Elemental ratio measurements of organic compounds using aerosol mass spectrometry: characterization, improved calibration, and implications

Elemental compositions of organic aerosol (OA) particles provide useful constraints on OA sources, chemical evolution, and effects. The Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) is widely used to measure OA elemental composition. This study evaluates AMS measurements of atomic oxygen-to-carbon (O : C), hydrogen-to-carbon (H : C), and organic mass-to-organic carbon (OM : OC) ratios, and of carbon oxidation state ([bar over OS][subscript C]) for a vastly expanded laboratory data set of multifunctional oxidized OA standards. For the expanded standard data set, the method introduced by Aiken et al. (2008), which uses experimentally measured ion intensities at all ions to determine elemental ratios (referred to here as "Aiken-Explicit"), reproduces known O : C and H : C ratio values within 20% (average absolute value of relative errors) and 12%, respectively. The more commonly used method, which uses empirically estimated H[subscript 2]O[superscript +] and CO[superscript +] ion intensities to avoid gas phase air interferences at these ions (referred to here as "Aiken-Ambient"), reproduces O : C and H : C of multifunctional oxidized species within 28 and 14% of known values. The values from the latter method are systematically biased low, however, with larger biases observed for alcohols and simple diacids. A detailed examination of the H[subscript 2]O[superscript +], CO[superscript +], and CO[subscript 2][superscript +] fragments in the high-resolution mass spectra of the standard compounds indicates that the Aiken-Ambient method underestimates the CO[superscript +] and especially H[subscript 2]O[superscript +] produced from many oxidized species. Combined AMS–vacuum ultraviolet (VUV) ionization measurements indicate that these ions are produced by dehydration and decarboxylation on the AMS vaporizer (usually operated at 600 °C). Thermal decomposition is observed to be efficient at vaporizer temperatures down to 200 °C. These results are used together to develop an "Improved-Ambient" elemental analysis method for AMS spectra measured in air. The Improved-Ambient method uses specific ion fragments as markers to correct for molecular functionality-dependent systematic biases and reproduces known O : C (H : C) ratios of individual oxidized standards within 28% (13%) of the known molecular values. The error in Improved-Ambient O : C (H : C) values is smaller for theoretical standard mixtures of the oxidized organic standards, which are more representative of the complex mix of species present in ambient OA. For ambient OA, the Improved-Ambient method produces O : C (H : C) values that are 27% (11%) larger than previously published Aiken-Ambient values; a corresponding increase of 9% is observed for OM : OC values. These results imply that ambient OA has a higher relative oxygen content than previously estimated. The [bar over OS][subscript C] values calculated for ambient OA by the two methods agree well, however (average relative difference of 0.06 [bar over OS][subscript C] units). This indicates that [bar over OS][subscript C] is a more robust metric of oxidation than O : C, likely since [bar over OS][subscript C] is not affected by hydration or dehydration, either in the atmosphere or during analysis.National Science Foundation (U.S.) (CHE-1012809)National Science Foundation (U.S.) (ATM-1238109

The Structure, Dynamics and Electronic Structure of Liquid Ag-Se Alloys Investigated by Ab Initio Simulation

Ab initio molecular-dynamics simulations have been used to investigate the structure, dynamics and electronic properties of the liquid alloy Ag(1-x)Se(x) at 1350 K and at the three compositions x=0.33, 0.42 and 0.65. The calculations are based on density-functional theory in the local density approximation and on the pseudopotential plane-wave method. The reliability of the simulations is confirmed by detailed comparisons with very recent neutron diffraction results for the partial structure factors and radial distribution functions (RDF) of the stoichiometric liquid Ag2Se. The simulations show a dramatic change of the Se-Se RDF with increasing Se content. This change is due to the formation of Se clusters bound by covalent bonds, the Se-Se bond length being almost the same as in pure c-Se and l-Se. The clusters are predominantly chain-like, but for higher x a large fraction of 3-fold coordinated Se atoms is also found. It is shown that the equilibrium fractions of Se present as isolated atoms and in clusters can be understood on a simple charge-balance model based on an ionic interpretation. The Ag and Se diffusion coefficients both increase with Se content, in spite of the Se clustering. An analysis of the Se-Se bond dynamics reveals surprisingly short bond lifetimes of less than 1 ps. The changes in the density of states with composition arise directly from the formation of Se-Se covalent bonds. Results for the electronic conductivity obtained using the Kubo-Greenwood approximation are in adequate agreement with experiment for l-Ag2Se, but not for the high Se contents. Possible reasons for this are discussed.Comment: 14 pages, Revtex, 14 Postscript figures embedded in the tex

Overnight Atmospheric Transport and Chemical Processing of Photochemically Aged Houston Urban and Petrochemical Industrial Plume

Overnight atmospheric transport and chemical evolution of photochemically aged Houston urban and petrochemical industrial plume were investigated in July 2005. We report here on the 26 July episode in which the aged plume was tagged 1.5 h before sunset with a pair of free-floating controlled meteorological balloons, which guided quasi-Lagrangian aircraft sampling in the plume as it was advected 300 km to the north over 8 h. The aged plume around sunset was well mixed within a 1600 m residual layer, and was characterized by enhanced levels of aerosol, O3, CO, olefins, acetaldehyde, total odd nitrogen compounds (NOy), and relatively small amounts (\u3c1 \u3eppbv) of NO x. The plume experienced appreciable shearing overnight due to the development of a low-altitude nocturnal jet between 300 and 500 m above mean sea level (MSL). However, the plume above 600 m MSL remained largely undiluted even after 8 h of transport due to lack of turbulent mixing above the jet. About 40-60% of the NOx present in the aged plume around sunset was found to be depleted over this 8 h period. A constrained plume modeling analysis of the quasi-Lagrangian aircraft observations suggested that by dawn this NO x was converted to nitric acid, organic nitrates, and peroxy acyl nitrates via reactions of NO3 radicals with enhanced levels of olefins and aldehydes in the plume. Sensitivity of NOx depletion to heterogeneous hydrolysis of N2O5 on aerosols was examined. These results have significant implications for the impacts of urban and industrial pollution on far downwind regions

Airborne measurements of western U.S. wildfire emissions: Comparison with prescribed burning and air quality implications

Wildfires emit significant amounts of pollutants that degrade air quality. Plumes from three wildfires in the western U.S. were measured from aircraft during the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) and the Biomass Burning Observation Project (BBOP), both in summer 2013. This study reports an extensive set of emission factors (EFs) for over 80 gases and 5 components of submicron particulate matter (PM1) from these temperate wildfires. These include rarely, or never before, measured oxygenated volatile organic compounds and multifunctional organic nitrates. The observed EFs are compared with previous measurements of temperate wildfires, boreal forest fires, and temperate prescribed fires. The wildfires emitted high amounts of PM1 (with organic aerosol (OA) dominating the mass) with an average EF that is more than 2 times the EFs for prescribed fires. The measured EFs were used to estimate the annual wildfire emissions of carbon monoxide, nitrogen oxides, total nonmethane organic compounds, and PM1 from 11 western U.S. states. The estimated gas emissions are generally comparable with the 2011 National Emissions Inventory (NEI). However, our PM1 emission estimate (1530 ± 570 Gg yr-1) is over 3 times that of the NEI PM2.5 estimate and is also higher thanthe PM2.5 emitted from all other sources in these states in the NEI. This study indicates that the source of OA from biomass burning in the western states is significantly underestimated. In addition, our results indicate that prescribed burning may be an effective method to reduce fine particle emissions

Resection of the liver for colorectal carcinoma metastases - A multi-institutional study of long-term survivors

In this review of a collected series of patients undergoing hepatic resection for colorectal metastases, 100 patients were found to have survived greater than five years from the time of resection. Of these 100 long-term survivors, 71 remain disease-free through the last follow-up, 19 recurred prior to five years, and ten recurred after five years. Patient characteristics that may have contributed to survival were examined. Procedures performed included five trisegmentectomies, 32 lobectomies, 16 left lateral segmentectomies, and 45 wedge resections. The margin of resection was recorded in 27 patients, one of whom had a positive margin, nine of whom had a less than or equal to 1-cm margin, and 17 of whom had a greater than 1-cm margin. Eighty-one patients had a solitary metastasis to the liver, 11 patients had two metastases, one patient had three metastases, and four patients had four metastases. Thirty patients had Stage C primary carcinoma, 40 had Stage B primary carcinoma, and one had Stage A primarycarcinoma. The disease-free interval from the time of colon resection to the time of liver resection was less than one year in 65 patients, and greater than one year in 34 patients. Three patients had bilobar metastases. Four of the patients had extrahepatic disease resected simultaneously with the liver resection. Though several contraindications to hepatic resection have been proposed in the past, five-year survival has been found in patients with extrahepatic disease resected simultaneously, patients with bilobar metastases, patients with multiple metastases, and patients with positive margins. Five-year disease-free survivors are also present in each of these subsets. It is concluded that five-year survival is possible in the presence of reported contraindications to resection, and therefore that the decision to resect the liver must be individualized. © 1988 American Society of Colon and Rectal Surgeons

An Innovative Option for Venous Reconstruction After Pancreaticoduodenectomy: the Left Renal Vein

INTRODUCTION: Pancreatic ductal adenocarcinoma has a high mortality rate with limited treatment options. One option is pancreaticoduodenectomy, although complete resection may require venous resection. Pancreaticoduodenectomy with venous resection and reconstruction is becoming a more common practice with many choices for venous reconstruction. We describe the technique of using the left renal vein as a conduit for venous reconstruction during pancreaticoduodenectomy. METHODS: The technique for use of the left renal vein as an interposition graft for venous reconstruction during pancreaticoduodenectomy is described as well as outcomes for nine patients that have undergone the procedure. RESULTS: Nine patients, seven men, with a mean age of 57 years, have undergone the operation. There were eight interposition grafts and one patch graft. Mean operating time was 7.8 hours, and mean tumor size was 3.4 cm. Eight patients had node-positive disease, and six had involvement of the vein. Mean hospital stay was 14 days and perioperative morbidity included a superficial wound infection, delayed gastric emptying, ascites, and gastrointestinal bleeding in one patient each. Creatinine ranged from 0.8–1.1 mg/dl preoperatively and from 0.7–1.3 mg/dl at discharge. Mean follow-up was 6.8 months with normal creatinine values noted through the follow-up period. Two patients had died during follow-up from recurrent disease at 8.3 and 18.2 months after the operation. CONCLUSIONS: The left renal vein provides an additional choice for an autologous graft during pancreaticoduodenectomy with venous resection. The ease of harvesting the graft and maintenance of renal function distinguish its use

Evaluation of the RADCHEM Diagnostic as an Assessment of Fuel-Ablator Mix and Fuel Rho R

The RADCHEM diagnostic consists of the collection of both gaseous and solid debris samples following a NIF shot. Small amounts of detector elements are doped into the inner-most layer of the ablator shell, which then undergo nuclear activations with neutrons and/or charged particles that are produced during the fusion process. Reaction products are collected and their radioactive decays are counted in order to determine the number and type of activations that occurred. Simulations have shown that these data can then be correlated to several capsule parameters, including fuel rhoR ({rho}R), implosion asymmetry, and fuel-ablator mix. In this document we present a brief summary of the simulations that have been performed, and evalute the ability of RADCHEM to assess capsule performance. A longer, follow-on document, which will include more details on the specific simulations and experimental techniques that have been considered for RADCHEM, is currently being written