Studies on Catalysis by Nano Titania Modified with Metals and Nonmetals

Semiconductor photocatalysis has received much attention during last three decades as a promising solution for both energy generation and environmental problems. Heterogeneous photocatalytic oxidation allows the degradation of organic compounds into carbon dioxide and water in the presence of a semiconductor catalyst and UV light source. The •OH radicals formed during the photocatalytic processes are powerful oxidizing agents and can mineralise a number of organic contaminants. Titanium dioxide (TiO2), due to its chemical stability, non-toxicity and low cost represents one of the most efficient photocatalyst. However, only the ultraviolet fraction of the solar radiation is active in the photoexcitation processes using pure TiO2 and although, TiO2 can treat a wide range of organic pollutants the effectiveness of the process for pollution abatement is still low. A more effective and efficient catalyst therefore must be formulated. Doping of TiO2 was considered with the aim of improving photocatalytic properties. In this study TiO2 catalyst was prepared using the sol-gel method. Metal and nonmetal doped TiO2 catalysts were prepared. The photoactivity of the catalyst was evaluated by the photodegradation of different dyes and pesticides in aqueous solution. High photocatalytic degradation of all the pollutants was observed with doped TiO2. Structural and optical properties of the catalysts were characterized using XRD, BET surface area, UV-Vis. DRS, CHNS analysis, SEM, EDX, TEM, XPS, FTIR and TG. All the catalysts showed the anatase phase. The presence of dopants shifts the absorption of TiO2 into the visible region indicating the possibility of using visible light for photocatalytic processes.

Modelling of Ultraviolet and Vissible Emissions in Comets

Comets are the spectacular objects in the night sky since the dawn of mankind. Due to their giant apparitions and enigmatic behavior, followed by coincidental calamities, they were termed as notorious and called as `bad omens'. With a systematic study of these objects modern scienti c community understood that these objects are part of our solar system. Comets are believed to be remnant bodies of at the end of evolution of solar system and possess the material of solar nebula. Hence, these are considered as most pristine objects which can provide the information about the conditions of solar nebula. These are small bodies of our solar system, with a typical size of about a kilometer to a few tens of kilometers orbiting the Sun in highly elliptical orbits. The solid body of a comet is nucleus which is a conglomerated mixture of water ice, dust and some other gases. When the cometary nucleus advances towards the Sun in its orbit the ices sublimates and produces the gaseous envelope around the nucleus which is called coma. The gravity of cometary nucleus is very small and hence can not in uence the motion of gases in the cometary coma. Though the cometary nucleus is a few kilometers in size they can produce a transient, extensive, and expanding atmosphere with size several orders of magnitude larger in space. By ejecting gas and dust into space comets became the most active members of the solar system. The solar radiation and the solar wind in uences the motion of dust and ions and produces dust and ion tails, respectively. Comets have been observed in di erent spectral regions from rocket, ground and space borne optical instruments. The observed emission intensities are used to quantify the chemical abundances of di erent species in the comets. The study of various physical and chemical processes that govern these emissions is essential before estimating chemical abundances in the coma. Cameron band emission of CO molecule has been used to derive CO2 abundance in the comets based on the assumption that photodissociation of CO2 mainly produces these emissions. Similarly, the atomic oxygen visible emissions have been used to probe H2O in the cometary coma. The observed green ([OI] 5577 A) to red-doublet emission ([OI] 6300 and 6364 A) ratio has been used to con rm H2O as the parent species of these emissions. In this thesis a model is developed to understand the photochemistry of these emissions and applied to several comets. The model calculated emission intensities are compared with the observations done by space borne instruments like International Ultraviolet Explorer (IUE) and Hubble Space Telescope (HST) and also by various ground based telescopes.

Water quality status and Primary productivity of Valanthakad Backwater in Kerala

The water quality and primary productivity of Valanthakad backwater (9° 55 10. 24 N latitude and 76° 20 01. 23 E longitude) was monitored from June to November 2007. Significant spatial and temporal variations in temperature, transparency, salinity, pH, dissolved oxygen, sulphides, carbon dioxide, alkalinity, biochemical oxygen demand, phosphatephosphorus, nitrate-nitrogen, nitrite-nitrogen as well as primary productivity could be observed from the study. Transparency was low (53.75 cm to 159 cm) during the active monsoon months when the intensity of solar radiation was minimum, which together with the run off from the land resulted in turbid waters in the study sites. The salinity in both the stations was low (0.10 ‰ to 4.69 ‰) except in August and November 2007. The presence of total sulphide (0.08 mg/ l to 1.84 mg/ l) and higher carbon dioxide (3 mg/ l to 17 mg/ l) could be due to hospital discharges and decaying slaughter house wastes in Station 1 and also from the mangrove vegetation in Station 2. Nitrate-nitrogen and phosphate-phosphorus depicted higher values and pronounced variations in the monsoon season. Maximum net primary production was seen in November (0.87 gC/ m3/ day) and was reported nil in September. The chlorophyll pigments showed higher values in July, August and November with a negative correlation with phosphate-phosphorus and nitrite-nitrogen. The study indicated that the water quality and productivity of Valanthakad backwater is impacted and is the first report from the region

Yield gap analysis and assessment of climate-induced yield trends of irrigated rice in selected provinces of the Philippines

This study describes a combined empirical/modeling approach to assess the possible impact of climate variability on rice production in the Philippines. We collated climate data of the last two decades (1985-2002) as well as yield statistics of six provinces of the Philippines, selected along a North-South gradient. Data from the climate information system of NASA were used as input parameters of the model ORYZA2000 to determine potential yields and, in the next steps, the yield gaps defined as the difference between potential and actual yields. Both simulated and actual yields of irrigated rice varied strongly between years. However, no climate-driven trends were apparent and the variability in actual yields showed no correlation with climatic parameters. The observed variation in simulated yields was attributable to seasonal variations in climate (dry/wet season) and to climatic differences between provinces and agro-ecological zones. The actual yield variation between provinces was not related to differences in the climatic yield potential but rather to soil and management factors. The resulting yield gap was largest in remote and infrastructurally disfavored provinces (low external input use) with a high production potential (high solar radiation and day-night temperature differences). In turn, the yield gap was lowest in central provinces with good market access but with a relatively low climatic yield potential. We conclude that neither long-term trends nor the variability of the climate can explain current rice yield trends and that agroecological, seasonal, and management effects are over-riding any possible climatic variations. On the other hand the lack of a climate-driven trend in the present situation may be superseded by ongoing climate change in the future.

Plan de mercadeo para el lanzamiento de la marca Coppertone® en Colombia

Las razones que motivan la realización de este trabajo de investigación radican en que los productos de filtración y protección solar ocupan una alta demanda en Colombia gracias a su posición geográfica y condición climática, lo que hace que sean de consumo masivo gracias a que abastecen necesidades tanto al nivel de salud como estético en personas de todas las edades. A pesar de que se reconoce que la marca a introducir en el mercado colombiano -Coppertone®- cuenta con una trayectoria de más de 60 años en el mercado internacional, y que además su primer producto fue el primer protector solar en el mercado, resulta necesario realizar un estudio y caracterización al nivel nacional, de manera que permita reconocer los distintos agentes que participan en el mismo, las oportunidades, amenazas, alternativas y mecanismos de comercialización con los cuales MSD puede contar y debe tener en cuenta a la hora de introducir en Colombia dicha marca.

Towards closure between measured and modelled UV under clear skies at four diverse sites

The purpose of this work is determine the extent of closure between measurements and models of UV irradiances at diverse sites using state of the art instruments, models, and the best available data as inputs to the models. These include information about aerosol optical depth (unfortunately not extending down as far into the UVB region as desirable because such information is not generally available), ozone column amounts, as well as vertical profiles of temperature. We concentrate on clear-sky irradiances, and report the results in terms of UV Index (UVI)

UV index measurement and model agreement: uncertainties and limitations

En les últimes dècades, l'increment dels nivells de radiació solar ultraviolada (UVR) que arriba a la Terra (principalment degut a la disminució d'ozó estratosfèric) juntament amb l'augment detectat en malalties relacionades amb l'exposició a la UVR, ha portat a un gran volum d'investigacions sobre la radiació solar en aquesta banda i els seus efectes en els humans. L'índex ultraviolat (UVI), que ha estat adoptat internacionalment, va ser definit amb el propòsit d'informar al públic general sobre els riscos d'exposar el cos nu a la UVR i per tal d'enviar missatges preventius. L'UVI es va definir inicialment com el valor màxim diari. No obstant, el seu ús actual s'ha ampliat i té sentit referir-se a un valor instantani o a una evolució diària del valor d'UVI mesurat, modelitzat o predit. El valor concret d'UVI està afectat per la geometria Sol-Terra, els núvols, l'ozó, els aerosols, l'altitud i l'albedo superficial. Les mesures d'UVI d'alta qualitat són essencials com a referència i per estudiar tendències a llarg termini; es necessiten també tècniques acurades de modelització per tal d'entendre els factors que afecten la UVR, per predir l'UVI i com a control de qualitat de les mesures. És d'esperar que les mesures més acurades d'UVI s'obtinguin amb espectroradiòmetres. No obstant, com que els costs d'aquests dispositius són elevats, és més habitual trobar dades d'UVI de radiòmetres eritemàtics (de fet, la majoria de les xarxes d'UVI estan equipades amb aquest tipus de sensors). Els millors resultats en modelització s'obtenen amb models de transferència radiativa de dispersió múltiple quan es coneix bé la informació d'entrada. No obstant, habitualment no es coneix informació d'entrada, com per exemple les propietats òptiques dels aerosols, la qual cosa pot portar a importants incerteses en la modelització. Sovint, s'utilitzen models més simples per aplicacions com ara la predicció d'UVI o l'elaboració de mapes d'UVI, ja que aquests són més ràpids i requereixen menys paràmetres d'entrada. Tenint en compte aquest marc de treball, l'objectiu general d'aquest estudi és analitzar l'acord al qual es pot arribar entre la mesura i la modelització d'UVI per condicions de cel sense núvols. D'aquesta manera, en aquest estudi es presenten comparacions model-mesura per diferents tècniques de modelització, diferents opcions d'entrada i per mesures d'UVI tant de radiòmetres eritemàtics com d'espectroradiòmeters. Com a conclusió general, es pot afirmar que la comparació model-mesura és molt útil per detectar limitacions i estimar incerteses tant en les modelitzacions com en les mesures. Pel que fa a la modelització, les principals limitacions que s'han trobat és la falta de coneixement de la informació d'aerosols considerada com a entrada dels models. També, s'han trobat importants diferències entre l'ozó mesurat des de satèl·lit i des de la superfície terrestre, la qual cosa pot portar a diferències importants en l'UVI modelitzat. PTUV, una nova i simple parametrització pel càlcul ràpid d'UVI per condicions de cel serens, ha estat desenvolupada en base a càlculs de transferència radiativa. La parametrització mostra una bona execució tant respecte el model base com en comparació amb diverses mesures d'UVI. PTUV ha demostrat la seva utilitat per aplicacions particulars com ara l'estudi de l'evolució anual de l'UVI per un cert lloc (Girona) i la composició de mapes d'alta resolució de valors d'UVI típics per un territori concret (Catalunya). En relació a les mesures, es constata que és molt important saber la resposta espectral dels radiòmetres eritemàtics per tal d'evitar grans incerteses a la mesura d'UVI. Aquest instruments, si estan ben caracteritzats, mostren una bona comparació amb els espectroradiòmetres d'alta qualitat en la mesura d'UVI. Les qüestions més importants respecte les mesures són la calibració i estabilitat a llarg termini. També, s'ha observat un efecte de temperatura en el PTFE, un material utilitzat en els difusors en alguns instruments, cosa que potencialment podria tenir implicacions importants en el camp experimental. Finalment, i pel que fa a les comparacions model-mesura, el millor acord s'ha trobat quan es consideren mesures d'UVI d'espectroradiòmetres d'alta qualitat i s'usen models de transferència radiativa que consideren les millors dades disponibles pel que fa als paràmetres òptics d'ozó i aerosols i els seus canvis en el temps. D'aquesta manera, l'acord pot ser tan alt dins un 0.1º% en UVI, i típicament entre menys d'un 3%. Aquest acord es veu altament deteriorat si s'ignora la informació d'aerosols i depèn de manera important del valor d'albedo de dispersió simple dels aerosols. Altres dades d'entrada del model, com ara l'albedo superficial i els perfils d'ozó i temperatura introdueixen una incertesa menor en els resultats de modelització.

Estimating surface CO2 fluxes from space-borne dry air mole fraction observations using an Ensemble Kalman filter

We have developed an ensemble Kalman Filter (EnKF) to estimate 8-day regional surface fluxes of CO2 from space-borne CO2 dry-air mole fraction observations (XCO2) and evaluate the approach using a series of synthetic experiments, in preparation for data from the NASA Orbiting Carbon Observatory (OCO). The 32-day duty cycle of OCO alternates every 16 days between nadir and glint measurements of backscattered solar radiation at short-wave infrared wavelengths. The EnKF uses an ensemble of states to represent the error covariances to estimate 8-day CO2 surface fluxes over 144 geographical regions. We use a 12×8-day lag window, recognising that XCO2 measurements include surface flux information from prior time windows. The observation operator that relates surface CO2 fluxes to atmospheric distributions of XCO2 includes: a) the GEOS-Chem transport model that relates surface fluxes to global 3-D distributions of CO2 concentrations, which are sampled at the time and location of OCO measurements that are cloud-free and have aerosol optical depths <0.3; and b) scene-dependent averaging kernels that relate the CO2 profiles to XCO2, accounting for differences between nadir and glint measurements, and the associated scene-dependent observation errors. We show that OCO XCO2 measurements significantly reduce the uncertainties of surface CO2 flux estimates. Glint measurements are generally better at constraining ocean CO2 flux estimates. Nadir XCO2 measurements over the terrestrial tropics are sparse throughout the year because of either clouds or smoke. Glint measurements provide the most effective constraint for estimating tropical terrestrial CO2 fluxes by accurately sampling fresh continental outflow over neighbouring oceans. We also present results from sensitivity experiments that investigate how flux estimates change with 1) bias and unbiased errors, 2) alternative duty cycles, 3) measurement density and correlations, 4) the spatial resolution of estimated flux estimates, and 5) reducing the length of the lag window and the size of the ensemble. At the revision stage of this manuscript, the OCO instrument failed to reach its orbit after it was launched on 24 February 2009. The EnKF formulation presented here is also applicable to GOSAT measurements of CO2 and CH4.

Vertical current flow through extensive layer clouds

The global atmospheric electrical circuit sustains a vertical current density between the ionosphere and the Earth's surface, the existence of which is well-established from measurements made in fair-weather conditions. In overcast, but non-thunderstorm, non-precipitating conditions, the current travels through the cloud present, despite cloud layers having low electrical conductivity. For extensive layer clouds, this leads to space charge at the upper and lower cloud boundaries. Using a combination of atmospheric electricity and solar radiation measurements at three UK sites, vertical current measurements have been categorised into clear, broken, and overcast cloud conditions. This approach shows that the vertical “fair weather” current is maintained despite the presence of cloud. In fully overcast conditions with thick cloud, the vertical current is reduced compared to thin cloud overcast conditions, associated with the cloud's resistance contributions. Contribution of cloud to the columnar resistance depends both on cloud thickness, and the cloud's height.

Modelling monsoons: understanding and predicting current and future behaviour

The global monsoon system is so varied and complex that understanding and predicting its diverse behaviour remains a challenge that will occupy modellers for many years to come. Despite the difficult task ahead, an improved monsoon modelling capability has been realized through the inclusion of more detailed physics of the climate system and higher resolution in our numerical models. Perhaps the most crucial improvement to date has been the development of coupled ocean-atmosphere models. From subseasonal to interdecadal time scales, only through the inclusion of air-sea interaction can the proper phasing and teleconnections of convection be attained with respect to sea surface temperature variations. Even then, the response to slow variations in remote forcings (e.g., El Niño—Southern Oscillation) does not result in a robust solution, as there are a host of competing modes of variability that must be represented, including those that appear to be chaotic. Understanding the links between monsoons and land surface processes is not as mature as that explored regarding air-sea interactions. A land surface forcing signal appears to dominate the onset of wet season rainfall over the North American monsoon region, though the relative role of ocean versus land forcing remains a topic of investigation in all the monsoon systems. Also, improved forecasts have been made during periods in which additional sounding observations are available for data assimilation. Thus, there is untapped predictability that can only be attained through the development of a more comprehensive observing system for all monsoon regions. Additionally, improved parameterizations - for example, of convection, cloud, radiation, and boundary layer schemes as well as land surface processes - are essential to realize the full potential of monsoon predictability. A more comprehensive assessment is needed of the impact of black carbon aerosols, which may modulate that of other anthropogenic greenhouse gases. Dynamical considerations require ever increased horizontal resolution (probably to 0.5 degree or higher) in order to resolve many monsoon features including, but not limited to, the Mei-Yu/Baiu sudden onset and withdrawal, low-level jet orientation and variability, and orographic forced rainfall. Under anthropogenic climate change many competing factors complicate making robust projections of monsoon changes. Absent aerosol effects, increased land-sea temperature contrast suggests strengthened monsoon circulation due to climate change. However, increased aerosol emissions will reflect more solar radiation back to space, which may temper or even reduce the strength of monsoon circulations compared to the present day. Precipitation may behave independently from the circulation under warming conditions in which an increased atmospheric moisture loading, based purely on thermodynamic considerations, could result in increased monsoon rainfall under climate change. The challenge to improve model parameterizations and include more complex processes and feedbacks pushes computing resources to their limit, thus requiring continuous upgrades of computational infrastructure to ensure progress in understanding and predicting current and future behaviour of monsoons.

Empirical evidence for a nonlinear effect of galactic cosmic rays on clouds

Galactic cosmic ray (GCR) changes have been suggested to affect weather and climate, and new evidence is presented here directly linking GCRs with clouds. Clouds increase the diffuse solar radiation, measured continuously at UK surface meteorological sites since 1947. The ratio of diffuse to total solar radiation-the diffuse fraction, (DF)-is used to infer cloud, and is compared with the daily mean neutron count rate measured at Climax; Colorado from 1951-2000, which provides a globally representative indicator of cosmic rays. Across the UK, oil days of high cosmic ray flux (above 3600 X 10(2) neutron counts h(-1), which occur 87% of the time on average) compared with low cosmic ray flux, (i) the chance of an overcast day increases by (19 +/- 4)%; and (ii) the diffuse fraction increases by (2 +/- 0.3)%. During sudden transient reductions in cosmic rays (e.g. Forbush events), simultaneous decreases occur in the diffuse fraction. The diffuse radiation changes are; therefore; unambiguously due to cosmic rays. Although the statistically significant nonlinear cosmic ray effect is small, it will have a considerably larger aggregate effect on longer timescale (e.g. centennial) climate variations when day-to-day variability averages out.

The importance of the diurnal and annual cycle of air traffic for contrail radiative forcing

Air traffic condensation trails, or contrails, are believed to have a net atmospheric warming effect(1), although one that is currently small compared to that induced by other sources of human emissions. However, the comparably large growth rate of air traffic requires an improved understanding of the resulting impact of aircraft radiative forcing on climate(2). Contrails have an effect on the Earth's energy balance similar to that of high thin ice clouds(3). Their trapping of outgoing longwave radiation emitted by the Earth and atmosphere (positive radiative forcing) is partly compensated by their reflection of incoming solar radiation (negative radiative forcing). On average, the longwave effect dominates and the net contrail radiative forcing is believed to be positive(1,2,4). Over daily and annual timescales, varying levels of air traffic, meteorological conditions, and solar insolation influence the net forcing effect of contrails. Here we determine the factors most important for contrail climate forcing using a sophisticated radiative transfer model(5,6) for a site in southeast England, located in the entrance to the North Atlantic flight corridor. We find that night-time flights during winter (December to February) are responsible for most of the contrail radiative forcing. Night flights account for only 25 per cent of daily air traffic, but contribute 60 to 80 per cent of the contrail forcing. Further, winter flights account for only 22 per cent of annual air traffic, but contribute half of the annual mean forcing. These results suggest that flight rescheduling could help to minimize the climate impact of aviation.

When smoke gets in our eyes: The multiple impacts of atmospheric black carbon on climate, air quality and health

With both climate change and air quality on political and social agendas from local to global scale, the links between these hitherto separate fields are becoming more apparent. Black carbon, largely from combustion processes, scatters and absorbs incoming solar radiation, contributes to poor air quality and induces respiratory and cardiovascular problems. Uncertainties in the amount, location, size and shape of atmospheric black carbon cause large uncertainty in both climate change estimates and toxicology studies alike. Increased research has led to new effects and areas of uncertainty being uncovered. Here we draw together recent results and explore the increasing opportunities for synergistic research that will lead to improved confidence in the impact of black carbon on climate change, air quality and human health. Topics of mutual interest include better information on spatial distribution, size, mixing state and measuring and monitoring. (c) 2006 Elsevier Ltd. All rights reserved.

A new Snow-SVAT to simulate the accumulation and ablation of seasonal snow cover beneath a forest canopy

A new snow-soil-vegetation-atmosphere transfer (Snow-SVAT) scheme, which simulates the accumulation and ablation of the snow cover beneath a forest canopy, is presented. The model was formulated by coupling a canopy optical and thermal radiation model to a physically-based multi-layer snow model. This canopy radiation model is physically-based yet requires few parameters, so can be used when extensive in-situ field measurements are not available. Other forest effects such as the reduction of wind speed, interception of snow on the canopy and the deposition of litter were incorporated within this combined model, SNOWCAN, which was tested with data taken as part of the Boreal Ecosystem-Atmosphere Study (BOREAS) international collaborative experiment. Snow depths beneath four different canopy types and at an open site were simulated. Agreement between observed and simulated snow depths was generally good, with correlation coefficients ranging between r^2=0.94 and r^2=0.98 for all sites where automatic measurements were available. However, the simulated date of total snowpack ablation generally occurred later than the observed date. A comparison between simulated solar radiation and limited measurements of sub-canopy radiation at one site indicates that the model simulates the sub-canopy downwelling solar radiation early in the season to within measurement uncertainty.

Flowering intensity in white yam (Dioscorea rotundata)

White or Guinea yam (Dioscorea rotundata), grown for its underground tubers, is an important food in West Africa. Progress in yam breeding is constrained by variable flowering behaviour, making hybridization difficult. Yam clones may be dioecious, monoecious or hermaphrodite with variable sex ratios. The proportion of plants that flower and the flowering intensity also vary with season and location. The objective of the present work was to investigate whether variation in flowering behaviour was related to factors determining rate of development (photoperiod and temperature through sowing date, location and year) or growth (cumulative solar radiation and temperature). Sex ratios, the proportion of plants that had flower buds and open flowers, and the number of flowers or spikes was recorded in one male (TDr 131) and one female (TDr 99-9) clone of white yam grown in the field in Nigeria at three locations and at different sowing dates. Clone TDr 131 was uniformly male flowering, while clone TDr 99-9 exhibited a number of sex types with gynoecious, monoecious and trimonoecious plants observed. The proportion of flowering plants was low in both clones, averaging 0.34 in clone TDr 131 and 0.13 in clone TDr 99-9. Day of vine emergence had a significant and contrasting effect on the proportion of flowering plants and on flowering intensity in the two clones. In clone TDr 131, the proportion of flowering plants and flowering intensity declined with later vine emergence at all locations (r=0.43-0.53, P<0.05), whereas in clone TDr 99-9 the proportion of flowering plants increased with later emergence (r=0.46, P<0.01). In clone TDr 131, this response was strongly associated with warmer temperatures (r=0.49-0.50; P<0.05) and greater cumulative radiation (r=0.85-0.93; P<0.001) between vine emergence and flowering, rather than photoperiod at vine emergence. This suggests that flowering behaviour in the male clone TDr 131 is strongly influenced by factors that affect growth rather than development. Clone TDr 99-9, on the other hand, exhibited no clear relations between flowering and growth or developmental factors, though the proportion of flowering plants and flowering intensity was greatest at planting dates close to the longest day and at temperatures of 25-26 degrees C. This might suggest that flowering behaviour in clone TDr 99-9 is controlled by photothermal responses.