Study of cyclohexanol decomposition reaction over the ferrospinels, A1−xCuxFe2O4 (A=Ni or Co and x=0, 0.3, 0.5, 0.7 and 1), prepared by ‘soft’ chemical methods

Preparation of simple and mixed ferrospinels of nickel, cobalt and copper and their sulphated analogues by the room temperature coprecipitation method yielded fine particles with high surface areas. Study of the vapour phase decomposition of cyclohexanol at 300 °C over all the ferrospinel systems showed very good conversions yielding cyclohexene by dehydration and/or cyclohexanone by dehydrogenation, as the major products. Sulphation very much enhanced the dehydration activity over all the samples. A good correlation was obtained between the dehydration activities of the simple ferrites and their weak plus medium strength acidities (usually of the Brφnsted type) determined independently by the n-butylamine adsorption and ammonia-TPD methods. Mixed ferrites containing copper showed a general decrease in acidities and a drastic decrease in dehydration activities. There was no general correlation between the basicity parameters obtained by electron donor studies and the ratio of dehydrogenation to dehydration activities. There was a leap in the dehydrogenation activities in the case of all the ferrospinel samples containing copper. Along with the basic properties, the redox properties of copper ion have been invoked to account for this added activity.

A Study on the Transport and Distribution of Atmospheric Aerosols and its Influence on Regional Meteorological Parameters over the Indian Subcontinent

This doctoral thesis addresses the growing concern about the significant changes in the climatic and weather patterns due to the aerosol loading that have taken place in the Indo Gangetic Plain(IGP)which includes most of the Northern Indian region. The study region comprises of major industrial cities in India (New Delhi, Kanpur, Allahabad, Jamshedpur and Kolkata). Northern and central parts of India are one of the most thickly populated areas in the world and have the most intensely farmed areas. Rapid increase in population and urbanization has resulted in an abrupt increase in aerosol concentrations in recent years. The IGP has a major source of coal; therefore most of the industries including numerous thermal power plants that run on coal are located around this region. They inject copious amount of aerosols into the atmosphere. Moreover, the transport of dust aerosols from arid locations is prevalent during the dry months which increase the aerosol loading in theatmosphere. The topography of the place is also ideal for the congregation of aerosols. It is bounded by the Himalayas in the north, Thar Desert in the west, the Vindhyan range in the south and Brahmaputra ridge in the east. During the non‐monsoon months (October to May) the weather in the location is dry with very little rainfall. Surface winds are weak during most of the time in this dry season. The aerosols that reach the location by means of long distance transport and from regional sources get accumulated under these favourable conditions. The increase in aerosol concentration due to the complex combination of aerosol transport and anthropogenic factors mixed with the contribution from the natural sources alters the optical properties and the life time of clouds in the region. The associated perturbations in radiative balance have a significant impact on the meteorological parameters and this in turn determines the precipitation forming process. Therefore, any change in weather which disturbs the normal hydrological pattern is alarming in the socio‐economic point of view. Hence, the main focus of this work is to determine the variation in transport and distribution of aerosols in the region and to understand the interaction of these aerosols with meteorological parameters and cloud properties.

A Study on Aerosol Transport Dynamics over the Indian Landmass and the Adjoining Oceanic Regions Using Satellite Data

The present study brings out the influence of transport dynamics on the aerosol distribution over the Indian region at a few selected geographically distinct locations. Over the Bay of Bengal the dominant pathway of aerosol transport during the pre-monsoon period is through higher altitudes (~ 3 km); directed from the Indian main land. In contrast, the aerosol pathways over the Arabian Sea during the same period are quite complex. They are directed from geographically different environments around the ocean through different altitudes. However in general, the day-to-day variability of AOD at both these regions is significantly influenced by the features of atmospheric circulation especially, the wind convergence at higher altitudes (around 3 km). Over the Ganga Basin during the winter period, the wind convergence at lower altitudes (< I km) govems the shon term variations in AOD, while the mean AOD distribution at this location is mainly governed by the local anthropogenic sources.

Studies on the horizontal and vertical distribution of clouds and their impact on energetics of the Atmosphere over the Indian Region

Motivation for the present study is to improve the scienti c understanding on the prominent gap areas in the average three-dimensional distribution of clouds and their impact on the energetics of the earth-atmosphere system. This study is focused on the Indian subcontinent and the surrounding oceans bound within the latitude-longitude bands of 30 S to 30 N and 30 E to 110 E. Main objectives of this study are to : (i) estimate the monthly and seasonal mean vertical distributions of clouds and their spatial variations (which provide the monthly and seasonal mean 3-dimensional distributions of clouds) using multi-year satellite data and investigate their association with the general circulation of the atmosphere, (ii) investigate the characteristics of the `pool of inhibited cloudiness' that appear over the southwest Bay of Bengal during the Asian summer monsoon season (revealed by the 3-dimensional distribution of clouds) and identify the potential mechanisms for its genesis, (iii) investigate the role of SST and atmospheric thermo-dynamical parameters in regulating the vertical development and distribution of clouds, (iv) investigate the vertical distribution of tropical cirrus clouds and their descending nature using lidar observations at Thiruvananthapuram (8.5 N, 77 E), a tropical coastal station at the southwest Peninsular India, and (v) assessment of the impact of clouds on the energetics of the earth-atmosphere system, by estimating the regional seasonal mean cloud radiative forcing at top-of-the-atmosphere (TOA) and latent heating of the atmosphere by precipitating clouds using satellite data

Characteristics of SST over the Arabian Sea and Bay of Bengal

Evolution of mini warm pool in the Arabian Sea just before the onset of southwest monsoon and behavior of SST in the vicinity of weather systems formed during the premonsoon, southwest monsoon and post monsoon seasons were studied using TMI SST data. The Arabian Sea mini warm pool is formed about three weeks ahead of onset of southwest monsoon. Maximum SST is found about one week ahead of monsoon onset and then the warm pool gradually dissipated. Generally, a low-pressure system is formed when the SST exceeds a certain threshold value for the formation of the system. Daily SST values are examined both in Arabian sea and Bay of Bengal to bring out the quantity of increase in SST just before the formation of the system, quantity of rapid decrease in SST during the formation of the system and the number of days required for returning to normal SST. Many cases were examined for pre-monsoon, southwest monsoon and post monsoon seasons to understand the behavior of SST pattern. It is found that the SST increases about 3° C just before the formation of the system and decreases about 4° C during the formation within 2 to 3 days and takes about 4 to 6 days to return to normal SST pattern. However, the SST pattern depends on the weather system

Study of the Oceanic Heat Budget Components over the Arabian Sea during the Formation and Evolution of Super Cyclone, Gonu

Oceans play a vital role in the global climate system. They absorb the incoming solar energy and redistribute the energy through horizontal and vertical transports. In this context it is important to investigate the variation of heat budget components during the formation of a low-pressure system. In 2007, the monsoon onset was on 28th May. A well- marked low-pressure area was formed in the eastern Arabian Sea after the onset and it further developed into a cyclone. We have analysed the heat budget components during different stages of the cyclone. The data used for the computation of heat budget components is Objectively Analyzed air-sea flux data obtained from WHOI (Woods Hole Oceanographic Institution) project. Its horizontal resolution is 1° × 1°. Over the low-pressure area, the latent heat flux was 180 Wm−2. It increased to a maximum value of 210 Wm−2 on 1st June 2007, on which the system was intensified into a cyclone (Gonu) with latent heat flux values ranging from 200 to 250 Wm−2. It sharply decreased after the passage of cyclone. The high value of latent heat flux is attributed to the latent heat release due to the cyclone by the formation of clouds. Long wave radiation flux is decreased sharply from 100 Wm−2 to 30 Wm−2 when the low-pressure system intensified into a cyclone. The decrease in long wave radiation flux is due to the presence of clouds. Net heat flux also decreases sharply to −200 Wm−2 on 1st June 2007. After the passage, the flux value increased to normal value (150 Wm−2) within one day. A sharp increase in the sensible heat flux value (20 Wm−2) is observed on 1st June 2007 and it decreased there- after. Short wave radiation flux decreased from 300 Wm−2 to 90 Wm−2 during the intensification on 1st June 2007. Over this region, short wave radiation flux sharply increased to higher value soon after the passage of the cyclone.

Variations of surface boundary layer parameters associated with Cyclone Gonu over the Arabian Sea using QuikSCAT data

This study attempted to quantify the variations of the surface marine atmospheric boundary layer (MABL) parameters associated with the tropical Cyclone Gonu formed over the Arabian Sea during 30 May–7 June 2007 (just after the monsoon onset). These characteristics were evaluated in terms of surface wind, drag coefficient, wind stress, horizontal divergence, and frictional velocity using 0.5◦ × 0.5◦ resolution Quick Scatterometer (QuikSCAT) wind products. The variation of these different surface boundary layer parameters was studied for three defined cyclone life stages: prior to the formation, during, and after the cyclone passage. Drastic variations of the MABL parameters during the passage of the cyclone were observed. The wind strength increased from 12 to 22 m s−1 in association with different stages of Gonu. Frictional velocity increased from a value of 0.1–0.6 m s−1 during the formative stage of the system to a high value of 0.3–1.4 m s−1 during the mature stage. Drag coefficient varied from 1.5 × 10−3 to 2.5 × 10−3 during the occurrence of Gonu. Wind stress values varied from 0.4 to 1.1 N m−2. Wind stress curl values varied from 10 × 10−7 to 45 × 10−7 N m−3. Generally, convergent winds prevailed with the numerical value of divergence varying from 0 to –4 × 10−5 s−1. Maximum variations of the wind parameters were found in the wall cloud region of the cyclone. The parameters returned to normally observed values in 1–3 days after the cyclone passage

Characteristic Study of the Boundary Layer Parameters over the Arabian Sea and the Bay of Bengal Using the QuikSCAT Dataset

The marine atmospheric boundary layer (MABL) plays a vital role in the transport of momentum and heat from the surface of the ocean into the atmosphere. A detailed study on the MABL characteristics was carried out using high-resolution surface-wind data as measured by the QuikSCAT (Quick scatterometer) satellite. Spatial variations in the surface wind, frictional velocity, roughness parameter and drag coe±cient for the di®erent seasons were studied. The surface wind was strong during the southwest monsoon season due to the modulation induced by the Low Level Jetstream. The drag coe±cient was larger during this season, due to the strong winds and was lower during the winter months. The spatial variations in the frictional velocity over the seas was small during the post-monsoon season (»0.2 m s¡1). The maximum spatial variation in the frictional velocity was found over the south Arabian Sea (0.3 to 0.5 m s¡1) during the southwest monsoon period, followed by the pre-monsoon over the Bay of Bengal (0.1 to 0.25 m s¡1). The mean wind-stress curl during the winter was positive over the equatorial region, with a maximum value of 1.5£10¡7 N m¡3, but on either side of the equatorial belt, a negative wind-stress curl dominated. The area average of the frictional velocity and drag coe±cient over the Arabian Sea and Bay of Bengal were also studied. The values of frictional velocity shows a variability that is similar to the intraseasonal oscillation (ISO) and this was con¯rmed via wavelet analysis. In the case of the drag coe±cient, the prominent oscillations were ISO and quasi-biweekly mode (QBM). The interrelationship between the drag coe±cient and the frictional velocity with wind speed in both the Arabian Sea and the Bay of Bengal was also studied.

Role of sea-surface wind and transport on enhanced aerosol optical depth observed over the Arabian Sea

The objective of this study is to understand the reasons for the enhancement in aerosol optical depth (AOD) over the Arabian Sea observed during June, July and August. During these months, high values of AOD are found over the sea beyond 10◦ N and adjacent regions. The Arabian Sea is bounded by the lands of Asia and Africa on its three sides. So the region is influenced by transported aerosols from the surroundings as well as aerosols of local origin (marine aerosols). During the summer monsoon season in India, strong surface winds with velocities around 15 m s−1 are experienced over most parts of the Arabian Sea. These winds are capable of increasing sea spray activity, thereby enhancing the production of marine aerosols. The strong winds increase the contribution of marine aerosols over the region to about 60% of the total aerosol content. The main components of marine aerosols include sea salt and sulphate particles. The remaining part of the aerosol particles comes from the western and northern land masses around the sea, of which the main component is transported dust particles. This transport is observed at higher altitudes starting from 600 m. At low levels, the transport occurs mainly from the Indian Ocean and the Arabian Sea itself, indicating the predominance of marine aerosols at these levels. The major portion of the total aerosol loading was contributed by coarse-mode particles during the period of study. But in the winter season, the concentration of coarse-mode aerosols is found to be less. From the analysis, it is concluded that the increase in marine aerosols and dust particles transported from nearby deserts results in an increase in aerosol content over the Arabian Sea during June, July and August.

Regional climate model applications on sub-regional scales over the Indian monsoon region: The role of domain size on downscaling uncertainty

Regional climate models are becoming increasingly popular to provide high resolution climate change information for impacts assessments to inform adaptation options. Many countries and provinces requiring these assessments are as small as 200,000 km2 in size, significantly smaller than an ideal domain needed for successful applications of one-way nested regional climate models. Therefore assessments on sub-regional scales (e.g., river basins) are generally carried out using climate change simulations performed for relatively larger regions. Here we show that the seasonal mean hydrological cycle and the day-to-day precipitation variations of a sub-region within the model domain are sensitive to the domain size, even though the large scale circulation features over the region are largely insensitive. On seasonal timescales, the relatively smaller domains intensify the hydrological cycle by increasing the net transport of moisture into the study region and thereby enhancing the precipitation and local recycling of moisture. On daily timescales, the simulations run over smaller domains produce higher number of moderate precipitation days in the sub-region relative to the corresponding larger domain simulations. An assessment of daily variations of water vapor and the vertical velocity within the sub-region indicates that the smaller domains may favor more frequent moderate uplifting and subsequent precipitation in the region. The results remained largely insensitive to the horizontal resolution of the model, indicating the robustness of the domain size influence on the regional model solutions. These domain size dependent precipitation characteristics have the potential to add one more level of uncertainty to the downscaled projections.

Local Hadley circulation over the Asian monsoon region associated with the Tropospheric Biennial Oscillation

The Tropospheric Biennial Oscillation (TBO), a major interannual variation phenomenon in the Indo-Pacific region, is the result of strong ocean-atmosphere coupling over the Asian-Australian monsoon area. Along with other meteorological and oceanographic parameters, the tropical circulation also exhibits interannual oscillations. Even though the TBO is the result of strong air–sea interaction, the circulation cells during TBO years are, as yet, not well understood. In the present study, an attempt has been made to understand the interannual variability of the mean meridional circulation and local monsoon circulation over south Asia in connection with the TBO. The stream function computed from the zonal mean meridional wind component of NCEP=NCAR reanalysis data for the years 1950–2003 is used to represent the meanmeridional circulation. Mean meridional mass transport in the topics reverses from a weak monsoon to a strong monsoon in the presence of ENSO, but in normal TBO yearsmean transport remains weak across the Northern Hemisphere. The meridional temperature gradient, which drives the mean meridional circulation, also shows no reversal during the normal TBO cycle. The local Hadley circulation over the monsoon area follows the TBO cycle with anomalous ascent (descent) in strong (weak) monsoon years. During normal TBO years, the Equatorial region and Indian monsoon areas exhibit opposite local Hadley circulation anomalies

Characteristics of aerosols over the Indian region and their variability associated with atmospheric conditions

The aerosols in the atmosphere play major role in the radiation balance of the Earthatmosphere system. Direct and indirect impact of aerosols on the weather and climate still remains as a topic to be investigated in detail. The effect of aerosols on the radiation budget and thereby circulation pattern is important and requires further study. A detailed analysis of the aerosol properties, their variability and meteorological processes that affect the aerosol properties and distribution over the Indian region is performed in the thesis. The doctoral thesis entitled “Characteristics of aerosols over the Indian region and their variability associated with atmospheric conditions” contains 7 chapters. This thesis presents results on the analysis on the distribution (spatial and temporal) and characteristics of the aerosols over the Indian region and adjoining seas. Regional and stationwise data were analysed and methods such as modeling and statistical analysis are implemented to understand the aerosol properties, classification and transportation. Chapter-1 presents a brief introduction on the aerosols, their measurement techniques, impact of aerosols on the atmospheric radiation budget, climatic and geographic features of the study area and the literature review on the previous studies. It provides a basic understanding in the field of study and objective of the thesis. Definition of the aerosols, their sources/sinks and classification of the particles according to optical and microphysical properties are described. Different measurement techniques such as sampling and remote sensing methods are explained in detail. Physical parameters used to describe aerosol properties and effect of aerosols on the radiation distribution are also discussed. The chapter also explains the objectives of the thesis and description of climatic features of the study area.

Influence of residual cations (Na+, K+ and Mg2+) in the alkylation activity of benzene with 1-octene over rare earth metal ion exchanged FAU–Y zeolite

The effect of residual cations in rare earth metal modified faujasite–Y zeolite has been monitored using magic angle spinning NMR spectral analysis and catalytic activity studies. The second metal ions being used are Na+, K+ and Mg+. From a comparison of the spectra of different samples, it is concluded that potassium and magnesium exchange causes a greater downfield shift in the 29Si NMR peaks. Also, lanthanum exchanged samples show migration behavior from large cages to small cages, which causes the redistribution of second counter cations. It is also observed that Mg2+ causes the most effective migration of lanthanum ions due to its greater charge. The prepared systems were effectively employed for the alkylation of benzene with 1-octene in the vapor phase. From the deactivation studies it is observed that the as-exchanged zeolites possess better stability towards reaction condition over the pure HFAU zeolite.