Exploring Oxidation in the Remote Free Troposphere: Insights from Atmospheric Tomography (ATom)

Earth's atmosphere oxidizes the greenhouse gas methane and other gases, thus determining their lifetimes and oxidation products. Much of this oxidation occurs in the remote, relatively clean free troposphere above the planetary boundary layer, where the oxidation chemistry is thought to be much simpler and better understood than it is in urban regions or forests. The NASA airborne Atmospheric Tomography study (ATom) was designed to produce cross sections of the detailed atmospheric composition in the remote atmosphere over the Pacific and Atlantic Oceans during four seasons. As part of the extensive ATom data set, measurements of the atmosphere's primary oxidant, hydroxyl (OH), and hydroperoxyl (HO₂) are compared to a photochemical box model to test the oxidation chemistry. Generally, observed and modeled median OH and HO₂ agree to with combined uncertainties at the 2σ confidence level, which is ~±40%. For some seasons, this agreement is within ~±20% below 6 km altitude. While this test finds no significant differences, OH observations increasingly exceeded modeled values at altitudes above 8 km, becoming ~35% greater, which is near the combined uncertainties. Measurement uncertainty and possible unknown measurement errors complicate tests for unknown chemistry or incorrect reaction rate coefficients that would substantially affect the OH and HO₂ abundances. Future analysis of detailed comparisons may yield additional discrepancies that are masked in the median values

Estimation of Time-varying Frequency and its Rate of Change in Low-inertia Power Systems

In this paper, a hierarchical estimation scheme is designed to track the frequency and its rate of change of non-stationary power signals. The frequency is retrieved by a kernel-based parameter estimator in the first step. Subsequently, the frequency estimates are injected into a kernel-based numerical differentiator to extract its changing rate. Thanks to the deployed Volterra integral operator and suitably designed kernel-functions, the proposed estimator can achieve very fast convergence speed without compromising the robustness against noise. Therefore, the real-time estimates are able to follow the time-varying frequency and its rate of change with satisfactory accuracy. The effectiveness and robustness of the proposed method are verified by numerical experiments considering typical practical scenarios under the disturbance of noise. The results of the proposed method are compared with a highly-concerned quadrature phase-locked-loop (QPLL) method

Observation of isoprene hydroxynitrates in the southeastern United States and implications for the fate of NO_x

Isoprene hydroxynitrates (IN) are tracers of the photochemical oxidation of isoprene in high NO_x environments. Production and loss of IN have a significant influence on the NO_x cycle and tropospheric O_3 chemistry. To better understand IN chemistry, a series of photochemical reaction chamber experiments was conducted to determine the IN yield from isoprene photooxidation at high NO concentrations (> 100 ppt). By combining experimental data and calculated isomer distributions, a total IN yield of 9(+4/−3) % was derived. The result was applied in a zero-dimensional model to simulate production and loss of ambient IN observed in a temperate forest atmosphere, during the Southern Oxidant and Aerosol Study (SOAS) field campaign, from 27 May to 11 July 2013. The 9 % yield was consistent with the observed IN/(MVK+MACR) ratios observed during SOAS. By comparing field observations with model simulations, we identified NO as the limiting factor for ambient IN production during SOAS, but vertical mixing at dawn might also contribute (~ 27 %) to IN dynamics. A close examination of isoprene's oxidation products indicates that its oxidation transitioned from a high-NO dominant chemical regime in the morning into a low-NO dominant regime in the afternoon. A significant amount of IN produced in the morning high NO regime could be oxidized in the low NO regime, and a possible reaction scheme was proposed

Sources, seasonality, and trends of southeast US aerosol: an integrated analysis of surface, aircraft, and satellite observations with the GEOS-Chem chemical transport model

We use an ensemble of surface (EPA CSN, IMPROVE, SEARCH, AERONET), aircraft (SEAC4RS), and satellite (MODIS, MISR) observations over the southeast US during the summer–fall of 2013 to better understand aerosol sources in the region and the relationship between surface particulate matter (PM) and aerosol optical depth (AOD). The GEOS-Chem global chemical transport model (CTM) with 25 × 25 km^2 resolution over North America is used as a common platform to interpret measurements of different aerosol variables made at different times and locations. Sulfate and organic aerosol (OA) are the main contributors to surface PM_(2.5) (mass concentration of PM finer than 2.5 μm aerodynamic diameter) and AOD over the southeast US. OA is simulated successfully with a simple parameterization, assuming irreversible uptake of low-volatility products of hydrocarbon oxidation. Biogenic isoprene and monoterpenes account for 60 % of OA, anthropogenic sources for 30 %, and open fires for 10 %. 60 % of total aerosol mass is in the mixed layer below 1.5 km, 25 % in the cloud convective layer at 1.5–3 km, and 15 % in the free troposphere above 3 km. This vertical profile is well captured by GEOS-Chem, arguing against a high-altitude source of OA. The extent of sulfate neutralization (f = [NH_4^+]/(2[SO_4^(2−)] + [NO_3^−]) is only 0.5–0.7 mol mol^(−1) in the observations, despite an excess of ammonia present, which could reflect suppression of ammonia uptake by OA. This would explain the long-term decline of ammonium aerosol in the southeast US, paralleling that of sulfate. The vertical profile of aerosol extinction over the southeast US follows closely that of aerosol mass. GEOS-Chem reproduces observed total column aerosol mass over the southeast US within 6 %, column aerosol extinction within 16 %, and space-based AOD within 8–28 % (consistently biased low). The large AOD decline observed from summer to winter is driven by sharp declines in both sulfate and OA from August to October. These declines are due to shutdowns in both biogenic emissions and UV-driven photochemistry. Surface PM_(2.5) shows far less summer-to-winter decrease than AOD and we attribute this in part to the offsetting effect of weaker boundary layer ventilation. The SEAC4RS aircraft data demonstrate that AODs measured from space are consistent with surface PM_(2.5). This implies that satellites can be used reliably to infer surface PM_(2.5) over monthly timescales if a good CTM representation of the aerosol vertical profile is available

Non-destructive Electromagnetic Wave Sensor for Hazardous Biological Materials

A novel non-destructive electromagnetic wave (EM) sensor for rapid identification of biological material is presented in this paper. Biological treats could be defined as biological agents such as bacteria spores, viruses and toxins. Spores can disable or kill people, animals and crops. Therefore, it is important to identify the hazard in rapid and non destructive manner to make a safer environment. In this research, a 2.45 GHz microwave resonator was used to detect the dipliconic acid (DPA), which is the bio-maker of bacillus spores. A promising results were obtained by detecting the DPA from 0.001M – 0.3M concentration at frequency of 2.4 GHz, which are the fundamental mode (TM101) of the designed cavity. In addition, different species of bacillus spores was detected at frequency approximate at 2.36 GHz. The results concluded that electromagnetic wave sensors may have the potential for use as a non-destructive and real time sensor to detect bacillus spores. The EM principle could be extended to detect different hazardous biological materials by identify the “finger print” of specific biological materials on different surfaces

Detecting and Characterizing Small Dense Bipartite-like Subgraphs by the Bipartiteness Ratio Measure

We study the problem of finding and characterizing subgraphs with small \textit{bipartiteness ratio}. We give a bicriteria approximation algorithm \verb|SwpDB| such that if there exists a subset $S$ of volume at most $k$ and bipartiteness ratio $\theta$, then for any $0<\epsilon<1/2$, it finds a set $S'$ of volume at most $2k^{1+\epsilon}$ and bipartiteness ratio at most $4\sqrt{\theta/\epsilon}$. By combining a truncation operation, we give a local algorithm \verb|LocDB|, which has asymptotically the same approximation guarantee as the algorithm \verb|SwpDB| on both the volume and bipartiteness ratio of the output set, and runs in time $O(\epsilon^2\theta^{-2}k^{1+\epsilon}\ln^3k)$, independent of the size of the graph. Finally, we give a spectral characterization of the small dense bipartite-like subgraphs by using the $k$th \textit{largest} eigenvalue of the Laplacian of the graph.Comment: 17 pages; ISAAC 201

A systematic review of air pollution and incidence of out-of-hospital cardiac arrest

Introduction: Studies have linked air pollution with the incidence of acute coronary artery events and cardiovascular mortality but the association with out-of-hospital cardiac arrest (OHCA) is less clear. Aim: To examine the association of air pollution with the occurrence of OHCA.Methods: Electronic bibliographic databases (until February 2013) were searched. Search terms included common air pollutants and OHCA. Studies of patients with implantable cardioverter defibrillators and OHCA not attended by paramedics were excluded. Two independent reviewers (THKT and TAW) identified potential studies. Methodological: quality was assessed by the Newcastle-Ottawa Scale.Results: Of 849 studies, 8 met the selection criteria. Significant associations between particulate matter (PM) exposure (especially PM2.5) and OHCA were found in 5 studies. An increase of OHCA risk ranged from 2.4% to 7% per interquartile increase in average PM exposure on the same day and up to 4 days prior to the event. A large study found ozone increased the risk of OHCA within 3 h prior to the event. The strongest risk OR of 3.8–4.6% per 20 parts per billion ozone increase of the average level was within 2 h prior to the event. Similarly, another study found an increased risk of 18% within 2 days prior to the event.Conclusions: Larger studies have suggested an increased risk of OHCA with air pollution exposure from PM 2.5 and ozone

First order magnetic transition in CeFe2_2 alloys: Phase-coexistence and metastability

First order ferromagnetic (FM) to antiferromagnetic (AFM) phase transition in doped-CeFe$_2$ alloys is studied with micro-Hall probe technique. Clear visual evidence of magnetic phase-coexistence on micrometer scales and the evolution of this phase-coexistence as a function of temperature, magnetic field and time across the first order FM-AFM transition is presented. Such phase-coexistence and metastability arise as natural consequence of an intrinsic disorder-influenced first order transition. Generality of this phenomena involving other classes of materials is discussed.Comment: 11 pages of text and 3 figure

Hydroxy nitrate production in the OH-initiated oxidation of alkenes

Alkenes are oxidized rapidly in the atmosphere by addition of OH and subsequently O_2 leading to the formation of β-hydroxy peroxy radicals. These peroxy radicals react with NO to form β-hydroxy nitrates with a branching ratio α. We quantify α for C_2–C_8 alkenes at 295 K ± 3 and 993 hPa. The branching ratio can be expressed as α = (0.045 ± 0.016) × N − (0.11 ± 0.05) where N is the number of heavy atoms (excluding the peroxy moiety), and listed errors are 2σ. These branching ratios are larger than previously reported and are similar to those for peroxy radicals formed from H abstraction from alkanes. We find the isomer distributions of β-hydroxy nitrates formed under NO-dominated peroxy radical chemistry to be different than the isomer distribution of hydroxy hydroperoxides produced under HO2-dominated peroxy radical chemistry. Assuming unity yield for the hydroperoxides implies that the branching ratio to form β-hydroxy nitrates increases with substitution of RO_2. Deuterium substitution enhances the branching ratio to form hydroxy nitrates in both propene and isoprene by a factor of ~ 1.5. The role of alkene chemistry in the Houston region is re-evaluated using the RONO_2 branching ratios reported here. Small alkenes are found to play a significant role in present-day oxidant formation more than a decade (2013) after the 2000 Texas Air Quality Study identified these compounds as major contributors to photochemical smog in Houston