Economical and Sustainable Synthesis of Small-Pore Chabazite Catalysts for NOx Abatement by Recycling Organic Structure-Directing Agents.

The application of small-pore chabazite-type SSZ-13 zeolites, key materials for the reduction of nitrogen oxides (NOx) in automotive exhausts and the selective conversion of methane, is limited by the use of expensive N,N,N-trimethyl-1-ammonium adamantine hydroxide (TMAdaOH) as an organic structure-directing agent (OSDA) during hydrothermal synthesis. Here, we report an economical and sustainable route for SSZ-13 synthesis by recycling and reusing the OSDA-containing waste liquids. The TMAdaOH concentration in waste liquids, determined by a bromocresol green colorimetric method, was found to be a key factor for SSZ-13 crystallization. The SSZ-13 zeolite synthesized under optimized conditions demonstrates similar physicochemical properties (surface area, porosity, crystallinity, Si/Al ratio, etc.) as that of the conventional synthetic approach. We then used the waste liquid-derived SSZ-13 as the parent zeolite to synthesize Cu ion-exchanged SSZ-13 (i.e., Cu-SSZ-13) for ammonia-mediated selective catalytic reduction of NOx (NH3-SCR) and observed a higher activity as well as better hydrothermal stability than Cu-SSZ-13 by conventional synthesis. In situ infrared and ultraviolet-visible spectroscopy investigations revealed that the superior NH3-SCR performance of waste liquid-derived Cu-SSZ-13 results from a higher density of Cu2+ sites coordinated to paired Al centers on the zeolite framework. The technoeconomic analysis highlights that recycling OSDA-containing waste liquids could reduce the raw material cost of SSZ-13 synthesis by 49.4% (mainly because of the higher utilization efficiency of TMAdaOH) and, meanwhile, the discharging of wastewater by 45.7%.

Rapid Simulation of Unprocessed DEER Decay Data for Protein Fold Prediction.

Despite advances in sampling and scoring strategies, Monte Carlo modeling methods still struggle to accurately predict de novo the structures of large proteins, membrane proteins, or proteins of complex topologies. Previous approaches have addressed these shortcomings by leveraging sparse distance data gathered using site-directed spin labeling and electron paramagnetic resonance spectroscopy to improve protein structure prediction and refinement outcomes. However, existing computational implementations entail compromises between coarse-grained models of the spin label that lower the resolution and explicit models that lead to resource-intense simulations. These methods are further limited by their reliance on distance distributions, which are calculated from a primary refocused echo decay signal and contain uncertainties that may require manual refinement. Here, we addressed these challenges by developing RosettaDEER, a scoring method within the Rosetta software suite capable of simulating double electron-electron resonance spectroscopy decay traces and distance distributions between spin labels fast enough to fold proteins de novo. We demonstrate that the accuracy of resulting distance distributions match or exceed those generated by more computationally intensive methods. Moreover, decay traces generated from these distributions recapitulate intermolecular background coupling parameters even when the time window of data collection is truncated. As a result, RosettaDEER can discriminate between poorly folded and native-like models by using decay traces that cannot be accurately converted into distance distributions using regularized fitting approaches. Finally, using two challenging test cases, we demonstrate that RosettaDEER leverages these experimental data for protein fold prediction more effectively than previous methods. These benchmarking results confirm that RosettaDEER can effectively leverage sparse experimental data for a wide array of modeling applications built into the Rosetta software suite.

Assessment, formation mechanism, and different source contributions of dissolved salt pollution in the shallow groundwater of Hutuo River alluvial-pluvial fan in the North China Plain.

With rapid urbanization and industrialization processes, the problem of groundwater pollution under the influence of various human activities has become increasingly severe in most developed areas of China. However, the problem of dissolved salt pollution caused by increasing concentrations of conventional ions is often overlooked and easier to be seen as a high background of natural formation rather than pollution. The Hutuo River alluvial fan in North China was selected as the study area; dissolved salt pollution is evaluated based on the factor analysis method (FA); groundwater exploitation, pollutant input, and the attenuation of the vadose zone were discussed to explain the salt pollution; the formation mechanism and different source contributions were also explored. The results show that the total hardness (TH) and nitrate are the main contributing indicators of salt pollution in the Hutuo River alluvial fan. The long-term overexploitation of groundwater promoted the leaching and nitrification reactions, resulting in a large area of moderate to strong salt pollution in the top unit of the alluvial fan, which accounted for 51.6% of the salt pollution according to the multivariate regression model. In addition, the input pollution generated by various types of pollution sources along with rainfall infiltration is also an important driving factor. The surface pollution load and hydrogeological conditions affected the cation exchange and leaching, resulting in a point distribution of strong salt pollution, with a contribution rate of 37.6%. The analysis of the factors that affect salt pollution and the specific contributions in different regions cannot only help decision-makers understand the causes of water quality deterioration but also propose solutions in a targeted manner.

Trajectory-Based Simulation of EPR Spectra: Models of Rotational Motion for Spin Labels on Proteins.

Direct time-domain simulation of continuous-wave (CW) electron paramagnetic resonance (EPR) spectra from molecular dynamics (MD) trajectories has become increasingly popular, especially for proteins labeled with nitroxide spin labels. Due to the time-consuming nature of simulating adequately long MD trajectories, two approximate methods have been developed to reduce the MD-trajectory length required for modeling EPR spectra: hindered Brownian diffusion (HBD) and hidden Markov models (HMMs). Here, we assess the accuracy of these two approximate methods relative to direct simulations from MD trajectories for three spin-labeled protein systems (a simple helical peptide, a soluble protein, and a membrane protein) and two nitroxide spin labels with differing mobilities (R1 and 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amino-4-carboxylic acid (TOAC)). We find that the HMMs generally outperform HBD. Although R1 dynamics partially resembles hindered Brownian diffusion, HMMs accommodate the multiple dynamic time scales for the transitions between rotameric states of R1 that cannot be captured accurately by a HBD model. The MD trajectories of the TOAC-labeled proteins show that its dynamics closely resembles slow multisite exchange between twist-boat and chair ring puckering states. This motion is modeled well by HMM but not by HBD. All MD-trajectory data processing, stochastic trajectory simulations, and CW EPR spectral simulations are implemented in EasySpin, a free software package for MATLAB.

Overview on the spatial-temporal characteristics of the ozone formation regime in China.

Ozone (O3), a main component in photochemical smog, is a secondary pollutant formed through complex photochemical reactions involving nitrogen oxides (NOx) and volatile organic compounds (VOCs). In the past few decades, with the rapid economic development, industrialization and urbanization, the mixing ratio of O3 has increased substantially in China. O3 non-attainment days have been frequently observed. Despite great efforts made in the past few years, it is still difficult to alleviate O3 pollution in China, due to its non-linear relationship with the precursors. In view of the severe situation in China, this study presents a comprehensive review on the spatial-temporal variations of the relationship between O3 and its precursors (i.e. O3 formation regime), built upon the previous reviews of the spatial-temporal variations of O3 and its precursor levels. Valuable findings from previous studies are laid out for a better understanding of O3 pollution, followed by implications for the control of O3 pollution. This literature review indicates that O3 formation in most areas of the North China Plain (NCP), Yangtze River Delta (YRD) and Pearl River Delta (PRD) regions is in a VOC-limited regime during the high-O3 seasons due to dramatic emissions from human activities in cities. Outside these metropolitan areas, a NOx-limited regime dominates rural/remote areas. From summer to winter, the O3 formation regime over China shows a tendency to shift to a VOC-limited regime. Furthermore, O3 formation in China shifted toward increasing sensitivity to VOC emissions before the 12th Five-Year-Plan. However, after the 12th Five-Year-Plan, successful reduction of NOx slowed down this trend. Further effective control of VOCs is expected to achieve sustained O3 attainment in the future. To timely solve the current O3 pollution problem, precise control of O3 precursors is proposed, together with the joint prevention and control of regional air pollution.

Evaluation of direct and alternating current on nitrate removal using a continuous electrocoagulation process: Economical and environmental approaches through RSM.

This study aims to investigate the effects of alternating current (AC) and direct current (DC) for nitrate removal and its operating costs by using a continuous electrocoagulation (CEC) process. For this purpose, two series of 31 experiments, which were designed by response surface method (RSM), were carried out in both cases of the AC and the DC modes. In each series, the effect of selected parameters, namely, initial nitrate concentration, inlet flow rate, current density and initial pH along with their interactions on the nitrate removal efficiency as well as its operating costs, as responses, were investigated separately. According to the analysis of variance (ANOVA), there is a reasonable agreement between achieving results and the experimental data for both responses. The nitrate removal in the AC mode was slightly more efficient than that of the DC mode. In addition, the average operating costs of the DC mode, including the energy and the electrode consumption for the CEC process were achieved 54 US$/(kg nitrate removed); whereas this amount was calculated 29 US$/(kg nitrate removed) for the AC mode. Therefore, the average of the operating costs was improved more than 40% using the AC mode, which was mainly related to reduction of aluminum electrode consumption.

Theoretical study on gas-phase reactions of nitrate radicals with methoxyphenols: Mechanism, kinetic and toxicity assessment.

Creosol and 4-ethylguaiacol are two important methoxyphenols, lignin pyrolysis products, which are discharge into the atmosphere in large quantities. In this work, theoretical calculations of the reaction mechanism towards the two compounds with NO3 radicals was performed using DFT method. The rate constants and toxicity assessment were also investigated. The atmospheric lifetime for creosol and 4-ethylguaiacol were 0.82 and 0.19 h, respectively. A new reaction pathway was proposed for the transformation of methoxyl into hydroxyl, which has not yet been clarified in previous studies. The toxicity of methoxyphenols and their degradation products is closely related to their hydrophobicity. Although most degradation products are less toxic, they also should be pay more attention, especially for nitro-substituents. A new reaction pathway was proposed for the transformation of methoxyl into hydroxyl. The toxicity is closely related to their hydrophobicity.

Catalytic decomposition performance for O3 and NO2 in humid indoor air on a MnOx/Al2O3 catalyst modified by a cost-effective chemical grafting method.

Processes based on non-thermal plasma (NTP) for indoor air treatment inevitably lead to the formation of toxic by-products such as ozone (O3) and nitrogen oxides (NOx). Adding a step of heterogeneous catalysis in series with NTP could allow for the decomposition of the by-products. Therefore, different catalysts were developed based on transition metal oxides, such as NiOx, CoOx and MnOx with different weight percentage 1, 5 and 10wt.%, deposited on a γ-Al2O3 support. The O3 removal efficiency (ORE) and the NOx removal efficiency (NRE) were very encouraging in dry air: about 65% and 80%, respectively, by using 2g 5wt.% MnOx/Al2O3 catalyst under the experimental conditions. However, strongly negative effects of relative humidity (RH) on the catalytic decomposition performance were observed. To overcome this limitation, the catalyst surface was modified to make it hydrophobic using a cost-effective chemical grafting method. This treatment consisted in impregnating the 5wt.% MnOx/Al2O3 catalyst with different trichloro(alkyl)silanes (TCAS). The effects of different linker lengths and amounts of TCAS for the hydrophobicity and the decomposition performance of surface-modified catalysts under humid conditions were investigated. Our results show that the surface-modified catalyst with the shortest linker and 0.25mmol/gcat of modifying agent represents the best catalytic decomposition performance for O3. Its ORE is 41% at 60% RH, which is twice that of the non-modified catalyst.

In Vivo EPR Assessment of pH, pO2, Redox Status, and Concentrations of Phosphate and Glutathione in the Tumor Microenvironment.

This protocol demonstrates the capability of low-field electron paramagnetic resonance (EPR)-based techniques in combination with functional paramagnetic probes to provide quantitative information on the chemical tumor microenvironment (TME), including pO2, pH, redox status, concentrations of interstitial inorganic phosphate (Pi), and intracellular glutathione (GSH). In particular, an application of a recently developed soluble multifunctional trityl probe provides unsurpassed opportunity for in vivo concurrent measurements of pH, pO2 and Pi in Extracellular space (HOPE probe). The measurements of three parameters using a single probe allow for their correlation analyses independent of probe distribution and time of the measurements.

Intercomparison of chemical mechanisms for air quality policy formulation and assessment under North American conditions.

The intercomparison of seven chemical mechanisms for their suitability for air quality policy formulation and assessment is described. Box modeling techniques were employed using 44 sets of background environmental conditions covering North America to constrain the chemical development of the longer lived species. The selected mechanisms were modified to enable an unbiased assessment of the adequacy of the parameterizations of photochemical ozone production from volatile organic compound (VOC) oxidation in the presence of NOx. Photochemical ozone production rates responded differently to 30% NOx and VOC reductions with the different mechanisms, despite the striking similarities between the base-case ozone production rates. The 30% reductions in NOx and VOCs also produced changes in OH. The responses in OH to 30% reductions in NOx and VOCs appeared to be more sensitive to mechanism choice, compared with the responses in the photochemical ozone production rates. Although 30% NOx reductions generally led to decreases in OH, 30% reductions in VOCs led to increases in OH, irrespective of mechanism choice and background environmental conditions. The different mechanisms therefore gave different OH responses to NOx and VOC reductions and so would give different responses in terms of changes in the fate and behavior of air toxics, acidification and eutrophication, and fine particle formation compared with others, in response to ozone control strategies. Policymakers need to understand that there are likely to be inherent differences in the responses to ozone control strategies between different mechanisms, depending on background environmental conditions and the extents of NOx and VOC reductions under consideration. IMPLICATIONS: The purpose of this paper is to compare predicted ozone responses to NOx and VOC reductions with seven chemical mechanisms under North American conditions. The good agreement found between the tested mechanisms should provide some support for their application in the air quality models used for policymaking.

Assessment of indoor HONO formation mechanisms based on in situ measurements and modeling.

The photolysis of HONO has been found to be the oxidation driver through OH formation in the indoor air measurement campaign SURFin, an extensive campaign carried out in July 2012 in a classroom in Marseille. In this study, the INCA-Indoor model is used to evaluate different HONO formation mechanisms that have been used previously in indoor air quality models. In order to avoid biases in the results due to the uncertainty in rate constants, those parameters were adjusted to fit one representative day of the SURFin campaign. Then, the mechanisms have been tested with the optimized parameters against other experiments carried out during the SURFin campaign. Based on the observations and these findings, we propose a new mechanism incorporating sorption of NO2 onto surfaces with possible saturation of these surfaces. This mechanism is able to better reproduce the experimental profiles over a large range of conditions.

Assessment of novel maleic anhydride copolymers prepared via nitroxide-mediated radical polymerization as CaSO4 crystal growth inhibitors.

Calcium sulfate is one of the dominant scales which, unlike carbonate scale, are not easily removable by acid. To inhibit CaSO4 scale formation in artificial cooling water systems, well-defined low molecular weight maleic anhydride and n-alkylacrylamide copolymers (YMR-S series) were synthesized via nitroxide-mediated radical polymerization initiated by benzoyl peroxide in the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy at varying concentrations. These polymerizations exhibit living polymerization characteristics; that is, they show linear growth in chain length as a function of monomer conversion, and have narrow molecular weight distributions. Resultant polymers were characterized by means of 1H-NMR and 13C-NMR. The inhibition behavior of these YMR-S series polymers against CaSO4 was evaluated using the static scale inhibition method and a dynamic tube block test. The inhibition ability on the CaSO4 scale is 99.5% with 9 ppm dosage level at pH 10.45 and temperature 70°C. Scanning electronic microscope analysis proved the morphological changes of the CaSO4 scales due to the strong inhibition action of YMR-S polymers. It is also observed that the antiscaling effect of the copolymers greatly depends on the molecular weight, and the optimum range is below 20,000 and approximately in the range 500-2000.

Production of activated carbons from waste tyres for low temperature NOx control.

Waste tyres were pyrolysed in a bench scale reactor and the product chars were chemically activated with alkali chemical agents, KOH, K2CO3, NaOH and Na2CO3 to produce waste tyre derived activated carbons. The activated carbon products were then examined in terms of their ability to adsorb NOx (NO) at low temperature (25°C) from a simulated industrial process flue gas. This study investigates the influence of surface area and porosity of the carbons produced with the different alkali chemical activating agents on NO capture from the simulated flue gas. The influence of varying the chemical activation conditions on the porous texture and corresponding NO removal from the flue gas was studied. The activated carbon sorbents were characterized in relation to BET surface area, micropore and mesopore volumes and chemical composition. The highest NO removal efficiency for the waste tyre derived activated carbons was ∼75% which was obtained with the adsorbent treated with KOH which correlated with both the highest BET surface area and largest micropore volume. In contrast, the waste tyre derived activated carbons prepared using K2CO3, NaOH and Na2CO3 alkali activating agents appeared to have little influence on NO removal from the flue gases. The results suggest problematic waste tyres, have the potential to be converted to activated carbons with NOx removal efficiency comparable with conventionally produced carbons.

Spin-inversion and spin-selection in the reactions FeO(+) + H2 and Fe(+) + N2O.

The reactions of FeO(+) with H2 and of Fe(+) with N2O were studied with respect to the production and reactivity of electronically excited (4)Fe(+) cations. The reaction of electronic ground state (6)FeO(+) with H2 was found to predominantly produce electronically excited (4)Fe(+) as opposed to electronic ground state (6)Fe(+) corresponding to a spin-allowed reaction. (4)Fe(+) was observed to react with N2O with a rate constant of 2.3 (+0.3/-0.8) × 10(-11) cm(3) molecule(-1) s(-1), smaller than the ground state (6)Fe(+) rate constant of 3.2 (±0.5) × 10(-11) cm(3) molecule(-1) s(-1) (at room temperature). While the overall reaction of (6)FeO(+) with H2 within the Two-State-Reactivity concept is governed by efficient sextet-quartet spin-inversion in the initial reaction complex, the observation of predominant (4)Fe(+) production in the reaction is attributed to a much less efficient quartet-sextet back-inversion in the final reaction complex. Average spin-inversion probabilities are estimated by statistical modeling of spin-inversion processes and related to the properties of spin-orbit coupling along the reaction coordinate. The reaction of FeO(+) with H2 served as a source for (4)Fe(+), subsequently reacting with N2O. The measured rate constant has allowed for a more detailed understanding of the ground state (6)Fe(+) reaction with N2O, leading to a significantly improved statistical modeling of the previously measured temperature dependence of the reaction. In particular, evidence for the participation of electronically excited states of the reaction complex was found. Deexcitation of (4)Fe(+) by He was found to be slow, with a rate constant <3 × 10(-14) cm(3) molecule(-1) s(-1).

Economical way to synthesize SSZ-13 with abundant ion-exchanged Cu+ for an extraordinary performance in selective catalytic reduction (SCR) of NOx by ammonia.

In this study, an economical way for SSZ-13 preparation with the essentially cheap choline chloride as template has been attempted. The as-synthesized SSZ-13 zeolite after ion exchange by copper nitrate solution exhibited a superior SCR performance (over 95% NOx conversion across a broad range from 150 to 400 °C) to the traditional zeolite-based catalysts of Cu-Beta and Cu-ZSM-5. Furthermore, the opportune size of pore opening (∼3.8 Å) made Cu-SSZ-13 exhibiting the best selectivity to N2 as well as satisfactory tolerance toward SO2 and C3H6 poisonings. The characterization (XRD, XPS, XRF, and H2-TPR) of samples confirmed that Cu-SSZ-13 possessed the most abundant Cu cations among three investigated Cu-zeolites; furthermore, either on the surface or in the bulk the ratio of Cu(+)/Cu(2+) ions for Cu-SSZ-13 is also the highest. New finding was announced that CHA-type topology is in favor of the formation of copper cations, especially generating much more Cu(+) ions than the others, rather than CuO. The activity test of Cu(CuCl)-ZSM-5 (prepared by a solid-state ion-exchange method) clearly indicated that Cu(+) ions could make a major contribution to the low-temperature deNOx activity. The activity of protonic zeolites (H-SSZ-13, H-Beta, H-ZSM-5) revealed the topology effect on SCR performances.

Exposure assessment through realistic laboratory simulation of a soccer stadium fire.

On Sunday April 13, 2008 a fire broke out on a grandstand in the Euroborg soccer stadium in Groningen The Netherlands. The polyamide chairs on the grandstand were set on fire and supporters were exposed to the emitted smoke which induced mild health effects. The Dutch government was concerned about potential health risks that such fires could have to exposed fans. Especially the exposure to toxic fumes was considered a risk because prior research has proven that large amounts of chemical compounds are emitted during the burning of chemical substances such as polyamide. Among these emitted compounds are HCN, CO, NO(x), NH(3) and volatile organic compounds. To study if supporters were exposed to hazardous chemical compounds we designed a laboratory controlled replica of a part of the grandstand of the Euroborg stadium to perform fire-experiments. This simulation of the fire under controlled circumstances proved that a wide variety of chemicals were emitted. Especially the emission of CO and NO(x) were high, but also the emission of formaldehyde might be toxicologically relevant. The emission of HCN and NH(3) were less than expected. Exposure assessment suggests that the exposure to NO(x) is the main health risk for the supporters that were present at the Euroborg fire.

W-band frequency-swept EPR.

This paper describes a novel experiment on nitroxide radical spin labels using a multiarm EPR W-band bridge with a loop-gap resonator (LGR). We demonstrate EPR spectroscopy of spin labels by linear sweep of the microwave frequency across the spectrum. The high bandwidth of the LGR, about 1 GHz between 3 dB points of the microwave resonance, makes this new experiment possible. A frequency-tunable yttrium iron garnet (YIG) oscillator provides sweep rates as high as 1.8x10(5) GHz/s, which corresponds to 6.3 kT/s in magnetic field-sweep units over a 44 MHz range. Two experimental domains were identified. In the first, linear frequency sweep rates were relatively slow, and pure absorption and pure dispersion spectra were obtained. This appears to be a practical mode of operation at the present level of technological development. The main advantage is the elimination of sinusoidal magnetic field modulation. In the second mode, the frequency is swept rapidly across a portion of the spectrum, and then the frequency sweep is stopped for a readout period; FID signals from a swept line oscillate at a frequency that is the difference between the spectral position of the line in frequency units and the readout position. If there is more than one line, oscillations are superimposed. The sweep rates using the YIG oscillator were too slow, and the portion of the spectrum too narrow to achieve the full EPR equivalent of Fourier transform (FT) NMR. The paper discusses technical advances required to reach this goal. The hypothesis that trapezoidal frequency sweep is an enabling technology for FT EPR is supported by this study.

The structure of p85ni in class IA phosphoinositide 3-kinase exhibits interdomain disorder.

Regulation of the class IA PI 3-kinase involves inhibition and stabilization of the catalytic subunit (p110) by the regulatory subunit (p85). Regulation is achieved by two major contacts: a stable interface involving the adapter-binding domain (ABD) of p110 and the inter-SH2 (iSH2) domain of p85 and a regulatory interaction between the N-terminal SH2 (nSH2) domain of p85 and the helical domain of p110. In the present study, we have examined the relative orientation of the nSH2 and iSH2 of p85alpha using site-directed spin labeling and pulsed EPR. Surprisingly, both distance measurements and distance distributions suggest that the nSH2 domain is highly disordered relative to the iSH2 domain. Molecular modeling based on EPR distance restraints suggests that the nSH2 domain moves in a hinge-like manner, sampling a torus space around the proximal end of the iSH2 domain. These data have important implications for the mechanism by which p85/p110 dimers are regulated by phosphopeptides.

Assessment of the ozone-nitrogen oxide-volatile organic compound sensitivity of Mexico City through an indicator-based approach: measurements and numerical simulations comparison.

The ozone (O3) sensitivity to nitrogen oxides (NOx, or nitric oxide [NO] + nitrogen dioxide [NO2]) versus volatile organic compounds (VOCs) in the Mexico City metropolitan area (MCMA) is a current issue of scientific controversy. To shed light on this issue, we compared measurements of the indicator species O3/NOy (where NOy represents the sum of NO + NO2 + nitric acid [HNO3] + peroxyacetyl nitrate [PAN] + others), NOy, and the semiempirically derived O3/NOz(surrogate) (where NOz(surrogate) is the derived surrogate NOz, and NOz represents NOx reaction products, or NOy - NOx) with results of numerical predictions reproducing the transition regimes between NOx and VOC sensitivities. Ambient air concentrations of O3, NOx, and NOy were measured from April 14 to 25, 2004 in one downwind receptor site of photochemically aged air masses within Mexico City. MCMA-derived transition values for an episode day occurring during the same monitoring period were obtained through a series of photochemical simulations using the Multiscale Climate and Chemistry Model (MCCM). The comparison between the measured indicator species and the simulated spatial distribution of the indicators O3/ NOy, O3/NOz(surrogate), and NOy in MCMA suggest that O3 in this megacity is likely VOC-sensitive. This is in opposition to past studies that, on the basis of the observed morning VOC/NOx ratios, have concluded that O3 in Mexico City is NOx-sensitive. Simulated MCMA-derived sensitive transition values for O3/NOy, hydrogen peroxide (H2O2)/HNO3, and NOy were found to be in agreement with threshold criteria proposed for other regions in North America and Europe, although the transition crossover for O3/NOz and O3/HNO3 was not consistent with values reported elsewhere. An additional empirical evaluation of weekend/weekday differences in average maximum O3 concentrations and 6:00- to 9:00-a.m. NOx and NO levels registered at the same site in April 2004 indirectly confirmed the above results. A preliminary conclusion is that additional reductions in NOx emissions in MCMA might cause an increase in presently high O3 levels.

Assessment of near-future policy instruments for oceangoing shipping: impact on atmospheric aerosol burdens and the earth's radiation budget.

We apply the global climate model ECHAM5/MESSy1-MADE with detailed aerosol and cloud microphysics to study the impact of shipping on tropospheric aerosol burdens, clouds, and the radiation budget for four near-future ship emission policy scenarios for the year 2012. We compare a "No Control" scenario with global sulfur limits and regionally applied reductions. We show that, if no control measures are taken, near surface sulfate increases by about 10-20% over the main transoceanic shipping routes from 2002 to 2012. A reduction of the maximum fuel sulfur (S) content allowed within 200 nautical miles of coastal areas ("global emission control areas") to 0.5% or 0.1% (5000 or 1000 ppm S, respectively) results in a distinctive reduction in near surface sulfate from shipping in coastal regions compared with the year 2002. The model results also show that if emissions of nitrogen oxides (NO(x)) remain unabated, a reduction of the fuel sulfur content favors a strong increase in aerosol nitrate (NO3) which could counteract up to 20% of the decrease in sulfate mass achieved by sulfur emission reductions. The most important impact of shipping on the radiation budget is related to the modification of low maritime stratus clouds resulting in an increased reflectivity and enhanced shortwave cloud forcing. The direct aerosol effect from shipping is small. Our study shows that one can expect a less negative (less cooling) radiative forcing due to reductions in the current fuel sulfur content of ocean-going ships. The global annual average net cloud forcings due to shipping (year 2012) are in the range of -0.27 to -0.58 W/m2 with regional cooling occurring most over the remote oceans.