Investigating the origin of PM2.5 in Baltimore using highly time-resolved organic molecular markers measured during the Baltimore PM-supersite

The detailed organic composition of atmospheric fine particles with an aerodynamic diameter smaller than or equal to 2.5 micrometers (PM2.5) is an integral part of the knowledge needed in order to fully characterize its sources and transformation in the environment. For the study presented here, samples were collected at 3-hour intervals. This high time resolution allows gaining unique insights on the influence of short- and long-range transport phenomena, and dynamic atmospheric processes. A specially designed sequential sampler was deployed at the 2002-2003 Baltimore PM-Supersite to collect PM2.5 samples at a 3-hourly resolution for extended periods of consecutive days, during both summer and winter seasons. Established solvent-extraction and GC-MS techniques were used to extract and analyze the organic compounds in 119 samples from each season. Over 100 individual compounds were quantified in each sample. For primary organics, averaging the diurnal ambient concentrations over the sampled periods revealed ambient patterns that relate to diurnal emission patterns of major source classes. Several short-term releases of pollutants from local sources were detected, and local meteorological data was used to pinpoint possible source regions. Biogenic secondary organic compounds were detected as well, and possible mechanisms of formation were evaluated. The relationships between the observed continuous variations of the concentrations of selected organic markers and both the on-site meteorological measurements conducted parallel to the PM2.5 sampling, and the synoptic patterns of weather and wind conditions were also examined. Several one-to-two days episodes were identified from the sequential variation of the concentration observed for specific marker compounds and markers ratios. The influence of the meteorological events on the concentrations of the organic compounds during selected episodes was discussed. It was observed that during the summer, under conditions of pervasive influence of air masses originated from the west/northwest, some organic species displayed characteristics consistent with the measured PM2.5 being strongly influenced by the aged nature of these long-traveling background parcels. During the winter, intrusions from more regional air masses originating from the south and the southwest were more important.

Investigating the origin of PM2.5 in Baltimore using highly time-resolved organic molecular markers measured during the Baltimore PM-supersite

The detailed organic composition of atmospheric fine particles with an aerodynamic diameter smaller than or equal to 2.5 micrometers (PM 2.5) is an integral part of the knowledge needed in order to fully characterize its sources and transformation in the environment. For the study presented here, samples were collected at 3-hour intervals. This high time resolution allows gaining unique insights on the influence of short- and long-range transport phenomena, and dynamic atmospheric processes. A specially designed sequential sampler was deployed at the 2002-2003 Baltimore PM Supersite to collect PM2.5 samples at a 3-hourly resolution for extended periods of consecutive days, during both summer and winter seasons. Established solvent-extraction and GC-MS techniques were used to extract and analyze the organic compounds in 119 samples from each season. Over 100 individual compounds were quantified in each sample. For primary organics, averaging the diurnal ambient concentrations over the sampled periods revealed ambient patterns that relate to diurnal emission patterns of major source classes. Several short-term releases of pollutants from local sources were detected, and local meteorological data was used to pinpoint possible source regions. Biogenic secondary organic compounds were detected as well, and possible mechanisms of formation were evaluated. The relationships between the observed continuous variations of the concentrations of selected organic markers and both the on-site meteorological measurements conducted parallel to the PM2.5 sampling, and the synoptic patterns of weather and wind conditions were also examined. Several one-to-two days episodes were identified from the sequential variation of the concentration observed for specific marker compounds and markers ratios. The influence of the meteorological events on the concentrations of the organic compounds during selected episodes was discussed. It was observed that during the summer, under conditions of pervasive influence of air masses originated from the west/northwest, some organic species displayed characteristics consistent with the measured PM2.5 being strongly influenced by the aged nature of these long-traveling background parcels. During the winter, intrusions from more regional air masses originating from the south and the southwest were more important.

Origin of the Grande Ronde Formation flows, Columbia River flood basalt group

Lavas belonging to the Grande Ronde Formation (GRB) constitute about 63% of the Columbia River Basalt Group (CRBG), a flood basalt province in the NW United States. A puzzling feature is the lack of phenocrysts (< 5%) in these chemically evolved lavas. Based mainly on this observation it has been hypothesized that GRB lavas were nearly primary melts generated by large-scale melting of eclogite. Another recent hypothesis holds that GRB magmas were extremely hydrous and rose rapidly from the mantle such that the dissolved water kept the magmas close to their liquidi. I present new textural and chemical evidence to show that GRB lavas were neither primary nor hydrous melts but were derived from other melts via efficient fractional crystallization and mixing in shallow intrusive systems. Texture and chemical features further suggest that the melt mixing process may have been exothermic, which forced variable melting of some of the existing phenocrysts. ^ Finally, reported here are the results of efforts to simulate the higher pressure histories of GRB using COMAGMAT and MELTS softwares. The intent was to evaluate (1) whether such melts could be derived from primary melts formed by partial melting of a peridotite source as an alternative to the eclogite model, or if bulk melting of eclogite is required; and (2) at what pressure such primary melts could have been in equilibrium with the mantle. I carried out both forward and inverse modeling. The best fit forward model indicates that most primitive parent melts related to GRB could have been multiply saturated at ∼1.5--2.0 GPa. I interpret this result to indicate that the parental melts last equilibrated with a peridotitic mantle at 1.5--2.0 GPa and such partial melts rose to ∼0.2 GPa where they underwent efficient mixing and fractionation before erupting. These models suggest that the source rock was not eclogitic but a fertile spinel lherzolite, and that the melts had ∼0.5% water. ^

Photochemical alteration of 3-oxygenated triterpenoids: Implications for the origin of 3,4-seco-triterpenoids in sediments

The reactivity of higher plant derived 3-oxy-triterpenoids to sunlight was investigated using a series of pure reference standards both under simulated and real solar exposure. The majority of the exposed compounds showed reactivity to light, particularly to simulated sunlight and among others generated seco-derivatives. While photochemical processes have been suggested for the formation of such compounds, their abundances in some sediments have often been assumed to be the result of diagenetic reworking of parent triterpenoids. Analyses of mangrove leaf waxes, an important known source of taraxerol in coastal ecosystems, showed the presence of the 3,4-seco-derivative dihydrolacunosic acid, which could represent an important biotic source for des-A-triterpenoid precursors to such sediments, and is unrelated to aquatic organic matter diagenesis.

Origin of salinity variations in Florida Bay

This note presents a method of distinguishing the source of freshwater that causes reductions in salinity in the coastal environment of South Florida. This technique, which uses the 18O and D of the water, allows for differentiation of the freshwater derived from precipitation as opposed to runoff, because surface waters in the Everglades have been highly evaporated and therefore have elevated 18O and dD values relative to precipitation. A time series of monthly 18O and D values of surface waters, collected from stations in Florida Bay between 1993 and 1999, has shown that, during this time, the major source of freshwaters causing depressions in the salinity in the western portion of Florida Bay was derived from precipitation rather than from the runoff of water from the Everglades. In the eastern portion of Florida Bay, close to the boundary between peninsular Florida and the Bay, the proportion of freshwater derived from precipitation drops steadily, reaching <10%. This method not only allows differentiation between the sources of freshwater but can, in a temporal sense, ascertain the effectiveness of water management practices on the salinity of the estuarine ecosystems of South Florida.