regime of the fine-mode aerosols largely from primary combustion origin.
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| 34. |
- Budhavant, Krishnakant, et al.
(author)
-
Apportioned contributions of PM2.5 fine aerosol particles over the Maldives (northern Indian Ocean) from local sources vs long-range transport
- 2015
-
In: Science of the Total Environment. - : Elsevier BV. - 0048-9697 .- 1879-1026. ; 536, s. 72-78
-
Journal article (peer-reviewed)abstract
- 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 main-land South Asia, there are also local Maldivian emissions. The local contributions to the load of fine particulate matter (PM2.5) in the Maldivian capital Male 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 Male 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 Male are higher (avg. 19 mu g/m(3)) than at MCOH (avg. 13 mu g/m(3)) with the difference being the largest during the summer, when local emissions play a larger role. The 24-hWorld Health Organization (WHO) PM2.5 health guideline was surpassed for the week-long collections in 71% of the cases in Male and in 74% of the cases for Hanimaadhoo. This study shows that in the dry/winter season 90 +/- 11% of PM2.5 levels in Male 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 Male and 13% at MCOH, suggesting larger contributions from incomplete combustion practices in the Male local region.
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| 35. |
- Budhavant, Krishnakant, et al.
(author)
-
Black carbon aerosols over Indian Ocean have unique source fingerprint and optical characteristics during monsoon season
- 2023
-
In: Proceedings of the National Academy of Sciences of the United States of America. - : Proceedings of the National Academy of Sciences. - 0027-8424 .- 1091-6490. ; 120:8
-
Journal article (peer-reviewed)abstract
- Effects of aerosols such as black carbon (BC) on climate and buildup of the monsoon over the Indian Ocean are insufficiently quantified. Uncertain contributions from various natural and anthropogenic sources impede our understanding. Here, we use observations over 5 y of BC and its isotopes at a remote island observatory in northern Indian Ocean to constrain loadings and sources during little-studied monsoon season. Carbon-14 data show a highly variable yet largely fossil (65 ± 15%) source mixture. Combining carbon-14 with carbon-13 reveals the impact of African savanna burning, which occasionally approach 50% (48 ± 9%) of the total BC loadings. The BC mass-absorption cross-section for this regime is 7.6 ± 2.6 m2/g, with higher values during savanna fire input. Taken together, the combustion sources, longevity, and optical properties of BC aerosols over summertime Indian Ocean are different than the more-studied winter aerosol, with implications for chemical transport and climate model simulations of the Indian monsoon.
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| 36. |
- Budhavant, Krishnakant, et al.
(author)
-
Enhanced Light-Absorption of Black Carbon in Rainwater Compared With Aerosols Over the Northern Indian Ocean
- 2020
-
In: Journal of Geophysical Research - Atmospheres. - 2169-897X .- 2169-8996. ; 125:2
-
Journal article (peer-reviewed)abstract
- Black carbon (BC) aerosols affect climate, especially in high aerosol loading regions such as South Asia. A key uncertainty for the climate effects of BC is the evolution of light-absorbing properties in the atmosphere. Here, we present a year-round comparison of the mass absorption cross section (MAC; 678 nm) of BC in air (PM10) and rain, for samples collected at the Maldives Climate Observatory at Hanimaadhoo. We develop a filter-loading correction scheme for estimating BC absorption on filters used in high-volume samplers. The year-round average MAC(678) of BC in the rain is almost twice (13.3 +/- 4.2 m(2)/g) compared to the PM10 aerosol (7.2 +/- 2.6 m(2)/g). A possible explanation is the elevated ratio of organic carbon (OC) to BC observed in rain particulate matter (9.4 +/- 6.3) compared to in the aerosols (OC/BC 2.6 +/- 1.4 and water-insoluble organic carbon/BC 1.2 +/- 0.8), indicating a coating-enhancement effect. In addition to BC, we also investigated the MAC(365) of water-soluble brown carbon in PM10 (0.4 +/- 0.4 m(2)/g, at 365 nm). In contrast to BC, MAC(365)brown carbon relates to air mass history, showing higher values for samples from air originating over the South Asian landmass. Furthermore, calculated washout ratios are much lower for BC compared to OC and inorganic ions such as sulfate, implying a longer atmospheric lifetime for BC. The wet deposition flux for BC during the high loading winter was 3 times higher than during the wet summer, despite much less precipitation in the winter.
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| 37. |
- Budhavant, Krishnakant, et al.
(author)
-
Radiocarbon-based source apportionment of elemental carbon aerosols at two South Asian receptor observatories over a full annual cycle
- 2015
-
In: Environmental Research Letters. - : IOP Publishing. - 1748-9326. ; 10:6
-
Journal article (peer-reviewed)abstract
- 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 C-14-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 (f(bio)) was 53 +/- 5% (n = 6) atMCOHand 56 +/- 3% at SINH (n = 5). The f(bio) for the non-winter remainder was 53 +/- 11% (n = 6) atMCOHand 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 (f(bio)) EI spanning 55-88%, suggesting that most current EI for Indian BC systematically under predict the relative contribution of fossil fuel combustion. Acontinued 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.
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| 38. |
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| 39. |
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| 40. |
- Carrizo, Daniel, et al.
(author)
-
Compound-specific bromine isotope compositions of one natural and six = dustrially synthesised organobromine substances
- 2011
-
In: Environmental Chemistry. - 1448-2517 .- 1449-8979. ; 8:2, s. 127-132
-
Journal article (peer-reviewed)abstract
- AB The stable bromine isotopic composition (delta(81)Br) was determined for six industrially synthesised brominated organic compounds (BOCs) and one natural BOC by gas-chromatography multi-collector inductively coupled plasma mass spectrometry (GC-mcICP-MS). The delta(81)Br compositions of brominated benzenes, phenols (both natural and industrial), anisoles, and naphthalenes were constrained with the standard differential measurement approach using as reference a monobromobenzene sample with an independently determined delta(81)Br value (-0.39 parts per thousand v. Standard Mean Ocean Bromide, SMOB). The delta(81)Br values for the industrial BOCs ranged from -4.3 to -0.4 parts per thousand. The average delta(81)Br value for the natural compound (2,4-dibromophenol) was 0.2 +/- 1.6% (1 s.d.), and for the identical industrial compound (2,4-dibromophenol) -1.1 +/- 0.9 parts per thousand (1 s.d.), with a statistically significant difference of similar to 1.4 (P<0.05). The delta(81)Br of four out of six industrial compounds was found to be significantly different from that of the natural sample. These novel results establish the bromine isotopic variability among the industrially produced BOCs in relation to a natural sample.
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| 41. |
- Carrizo, Daniel, et al.
(author)
-
Distribution and Inventories of Polychlorinated Biphenyls in the Polar Mixed Layer of Seven Pan-Arctic Shelf Seas and the Interior Basins
- 2011
-
In: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 45:4, s. 1420-1427
-
Journal article (peer-reviewed)abstract
- Assessment of the Arctic as a global repository of polychlorinated biphenyls (PCBs) and of uptake processes in the base of its marine food chain hinges on reliable information of PCB distribution in surface seawater, yet there is a scarcity of quality-assured PCB measurements in this key compartment. Here, surface seawater PCB concentrations and congener fingerprints are evaluated for all seven pan-Arctic shelf seas and for the interior basins. Particulate and dissolved PCBs were collected via trace-clean protocols on three basin-wide expeditions (AO-01, Beringia-2005, and ISSS-08). Concentrations of the sum of 13 abundant congeners (Sigma(13)PCB) were 0.13-21 pg/L, with higher concentrations in the shelf seas and lower concentrations in the Central Arctic Basin. Trichlorinated PCBs constituted about half of the total loadings in the Eastern Arctic (Beaufort, Chukchi, East Siberian, and Laptev Seas) and in the Central Basin, indicating an atmospheric source. In contrast, hexachlorinated PCBs were more abundant than tri-PCBs in the western sector, suggesting a role also for waterborne transport from regions of heavy PCB consumption in North America and Europe. Finally, the inventory of Sigma(13)PCB in the polar mixed layer of the entire Arctic Ocean was 0.39 ton, which implies that only 0.0008% of historical PCB emissions are now residing in Arctic surface waters.
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| 42. |
- Carrizo, Daniel, et al.
(author)
-
Pan-Arctic River Fluxes of Polychlorinated Biphenyls
- 2011
-
In: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 45:19, s. 8377-8384
-
Journal article (peer-reviewed)abstract
- Observations of polychlorinated biphenyls (PCB) concentrations in fluvial surface sediments near the mouths of the six Great Arctic Rivers (GARs; Ob, Yenisey, Lena, Indigirka, Kolyma, and Mackenzie) were combined with annual dissolved organic carbon (DOC) and particulate organic carbon (POC) loadings and hydraulic discharge to estimate the pan-Arctic river flux of PCBs. The highest total-phase fluxes of Sigma(13)PCB were found for the Ob River, with 184 kg/yr and the smallest for the Indigirka River with 3.9 kg/yr. Consistent with a continent-scale trend among the Eurasian GARs of increasing POC concentrations eastward, which is extending to the North American Mackenzie River, a general shift in the estimated PCB partitioning from dissolved to particle-associated flux was found toward the east. Pentachlorinated and hexachlorinated PCBs constituted the majority (>70%) of the total PCB fluxes in the Eurasian Rivers. In contrast, trichlorinated and tetrachlorinated congeners were the most abundant in the Mackenzie (approximate to 75%). The total Sigma(13)PCB fluxes from the pan-Arctic rivers are here estimated to be similar to 0.4 tonne/yr. This is geochemically consistent with the inventory of total PCBs in the Polar Mixed Layer of the entire Arctic Ocean (0.39 tonne) and about a factor 2 less than two new estimates of the PCB settling export to Arctic subsurface waters. Hence, the yearly Great Arctic River PCB fluxes only represent 0.001% of the historical PCB emission into the global environment. To our knowledge, this is the first estimate of circum-Arctic river flux of any organic pollutant based on a comprehensive investigation of the pollutants in several rivers and it contributes toward a more complete understanding of large-scale contaminant cycling in the Arctic.
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| 43. |
- Carrizo, Daniel, et al.
(author)
-
Spatial Distributions of DDTs in the Water Masses of the Arctic Ocean
- 2017
-
In: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 51:14, s. 7913-7919
-
Journal article (peer-reviewed)abstract
- There is a scarcity of data on the amount and distribution of the organochlorine pesticide dichlorodiphenyltrichloroethane (DDT) and its metabolites in intermediate and deep ocean water masses. Here, the distribution and inventories of DDTs in water of the Arctic shelf seas and the interior basin are presented. The occurrence of Sigma 6DDT (0.10-66 pg L-1) in the surface water was dominated by 4,4'-DDE. In the Central Arctic Ocean increasing concentrations of DDE with depth were observed in the Makarov and Amundsen basins. The increasing concentrations down to 2500 m depth is in accordance with previous findings for PCBs and PBDEs. Similar concentrations of DDT and DDEs were found in the surface water, while the relative contribution of DDEs increased with depth, demonstrating a transformation over time and depth. Higher concentrations of DDTs were found in the European part of the Arctic Ocean; these distributions likely reflect a combination of different usage patterns, transport, and fate of these compounds. For instance, the elevated concentrations of DDTs in the Barents and Atlantic sectors of the Arctic Ocean indicate the northbound Atlantic current as a significant conveyor of DDTs. This study contributes to the very rare data on OCPs in the vast deep-water compartments and combined with surface water distribution across the Arctic Ocean helps to improve our understanding of the large-scale fate of DDTs in the Arctic.
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| 44. |
- Chandrika Ranjendra Nair, Hari Ram, 1989-, et al.
(author)
-
Aerosol demasking enhances climate warming over South Asia
- 2023
-
In: npj Climate and Atmospheric Science. - 2397-3722. ; 6
-
Journal article (peer-reviewed)abstract
- Anthropogenic aerosols mask the climate warming caused by greenhouse gases (GHGs). In the absence of observational constraints, large uncertainties plague the estimates of this masking effect. Here we used the abrupt reduction in anthropogenic emissions observed during the COVID-19 societal slow-down to characterize the aerosol masking effect over South Asia. During this period, the aerosol loading decreased substantially and our observations reveal that the magnitude of this aerosol demasking corresponds to nearly three-fourths of the CO2-induced radiative forcing over South Asia. Concurrent measurements over the northern Indian Ocean unveiled a ~7% increase in the earth’s surface-reaching solar radiation (surface brightening). Aerosol-induced atmospheric solar heating decreased by ~0.4 K d−1. Our results reveal that under clear sky conditions, anthropogenic emissions over South Asia lead to nearly 1.4 W m−2 heating at the top of the atmosphere during the period March–May. A complete phase-out of today’s fossil fuel combustion to zero-emission renewables would result in rapid aerosol demasking, while the GHGs linger on.
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| 45. |
- Chandrika Ranjendra Nair, Hari Ram, 1989-, et al.
(author)
-
Aerosol demasking enhances climate warming over South Asia
- 2023
-
In: npj Climate and Atmospheric Science. - 2397-3722. ; 6:1
-
Journal article (peer-reviewed)abstract
- Anthropogenic aerosols mask the climate warming caused by greenhouse gases (GHGs). In the absence of observational constraints, large uncertainties plague the estimates of this masking effect. Here we used the abrupt reduction in anthropogenic emissions observed during the COVID-19 societal slow-down to characterize the aerosol masking effect over South Asia. During this period, the aerosol loading decreased substantially and our observations reveal that the magnitude of this aerosol demasking corresponds to nearly three-fourths of the CO2-induced radiative forcing over South Asia. Concurrent measurements over the northern Indian Ocean unveiled a ~7% increase in the earth’s surface-reaching solar radiation (surface brightening). Aerosol-induced atmospheric solar heating decreased by ~0.4 K d−1. Our results reveal that under clear sky conditions, anthropogenic emissions over South Asia lead to nearly 1.4 W m−2 heating at the top of the atmosphere during the period March–May. A complete phase-out of today’s fossil fuel combustion to zero-emission renewables would result in rapid aerosol demasking, while the GHGs linger on.
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| 46. |
- Chandrika Ranjendra Nair, Hari Ram, 1989-, et al.
(author)
-
Roles of water-soluble aerosol coatings for the enhanced radiative absorption of black carbon over south asia and the northern indian ocean
- 2024
-
In: Science of the Total Environment. - 0048-9697 .- 1879-1026. ; 926
-
Journal article (peer-reviewed)abstract
- Black Carbon (BC), formed by incomplete combustion, absorbs solar radiation and heats the atmosphere. We investigated the enhancement in optical absorption of BC due to coatings of water-soluble (WS) species in the polluted South Asian atmosphere. The BC Mass Absorption Cross-section (MAC; 678 nm) was estimated before and after removal of the WS components. Wintertime samples were collected from three South Asian receptor observatories intercepting large-footprint outflow: Bangladesh Climate Observatory Bhola (BCOB; integrating outflow of the Indo-Gangetic Plain), Maldives Climate Observatories at Hanimaadhoo (MCOH) and at Gan (MCOG), both reflecting outflow from the South Asian region. The ambient MAC observed at BCOB, MCOH and MCOG were 4.2 ± 1.4, 7.9 ± 1.9 and 7.1 ± 1.5 m2 g−1, respectively.The average enhancement of the BC MAC due to WS coatings (i.e., ws-EMAC) was identical at all three sites (1.6 ± 0.5) indicating that the anthropogenic aerosols had already evolved to a fully coated morphology at BCOB and/or that subsequent aging involved two compensating evolution processes of the coating. Inspecting the key coating component sulfate; the sulfate-to-BC ratio increased threefold when transitioning from BCOB to MCOH and by about 1.5 times from BCOB to MCOG. Conversely, both WS organic carbon (WSOC)/BC and water-insoluble OC (WIOC)/BC ratios declined with distance: WSOC/BC diminished by 84 % from BCOB to MCOH and by 80 % from BCOB to MCOG, while WIOC/BC dropped by about 63 % and 59 %, respectively. Such declines in WSOC and WIOC reflect a combination of photochemical oxidation and more efficient washout of OC compared to BC. The observed changes in the SO42−/BC and WSOC/BC ratios across South Asia highlight the significant impact of aerosol composition on the optical properties of Black Carbon (BC). These findings emphasize the need for detailed studies on aerosol composition to improve climate models and develop effective strategies for reducing the impact of anthropogenic aerosols on the climate.
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| 47. |
- Charkin, Alexander N., et al.
(author)
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Discovery and characterization of submarine groundwater discharge in the Siberian Arctic seas : a case study in the Buor-Khaya Gulf, Laptev Sea
- 2017
-
In: The Cryosphere. - : Copernicus GmbH. - 1994-0416 .- 1994-0424. ; 11:5, s. 2305-2327
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Journal article (peer-reviewed)abstract
- It has been suggested that increasing terrestrial water discharge to the Arctic Ocean may partly occur as submarine groundwater discharge (SGD), yet there are no direct observations of this phenomenon in the Arctic shelf seas. This study tests the hypothesis that SGD does exist in the Siberian Arctic Shelf seas, but its dynamics may be largely controlled by complicated geocryological conditions such as permafrost. The field-observational approach in the southeastern Laptev Sea used a combination of hydrological (temperature, salinity), geological (bottom sediment drilling, geoelectric surveys), and geochemical (Ra-224, Ra-223, Ra-228, and Ra-226) techniques. Active SGD was documented in the vicinity of the Lena River delta with two different operational modes. In the first system, groundwater discharges through tectonogenic permafrost talik zones was registered in both winter and summer. The second SGD mechanism was cryogenic squeezing out of brine and water-soluble salts detected on the periphery of ice hummocks in the winter. The proposed mechanisms of groundwater transport and discharge in the Arctic land-shelf system is elaborated. Through salinity vs. Ra-224 and Ra-224/Ra-223 diagrams, the three main SGD-influenced water masses were identified and their end-member composition was constrained. Based on simple mass-balance box models, discharge rates at sites in the submarine permafrost talik zone were 1.7 x 10(6) m(3) d(-1) or 19.9 m(3) s(-1), which is much higher than the April discharge of the Yana River. Further studies should apply these techniques on a broader scale with the objective of elucidating the relative importance of the SGD transport vector relative to surface freshwater discharge for both water balance and aquatic components such as dissolved organic carbon, carbon dioxide, methane, and nutrients.
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| 48. |
- Charkin, A. N., et al.
(author)
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Seasonal and interannual variability of sedimentation and organic matter distribution in the Buor-Khaya Gulf : the primary recipient of input from Lena River and coastal erosion in the southeast Laptev Sea
- 2011
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In: Biogeosciences. - : Copernicus GmbH. - 1726-4170 .- 1726-4189. ; 8:9, s. 2581-2594
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Journal article (peer-reviewed)abstract
- Climate warming is amplified in the land-sea system of the East Siberian Arctic, which also holds large pools of vulnerable carbon in permafrost. This coastal area is strongly influenced by sediment and carbon transport from both its large rivers and extensive erosion of Pleistocene permafrost along its coastline. This study is investigating the coastal fate of the sediment and organic carbon delivered to the Buor-Khaya Gulf, which is the first recipient of the overwhelming fluvial discharge from the Lena River and is additionally receiving large input from extensive erosion of the coastal ice-complex (permafrost a. k.a. Yedoma; loess soil with high organic carbon content). Both water column suspended particulate matter (SPM) and surface sediments were sampled at about 250 oceanographic stations in the Gulf in this multi-year effort, including one winter campaign, and analyzed for the distribution and sorting of sediment size, organic carbon content, and stable carbon isotope signals. The composition of the surface sediment suggests an overwhelmingly terrestrial contribution from both river and coastal erosion. The objective of this paper is to improve our understanding of the seasonal (i.e., winter vs summer) and interannual variability of these coastal sedimentation processes and the dynamics of organic carbon (OC) distribution in both the water column SPM and the surface sediments of the Buor-Khaya Gulf. Based on data collected during several years in the period 2000-2008, two different sedimentation regimes were revealed for the Buor-Khaya Gulf, the relative importance of each at a given time depend on hydrometeorological conditions, the Lena River water discharge and sea-ice regime: Type 1 erosion-accumulation and Type 2 accumulation. The Type 1 erosion-accumulation sedimentation regime is typical (2000-2006) for the ice-free period of the year (here considered in detail for August 2005). Under such conditions terrigenous sources of SPM and particulate organic carbon (POC) stem predominantly from river discharge, thermal erosion of coastal ice-complex and remobilized bottom sediments. The Type 2 accumulation sedimentation regime develops under ice-covered conditions, and only occasionally during the ice-free period (August 2008). In Type 2 winter, combined terrigenous and marine-biogenic SPM and POC sources are dominating due to relatively low overall terrigenous input (April 2007). In Type 2 summer, river alluvium becomes the major SPM and POC source (August 2008). The water column SPM and POC loadings vary by more than a factor of two between the two regimes. This study underscores the necessity of multi-year investigations to better understand the functioning of the primary recipient of terrestrially expulsed matter in the East Siberian Arctic.
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| 49. |
- Chen, Bing, et al.
(author)
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Light absorption enhancement of black carbon from urban haze in Northern China winter
- 2017
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In: Environmental Pollution. - : Elsevier BV. - 0269-7491 .- 1873-6424. ; 221, s. 418-426
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Journal article (peer-reviewed)abstract
- Atmospheric black carbon (BC) is an important pollutant for both air quality and Earth's energy balance. Estimates of BC climate forcing remain highly uncertain, e.g., due to the mixing with non-absorbing components. Non-absorbing aerosols create a coating on BC and may thereby act as a lens which may enhance the light absorption. However, this absorption enhancement is poorly constrained. To this end a two-step solvent dissolution protocol was employed to remove both organic and inorganic coatings, and then investigate their effects on BC light absorption. Samples were collected at a severely polluted urban area, Jinan, in the North China Plain (NCP) during February 2014. The BC mass absorption cross-section (MAC) was measured for the aerosol samples before and after the solvent-decoating treatment, and the enhancement of MAC (E-MAC) from the coating effect was defined as the ratio. A distinct diurnal pattern for the enhancement was observed, with EMAC 1.3 +/- 0.3 (1 S.D.) in the morning, increasing to 2.2 +/- 1.0 in the afternoon, after that dropping to 1.5 +/- 0.8 in the evening-night. The BC absorption enhancement primarily was associated with urban-scale photochemical production of nitrate and sulfate aerosols. In addition to that, regional-scale haze plume with increasing sulfate levels strengthened the absorption enhancement. These observations offer direct evidence for an increased absorption enhancement of BC due to severe air pollution in China.
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| 50. |
- Chen, Bing, et al.
(author)
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Reconciling modeling with observations of radiative absorption of black carbon aerosols
- 2017
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In: Journal of Geophysical Research - Atmospheres. - 2169-897X .- 2169-8996. ; 122:11, s. 5932-5942
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Journal article (peer-reviewed)abstract
- The physical treatment of internal mixing and aging of black carbon (BC) aerosols that allow for enhanced solar absorption of the BC is an important parameterization in climate models. Many climate models predict a factor of 2-3 lower aerosol absorption optical depth (AAOD) than the atmospheric columnar absorption observed from ground-based networks such as AERONET, likely because these models do not parameterize properly the BC absorption enhancement (E-MAC). Models that are configured with an internal mixing have predicted large variations of E-MAC, which are poorly constrained from ambient measurements. We determined the BC E-MAC from aerosol coatings with a two-step solvent experiment to remove both organic and inorganic coatings in ambient fine particulate matter (PM2.5). Observations in a rural North China site showed that the E-MAC varied from 1.4 to 3. The E-MAC increases simultaneously with SO42-/EC ratios, suggesting the photochemical production of sulfate coatings enhanced BC absorption. A global climate model, parameterized to account for these observational constraints, verifies that sulfates are primary drivers of the BC absorption enhancement in severely polluted area in China. This magnification of the radiative forcing of coated BC is stronger by a factor of similar to 2 than predicted by the standard parameterization (external mixing) in the climate model and is in better agreement with AERONET observations of AAOD. This result would be useful for testing the representation of solar absorption by BC-containing particles in the newer generation of climate models. Plain Language Summary Atmospheric black carbon (BC) or soot in fine particulate matter (PM2.5) is emitted from incomplete combustion of fossil fuel or biomass/biofuel. The BC is an important pollutant for both air quality and Earth's energy balance, and the BC radiative forcing maybe second only to that of CO2. The photochemical production of nonabsorbing secondary aerosols may create a coating on BC and may thereby act as a lens which may enhance the light absorption. However, this absorption enhancement is poorly constrained by ambient measurements, and thus the estimates of BC climate forcing remain highly uncertain. To this end, an aerosol filter dissolution-filtration (AFD) with two-step solvent dissolution protocol was employed to remove both organic and inorganic coatings and then investigate their effects on BC light absorption. The observations and model simulation showed that the BC warming effect likely doubled due to lens effect from secondary aerosols.
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