Analysis of polycyclic aromatic hydrocarbons in atmospheric particulate samples by microwaveassisted extraction and liquid chromatography

A methodology based on microwave-assisted extraction (MAE) and LC with fluorescence detection (FLD) was investigated for the efficient determination of 15 polycyclic aromatic hydrocarbons (PAHs) regarded as priority pollutants by the US Environmental Protection Agency and dibenzo(a,l)pyrene in atmospheric particulate samples. PAHs were successfully extracted from real outdoor particulate matter (PM) samples with recoveries ranging from 81.4±8.8 to 112.0±1.1%, for all the compounds except for naphthalene (62.3±18.0%) and anthracene (67.3±5.7%), under the optimum MAE conditions (30.0 mL of ACN for 20 min at 110ºC). No clean-up steps were necessary prior to LC analysis. LOQs ranging from 0.0054 ng/m3 for benzo( a)anthracene to 0.089 ng/m3 for naphthalene were reached. The validated MAE methodology was applied to the determination of PAHs from a set of real world PM samples collected in Oporto (north of Portugal). The sum of particulate-bound PAHs in outdoor PM ranged from 2.5 and 28 ng/m3.

Identification of atmospheric pollutants control mechanisms during co-combustion of coal and non-toxic wastes

Doctoral dissertation for Ph.D. degree in Sustainable Chemistry

Dynamic characteristics of Atmospheric boundary Layer during different phases of Monsoon

Atmospheric Boundary layer (ABL) is the layer just above the earth surface and is influenced by the surface forcing within a short period of an hour or less. In this thesis, characteristics of the boundary layer over ocean, coastal and inland areas of the atmosphere, especially over the monsoon regime are thoroughly studied. The study of the coastal zone is important due to its high vulnerability mainly due to sea breeze circulation and associated changes in the atmospheric boundary layer. The major scientific problems addressed in this thesis are diurnal and seasonal variation of coastal meteorological properties, the characteristic difference in the ABL during active and weak monsoons, features of ABL over marine environment and the variation of the boundary layer structure over an inland station. The thesis describes the various features in the ABL associated with the active and weak monsoons and, the surface boundary layer properties associated with the active and weak epochs. The study provides knowledge on MABL and can be used as the estimated values of boundary layer parameters over the marine atmosphere and to know the values and variabilities of the ABL parameters such as surface wind, surface friction, drag coefficient, wind stress and wind stress curl.

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.

Studies on ocean surface layer responses to atmospheric forcing in the North Indian Ocean

The present study on upper ocean responses to atmospheric forcing (associated with cyclone passage) in North Indian Ocean revealed significant variability between AS and BoB. The analysis of cyclone frequency during 1947 to 2006 exhibited lesser frequency of cyclones in AS than that of BoB. The analysis also revealed significant reduction in cyclone frequency after the year 1976 with substantial reduction during monsoon season. The long term SST data at selected points in AS and BoB could not reveal any relation with reduction in cyclone frequency. However the SLP at same locations exhibited considerable increase during mid 1970’s, which could have contributed to the observed reduction in cyclone frequency after the year 1976.The response in waves during cyclone passage exhibited significant asymmetry on either side of the track in AS and BoB and the response is observed at 100’s of kilometers away from the track. The significant clockwise rotation in wave direction is observed on the right side of the track starting from near the track to far away locations, which existed for a longer duration. However, the anticlockwise rotation in wave direction is observed over a shorter distance on the left side of the track and dissipated immediately.Inertial oscillation is observed in surface current and in the mixed layer temperature associated with cyclone passage, which revealed the role of relative location(s) on either side of the track. The inertial peak closer to the local inertial period indicates maximum transfer of energy during the cyclone passage in both AS and BoB. The absence of strong inertial oscillation even with clockwise rotation in surface current and wind indicates the dominant role of duration of strong wind in generating inertial oscillation.The oceanic response associated with cyclone passage reveal the variable response(s) which depends on cyclone intensity, the proximity to track and cyclone translation speed. It is observed that resonance with wind generates higher response in surface current, wave and SST on the right side of the track and it lasts for a longer duration. The maximum oceanic response is observed at a few kilometers away on right side of the track. However lesser rightward bias in the location of maximum cooling is observed for cyclones with low cyclone translation speed. The response on the left side of the track is less and is limited over a shorter distance and dissipates immediately. It is observed that the ocean response, in general, increases with intensity of cyclones. However the differential cooling produced by the same intensity cyclones in AS and in BoB indicates the dominant role of low cyclone translation speed in oceanic response.The surface cooling exhibited strikingly differential responses between AS and BoB. The TMI-SST and buoy observations exhibited significant cooling for a longer duration in AS compared to that of BoB. The spatial extent of cooling is also much higher in AS than that of BoB. The wide spread cooling associated with cyclone passage in AS indicates the dominant role of thermal structure in oceanic response in AS than that of BoB.

Spatio-temporal Variability of Atmospheric Ozone over Indian Subcontinent and its Relation to Meteorological Parameters

Ozone present in the atmosphere not only absorbs the biologically harmful ultraviolet radiation but also is an important ingredient of the climate system. The radiative absorption properties of ozone make it a determining factor in the structure of the atmosphere. Ozone in the troposphere has many negative impacts on humans and other living beings. Another significant aspect is the absorption of outgoing infrared radiation by ozone thus acting as a greenhouse gas. The variability of ozone in the atmosphere involves many interconnections with the incoming and outgoing radiation, temperature circulation etc. Hence ozone forms an important part of chemistry-climate as well as radiative transfer models. This aspect also makes the quantification of ozone more important. The discovery of Antarctic ozone hole and the role of anthropogenic activities in causing it made it possible to plan and implement necessary preventive measures. Continuous monitoring of ozone is also necessary to identify the effect of these preventive steps. The reactions involving the formation and destruction of ozone are influenced significantly by the temperature fluctuations of the atmosphere. On the other hand the variations in ozone can change the temperature structure of the atmosphere. Indian subcontinent is a region having large weather and climate variability which is evident from the large interannual variability of monsoon system over the region. Nearly half of Indian region comprises the tropical region. Most of ozone is formed in the tropical region and transported to higher latitudes. The formation and transport of ozone can be influenced by changes in solar radiation and various atmospheric circulation features. Besides industrial activities and vehicular traffic is more due to its large population. This may give rise to an increase in the production of tropospheric ozone which is greenhouse gas. Hence it becomes necessary to monitor the atmospheric ozone over this region. This study probes into the spatial distribution and temporal evolution of ozone over Indian subcontinent and discusses the contributing atmospheric parameters.

Application of ocean colour data to study the oceanographic and atmospheric features off the southwest coast of India with special reference to upwelling

Satellite remote sensing is being effectively used in monitoring the ocean surface and its overlying atmosphere. Technical growth in the field of satellite sensors has made satellite measurement an inevitable part of oceanographic and atmospheric research. Among the ocean observing sensors, ocean colour sensors make use of visible band of electromagnetic spectrum (shorter wavelength). The use of shorter wavelength ensures fine spatial resolution of these parameters to depict oceanographic and atmospheric characteristics of any region having significant spaio-temporal variability. Off the southwest coast of India is such an area showing very significant spatio-temporal oceanographic and atmospheric variability due to the seasonally reversing surface winds and currents. Consequently, the region is enriched with features like upwelling, sinking, eddies, fronts, etc. Among them, upwelling brings nutrient-rich waters from subsurface layers to surface layers. During this process primary production enhances, which is measured in ocean colour sensors as high values of Chl a. Vertical attenuation depth of incident solar radiation (Kd) and Aerosol Optical Depth (AOD) are another two parameters provided by ocean colour sensors. Kd is also susceptible to undergo significant seasonal variability due to the changes in the content of Chl a in the water column. Moreover, Kd is affected by sediment transport in the upper layers as the region experiences land drainage resulting from copious rainfall. The wide range of variability of wind speed and direction may also influence the aerosol source / transport and consequently AOD. The present doctoral thesis concentrates on the utility of Chl a, Kd and AODprovided by satellite ocean colour sensors to understand oceanographic and atmospheric variability off the southwest coast of India. The thesis is divided into six Chapters with further subdivisions

Atmospheric downwelling longwave radiation at the surface during cloudless and overcast conditions. Measurements and modeling

Atmospheric downwelling longwave radiation is an important component of the terrestrial energy budget; since it is strongly related with the greenhouse effect, it remarkably affects the climate. In this study, I evaluate the estimation of the downwelling longwave irradiance at the terrestrial surface for cloudless and overcast conditions using a one-dimensional radiative transfer model (RTM), specifically the Santa Barbara DISORT Atmospheric Radiative Transfer (SBDART). The calculations performed by using this model were compared with pyrgeometer measurements at three different European places: Girona (NE of the Iberian Peninsula), Payerne (in the East of Switzerland), and Heselbach (in the Black Forest, Germany). Several studies of sensitivity based on the radiative transfer model have shown that special attention on the input of temperature and water content profiles must be held for cloudless sky conditions; for overcast conditions, similar sensitivity studies have shown that, besides the atmospheric profiles, the cloud base height is very relevant, at least for optically thick clouds. Also, the estimation of DLR in places where radiosoundings are not available is explored, either by using the atmospheric profiles spatially interpolated from the gridded analysis data provided by European Centre of Medium-Range Weather Forecast (ECMWF), or by applying a real radiosounding of a nearby site. Calculations have been compared with measurements at all sites. During cloudless sky conditions, when radiosoundings were available, calculations show differences with measurements of -2.7 ± 3.4 Wm-2 (Payerne). While no in situ radiosoundings are available, differences between modeling and measurements were about 0.3 ± 9.4 Wm-2 (Girona). During overcast sky conditions, when in situ radiosoundings and cloud properties (derived from an algorithm that uses spectral infrared and microwave ground based measurements) were available (Black Forest), calculations show differences with measurements of -0.28 ± 2.52 Wm2. When using atmospheric profiles from the ECMWF and fixed values of liquid water path and droplet effective radius (Girona) calculations show differences with measurements of 4.0 ± 2.5 Wm2. For all analyzed sky conditions, it has been confirmed that estimations from radiative transfer modeling are remarkably better than those obtained by simple parameterizations of atmospheric emissivity.

Trace elements biogeochemistry in high mountain lake catchments: identifying anthropogenic versus natural components from the atmospheric contamination legacy in remote natural areas

Human activities have been interfering with the natural biogeochemical cycles of trace elements since the ancient civilizations. Although they are inaccessible and remote, high mountain lake catchments are irrefutably trace-element contaminated by anthropogenic emissions, which can travel by long-range atmospheric transport before they are deposited. This has been revealed by several natural archives. High mountain lake catchments are thus excellent sentinels of long-range contamination. Continuous accumulation can lead to a build up of potentially toxic trace elements in these remote, or relatively remote, ecosystems. The thesis focuses on the biogeochemistry of a suite of trace elements of environmental concern (Ni, Cu, Zn, As, Se, Cd and Pb) in Pyrenean lake catchments, with special emphasis on discerning the “natural” components from the “anthropogenic” contributions. Five other metallic elements (Al, Fe, Ti, Mn and Zr) have also been studied to trace natural fluxes and biogeochemical processes within the lake catchment systems.

The impact of North Atlantic Oscillation on the atmospheric pollutant variability in the Porto region, Portugal

The North Atlantic Oscillation (NAO) is an important large-scale atmospheric circulation that influences the European countries climate. This study evaluated NAO impact in air quality in Porto Metropolitan Area (PMA), Portugal, for the period 2002-2006. NAO, air pollutants and meteorological data were statistically analyzed. All data were obtained from PMA Weather Station, PMA Air Quality Stations and NOAA analysis. Two statistical methods were applied in different time scale : principal component and correlation coefficient. Annual time scale, using multivariate analysis (PCA, principal component analysis), were applied in order to identified positive and significant association between air pollutants such as PM10, PM2.5, CO, NO and NO2, with NAO. On the other hand, the correlation coefficient using seasonal time scale were also applied to the same data. The results of PCA analysis present a general negative significant association between the total precipitation and NAO, in Factor 1 and 2 (explaining around 70% of the variance), presented in the years of 2002, 2004 and 2005. During the same years, some air pollutants (such as PM10, PM2.5, SO2, NOx and CO) present also a positive association with NAO. The O3 shows as well a positive association with NAP during 2002 and 2004, at 2nd Factor, explaining 30% of the variance. From the seasonal analysis using correlation coefficient, it was found significant correlation between PM10 (0.72., p<0.05, in 2002), PM2.5 (0 74, p<0.05, in 2004), and SO2 (0.78, p<0.01, in 2002) with NAO during March-December (no winter period) period. Significant associations between air pollutants and NAO were also verified in the winter period (December to April) mainly with ozone (2005, r=-0.55, p.<0.01). Once that human health and hospital morbidities may be affected by air pollution, the results suggest that NAO forecast can be an important tool to prevent them, in the Iberian Peninsula and specially Portugal.