Atmospheric PM and volatile organic compounds released from Mediterranean shrubland wildfires

Wildfires produce a significant release of gases and particles affecting climate and air quality. In the Mediterranean region, shrublands significantly contribute to burned areas and may show specific emission profiles. Our objective was to depict and quantify the primary-derived aerosols and precursors of secondary particulate species released during shrubland experimental fires, in which fire-line intensity values were equivalent to those of moderate shrubland wildfires, by using a number of different methodologies for the characterization of organic and inorganic compounds in both gas-phase and particulate-phase. Emissions of PM mass, particle number concentrations and organic and inorganic PMx components during flaming and smouldering phases were characterized in a field shrubland fire experiment. Our results revealed a clear prevalence of K+ and SO42- as inorganic ions released during the flaming-smouldering processes, accounting for 68 to 80% of the inorganic soluble fraction. During the residual-smouldering phases, in addition to K+ and SO42-, Ca2+ was found in significant amounts probably due the predominance of re-suspension processes (ashes and soil dust) over other emission sources during this stage. Concerning organic markers, the chromatograms were dominated by phenols, n-alkanals and n-alkanones, as well as by alcohol biomarkers in all the PMx fractions investigated. Levoglucosan was the most abundant degradation compound with maximum emission factors between 182 and 261 mg kg-1 in PM2.5 and PM10 respectively. However, levoglucosan was also observed in significant amounts in the gas-phase. The most representative organic volatile constituents in the smoke samples were alcohols, carbonyls, acids, monocyclic and bicyclic arenes, isoprenoids and alkanes compounds. The emission factors obtained in this study may contribute to the validation and improvement of national and international emission inventories of this intricate and diffuse emission source.

Fossil and Nonfossil Sources of Organic and Elemental Carbon Aerosols in the Outflow from Northeast China

Source quantification of carbonaceous aerosols in the Chinese outflow regions still remains uncertain despite their high mass concentrations. Here, we unambiguously quantified fossil and nonfossil contributions to elemental carbon (EC) and organic carbon (OC) of total suspended particles (TSP) from a regional receptor site in the outflow of Northeast China using radiocarbon measurement. OC and EC concentrations were lower in summer, representing mainly marine air, than in other seasons, when air masses mostly traveled over continental regions in Mongolia and northeast China. The annual-mean contribution from fossil-fuel combustion to EC was 76 ± 11% (0.1−1.3 μg m−3). The remaining 24 ± 11% (0.03−0.42 μg m−3) was attributed to biomass burning, with slightly higher contribution in the cold period (∼31%) compared to the warm period (∼21%) because of enhanced emissions from regional biomass combustion sources in China. OC was generally dominated by nonfossil sources, with an annual average of 66 ± 11% (0.5−2.8 μg m−3), approximately half of which was apportioned to primary biomass burning sources (34 ± 6%). In winter, OC almost equally originated from primary OC (POC) emissions and secondary OC (SOC) formation from fossil fuel and biomass-burning sources. In contrast, summertime OC was dominated by primary biogenic emissions as well as secondary production from biogenic and biomass-burning sources, but fossil-derived SOC was the smallest contributor. Distinction of POC and SOC was performed using primary POC-to-EC emission ratios separated for fossil and nonfossil emissions.

Dissolved organic carbon in sediments of the central Arctic Ocean collected during POLARSTERN cruise ARK-XXVII/3 from August-September 2012

Marine organic matter (OM) sinks from surface waters to the seafloor via the biological pump. Benthic communities, which use this sedimented OM as energy and carbon source, produce dissolved organic matter (DOM) in the process of remineralization, enriching the sediment porewater with fresh DOM compounds. We hypothesized that in the oligotrophic deep Arctic basin the molecular signal of freshly deposited primary produced OM is restricted to the surface sediment pore waters which should differ from bottom water and deeper sediment pore water in DOM composition. This study focused on: 1) the molecular composition of the DOM in sediment pore waters of the deep Eurasian Arctic basins, 2) whether the signal of marine vs. terrigenous DOM is represented by different compounds preserved in the sediment pore waters and 3) whether there is any relation between Arctic Ocean ice cover and DOM composition. Molecular data, obtained via 15 Tesla Fourier transform ion cyclotron resonance mass spectrometer, were correlated with environmental parameters by partial least square analysis. The fresher marine detrital OM signal from surface waters was limited to pore waters from < 5 cm sediment depth. The productive ice margin stations showed higher abundances of peptides, unsaturated aliphatics and saturated fatty acids formulae, indicative of fresh OM/pigments deposition, compared to northernmost stations which had stronger aromatic signals. This study contributes to the understanding of the coupling between the Arctic Ocean productivity and its depositional regime, and how it will be altered in response to sea ice retreat and increasing river runoff.

Organic geochemistry of ODP Hole 162-985A sediments

Dark, organic-rich sediments were recovered from the lower Miocene section (~16.6 Ma) in Hole 985A in the Norway Basin during Ocean Drilling Program Leg 162. Organic carbon and total sulfur contents of the dark sediments showed a maximum concentration of 5.6 and 26.1 wt%, respectively. Sulfur enrichment in the sediments indicates that these dark layers were formed under anoxic conditions in bottom water. Four dark and eight greenish gray sediment samples, ranging in age from early Miocene to Pleistocene, were analyzed for lipid-class compounds (aliphatic hydrocarbons, fatty alcohols, and sterols) using gas chromatography (GC) and GC/mass spectrometry to better understand the formation processes of the organic-rich dark layers and to reconstruct the paleoenvironmental changes. The molecular distributions of n-alkanes and fatty alcohols indicate that terrigenous organic matter largely contributed to both types of sediments. Significant amounts of hopanoid hydrocarbons, such as diploptene and hop-17(21)-ene, however, were detected characteristically in the dark sediments, which suggests that prokaryotes such as methane-oxidizing bacteria or cyanobacteria may have significantly contributed to the formation of these organic-rich, dark sediments. These results indicate that the bottom waters of the Norway Basin had been subjected to anoxic conditions during the early Miocene.

(Table 1) Carbon and isotopic composition of organic carbon in sediments from DSDP Leg 56 Holes

We have analyzed inorganic and organic carbons and determined the isotopic composition of both sedimentary organic carbon and inorganic carbon in carbonates contained in sediments recovered from Holes 434, 434A, 434B, 435, and 435A in the landward slope of Japan and from Hole 436 in the oceanic slope of the Japan Trench. Both inorganic and organic carbons were assayed at the P. P. Shirshov Institute of Oceanology, in the same sample, using the Knopp technique and measuring evolved CO2 gravimetrically. Each sample was analyzed twice in parallel. Measurements were of a ±0.05 per cent accuracy and a probability level of 0.95. Carbon isotopic analysis was carried out on a MI-1305 mass spectrometer at the I. M. Gubkin Institute of Petrochemical and Gas Industry and the results presented as dC13 values related to the PDB standard. The procedure for preparing samples for organic carbon isotopic analysis involved (1) drying damp sediments at 60°C; (2) treating samples, while heating, with 10 N HCl to remove carbonate carbon; and (3) evaporating surplus HCl at 60°C. The organic substance was turned to CO2 by oxidizing it in an oxygen atmosphere. To prepare samples for inorganic carbon isotopic analysis we decomposed the carbonates with orthophosphoric acid and refined the gas evolved. The dC13 measurements, including a full cycle of sample preparation, were of a ±0.5 per cent accuracy and a probability level of 0.95.

(Table 2) Methane to ethane ratio, and d13C-methane at DSDP Hole 76-533

Natural gas hydrates are clathrates in which water molecules form a crystalline framework that includes and is stabilized by natural gas (mainly methane) at appropriate conditions of high pressures and low temperatures. The conditions for the formation of gas hydrates are met within continental margin sediments below water depths greater than about 500 m where the supply of methane is sufficient to stabilize the gas hydrate. Observations on DSDP Leg 11 suggested the presence of gas hydrates in sediments of the Blake Outer Ridge. Leg 76 coring and sampling confirms that, indeed, gas hydrates are present there. Geochemical evidence for gas hydrates in sediment of the Blake Outer Ridge includes (1) high concentrations of methane, (2) a sediment sample with thin, matlike layers of white crystals that released a volume of gas twenty times greater than its volume of pore fluid, (3) a molecular distribution of hydrocarbon gases that excluded hydrocarbons larger than isobutane, (4) results from pressure core barrel experiments, and (5) pore-fluid chemistry. The molecular composition of the hydrocarbons in these gas hydrates and the isotopic composition of the methane indicate that the gas is derived mainly from microbiological processes operating on the organic matter within the sediment. Although gas hydrates apparently are widespread on the Blake Outer Ridge, they probably are not of great economic significance as a potential, unconventional, energy resource or as an impermeable cap for trapping upwardly migrating gas at Site 533.

Organic d13C values, kerogen atomic C/N ratios and relative weights of some kerogen pyrolysis products of ODP Hole 112-682A (Table 1)

Carbon isotopic composition of predominantly marine kerogen in latest Oligocene mudstones of the Peru Margin ODP 682A Hole shows an about 3.5? increase with decreasing age. Py-GC and elemental (C=N ratio) analysis of the kerogen plus sulphur isotopic study together with earlier knowledge on geological setting and organic geochemistry results in a better understanding of depositionary environment and allows to separation of the influence of concentration of water dissolved carbon dioxide (ce) on kerogen delta13C from that of other factors (bacterial degradation, sea surface temperature, DIC delta13C, productivity, and admixture of land plant OM). Based on this analysis, the major part of the kerogen shift is considered as a result of the latest Oligocene decrease of marine photosynthetic carbon isotopic fractionation in the Peru Margin photic zone, which in turn possibly reflects a simultaneous drop in atmospheric CO2 level. Uncertainties in the evaluation of the factors affecting the marine photosynthetic carbon isotopic fractionation and the extent of ocean-atmosphere disequilibrium do not permit calculation of the decrease of the atmospheric CO2.

Isotopic ratios and concentrations for mineral-associated and particulate organic fractions of sediment core Wilson_Lake samples

The flux of sediment and organic carbon from continents to the coastal ocean is an important factor governing organic burial in coastal sediments, and these systems preserve important records of environmental and biogeochemical conditions during past global change events. Burial of organic materials in coastal systems can be promoted by chemical resilience or through protection by association with mineral surfaces, but the role and influence of these processes on organic records from ancient sediments is poorly known. We studied sediment and organic matter burial as particulate organic matter (POM) and mineral-bound organic matter (MOM) in near-shore marine sediments from the Wilson Lake core (New Jersey, USA) that span the Paleocene-Eocene thermal maximum (PETM), a climatic perturbation 55.9 Myr ago. Our results show that distinct POM and MOM fractions can be isolated from sediments. Both fractions appear to be dominated by terrestrial material, but POM consisted primarily of recently synthesized material whereas MOM included a significant fraction of pre-aged organic matter from soils or ancient sediments. Variation in organic burial through the PETM is associated with changes in inorganic nitrogen burial, clay mineralogy, and clastic grain size that we associate with enhanced continental weathering, erosion and redeposition of ancient kaolinites, and eustatic sea level variation, respectively. These results provide a new perspective on factors governing carbon burial and carbon isotope records in ancient marine margin settings and offer information on rate and phasing of late Paleocene/early Eocene Earth system changes that may constrain interpretations of the cause of the PETM climate change event.

Organic carbon, reduced sulfur, and iron in Miocene to Holocene sediments from the Oman and Beguela upwelling systems

We examined sediments from Neogene and Quaternary sections of the Benguela and Oman upwelling systems (DSDP Site 532, ODP Sites 723 and 722) to determine environmental and geochemical factors which control and limit pyrite formation in organic-carbon-rich marine sediments. Those samples from the upwelling sites, which contained low to moderate concentrations of total organic carbon (0.7%-3%), had C/S ratios typical of normal marine sediments, i.e., around 2.8. In these sediments, TOC availability probably limited pyrite formation. Results that do not conform with accepted models were found for the sediments high in TOC (3^0-12.4%). The organic matter was of marine origin and contained considerable pyrolytic hydrocarbons, a fact that we take as a sign of low degradation, yet significant concentrations of dissolved sulfate coexisted with it (> 5 mmol/L in the case of Sites 532 and 723). Detrital iron was probably not limiting in either case, because the degree of pyritization was always less than 0.65. Therefore, controls on sulfate reduction and pyrite formation in the organic matter-rich sediments do not appear to conform simply to generally accepted diagenetic models. The data from these thermally immature, old, and organic-rich marine sediments imply that (1) the total reduced sulfur content of organic-rich marine upwelling sediments rarely exceeds an approximate boundary of 1.5% by weight, (2) the C/S ratio of these sediments is not constant and usually much higher than the empirical values proposed for marine sediments. We conclude that sedimentary pyrite formation in upwelling sediments is limited by an as yet unknown factor, and that caution is advised in using C/S ratios and C vs. S diagrams in paleoenvironmental reconstructions for organic-rich sediments.

Stable carbon and nitrogen isotope composition of organic matter in sediments of the Oman Margin

Stable isotopic compositions of carbon and nitrogen and organic carbon content of sediments ranging from the Pliocene to the Pleistocene-Holocene in age from the Oman Margin (ODP Sites 724 and 725) are reported. In general, the organic carbon content is greater than 2% at Site 724. Prior to the Pleistocene-Holocene at this site, sediments with higher content of organic matter were deposited owing to favorable preservation conditions and/or higher productivity. In the Pleistocene, lower amounts of organic matter have been preserved; this material generally has more enriched nitrogen isotopic compositions. This may indicate intensification of the Oxygen Minimum Zone and denitrification with the onset of the Pleistocene. A correlation of carbon isotope content of these sediments with oxygen isotope stages at Site 724 indicates an enrichment in 13C during glacial events. Based on the stable isotope evidence of both carbon and nitrogen, there does not appear to be major input of terrigenous-derived allochthonous material in this marine environment. The timing and extent of monsoon winds on the productivity of this region are not evident, but require further studies for collaborative interpretation of small-scale features in the isotopic and carbon content of this environment.

An evaluation of the trainer-tester and punchboard tutor as electronics trouble-shooting training aids,

Mode of access: Internet.

Organic Semiconducing Thin Films: Device Applications and Beyond

Thesis (Master's)--University of Washington, 2016-06

Hydrothermal control on organic matter alteration and illite precipitation, Mt Isa Basin, Australia

Abundant illite precipitation, in Proterozoic rocks from Northern Lawn Hill Platform, Mt Isa Basin, Australia, occurred in organic matter-rich black shales rather than in sandstones, siltstones and organic matter-poor shales. Sandstones and siltstones acted as impermeable rocks, as early diagenetic quartz and carbonate minerals reduced the porosity-permeability. Scanning and transmission electron microscopy (SEM and TEM) studies indicate a relation between creation of microporosity-permeability and organic matter alteration, suitable for subsequent mineral precipitation. K-Ar data indicate that organic matter alteration and the subsequent illite precipitation within the organic matter occurred during the regional hydrothermal event at 1172 +/- 150 (2sigma) Ma. Hot circulating fluids are considered to be responsible for organic matter alteration, migration and removal of volatile hydrocarbon, and consequently porosity-permeability creation. Those rocks lacking sufficient porosity-permeability, such as sandstones, siltstones and organic matter poor shales, may not have been affected by fluid movement. In hydrothermal systems, shales and mudstones may not be impermeable as usually assumed because of hydrocarbons being rapidly removed by fluid, even with relatively low total organic carbon.