Abundances and variability of tropospheric volatile organic compounds at the South Pole and other Antarctic locations

Multiyear (2000-2006) seasonal measurements of carbon monoxide, hydrocarbons, halogenated species, dimethyl sulfide, carbonyl sulfide and C1-C4 alkyl nitrates at the South Pole are presented for the first time. At the South Pole, short-lived species (such as the alkenes) typically were not observed above their limits of detection because of long transit times from source regions. Peak mixing ratios of the longer lived species with anthropogenic sources were measured in late winter (August and September) with decreasing mixing ratios throughout the spring. In comparison, compounds with a strong oceanic source, such as bromoform and methyl iodide, had peak mixing ratios earlier in the winter (June and July) because of decreased oceanic production during the winter months. Dimethyl sulfide (DMS), which is also oceanically emitted but has a short lifetime, was rarely measured above 5 pptv. This is in contrast to high DMS mixing ratios at coastal locations and shows the importance of photochemical removal during transport to the pole. Alkyl nitrate mixing ratios peaked during April and then decreased throughout the winter. The dominant source of the alkyl nitrates in the region is believed to be oceanic emissions rather than photochemical production due to low alkane levels.Sampling of other tropospheric environments via a Twin Otter aircraft included the west coast of the Ross Sea and large stretches of the Antarctic Plateau. In the coastal atmosphere, a vertical gradient was found with the highest mixing ratios of marine emitted compounds at low altitudes. Conversely, for anthropogenically produced species the highest mixing ratios were measured at the highest altitudes, suggesting long-range transport to the continent. Flights flown through the plume of Mount Erebus, an active volcano, revealed that both carbon monoxide and carbonyl sulfide are emitted with an OCS/CO molar ratio of 3.3 × 10-3 consistent with direct observations by other investigators within the crater rim. © 2010

Latitudinal, vertical, and seasonal variations of C-1-C-4 alkyl nitrates in the troposphere over the Pacific Ocean during PEM-Tropics A and B: Oceanic and continental sources

We present concentration distributions of C1‐C4 alkyl nitrates observed during the NASA airborne campaigns Pacific Exploratory Mission (PEM) ‐Tropics A (September–October 1996) and PEM‐Tropics B (March–April 1999). The total geographic range for PEM‐Tropics A was 45°N–72°S latitude and 153°E–75°W longitude, and for PEM‐Tropics B was 40°N–36°S latitude and 149°E–75°W longitude. The maximum altitude for these missions was 12 km. These experiments provide the most extensive set of tropospheric measurements collected to date over the tropical Pacific Ocean. We observed high methyl nitrate (MeONO2, CH3ONO2) mixing ratios (approximately 50 pptv) at low altitudes in a latitude band between 8°N to 13°S stretching across the equatorial Pacific, illustrating the oceanic source of MeONO2. This source may be associated with the high‐nutrient, low‐chlorophyll character of equatorial Pacific waters. We discuss MeONO2 and ethyl nitrate (EtONO2, C2H5ONO2), whose abundance is dominated by equatorial oceanic sources, 2‐Propyl nitrate (2‐PrONO2, 2‐C3H7ONO2), which has significant oceanic and northern hemispheric (NH) sources associated with urban/industrial hydrocarbon emissions, and 2‐butyl nitrate (2‐BuONO2 2‐C4H8ONO2), which has mostly NH sources. PEM‐Tropics A and B resulted in remarkably similar equatorial mixing ratios. The excellent correlations between MeONO2 and the other alkyl nitrates in this region produced comparable correlation slopes between the two expeditions. By contrast, NH air masses influenced by urban/industrial emissions typically exhibited much lower MeONO2:EtONO2, MeONO2:2‐PrONO2, and MeONO2:2‐BuONO2 ratios. These relationships can be useful as a diagnostic of air mass origin. North of 10°N, the springtime PEM‐Tropics B mixing ratios of C2‐C4 alkyl nitrates were many‐fold higher at low‐mid altitudes than for late summer PEM‐Tropics A, consistent with strong continental outflow of NMHC precursors during spring

Hydroxyl concentration estimates in the sunlit snowpack at Summit, Greenland

Experiments were performed at Summit, Greenland (72°34′ N, 38°29′ W) to investigate hydroxyl mixing ratios in the sunlit surface snowpack (or firn). We added a carefully selected mixture of hydrocarbon gases (with a wide range of hydroxyl reactivities) to a UV and visible light transparent flow chamber containing undisturbed natural firn. The relative decrease in mixing ratios of these gases allowed estimation of the lower limit mixing ratio of hydroxyl radicals in the near-surface firn pore spaces. Hydroxyl mixing ratios in the firn air followed a diurnal cycle in summer 2003 (10-12 July), with peak values of more than 3.2×106 molecules cm-3 between 13:00 and 16:00 local time. The minimum value estimated was 1.1×106 molecules cm-3 at 20:00 local time. Results during spring of 2004 showed lower, but rapidly increasing, peak hydroxyl mixing ratios of 1.1×106 molecules cm-3 in the early afternoon on 15 April and 1.5×106 molecules cm-3 on 1 May. Our firn hydroxyl estimates were similar to directly measured above-snow ambient levels during the spring field season, but were only about 30% of ambient levels during summer. © 2007 Elsevier Ltd. All rights reserved

Selective Metal Cation Capture by Soft Anionic Metal-Organic Frameworks via Drastic Single-Crystal-to-Single-Crystal Transformations

In this paper we describe a novel framework for the discovery of the topical content of a data corpus, and the tracking of its complex structural changes across the temporal dimension. In contrast to previous work our model does not impose a prior on the rate at which documents are added to the corpus nor does it adopt the Markovian assumption which overly restricts the type of changes that the model can capture. Our key technical contribution is a framework based on (i) discretization of time into epochs, (ii) epoch-wise topic discovery using a hierarchical Dirichlet process-based model, and (iii) a temporal similarity graph which allows for the modelling of complex topic changes: emergence and disappearance, evolution, and splitting and merging. The power of the proposed framework is demonstrated on the medical literature corpus concerned with the autism spectrum disorder (ASD) - an increasingly important research subject of significant social and healthcare importance. In addition to the collected ASD literature corpus which we will make freely available, our contributions also include two free online tools we built as aids to ASD researchers. These can be used for semantically meaningful navigation and searching, as well as knowledge discovery from this large and rapidly growing corpus of literature.Comment: In Proc. Pacific-Asia Conference on Knowledge Discovery and Data Mining (PAKDD), 201

MKEM: a Multi-level Knowledge Emergence Model for mining undiscovered public knowledge

<p>Abstract</p> <p>Background</p> <p>Since Swanson proposed the Undiscovered Public Knowledge (UPK) model, there have been many approaches to uncover UPK by mining the biomedical literature. These earlier works, however, required substantial manual intervention to reduce the number of possible connections and are mainly applied to disease-effect relation. With the advancement in biomedical science, it has become imperative to extract and combine information from multiple disjoint researches, studies and articles to infer new hypotheses and expand knowledge.</p> <p>Methods</p> <p>We propose MKEM, a Multi-level Knowledge Emergence Model, to discover implicit relationships using Natural Language Processing techniques such as Link Grammar and Ontologies such as Unified Medical Language System (UMLS) MetaMap. The contribution of MKEM is as follows: First, we propose a flexible knowledge emergence model to extract implicit relationships across different levels such as molecular level for gene and protein and Phenomic level for disease and treatment. Second, we employ MetaMap for tagging biological concepts. Third, we provide an empirical and systematic approach to discover novel relationships.</p> <p>Results</p> <p>We applied our system on 5000 abstracts downloaded from PubMed database. We performed the performance evaluation as a gold standard is not yet available. Our system performed with a good precision and recall and we generated 24 hypotheses.</p> <p>Conclusions</p> <p>Our experiments show that MKEM is a powerful tool to discover hidden relationships residing in extracted entities that were represented by our Substance-Effect-Process-Disease-Body Part (SEPDB) model. </p

Large-scale latitudinal and vertical distributions of NMHCs and selected halocarbons in the troposphere over the Pacific Ocean during the March-April 1999 Pacific Exploratory Mission (PEM-Tropics B)

Nonmethane hydrocarbons (NMHCs) and selected halocarbons were measured in whole air samples collected over the remote Pacific Ocean during NASA's Global Tropospheric Experiment (GTE) Pacific Exploratory Mission-Tropics B (PEM-Tropics B) in March and early April 1999. The large-scale spatial distributions of NMHCs and C2Cl4 reveal a much more pronounced north-south interhemispheric gradient, with higher concentrations in the north and lower levels in the south, than for the late August to early October 1996 PEM-Tropics A experiment. Strong continental outflow and winter-long accumulation of pollutants led to seasonally high Northern Hemisphere trace gas levels during PEM-Tropics B. Observations of enhanced levels of Halon 1211 (from developing Asian nations such as the PRC) and CH3Cl (from SE Asian biomass burning) support a significant southern Asian influence at altitudes above 1 km and north of 10° N. By contrast, at low altitude over the North Pacific the dominance of urban/industrial tracers, combined with low levels of Halon 1211 and CH3Cl, indicate a greater influence from developed nations such as Japan, Europe, and North America. Penetration of air exhibiting aged northern hemisphere characteristics was frequently observed at low altitudes over the equatorial central and western Pacific south to ∼5° S. The relative lack of southern hemisphere biomass burning sources and the westerly position of the South Pacific convergence zone contributed to significantly lower PEM-Tropics B mixing ratios of the NMHCs and CH3Cl south of 10° S compared to PEM-Tropics A. Therefore the trace gas composition of the South Pacific troposphere was considerably more representative of minimally polluted tropospheric conditions during PEM-Tropics B. Copyright 2001 by the American Geophysical Union