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  • Mangroves are a unique group of plants, which offer a great variety of goods and services to the ecosystem and to the society. Regrettably, they have been globally threatened by urbanization and industrialization, among others, triggering overexploitation of the world’s mangrove forests despite their ecological and economic importance. As a result, mangroves are often under pollution stress as sinks or receivers for numerous man-made pollutants such as pesticides, which are the main focus of this thesis. One of the most widely applied chemicals in the word are the organochlorine pesticides (OCPs) that even after their supposedly worldwide ban between 1950s-1990s, they can still be detected in the environment. Numerous studies have been done in phytoremediation of pollutants by mangroves, but little attention has been given to the role of mangroves in the remediation of OCPs. For this reason, part of this thesis will focus on the occurrence and distribution of OCPs in intertidal tropical and sub-tropical areas around the world with and without mangroves. As a first goal (I), we evaluate —in a theoretical way— if the presence of mangroves affects or modifies the levels of OCPs in the surrounding environment. For this purpose, data from different matrices, such as water, sediment, benthic fauna and plants were included and discussed in this work. Moreover, and considering Macao’s location, we also quantified OCPs from surface waters of this region from areas with and without mangroves and included in this task. Besides this theoretical approach, this thesis also included some laboratoy and field work specifically focused on dicofol and 4,4’-dichlorobenzophenone (4,4’-DCBP, its main metabolite). Dicofol is an OCP strongly related to dichlorodiphenyltrichloroethane (DDT), which has been extensively used in China and more specifically, in the Pearl River Delta (PRD), a region under anthropogenic pressure. However, due to dicofol’s instability (i.e., sensitive to low pH, light exposure and high temperature), we expected to quantify 4,4′-DCBP (which is also common to DDT) as the main form present in the environment. As a second goal (II), we conducted a monitoring study in surface waters from Macao and Hong Kong, to evaluate the contamination status and water quality of these regions. Concentrations of 4,4’-DCBP, nutrients and physicochemical parameters were measured during transition and wet season, and at high and low tide. In addition, since the toxicity of this metabolite was totally unknown, we assessed it via two biological models: Daphnia magna and Artemia salina. Since 4,4’-DCBP was detected and quantified in both regions (2.8-30.0 ng/L), this thesis also includes experimental work focused on the assimilation and depuration pattern by a marine organism. For that purpose and as a final goal (III), we selected the common edible bivalve Meretrix as a model to evaluate the dynamics of accumulation and depuration of the pesticide dicofol. The Vietnamese clams were exposed during 15 days under two different concentrations of dicofol, and decontaminated for the same period of time. Quantification of 4,4’-DCBP was done during both phases (uptake and depuration) and at different sampling times. In summary, all these different works helped us to conclude that: I.1) As expected, vegetated areas with mangroves presented lower concentrations of OCPs for all the matrices, and also better quality in terms of pesticide pollution for water and sediments. Results obtained from Macao’s waters also revealed the same pattern, with mangroves areas having lower levels of contamination. Although the gathered data presented methodological variability (i.e. different quantification methods, extraction protocols, equipment used), the same pattern was observed among matrices, showing how robust and solid the results herein obtained are. II.1). Hong Kong presented higher concentrations of 4,4’-DCBP than Macao, which may be due to the use of dicofol as a pesticide and the use of antifouling-paint for ships. Moreover, concentrations of 4,4’-DCBP during wet season were below limits of quantification, demonstrating a seasonal pattern and a dilution effect due to higher river discharges during this period. II.2). Both regions showed possible eutrophication problems due to the high nutrient concentrations. These levels presented also a seasonal variability, with dissolved inorganic nitrogen and total dissolved solids higher during transition; and dissolved inorganic phosphorous, total suspended solids and chlorophyll a higher during wet season. II.3). Toxicity of 4,4’-DCBP was lower than the parent compound dicofol, and the levels quantified indicated a low environmental risk. However, it is important to pay attention to this compound since interaction with other contaminants could enhance their toxicity, or processes such as biomagnification or bioaccumulation could make low concentrations a threat for the environment. III.1). Different concentrations of dicofol presented different uptake and depuration kinetics. Animals exposed to higher concentrations (500 ng/L), had levels above limits of quantification (LOQ) after 24h exposure, unlike the ones exposed to lower concentrations (50 ng/L), which had levels <LOQ after the same period. The first ones also, presented lower uptake rates, and this could indicate that high dicofol concentrations in the system could affect the respiration rates of the organism. In addition, this work also showed that animals exposed to high concentrations of dicofol will need more than 15 days to depurate in order to reach safe levels for human consumption. The compilation of the work done in this thesis allowed us to better understand the role of mangroves ecosystems on the accumulation of OCPs and to provide solid information that could create strategies for mangroves management and conservation. Moreover, and as a first attempt, we were able to quantify this pesticide metabolite in the PRD (one of the most seriously contaminated areas in China), to determine its toxicity and to define its kinetics in an important organism such as the edible bivalve M. meretrix. We intend that this thesis will be helpful for the scientific community providing new insights regarding metabolite interactions (within and with other molecules) and toxicity (LC50 and theoretical risk assessment), which were unknown until now

  • The territory of Macao is composed of several granitic intrusions belonging to one of the biggest granite provinces in the world, the Southeast China Magmatic Belt (SCMB), located in the southeast (SE) area of the Cathaysia Block. The SCMB is known by the occurrence of large volumes of Mesozoic magmatic rocks (over 90% are granitic rocks and equivalent volcanic rocks with minor basalts), occupying a total outcrop area of nearly 200.000 km2. The geology of Macao (~30 Km2) is dominated by granitic rocks displaying a wide range of textural, mineralogical and chemical features, making it an ideal region to study these rocks and the petrogenetic processes responsible for their diversity. This study employed a wide range of research methodologies, namely field studies, petrography, zircon geochronology, mineral chemistry, whole-rock elemental and isotopic geochemistry to determine the nature of the source, the petrogenetic processes and the tectonic regimes of the Mesozoic magmatism in this region. Thus, the data collected along this study aims to provide new knowledge on the tectono-magmatic evolution of Macao, in particular, and of SE China, in general. The results obtained from the high-precision U–Pb zircon geochronology, acquired through isotope dilution thermal ionization mass spectrometry (ID-TIMS) and in-situ laser ablation multi-collector inductively coupled mass spectrometry (LA-MC-ICPMS), revealed different ages for Macao granites. Despite its relatively small area, the determined ages tightly constrain the Macao granitic magmatism to two periods, ranging from 164.5 ± 0.6 to 162.9 ± 0.7 Ma (MGI – Macao Group I granites) and 156.6 ± 0.2 to 155.5 ± 0.8 Ma (MGII – Macao Group II granites). In addition, younger dacitic rocks were dated at 150.6 ± 0.6 Ma and <120 Ma. The existence of two proximal but distinct granitic pulses, spanning for a time of about 9 Ma and separated by ca. 6 Ma, in the Macao granitic suite suggests that it was incrementally assembled. This hypothesis is also extendable to the neighbouring Hong Kong region, where the magmatic activity occurred in four major pulses spanning for about 24 Ma. However, the MGII granites indicate the occurrence, on the Pearl River Delta region, of a magmatic pulse between those defined in Hong Kong at the origin of Lamma Suite (165–160 Ma) and the Kwai Chung Suite (148–146 Ma). In addition, Rare Element Earth (REE) ratios suggest that this pulse may only occur in Macao area, while MGI granites show evolving trends of REE ratios similar to those of Jurassic granites outcropping in vast areas of the Cathaysia Block (SE China). Inheritance patterns in the zircon U–Pb data indicate the presence of a population of antecrysts (165–180 Ma) crystallized from earlier magmatic pulses and a population of inherited zircons, from Precambrian to Phanerozoic sources, incorporated into the magmas during melting and/or ascent/emplacement at crustal levels. The oldest inherited ages (2.4 Ga and possibly 2.9 Ga) suggest contribution of Proterozoic and possibly of late Archaean crustal sources for the Macao magmatism. The granitic rocks of Macao are mainly high-K calc-alkaline metaluminous to weakly peraluminous I-type granites with variable degrees of fractionation. Fractional crystallization played an important role in the evolution of these granites, though the fractionation paths differ for the highly fractionated facies of both groups mainly due to distinct accessory fractionating phases. Such difference is evident by distinct REE evolution trends: while MGI magmas seem to have evolved by gradual enrichment in heavy REE relatively to light REE, originating progressively flatter REE patterns, magmas from MGII are marked by depletion of middle REE, leading to progressively concave upward REE patterns. However, while most of the geochemical variation of the MGII granites can be explained by fractional crystallization, the same is not true for MGI granites. The MGI highly fractionated granites show evidence for the REE tetrad effect and are characterized by non-CHArge-and-RAdius-Controlled (non-CHARAC) behaviour of trace elements, suggesting late-stage melt/fluid interactions involving F-rich fluids. The stage of evolution represented by the MGI highly fractionated granites corresponds to the onset of fluid/melt interaction in a highly evolved granitic system, which may have led to enhanced hydrothermal activity in more evolved stages, as those represented in neighbouring areas in SE China. Significant differences in isotopic composition were also observed, with the MGII being characterized by a much narrow range of initial 87Sr/86Sr ratios and εNd(t) and εHf(t) values than MGI. Based on these differences, the MGII granites are considered to be part of a comagmatic suite that has evolved in closed system, contrasting with what can be inferred for MGI. The increase in initial 87Sr/86Sr ratios with degree of evolution, the presence of metasedimentary enclaves and the high percentage of inherited zircon with Paleozoic ages in MGI, suggest the occurrence of an assimilation fractionation crystallization (AFC) process. The AFC processes were a major cause for the I-S transitional characteristics of the MGI highly fractionated granites and possibly of the other similar Jurassic biotite granites in SE China. The observed decoupling of Sr, Nd and Hf isotope systems might have resulted from magma mixing between the granitic and more mafic magmas, which caused the homogenization of Sr isotope ratios but not of the Nd and Hf ones. Such process is also supported by the occurrence of Microgranular Mafic Enclaves (MME) hosted by the granites. Isotope and major element compositions together with model ages strongly suggest that Macao granitic magmas were generated by partial melting of infracrustal medium-to-high K basaltic Paleo-Proterozoic to Mesoproterozoic protoliths heated by, and mixed to some degree with mantle-derived magmas. The temporal and spatial association of Macao and SE China Jurassic I-type granites with basaltic/gabbroic rocks, syenites and A-type granites, displaying typical intraplate chemical features, indicates an extensional regime rather than an active margin for the origin of these rocks. It also points to an important role of mantle-derived magmas in the production of SE China Jurassic granites. Adiabatic decompression melting of the asthenospheric mantle produced mafic magmas, which underplated at the base of the crust (Moho), subsequently triggering partial melting of the lower crust to generate the granitic magmas. The Jurassic Macao granites are interpreted as being produced in an intraplate extensional setting related to the break-off and foundering of a previously flat-slab (Paleo-Pacific plate) beneath the Eurasian plate. The boundary between east and west Cathaysia blocks is roughly along the Zhenghe-Dapu Fault (ZDF), which intersects the SE China coast near Hong Kong and is thought to have played a major role for the Mesozoic magmatic activity in this region. The stronger isotopic affinities of Macao granites with the other granitic rocks and lower crustal xenoliths from the western Cathaysia Block suggest that the ZDF is likely to pass south of Macao, a fact that has not been mentioned before. In addition to the Early Yanshanian (Jurassic) granitic magmatism in Macao, the younger ages obtained for the dacite dykes indicate that the territory was also affected, to a lesser degree, by Late Yanshanian (Cretaceous) magmatism. The transition from granitic to dacitic magmatism most likely corresponds to a change in the regional tectonic regime, which induced a significant change in the magma genesis processes. In contrast with the intraplate features of Macao and SE China Jurassic granites and coeval mafic rocks, the geochemical features of the Macao dacite dykes (e.g. high LILE/HFSE ratios and negative anomalies of Nb, Ta and Ti) are identical to those characterizing arc-like subduction-related magmas. These dacites are most likely evolved products of arc-like magmatism and may testify the reestablishment of a normal subduction system in this area of SE China.

  • Fishes are highly specialized in extracting ecologically relevant information from their diverse acoustic habitats since early developmental stages. The zebrafish (Danio rerio) is a valuable and well-stablished vertebrate model for investigating hearing functioning and disorders, development of the inner ear in vertebrates including humans, drug discovery, ecotoxicology assessments and behavioral research. Although the acoustic environment is known to shape the structure and sensitivity of auditory systems, there is no information on the natural soundscape of this species. Zebrafish are typically reared in large-scale artificial housing systems, which acoustic properties and potential effects on hearing remain largely unknown. Even though elevated levels of noise are widely present in most aquatic soundscapes and to an even greater extent in artificial environments, very limited information is known on how this important environmental stressor impacts species’ development and physiology, hearing capabilities and inner ear morphology, and behaviour. Considering that noise pollution is rapidly increasing in aquatic ecosystems, causing detrimental effects on survivability and growth and altering physiology and behaviour of organisms, it is of paramount importance to assess how this stressor affects wildlife, especially in early ontogeny, a critical period for development and establishment of phenotypic traits. For this thesis I aimed to 1) characterize the soundscape of both zebrafish natural habitats and laboratory captive conditions, and discuss possible impact on auditory sensitivity. Sound recordings were conducted in five distinct zebrafish habitats (Southwest India), from quieter stagnant environments with diverse biological/abiotic sounds to louder watercourses characterized by current and moving substrate, while artificial environmental characterization was conducted on three typical zebrafish housing systems. 8 In order to assess the impact of noise exposure on early development, my next goal was to 2) perform a split-brood experiment to test the effects of chronic noise exposure to increasing levels (130 and 150 dB re 1 μPa, continuous white noise) and different temporal regimes (mimicking shipping activity) on larval zebrafish in regards to general development, physiological stress, and behavioural patterns. Finally, the last objective consisted on 3) testing the effects of chronic noise exposure on auditory sensitivity measured based on inner ear saccular microphonics and acoustic-evoked startle responses (prepulse inhibition paradigm) in larval zebrafish, as well as evaluating whether sensitivity changes were paralleled by altered inner ear morphology. Based on bioacoustics methods, my first study found that zebrafish natural soundscape varied between 98 and 126 dB re 1 lPa in sound pressure levels. Sound spectra presented most energy below 3000 Hz and quieter noise windows were found in the noisiest habitats matching the species best hearing range. Contrastingly, recordings from zebrafish housing systems revealed higher sound levels (122–143 dB) and most energy below 1000Hz with more spectral peaks, which might cause significant impact such as auditory masking or even hearing loss. In my second research work, the acoustic treatments did not affect general development or hatching but increased noise levels led to a significant increase in mortality of larval zebrafish. The cardiac rate, yolk sac consumption and cortisol levels increased significantly with increasing noise level at both 3 and 5 dpf (days post fertilization). Variations in noise time presentations (different random noise periods similar to shipping activity) suggested that the presence of longer silent intervals is important to down-regulate physiological stress. Moreover, 5 dpf larvae exposed to 150 dB continuous noise regimes displayed increased dark avoidance in an anxiety-related dark/light preference test and displayed a significant 9 impairment in spontaneous alternation behaviour (SAB) a memory and sensorimotor related behaviour. Finally, in the last thesis goal, I found that noise-exposed specimens displayed significantly lower hair cell number and saccular epithelial area. This change in sensory morphology was paralleled by a significant decrease in inner ear saccular sensitivity at lower frequencies (100 to 200 Hz) in 5 dpf larvae. Sensorimotor hearing assessment revealed a hypersensitisation effect in noise-exposed group that displayed higher startle swimming velocity, but also significant decrease in sensitivity at 200 Hz. Altogether, this thesis provides an important ground for future research on the adaptation of zebrafish auditory system to the natural soundscapes, and highlights the importance of controlling noise conditions in captivity systems. Furthermore, results provide first evidence of noise-induced physiological stress, anxiety-driven behaviours and memory impairment in larval zebrafish larvae, showing that both noise amplitude and timing may negatively impact key physiological and behavioural endpoints in early ontogeny. The thesis also reports new findings on how acoustic stress may impact the structure and function of the inner ear in larval fish, which was followed by decreased sensitivity in sensorimotor responses to acoustic stimuli. My research highlights the importance of investigating how altered soundscapes and associated physiological and behavioural stress may affect important sensitive windows in development and impose new evolutionary challenges under a scenario of global change

  • A combination of assessment, operational forecast, and future perspective was thoroughly explored to provide an overview of the existing air quality problems in Macao. The levels of air pollution in Macao often exceed those recommended by the World Health Organization (WHO). In order for the population to take precautionary measures and avoid further health risks during high pollution episodes, it is important to develop a reliable air quality forecast. Statistical models based on linear multiple regression (MLR) and classification and regression trees (CART) analysis were successfully developed for Macao, to predict the next day concentrations of NO2, PM10, PM2.5, and O3. Meteorological variables were selected from an extensive list of possible variables, including geopotential height, relative humidity, atmospheric stability, and air temperature at different vertical levels. Air quality variables translate the resilience of the recent past concentrations of each pollutant and usually are maximum and/or the average of latest 24-hour levels. The models were applied in forecasting the next day average daily concentrations for NO2 and PM and maximum hourly O3 levels for five air quality monitoring stations. The results are expected to support an operational air iv quality forecast for Macao. The work involved two phases. On a first phase, the models utilized meteorological and air quality variables based on five years of historical data, from 2013 to 2017. Data from 2013 to 2016 were used to develop the statistical models and data from 2017 was used for validation purposes. All the developed models were statistically significantly valid with a 95% confidence level with high coefficients of determination (from 0.78 to 0.93) for all pollutants. On a second phase, these models were used with 2019 validation data, while a new set of models based on a more extended historical data series, from 2013 to 2018, were also validated with 2019 data. There were no significant differences in the coefficients of determination (R2) and minor improvements in root mean square errors (RMSE), mean absolute errors (MAE) and biases (BIAS) between the 2013 to 2016 and the 2013 to 2018 data models. In addition, for one air quality monitoring station (Taipa Ambient), the 2013 to 2018 model was applied for two days ahead (D2) forecast and the coefficient of determination (R2) was considerably less accurate to the one day ahead (D1) forecast, but still able to provide a reliable air quality forecast for Macao. To understand if the prediction model was robust to extreme variations in v pollutants concentration, a test was performed under the circumstances of a high pollution episode for PM2.5 and O3 during 2019, and a low pollution episode during 2020. Regarding the high pollution episode, the period of the Chinese National Holiday of 2019 was selected, in which high concentration levels were identified for PM2.5 and O3, with peaks of daily concentration for PM2.5 levels exceeding 55 μg/m3 and the maximum hourly concentration for O3 levels exceeding 400 μg/m3. For the low pollution episode, the 2020 period of implementation of the preventive measures for COVID-19 pandemic was selected, with a low record of daily concentration for PM2.5 levels at 2 μg/m3 and maximum hourly concentration for O3 levels at 50 μg/m3. The 2013 to 2018 model successfully predicted the high pollution episode with high coefficients of determination (0.92 for PM2.5 and 0.82 for O3). Likewise, the low pollution episode was also correctly predicted with high coefficients of determination (0.86 and 0.84 for PM2.5 and O3, respectively). Overall, the results demonstrate that the statistical forecast model is robust and able to correctly reproduce extreme air pollution events of both high and low concentration levels. Machine learning methods maybe adopted to provide significant improvements in combination of multiple linear regression (MLR) and classification and regression vi tree (CART) to further improve the accuracy of the statistical forecast. The developed air pollution forecasting model may be combined with other measures to mitigate the impact of air pollution in Macao. These may include the establishment of low emission zones (LEZ), as enforced in some European cities, license plate restrictions and lottery policy, as used in some Asian, tax exemptions on electric vehicles (EVs) and exclusive corridors for public transportations. Keywords: Air pollution; Particulate Matter; Ozone; Macao; Statistical air quality forecast; Pollution episodes; Chinese national holiday; COVID-19

Last update from database: 1/31/23, 3:23 AM (UTC)

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