The aqueous photochemistry of 4-hydroxy-3,5-dimethoxybenzoic acid (syringic acid) has been studied as a model humic substance in order to better understand the reactions that compounds of this type undergo in the natural environment. Syringic acid was chosen since it has been identified as a component of humic substances in the environment and bears many of chemical moieties found in structures of this type. In addition, there has been speculation that humic substances are responsible for some of the production of halomethanes that are released into the environment. Photolysis of these compounds in marine and estuarine waters may be responsible for the release of halomethanes which are known stratospheric ozone depleters. Photochemical product studies of syringic acid and related compounds along with UV-Vis spectrometry, laser flash photolysis and membrane introduction mass spectrometry were carried out in aqueous solutions to study its photochemical transformations. Syringic acid was found to form methanol at a 0.01 quantum yield upon its photolysis in basic solution. Other major photoproducts included 3-methoxygallic acid and 3,5-dimethoxybenzoic acid. Chloromethane was identified as a minor photoproduct in chloride enriched solution by following its production via membrane introduction mass spectrometry. The proposed mechanism for the formation of these photoproducts involves an initial photoprotonation of the benzene ring, resulting in a carbocation that can facilitate the nucleophilic attack by water or chloride, to produce methanol or chloromethane, respectively. The formation of 3,5-dimethoxybenzoic acid is via a novel pathway that involves the loss of the hydroxy group from the aromatic ring after the photoprotonation.

The aqueous photochemistry of 4-hydroxy-3,5-dimethoxybenzoic acid (syringic acid) has been studied as a model humic substance in order to better understand the reactions that compounds of this type undergo in the natural environment. Syringic acid was chosen since it has been identified as a component of humic substances in the environment and bears many of chemical moieties found in structures of this type. In addition, there has been speculation that humic substances are responsible for some of the production of halomethanes that are released into the environment. Photolysis of these compounds in marine and estuarine waters may be responsible for the release of halomethanes which are known stratospheric ozone depleters. Photochemical product studies of syringic acid and related compounds along with UV-Vis spectrometry, laser flash photolysis and membrane introduction mass spectrometry were carried out in aqueous solutions to study its photochemical transformations. Syringic acid was found to form methanol at a 0.01 quantum yield upon its photolysis in basic solution. Other major photoproducts included 3-methoxygallic acid and 3,5-dimethoxybenzoic acid. Chloromethane was identified as a minor photoproduct in chloride enriched solution by following its production via membrane introduction mass spectrometry. The proposed mechanism for the formation of these photoproducts involves an initial photoprotonation of the benzene ring, resulting in a carbocation that can facilitate the nucleophilic attack by water or chloride, to produce methanol or chloromethane, respectively. The formation of 3,5-dimethoxybenzoic acid is via a novel pathway that involves the loss of the hydroxy group from the aromatic ring after the photoprotonation.

No description available.

Halogen-driven ozone and nonmethane hydrocarbon losses in springtime Arctic boundary layer are investigated using a regional chemical transport model (CTM). Surface observation of O3 at Alert and Barrow and aircraft observations of O3 and hydrocarbons during the TOPSE experiment from February to May in 2000 are analyzed. We prescribe halogen radical distributions based on GOME BrO observations and calculated or observed other halogen radical to BrO ratios. GOME BrO shows an apparent anti-correlation with surface temperature over high BrO regions. At its peak, area of simulated near-surface O3 depletions (O3 LT 20ppbv) covers GT 50% of the north high latitudes. Model simulated O3 losses are in agreement with surface and aircraft O3 observations. Simulation of halogen distributions are constrained using aircraft hydrocarbon measurements. We find the currently chemical mechanism overestimate the Cl/BrO ratios. The model can reproduce the observed halogen loss of NMHCs using the empirical Cl/BrO ratios. We find that the hydrocarbon loss is not as sensitive to the prescribed boundary layer height of halogen as that of O3, therefore producing a more robust measure for evaluating satellite column measurement. Tropospheric tracer transport and chemical oxidation processes are examined on the basis of the observations at northern mid-high latitudes and over the tropical Pacific and the corresponding global 3D CTM (GEOS-CHEM) simulations. The correlation between propane and ethane/propane ratio is employed using a finite mixing model to examine the mixing in addition to the OH oxidations. At northern mid-high latitudes the model agrees with the observations before March. The model appears to overestimate the transport from lower to middle latitudes and the horizontal transport and mixing at high latitudes in May. Over the tropical Pacific the model reproduces the observed two-branch slope values reflecting an underestimate of continental convective transport at northern mid-latitudes and an overestimate of latitudinal transport into the tropics. Inverse modeling using the subsets of observed and simulated data is more reliable by reducing (systematic) biases introduced by systematic model transport model transport errors. On the basis of this subset we find the model underestimates the emissions of ethane and propane by 14 5%.

Reactive halogen species (RHS) are responsible for ozone depletion and oxidation of gaseous elemental mercury and dimethyl sulphide in the polar boundary layer, but the sources and mechanisms controlling their catalytic reaction cycles are still not completely understood. To further investigate these processes, ground– based Multi–Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations of boundary layer BrO and IO were made from a portable instrument platform in McMurdo Sound during the Antarctic spring of 2006 and 2007. Measurements of surface ozone, temperature, pressure, humidity, and wind speed and direction were also made, along with fourteen tethersonde soundings and the collection of snow samples for mercury analysis. A spherical multiple scattering Monte Carlo radiative transfer model (RTM) was developed for the simulation of box-air-mass-factors (box-AMFs), which are used to determine the weighting functions and forward model differential slant column densities (DSCDs) required for optimal estimation. The RTM employed the backward adjoint simulation technique for the fast calculation of box-AMFs for specific solar zenith angles (SZA) and MAX-DOAS measurement geometries. Rayleigh and Henyey-Greenstein scattering, ground topography and reflection, refraction, and molecular absorption by multiple species were included. Radiance and box-AMF simulations for MAX-DOAS measurements were compared with nine other RTMs and showed good agreement. A maximum a posteriori (MAP) optimal estimation algorithm was developed to retrieve trace gas concentration profiles from the DSCDs derived from the DOAS analysis of the measured absorption spectra. The retrieval algorithm was validated by performing an inversion of artificial DSCDs, simulated from known NO2 profiles. Profiles with a maximum concentration near the ground were generally well reproduced, but the retrieval of elevated layers was less accurate. Retrieved partial vertical column densities (VCDs) were similar to the known values, and investigation of the averaging kernels indicated that these were the most reliable retrieval product. NO₂ profiles were also retrieved from measurements made at an NO₂ measurement and profiling intercomparison campaign in Cabauw, Netherlands in July 2009. Boundary layer BrO was observed on several days throughout both measurement periods in McMurdo Sound, with a maximum retrieved surface mixing ratio of 14.4±0.3 ppt. The median partial VCDs up to 3km were 9.7±0.07 x 10¹² molec cm ⁻ in 2007, with a maximum of 2.3±0.07 x 10¹³ molec cm⁻², and 7.4±0.06 x 10¹² molec cm⁻² in 2006, with a maximum of 1.05 ± 0.07 x 1013 molec cm⁻². The median mixing ratio of 7.5±0.5 ppt for 2007 was significantly higher than the median of 5.2±0.5 ppt observed in 2006, which may be related to the more extensive first year sea ice in 2007. These values are consistent with, though lower than estimated boundary layer BrO concentrations at other polar coastal sites. Four out of five observed partial ozone depletion events (ODEs) occurred during strong winds and blowing snow, while BrO was present in the boundary layer in both stormy and calm conditions, consistent with the activation of RHS in these two weather extremes. Air mass back trajectories, modelled using the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model, indicated that the events were locally produced rather than transported from other sea ice zones. Boundary layer IO mixing ratios of 0.5–2.5±0.2 ppt were observed on several days. These values are low compared to measurements at Halley and Neumayer Stations, as well as mid-latitudes. Significantly higher total mercury concentrations observed in 2007 may be related to the higher boundary layer BrO concentrations, but further measurements are required to verify this.

Freoner är ett stort problem för människors hälsa och andra levande organismer på grund av freons nedbrytande effekt på ozonlagret. Forskare upptäckte problemen med freon och varningar från forskningssamhället uppmärksammades av huvudproducenter av freoner samt av allmänheten då påverkan på ozonlagret ökar risken för bland annat hudcancer. Montrealprotokollet blev starten på de internationella konventioner som senare implementerades. Dock finns det ett flertal växthusgaser idag som också är ozonnedbrytande som inte ingår under någon konvention. Den globala uppvärmningen är en effekt av ökad mängd växthusgaser i atmosfären och detta kräver ett internationellt samarbete för att kunna lösas. I Montrealprotokollet ingår ODS (Ozonnedbrytande substanser) där freon innefattas. Syftet för denna studie var att belysa vad som gjorde freonförbudet lyckat, och om det är möjligt att tillämpa dessa nyckelaspekter på en av dagens växthusgaser som liknar freon. NO2 valdes för att begränsa urvalet.  Denna litteraturstudie använde sig av databaser för att finna relevanta källor genom nyckelord, därefter valdes källor utefter relevansen till frågeställningen samt att de skulle vara opartiska. Resultatet av denna studie pekar på svårigheterna med att implementera det arbetssätt som ledde till freonförbudet, på gasen NO2, som hade liknande egenskaper som freon. Detta på grund av att dagens växthusgaser är svåra att reglera utsläppet på. Växthusgaser finns globalt och det finns inte en tydlig utsläppskälla som går att reglera samt hitta ett substitut för. Korrelationen till den mänskliga hälsan och miljön, är också en nyckelaspekt till varför förbudet mot freoner var lyckat. / Freons became a large problem for society when scientists proved the ozone depletion effect, which proved to have a negative effect on human health and other living organisms. The ozone layer which was known for its protective qualities against UV-radiation lead to a new field of study, ODS (ozone depleting substances). The warnings from the scientist society and the public were eminent. The research pointed out, among other things, the increasing risk of skin cancer. This forced fast new research and several international conventions to save the ozone layer. But there are several greenhouse gases, which also have the degrading effect on the ozone layer, that are in use today. This require an international cooperation for the environment to be able to solve. The aim of this report was to illustrate why the freon ban was a success and why it would be hard to implement these key concepts on a similar present greenhouse gas. In this literature study, several databases were used to find relevant sources for the main questions and unbiased for the topic. The key aspects in this study is presented in the result section. The result pointed at the difficulties with implementing the same way of work as at the freon ban to the greenhouse gas ban. Different aspects play an important role in this, but one of the greater difficulties for implementing this is to pinpoint it to a specific source for gas emissions and finding a sustainable solution for it. The correlation between human health and environmental issues was a key factor in the freon ban.

Thesis (M. Sc. (Statistics)) -- University of Limpopo, 2021 / The effects of ozone depletion on climate change has, in recent years, become a reality, impacting on changes in rainfall patterns and severity of extreme floods or extreme droughts. The majority of people across the entire African continent live in semi-arid and drought-prone areas. Extreme droughts are prevalent in Somalia and eastern Africa, while life-threatening floods are common in Mozambique and some parts of other SADC (Southern African Development Community) countries. Research has cautioned that climate change in South Africa might lead to increased temperatures and reduced amounts of rainfall, thereby altering their timing and putting more pressure on the country’s scarce water resources, with implications for agriculture, employment and food security. The average annual rainfall for South Africa is about 464mm, falling far below the average annual global rainfall of 860mm. The Limpopo Province, which is one of the nine provinces in South Africa, and of interest to this study, is predominantly agrarian, basically relying on availability of water, with rainfall being the major source for water supply. It is, therefore, pertinent that the rainfall pattern in the province be monitored effectively to ascertain the rainy period for farming activities and other uses. Modelling and forecasting rainfall have been studied for a long time worldwide. However, from time to time, researchers are always looking for new models that can predict rainfall more accurately in the midst of climate change and capture the underlying dynamics such as seasonality and the trend, attributed to rainfall. This study employed Exponetial Smoothing (ETS) State Space and Seasonal Autoregressive Integrated Moving Average (SARIMA) models and compared their forecasting ability using root mean square error (RMSE). Both models were used to capture the sporadic behaviour of rainfall. These two models have been widely applied to climatic data by many scholars and adjudged to perform creditably well. In an attempt to find a suitable prediction model for monthly rainfall patterns in Limpopo Province, data ranging from January 1900 to December 2015, for seven weather stations: Macuville Agriculture, Mara Agriculture, Marnits, Groendraal, Letaba, Pietersburg Hospital and Nebo, were analysed. The results showed that the two models were adequate in predicting rainfall patterns for the different stations in the Limpopo Province. / National Research Foundation (NRF)

No description available.

Global civilisation, and therefore population health, is threatened by excessive inequality, weapons of mass destruction, inadequate economic and political theory and adverse global environmental change. The unequal distribution of global foreign exchange adjusted income is both a cause and a reflection of global social characteristics responsible for many aspects of these inter-related crises. ¶ The global distribution of foreign exchange adjusted income for the period 1964-1999 is examined. Using data for more than 99% of the global population, a substantial divergence in its distribution is found. The global Gini co-efficient, adjusted for national income inequality, increased from an already high value of 71% in 1964 to peak at more than 80% in 1995, before falling, very slightly, to 79% in 1999. The global distribution of purchasing parity power income is also examined, for a similar period. Though also found to be extremely unequal, its trend has not been to increased inequality. Implications of the differences between these two trends are discussed. ¶ A weighted time series index of global environmental change (IGEC) for the period 1960-1997 was also calculated. This uses nine categories of global time series environmental data, each scaled so that 100% represents the level of each category in nature prior to anthropogenic change; zero represents decline to a critical point. This index fell from 82% in 1960 to 55% in 1997, and will further decline during this century. ¶ Using evidence from several disciplines, it is argued that the decline in the IGEC correlates with major macro-environmental changes, which, combined with flawed social responses to scarcity and its perception, place at risk the ability of civilisation to function. This could occur because of the interaction of conflict, economically disastrous extreme climatic events, deterioration of other ecosystem services, regional food and water insecurity, and currently unforeseen events. Uncertainty regarding both a safe rate of decline and the tolerable nadir of the IGEC is substantial. ¶ Substantial reduction in the inequality of foreign exchange adjusted income is vital to enhance the development of policies able to reverse the decline in the environmental goods which underpin civilisation, and to promote the co-operation needed to maximise the chance that civilisation will survive.

A new experimental approach is reported that focuses on photoionization mass spectrometry of primary photofragments. Photodissociation of molecules and radicals is carried out by using a tunable, pulsed dye laser. Nascent photofragments are subsequently photoionized by time-correlated vacuum-ultraviolet (VUV) radiation, so that only single-photon ionization occurs. Several experimental approaches are used in order to optimize pulsed radiation sources in the VUV that are suitable for pump-probe experiments. Laser systems that rely on frequency tripling in suitable non-linear media are used as an intense VUV radiation source of narrow bandwidth and limited tuning range. Monochromatized laser-produced plasma radiation is also used, which provides tunable VUV radiation throughout the entire VUV energy regime (8-25 eV). Ionized photofragments are finally detected by time-of-flight mass spectrometry. This experimental approach is used in order to investigate the following issues: * Absolute photoionization cross sections of atomic and molecular photofragments are derived from photoionization mass spectrometry. This is shown for the photolysis of chlorine dioxide (OClO), chlorine monoxide (ClO) and ozone (O3). The latter species generates O(1D), so that photoionization and autoionization of this excited species was studied for the first time. * Quantum states and quantum state distributions are derived from photoion yields of primary photofragments in order to characterize photodissociation processes. This is shown for the predissociation of OClO, which yields vibrationally excited ClO in its electronic ground state. * Branching ratios and quantum yields of competing photochemical pathways are determined from photoionization mass spectrometry. The accuracy of this approach is superior to other techniques. These investigations allowed us to investigate photolysis processes of molecules and radicals that are of significant importance with respect to recent issues of atmospherical photoprocesses, such as polar ozone depletion.