Methoxy formation in the reaction of CH3O2 radicals with NO

Formation of methoxy (CH₃O) radicals in the reaction (1) CH₃O₂+NOCH₃O+NO₂ at 298 K has been observed directly using time resolved LIF. The branching ratio % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaeqOXdyMaae% 4qaiaabIeadaWgaaWcbaGaae4maaqabaGccaqGpbGaaeiiaiaabIca% ieqacaWF9aGaa8hiaiaa-nbicaWFGaGaeuiLdqKaai4waiaaboeaca% qGibWaaSbaaSqaaiaabodaaeqaaOGaae4taiaac2facaWFVaGaeuiL% dqKaai4waiaaboeacaqGibWaaSbaaSqaaiaabodaaeqaaOGaae4tam% aaBaaaleaacaqGYaaabeaakiaac2facaqGPaaaaa!4E31!\[\phi {\rm{CH}}_{\rm{3}} {\rm{O (}} = -- \Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}]/\Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}_{\rm{2}} ]{\rm{)}}\] has been determined by quantitative cw-UV-laser absorption at 257 nm of CH₃O₂ and CH₃ONO, the product of the consecutive methoxy trapping reaction (2) % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaae4qaiaabI% eadaWgaaWcbaGaae4maaqabaGccaqGpbacbeGaa83kaiaa-bcaieaa% caGFobGaa43taiaa+bcacaGFOaGaa83kaiaa+1eacaGFPaGaa4hiai% abgkziUkaabccacaqGdbGaaeisamaaBaaaleaacaqGZaaabeaakiaa% b+eacaqGGaGaaeOtaiaab+eacaqGGaGaa4hkaiaa-TcacaGFnbGaa4% xkaiaa+5cacaGFGaGaa4hiaiabeA8aMnaaBaaajqwaacqaaiaaboea% caqGibWaaSbaaKazcaiabaGaae4maaqabaqcKfaGaiaab+eaaSqaba% aaaa!55AC!\[{\rm{CH}}_{\rm{3}} {\rm{O}} + NO ( + M) \to {\rm{ CH}}_{\rm{3}} {\rm{O NO }}( + M). \phi _{{\rm{CH}}_{\rm{3}} {\rm{O}}} \] is found to be (1.0±0.2). The rate constant k ₁ is (7±2) 10^-12 cm³/molecule · s in good agreement with previous results.     

Assessment of Indian summer monsoon simulation by Community Atmosphere Model (CAM3)

Seasonal prediction of Indian Summer Monsoon (ISM) has been attempted for the current year 2011 using Community Atmosphere Model (CAM) developed at the National Centre for Atmospheric Research (NCAR). First, 30?years of model climatology starting from 1981 to 2010 has been generated to capture the variability of ISM over the Indian region using 30 seasonal simulations. The simulated model climatology has been validated with different sets of observed climatology, and it was observed that the simulated climatological rainfall is affected by model bias. Subsequently, a bias correction procedure using the Tropical Rainfall Measuring Mission (TRMM) 3B43 rainfall has been proposed. The bias-corrected rainfall climatology shows both spatial and temporal variability of ISM satisfactorily. Further, four sets of 10-member ensemble simulations of ISM 2009 and 2010 have been performed in hindcast mode using observed sea surface temperature (SST) and persistence of April SST anomaly, and it has been found that the bias-corrected model rainfall captures the seasonal variability of ISM reasonably well with some discrepancies in these two contrasting monsoon years. With this positive background, the seasonal prediction of ISM 2011 has been carried out in forecast mode with the assumption of persistence of May SST anomaly from June through September 2011. The model assessment shows an 11% deficiency in All-India Rainfall (AIR) of ISM 2011. In particular, the monthly accumulated rains are predicted to be 101% (17.6?cm), 86% (24.3?cm), 83% (21.0?cm) and 95% (15.5?cm) of normal AIR for the months of June, July, August and September, respectively.     

Developing a Marine Information System by Integrating Existing Ocean Models Using Object-Oriented Technology

Information systems developed for different applications within the environmental domain have common characteristics, which can potentially be abstracted for sharing and reuse of design and software modules. This article presents an approach to designing for reuse by abstracting commonalities in the design of a Marine Information System (MIS), facilitating data management in a prototype operational monitoring, forecasting, and management system for the North Atlantic and the Nordic Seas. A detailed study of the requirements and data analysis was carried out, and Object-Oriented Technology (OOT) is employed to encapsulate abstractions and to promote reuse of code and design. This article identifies the Object-Oriented Frameworks (OOFW) required to build the MIS. It also provides guidelines to environmental scientists for restructuring legacy software and employing modern programming techniques.     

Dissociation constants of protonated cysteine species in seawater media

The dissociation constants (pK₁, pK₂ and pK₃) for cysteine have been measured in seawater as a function of temperature (5 to 45 °C) and salinity (S = 5 to 35). The seawater values were lower than the values in NaCl at the same ionic strength. In an attempt to understand these differences, we have made measurements of the constants in Na–Mg–Cl solutions at 25 °C. The measured values have been compared to those calculated from the Pitzer ionic interaction model. The lower values of pK₃ in the Na–Mg–Cl solutions have been attributed to the formation of Mg²⁺ complexes with Cys²⁻ anions

Mg²⁺ + Cys²⁻ = MgCys

The stability constants have been fitted to

after corrections are made for the interaction of Mg²⁺ with H⁺.The pK₁ seawater measurements indicate that H₃Cys⁺ interacts with SO₄²⁻. The Pitzer parameters β⁰(H₃CysSO₄), β¹(H₃CysSO₄) and C(H₃CysSO₄) have been determined for this interaction. The formation of CaCys as well as MgCys are needed to account for the values of pK₂ and pK₃ in seawater.The consideration of the formation of MgCys and CaCys in seawater yields model calculated values of pK₁, pK₂ and pK₃ that agree with the measured values to within the experimental error of the measurements. This study shows that it is important to consider all of the ionic interactions in natural waters when examining the dissociation of organic acids.     

Trends in the solubility of iron,aluminium, manganese and phosphorus in aerosol collected over the Atlantic Ocean

The solubility of iron, aluminium, manganese and phosphorus has been determined in aerosol samples collected between 49°N and 52°S during three cruises conducted in the Atlantic Ocean as part of the European Union funded IRONAGES programme. Solubilities (defined at pH 4.7) determined for Fe and Al in samples of Saharan dust were significantly lower (medians 1.7% and 3.0%, respectively) than the solubilities of these metals in aerosols from other source regions (whole dataset medians 5.2% and 9.0%, respectively). Mn solubility also varied with aerosol source, but the median solubility of Mn in Saharan dust was very similar to the median for the dataset as a whole (55% and 56%, respectively). The observed solubility of aerosol P was ∼ 32%, with P solubility in Saharan aerosol perhaps as low as 10%. Laboratory studies have indicated that aerosol Fe solubility is enhanced by acid processing. No relationship could be found between Fe solubility and the concentrations of acid species (non-seasalt SO₄²⁻, NO₃⁻) nor the net acidity of the aerosol, so we are unable to confirm that this process is significant in the atmosphere. In terms of the supply of soluble Fe to oceanic ecosystems on a global scale, the observed higher solubility for Fe in non-Saharan aerosols is probably not significant because the Sahara is easily the dominant source of Fe to the Atlantic. On a smaller scale however, higher solubility for aerosol Fe may alter our understanding of Fe cycling in regions such as the remote Southern Ocean.     

Stress Sharing Behavior and Its Mechanism during Consolidation Process in Composite Ground Improved by Sand Compaction Piles with Low Replacement Area Ratio

In order to accurately design a sand compaction pile (SCP) with low replacement area ratio, it is important to understand the mechanical interaction between the sand pile and clay ground and its mechanism during consolidation process in composite ground. In this article, therefore, a series of numerical analyses on composite ground improved by SCP with low replacement area ratio were carried out. The applicability of numerical analyses, in which an elasto-viscoplastic consolidation finite element method was applied, were confirmed by comparing the results obtained from a series of laboratory model tests with the composite ground improved by SCP. Through the results of the numerical analyses, mechanical behavior of the sand pile and clay in composite ground during consolidation is elucidated, together with a stress sharing mechanism between sand pile and clay.     

Viscous model of plate tectonics for the Black Sea region (in relation to the problem of the late Cenozoic evolution of the Black Sea basins)

A numerical model of the Black Sea region (Northeastern Mediterranean) is presented in which it is regarded as a part of the mosaic plate ensemble consisting of the fixed East European platform; the active Arabian, Adriatic, and Pannonian plates; and passive East and West Black Sea and Mysian microplates, which are embedded in a plastically deformable regional orogenic matrix. The fields of displacements, stresses, and deformations in the region are calculated by means of the finite element method within the framework of a linear-viscous rheology approach to a system with nonhomogeneous viscosities. The velocity field obtained is in good agreement with published data of direct observations of plate displacements in the region. In the pressure field, areas of low pressure and decompression are established in the western part of Black Sea and in the south of the Mysian microplate. The poles of rotation of the East and West Black Sea microplates and of the Mysian microplate are computed. For the latter two microplates, significant rotational components are suggested. The East Black Sea microplate acts mostly as indenter, which transmits the collisional motion from the Arabian plate to the southern edge of the East European platform including the Crimea. According to the geodynamical model, the rates of the Cenozoic sedimentation in the Black Sea depression at the collision stage (Oligocene-Pliocene) result from the greater compression of the East Black Sea microplate as compared to the West Black Sea microplate, which, probably, experienced a kind of extension.     

GEBCO Centennial Special Issue – Charting the Secret World of the Ocean Floor: The GEBCO Project 1903–2003

This special issue of Marine Geophysical Researches presents five papers dealing with GEBCO, the General Bathymetric Chart of the Oceans, which celebrated its Centennial in April 2003, hosted by the International Hydrographic Bureau and the Principality of Monaco. Over the past 103 years GEBCO has been the sole body dedicated to compiling all available data to produce standardized maps of the oceans and seas covering 71% of planet Earth. Over time GEBCO has undergone a complete transformation as sparse 500 m contours on paper charts were replaced by digital grids with ever-increasing resolution. The 2003 Centennial saw the release on two CDROMS with the first global 1′ grid, produced by methods unheard of in 1984, when GEBCO’s last 6th Edition paper chart set was published. In GEBCO’s second century, the thrust is towards global grids that will capture the resolutions available with evolving deep-water swath mapping technologies, as well as vast improvement in the details of the shallow continental shelves that have traditionally been the preserve of the hydrographic community. As little more than 10% of the oceans have been mapped to the desired level of detail, there is much to be done. However refinements in satellite altimetry appear to offer an interim stop-gap as more multi-beam sonars ply the oceans and as the littoral countries of the world map their adjacent marine areas for submission under Article 76 of UNCLOS (United Nations, 1983, 1999). In addition GEBCO is becoming increasingly proactive, with outreach to the public via the internet and a new GEBCO Map of the World, active data-scrounging, and encouraging development of the first drifting buoys for acquiring data in the inaccessible areas of the Antarctic, SW Pacific, and Arctic Oceans.