| 1. |
- Dasari, Sanjeev, 1989-
(författare)
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Isotope-based constraints on sources and processing of black carbon, carbon monoxide, and brown carbon in South Asia
- 2021
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The highly populated South Asian region is facing rapid economic growth and urbanization. Here, both climate- and health-affecting atmospheric agents such as light-absorbing aerosols black carbon (BC) and brown carbon (BrC), trace gas carbon monoxide (CO), are often found in relatively high levels compared to in other regions. However, atmospheric chemistry-transport/climate models are unable to fully capture the extent of the abundance of BC, CO, and BrC in the regional atmosphere during winter. The Thesis aims to address potentially important uncertainties that may be contributing to the model-observation offset — uncertainties in the ambient optical properties of BrC, uncertainties in the relative source contributions of BC (biomass burning vs. fossil fuel combustion) and CO (direct emission-derived vs. atmospheric chemical oxidation-derived), uncertainties in the regional lifetime and absolute emission fluxes of BC. For the Thesis work, field sampling was conducted at three sites, megacity Delhi (key source region), the Bangladesh Climate Observatory–Bhola Island (BCOB; receptor site for the highly-polluted Indo-Gangetic Plain) and the Maldives Climate Observatory–Hanimaadhoo Island (MCOH; receptor site for wider South Asia).The light-absorptivity of water-soluble BrC is found to decrease by ~84% during transport of haze from source-to-receptor regions i.e., Delhi-to-BCOB-to-MCOH — much greater than estimated in chamber studies and accounted in models. Atmospheric photochemical oxidation is found to be a likely driver for the loss of water-soluble BrC light-absorption in the S Asian outflow (with an estimated bleaching rate of 0.20±0.05 day−1) (Paper I). Radiocarbon (Δ14C)-based source apportionment of BC aerosols shows a stark similarity in the relative contributions of fossil (~50%) and biomass sources (~50%) at BCOB as well as at MCOH, suggesting a regional homogeneity in BC source contributions. However, a distinct stable isotopic fingerprint (δ13C) of BC in the N Indian Ocean is found to be arising from a small yet significant contribution (upto 10%) from C4-biomass burning in peninsular India (region south of 23.4°N) (Paper II). Comparison of source-segregated observed and emission inventory-driven modeled BC concentrations indicates regional offsets in the anthropogenic emission fluxes of BC in emission inventories—overestimated fossil-BC in the Indo-Gangetic Plain and underestimated biomass-BC in peninsular India (Paper II). Dual-isotope (δ13C, δ18O)-based source apportionment of CO shows a significantly large contribution (~80%) from direct emissions of primary sources (biomass burning and fossil fuel combustion) in South Asia, in contrast to modeled CO budget (Paper III). The BC-to-CO ratio in South Asia is found to be higher, by a factor of 2-3, than in other polluted regions such as in East Asia during winter. The regional lifetime and emission flux of BC are estimated to be 8±0.5 days (higher than values used in models) and ~2.4±1 Tg/yr (significantly higher than estimated in current emission inventories), respectively (Paper IV).Taken together, for convergence between models and observations in wintertime South Asia, i) the ‘dynamic’ nature of BrC light-absorption should be considered in models, ii) improvements in emission information of BC and CO are needed for better-simulating concentrations. Controls on activities such as open burning (such as agricultural crop residue burning, domestic burning of wood and dung as fuel) in South Asia could enable a reduction in BC, CO, and BrC, thereby leading to improved air quality and paving the way for achieving some of the key sustainable development goals outlined by the United Nations.
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| 2. |
- Elmquist, Marie
(författare)
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Measurement and source apportionment of ubiquitous soot black carbon in sediments
- 2007
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The pyrogenic particles formed from incomplete combustion of organic matter are often termed black carbon (BC) and they partake in many important biogeochemical processes. For instance, BC in water and sediment affects the solid-water partitioning of hydrophobic organic pollutants reducing their bioavailability.The key objective of this thesis was to test the chemothermal oxidation method (CTO) to quantify soot-BC in sediments. In the CTO method, sedimentary BC is isolated by removing non-pyrogenic organic matter through thermal combustion at 375°C under active airflow and subsequent removal of inorganic carbonates by adding hydrochloric acid. The CTO method was here shown to work well for quantifying the thermally more stable soot-BC phase.Another objective was to study sediment samples to measure the historical and spatial distribution of combustion products. First, historical fluxes of BC and polycyclic aromatic hydrocarbons (PAH) were investigated in a Swedish lake sediment. Increasing fluxes of BC and PAH were seen in sediment dated to the industrial revolution in the 1850s, the high coal usage in the early 1900s lead to a 5 time increase in BC flux relative to the pre-industrial flux, and the switch from coal to oil usage in the 1950s lead to a 46 time increase in PAH flux relative to the pre-industrial flux. Further, lower fluxes came from stricter emission controls in the 1960s, improvements in combustion technology and the usage of catalytic filters from mid-1980s. Modern sediment measured 20% lower BC flux and 5 times higher PAH flux relative to the pre-industrial fluxes.Secondly, the spatial distribution and sources of sedimentary soot-BC were studied in rivers in the Arctic region. The estimated BC flux was highest in the McKenzie (99 kton yr-1) whereas it was lowest in Yukon (1.1 kton yr-1). Contemporary biomass-derived BC was detected for the Yenisey, whereas fossil fuel derived BC was found for the Lena, Yukon and McKenzie.
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| 3. |
- Holmstrand, Henry, 1974-
(författare)
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Compound-specific stable chlorine isotope analysis : A versatile tool for investigating biochemical and geochemical processes of organochlorine substances
- 2006
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Chlorinated organic compounds (OCls) from anthropogenic sources are generally considered to be a class of chemicals with high potential for ecotoxicity, including infamous substances such as polychlorinated biphenyls (PCB), dichloro-dibenzo-trichloroethane (DDT) and polychlorinated dibenzo-p-dioxins (PCDD). OCls are also produced naturally, sometimes at the same order of magnitude as anthropogenic compounds. The scope of this thesis was to develop and apply a method for isotope analysis of OCls, as a part of compound-specific chlorine isotope analysis (CSIA-δ37Cl) of trace level compounds. Isotope analysis of chlorine was performed with sealed-tube combustion and thermal-ionization mass spectrometry (TIMS), in order to improve the analytical sensitivity by a factor 20 relative to conventional techniques. Chlorine isotope signatures of organochlorines (δ37Cl-OCl) can be used for source apportionment in the natural vs. anthropogenic spectrum. CSIA-δ37Cl was tested as a tool to resolve the origin of putatively natural PCDD found in ball clay from the Mississippi Embayment, USA. Combined with results from 14C analysis, the δ37Cl-PCDD was consistent with a natural abiotic formation of PCDD. Reactions involving the scission of a chemical bond to a molecular chlorine substituent will induce a shift in the δ37Cl-OCl of the remaining reactant. This concept was used to calculate the undegraded fraction of DDT in the Baltic marine environment (~7% DDT remaining) based on δ37Cl-OCl measurements of DDT harvested from seal blubber. Hence, it is suggested that CSIA-δ37Cl may be very useful in studies of fate and origin of OCls in the environment, and that further applications of the technique are warranted.
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| 4. |
- Jönsson, Anders, 1969-
(författare)
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An evaluation of the distributions of polychlorinated biphenyls and organic matter in coastal sediments
- 2004
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The objective of this thesis is to improve the understanding of what processes and mechanism affects the distribution of polychlorinated biphenyls (PCBs) and organic carbon in coastal sediments. Because of the strong association of hydrophobic organic contaminants (HOCs) such as PCBs with organic matter in the aquatic environment, these two entities are naturally linked. The coastal environment is the most complex and dynamic part of the ocean when it comes to both cycling of organic matter and HOCs. This environment is characterised by the largest fluxes and most diverse sources of both entities. A wide array of methods was used to study these processes throughout this thesis. In the field sites in the Stockholm archipelago of the Baltic proper, bottom sediments and settling particulate matter were retrieved using sediment coring devices and sediment traps from morphometrically and seismically well-characterized locations. In the laboratory, the samples have been analysed for PCBs, stable carbon isotope ratios, carbon-nitrogen atom ratios as well as standard sediment properties. From the fieldwork in the Stockholm Archipelago and the following laboratory work it was concluded that the inner Stockholm archipelago has a low (≈ 4%) trapping efficiency for freshwater-derived organic carbon. The corollary is a large potential for long-range waterborne transport of OC and OC-associated nutrients and hydrophobic organic pollutants from urban Stockholm to more pristine offshore Baltic Sea ecosystems.Theoretical work has been carried out using Geographical Information Systems (GIS) and statistical methods on a database of 4214 individual sediment samples, each with reported individual PCB congener concentrations. From this work it was concluded that the continental shelf sediments are key global inventories and ultimate sinks of PCBs. Depending on congener, 10-80% of the cumulative historical emissions to the environment are accounted for in continental shelf sediments. Further it was concluded that the many infamous and highly contaminated surface sediments of urban harbours and estuaries of contaminated rivers cannot be of importance as a secondary source to sustain the concentrations observed in remote sediments. Of the global shelf PCB inventory < 1% are in sediments near population centres while ≥ 90% is in remote areas (> 10 km from any dwellings). The remote sub-basin of the North Atlantic Ocean contains approximately half of the global shelf sediment inventory for most of the PCBs studied.
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| 5. |
- Karlsson, Emma, 1980-
(författare)
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Compositional clues to sources and sinks of terrestrial organic matter transported to the Eurasian Arctic shelf
- 2015
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The amount of organic carbon (OC) present in Siberian Arctic permafrost soils is estimated at twice the amount of carbon currently in the atmosphere. The shelf seas of the Arctic Ocean receive large amounts of this terrestrial OC from Eurasian Arctic rivers and from coastal erosion. Degradation of this land-derived material in the sea would result in the production of dissolved carbon dioxide and may then add to the atmospheric carbon dioxide reservoir. Observations from the Siberian Arctic suggest that transfer of carbon from land to the marine environment is accelerating. However, it is not clear how much of the transported OC is degraded and oxidized, nor how much is removed from the active carbon cycle by burial in marine sediment.Using bulk geochemical parameters, total OC, d13C and D14C isotope composition, and specific molecular markers of plant wax lipids and lignin phenols, the abundance and composition of OC was determined in both dissolved and particulate carrier phases: the colloidal OC (COC; part of the dissolved OC), particulate OC (POC), and sedimentary OC (SOC). Statistical modelling was used to quantify the relative contribution of OC sources to these phases. Terrestrial OC is derived from the seasonally thawing top layer of permafrost soil (topsoil OC) and frozen OC derived from beneath the active layer eroded at the coast, commonly identified as yedoma ice complex deposit OC (yedoma ICD-OC). These carbon pools are transported differently in the aquatic conduits. Topsoil OC was found in young DOC and POC, in the river water, and the shelf water column, suggesting long-distance transport of this fraction. The yedoma ICD-OC was found as old particulate OC that settles out rapidly to the underlying sediment and is laterally transported across the shelf, likely dispersed by bottom nepheloid layer transport or via ice rafting.These two modes of OC transport resulted in different degradation states of topsoil OC and yedoma ICD-OC. Terrestrial CuO oxidation derived biomarkers indicated a highly degraded component in the COC. In contrast, the terrestrial component of the SOC was much less degraded. In line with earlier suggestions the mineral component in yedoma ICD functions as weight and surface protection of the associated OC, which led to burial in the sediment, and limited OC degradation. The degradability of the terrestrial OC in shelf sediment was also addressed in direct incubation studies. Molecular markers indicate marine OC (from primary production) was more readily degraded than terrestrial OC. Degradation was also faster in sediment from the East Siberian Sea, where the marine contribution was higher compared to the Laptev Sea. Although terrestrial carbon in the sediment was degraded slower, the terrestrial component also contributed to carbon dioxide formation in the incubations of marine sediment.These results contribute to our understanding of the marine fate of land-derived OC from the Siberian Arctic. The mobilization of topsoil OC is expected to grow in magnitude with climate warming and associated active layer deepening. This translocated topsoil OC component was found to be highly degraded, which suggests degradation during transport and a possible contribution to atmospheric carbon dioxide. Similarly, the yedoma ICD-OC (and or old mineral soil carbon) may become a stronger source with accelerated warming, but slow degradation may limit its impact on active carbon cycling in the Siberian Shelf Seas.
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| 6. |
- Karlsson, Emma, 1980-
(författare)
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Organic geochemical investigation of sources, transport and fate of terrestrial organic matter in the southeast Laptev Sea
- 2012
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Permafrost carbon stores have been suggested to react to warming trends with increased terrestrial loading to its coastal waters. Presently, the warming has been seen to be especially high in the East Siberian Arctic and the fate of the major release of terrestrial matter to these coasts is yet to be detailed.Our work is focused on the East Siberian Shelf (ESS) – which is the largest continental shelf in the world. It receives substantial inputs of terrestrial organic matter both from the large Russian rivers and from eroding coastlines. The largest of its rivers, the Lena, discharges in Buor-Khaya Bay, which is also a hot spot for coastal erosion.Previous studies of molecular and δ¹3C and Δ¹⁴C composition of terrestrial organic matter received by Arctic coastal waters have suggested a different propensity of different terrestrial source materials towards bacterial degradation. This detailed isotopic and molecular marker survey which is the basis for this thesis reveals clearly distinguished source patterns both between surface water (POC) and sea floor (SOC) as well as with distance away from the sources. The heavy terrestrial dominance over marine/planktonic sources are clearly detected in gradients of high POC and SOC levels, as well as depleted δ13C -OC and high HMW/LMW n-alkane ratios. Furthermore, data suggests that terr-OC was substantially older yet less degraded in the surface sediment than in the surface waters. This unusual vertical degradation trend was only recently found also for the coastal and central East Siberian Sea. It seems that the riverine terr-OC component comprising mainly annual thaw layer surface soil dominates the buoyant surface water POC and is readily degraded. This is in contrast to the coastline-erosion terr-OC which is associated with minerals and therefore ballasted to the sediments where it makes up the key OC component and seems relatively protected from degradation.The study area of this work is a region with strong terrestrial influence hosting many of the important carbon cycling processes, and data reveal two important OC contributors of different origin, mineral associated coastal erosion matter and riverine borne surface soil matter. These two components may well represent different propensities to contribute to a positive feedback to climate warming by converting OC from coastal and inland permafrost into CO₂.
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| 7. |
- Kirago, Leonard, 1987-
(författare)
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Isotopic and Molecular Characterization of Incomplete Combustion Products in sub-Saharan Africa
- 2023
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Sub-Saharan Africa (SSA) is a global hotspot for incomplete combustion emissions from large-scale savanna fires, agricultural burning and growing city emissions. However, air pollution is understudied in the SSA region, resulting in a gap in the scientific understanding of regional emissions, source contributions, and impacts of air pollutants on regional climate and health. This thesis aimed to characterize fine particulate matter (PM2.5) and particularly to investigate the sources of black carbon (BC), polycyclic hydrocarbons (PAHs) and carbon monoxide (CO) in both the urban and the remote SSA atmosphere. Field sampling was conducted in Nairobi and at two regional background sites, Rwanda Climate Observatory and Mt. Kenya Global Atmospheric Watch (GAW) station.Air pollution in Nairobi city exceeded the World Health Organization (WHO) health guidelines (Paper I and IV). Of particular concern is the constantly elevated BC and PAHs (particularly toxic PM2.5 components) levels in Nairobi, also seen in some other SSA cities. Radiocarbon-based source quantification shows fossil fuel combustion emissions, specifically from traffic, dominate BC emissions in Nairobi (Paper I). Similarly, molecular source tracers suggested PAHs likely originated from combustion sources (Paper IV). The aerosol regime of the regional background SSA atmosphere was, in sharp contrast, dominated by savanna fire emissions (Paper II). In the remote background regimes integrating large SSA emission footprints, we find strong seasonality for all investigated aerosol species, with highly elevated concentrations coinciding with upwind savanna fires. The dual-carbon isotopes (Δ14C and ẟ13C) show a clear and strong savanna-burning imprint, accounting for up to 95% of BC burden. Similarly for CO, isotopic constraints reveal seasonality with savanna fires contributing over 70% of CO in the background atmosphere. This is significantly higher than the global average primary contribution (55 ± 5%). An almost exclusive primary CO component in Nairobi was observed, largely reflecting the fossil combustion emissions in the city (Paper III). Taken together, these largely isotope-based quantitative source constraints of incomplete combustion emissions in SSA provide evidence for informed policy decisions, with implications also for parameterization of satellite fires and bottom-up emission inventories as well as for regional climate and chemical-transport modelling.
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