Mechanistic studies on the advanced oxidation and photochemical transformation of cyanotoxins (microcystins)

The increased occurrence of cyanobacteria (blue-green algae) blooms and the production of associated cyanotoxins have presented a threat to drinking water sources. Among the most common types of cyanotoxins found in potable water are microcystins (MCs), a family of cyclic heptapeptides containing substrates. MCs are strongly hepatotoxic and known to initiate tumor promoting activity. The presence of sub-lethal doses of MCs in drinking water is implicated as one of the key risk factors for an unusually high occurrence of primary liver cancer. ^ A variety of traditional water treatment methods have been attempted for the removal of cyanotoxins, but with limited success. Advanced Oxidation Technologies (AOTs) are attractive alternatives to traditional water treatments. We have demonstrated ultrasonic irradiation and UV/H2O2 lead to the degradation of cyanotoxins in drinking water. These studies demonstrate AOTs can effectively degrade MCs and their associated toxicity is dramatically reduced. We have conducted detailed studies of different degradation pathways of MCs and conclude that the hydroxyl radical is responsible for a significant fraction of the observed degradation. Results indicate preliminary products of the sonolysis of MCs are due to the hydroxyl radical attack on the benzene ring and substitution and cleavage of the diene of the Adda peptide residue. AOTs are attractive methods for treatment of cyanotoxins in potable water supplies. ^ The photochemical transformation of MCs is important in the environmental degradation of MCs. Previous studies implicated singlet oxygen as a primary oxidant in the photochemical transformation of MCs. Our results indicate that singlet oxygen predominantly leads to degradation of the phycocyanin, pigments of blue green algae, hence reducing the degradation of MCs. The predominant process involves isomerization of the diene (6E to 6Z) in the Adda side chain via photosensitized isomerization involving the photoexcited phycocyanin. Our results indicate that photosensitized processes play a key role in the environmental fate and elimination of MCs in the natural waters. ^

Impact of Late Holocene climate variability and anthropogenic activities on Biscayne Bay (Florida, U.S.A.): Evidence from diatoms

Shallow marine ecosystems are experiencing significant environmental alterations as a result of changing climate and increasing human activities along coasts. Intensive urbanization of the southeast Florida coast and intensification of climate change over the last few centuries changed the character of coastal ecosystems in the semi-enclosed Biscayne Bay, Florida. In order to develop management policies for the Bay, it is vital to obtain reliable scientific evidence of past ecological conditions. The long-term records of subfossil diatoms obtained from No Name Bank and Featherbed Bank in the Central Biscayne Bay, and from the Card Sound Bank in the neighboring Card Sound, were used to study the magnitude of the environmental change caused by climate variability and water management over the last ~ 600 yr. Analyses of these records revealed that the major shifts in the diatom assemblage structures at No Name Bank occurred in 1956, at Featherbed Bank in 1966, and at Card Sound Bank in 1957. Smaller magnitude shifts were also recorded at Featherbed Bank in 1893, 1942, 1974 and 1983. Most of these changes coincided with severe drought periods that developed during the cold phases of El Niño Southern Oscillation (ENSO), Atlantic Multidecadal Oscillation (AMO) and Pacific Decadal Oscillation (PDO), or when AMO was in warm phase and PDO was in the cold phase. Only the 1983 change coincided with an unusually wet period that developed during the warm phases of ENSO and PDO. Quantitative reconstructions of salinity using the weighted averaging partial least squares (WA-PLS) diatom-based salinity model revealed a gradual increase in salinity at the three coring locations over the last ~ 600 yr, which was primarily caused by continuously rising sea level and in the last several decades also by the reduction of the amount of freshwater inflow from the mainland. Concentration of sediment total nitrogen (TN), total phosphorus (TP) and total organic carbon (TOC) increased in the second half of the 20th century, which coincided with the construction of canals, landfills, marinas and water treatment plants along the western margin of Biscayne Bay. Increased magnitude and rate of the diatom assemblage restructuring in the mid- and late-1900s, suggest that large environmental changes are occurring more rapidly now than in the past.

The investigation of photocatalysts and iron based materials in the oxidation and adsorption of toxic organic and chromium materials

The presences of heavy metals, organic contaminants and natural toxins in natural water bodies pose a serious threat to the environment and the health of living organisms. Therefore, there is a critical need to identify sustainable and environmentally friendly water treatment processes. In this dissertation, I focus on the fundamental studies of advanced oxidation processes and magnetic nano-materials as promising new technologies for water treatments. Advanced oxidation processes employ reactive oxygen species (ROS) which can lead to the mineralization of a number of pollutants and toxins. The rates of formation, steady-state concentrations, and kinetic parameters of hydroxyl radical and singlet oxygen produced by various TiO2 photocatalysts under UV or visible irradiations were measured using selective chemical probes. Hydroxyl radical is the dominant ROS, and its generation is dependent on experimental conditions. The optimal condition for generation of hydroxyl radical by of TiO2 coated glass microspheres is studied by response surface methodology, and the optimal conditions are applied for the degradation of dimethyl phthalate. Singlet oxygen (1O2) also plays an important role for advanced processes, so the degradation of microcystin-LR by rose bengal, an 1O2 sensitizer was studied. The measured bimolecular reaction rate constant between MC-LR and 1O2 is ∼ 106 M-1 s-1 based on competition kinetics with furfuryl alcohol. The typical adsorbent needs separation after the treatment, while magnetic iron oxides can be easily removed by a magnetic field. Maghemite and humic acid coated magnetite (HA-Fe3O4) were synthesized, characterized and applied for chromium(VI) removal. The adsorption of chromium(VI) by maghemite and HA-Fe3O4 follow a pseudo-second-order kinetic process. The adsorption of chromium(VI) by maghemite is accurately modeled using adsorption isotherms, and solution pH and presence of humic acid influence adsorption. Humic acid coated magnetite can adsorb and reduce chromium(VI) to non-toxic chromium (III), and the reaction is not highly dependent on solution pH. The functional groups associated with humic acid act as ligands lead to the Cr(III) complex via a coupled reduction-complexation mechanism. Extended X-ray absorption fine structure spectroscopy demonstrates the Cr(III) in the Cr-loaded HA-Fe 3O4 materials has six neighboring oxygen atoms in an octahedral geometry with average bond lengths of 1.98 Å.

Impact of Late Holocene Climate Variability and Anthropogenic Activities on Biscayne Bay (Florida, U.S.A.): Evidence From Diatoms

Shallow marine ecosystems are experiencing significant environmental alterations as a result of changing climate and increasing human activities along coasts. Intensive urbanization of the southeast Florida coast and intensification of climate change over the last few centuries changed the character of coastal ecosystems in the semi-enclosed Biscayne Bay, Florida. In order to develop management policies for the Bay, it is vital to obtain reliable scientific evidence of past ecological conditions. The long-term records of subfossil diatoms obtained from No Name Bank and Featherbed Bank in the Central Biscayne Bay, and from the Card Sound Bank in the neighboring Card Sound, were used to study the magnitude of the environmental change caused by climate variability and water management over the last ~ 600 yr. Analyses of these records revealed that the major shifts in the diatom assemblage structures at No Name Bank occurred in 1956, at Featherbed Bank in 1966, and at Card Sound Bank in 1957. Smaller magnitude shifts were also recorded at Featherbed Bank in 1893, 1942, 1974 and 1983. Most of these changes coincided with severe drought periods that developed during the cold phases of El Niño Southern Oscillation (ENSO), Atlantic Multidecadal Oscillation (AMO) and Pacific Decadal Oscillation (PDO), or when AMO was in warm phase and PDO was in the cold phase. Only the 1983 change coincided with an unusually wet period that developed during the warm phases of ENSO and PDO. Quantitative reconstructions of salinity using the weighted averaging partial least squares (WA-PLS) diatom-based salinity model revealed a gradual increase in salinity at the three coring locations over the last ~ 600 yr, which was primarily caused by continuously rising sea level and in the last several decades also by the reduction of the amount of freshwater inflow from the mainland. Concentration of sediment total nitrogen (TN), total phosphorus (TP) and total organic carbon (TOC) increased in the second half of the 20th century, which coincided with the construction of canals, landfills, marinas and water treatment plants along the western margin of Biscayne Bay. Increased magnitude and rate of the diatom assemblage restructuring in the mid- and late-1900s, suggest that large environmental changes are occurring more rapidly now than in the past.

Response of spring diatoms to CO2 availability in the Western North Pacific as determined by next-generation sequencing

Next-generation sequencing (NGS) technologies have enabled us to determine phytoplankton community compositions at high resolution. However, few studies have adopted this approach to assess the responses of natural phytoplankton communities to environmental change. Here, we report the impact of different CO2 levels on spring diatoms in the Oyashio region of the western North Pacific as estimated by NGS of the diatom-specific rbcL gene (DNA), which encodes the large subunit of RubisCO. We also examined the abundance and composition of rbcL transcripts (cDNA) in diatoms to assess their physiological responses to changing CO2 levels. A short-term (3-day) incubation experiment was carried out on-deck using surface Oyashio waters under different pCO2 levels (180, 350, 750, and 1000 µatm) in May 2011. During the incubation, the transcript abundance of the diatom-specific rbcL gene decreased with an increase in seawater pCO2 levels. These results suggest that CO2 fixation capacity of diatoms decreased rapidly under elevated CO2 levels. In the high CO2 treatments (750 and 1000 µatm), diversity of diatom-specific rbcL gene and its transcripts decreased relative to the control treatment (350µatm), as well as contributions of Chaetocerataceae, Thalassiosiraceae, and Fragilariaceae to the total population, but the contributions of Bacillariaceae increased. In the low CO2 treatment, contributions of Bacillariaceae also increased together with other eukaryotes. These suggest that changes in CO2 levels can alter the community composition of spring diatoms in the Oyashio region. Overall, the NGS technology provided us a deeper understanding of the response of diatoms to changes in CO2 levels in terms of their community composition, diversity, and photosynthetic physiology.

Environmental stability affects phenotypic evolution in a globally distributed marine picoplankton

Marine phytoplankton can evolve rapidly when confronted with aspects of climate change because of their large population sizes and fast generation times. Despite this, the importance of environment fluctuations, a key feature of climate change, has received little attention-selection experiments with marine phytoplankton are usually carried out in stable environments and use single or few representatives of a species, genus or functional group. Here we investigate whether and by how much environmental fluctuations contribute to changes in ecologically important phytoplankton traits such as C:N ratios and cell size, and test the variability of changes in these traits within the globally distributed species Ostreococcus. We have evolved 16 physiologically distinct lineages of Ostreococcus at stable high CO2 (1031±87?µatm CO2, SH) and fluctuating high CO2 (1012±244?µatm CO2, FH) for 400 generations. We find that although both fluctuation and high CO2 drive evolution, FH-evolved lineages are smaller, have reduced C:N ratios and respond more strongly to further increases in CO2 than do SH-evolved lineages. This indicates that environmental fluctuations are an important factor to consider when predicting how the characteristics of future phytoplankton populations will have an impact on biogeochemical cycles and higher trophic levels in marine food webs.

Maintained larval growth in mussel larvae exposed to acidified undersaturated seawater

Ocean acidification (OA) is known to affect bivalve early life-stages. We tested responses of blue mussel larvae to a wide range of pH in order to identify their tolerance threshold. Our results confirmed that decreasing seawater pH and decreasing saturation state increases larval mortality rate and the percentage of abnormally developing larvae. Virtually no larvae reared at average pHT 7.16 were able to feed or reach the D-shell stage and their development appeared to be arrested at the trochophore stage. However larvae were capable of reaching the D-shell stage under milder acidification (pHT=7.35, 7.6, 7.85) including in under-saturated seawater with omega Aragonite as low as 0.54±0.01 (mean±s. e. m.), with a tipping point for normal development identified at pHT 7.765. Additionally growth rate of normally developing larvae was not affected by lower pHT despite potential increased energy costs associated with compensatory calcification in response to increased shell dissolution. Overall, our results on OA impacts on mussel larvae suggest an average pHT of 7.16 is beyond their physiological tolerance threshold and indicate a shift in energy allocation towards growth in some individuals revealing potential OA resilience.

Seawater carbonate chemistry and growth rate of Emiliania huxleyi in lab experiment

Predicting the impacts of environmental change on marine organisms, food webs, and biogeochemical cycles presently relies almost exclusively on short-term physiological studies, while the possibility of adaptive evolution is often ignored. Here, we assess adaptive evolution in the coccolithophore Emiliania huxleyi, a well-established model species in biological oceanography, in response to ocean acidification. We previously demonstrated that this globally important marine phytoplankton species adapts within 500 generations to elevated CO2. After 750 and 1000 generations, no further fitness increase occurred, and we observed phenotypic convergence between replicate populations. We then exposed adapted populations to two novel environments to investigate whether or not the underlying basis for high CO2-adaptation involves functional genetic divergence, assuming that different novel mutations become apparent via divergent pleiotropic effects. The novel environment "high light" did not reveal such genetic divergence whereas growth in a low-salinity environment revealed strong pleiotropic effects in high CO2 adapted populations, indicating divergent genetic bases for adaptation to high CO2. This suggests that pleiotropy plays an important role in adaptation of natural E. huxleyi populations to ocean acidification. Our study highlights the potential mutual benefits for oceanography and evolutionary biology of using ecologically important marine phytoplankton for microbial evolution experiments.

Adaptive evolution of a key phytoplankton species to ocean acidification

Ocean acidification, the drop in seawater pH associated with the ongoing enrichment of marine waters with carbon dioxide from fossil fuel burning, may seriously impair marine calcifying organisms. Our present understanding of the sensitivity of marine life to ocean acidification is based primarily on short-term experiments, in which organisms are exposed to increased concentrations of CO2. However, phytoplankton species with short generation times, in particular, may be able to respond to environmental alterations through adaptive evolution. Here, we examine the ability of the world's single most important calcifying organism, the coccolithophore Emiliania huxleyi, to evolve in response to ocean acidification in two 500-generation selection experiments. Specifically, we exposed E. huxleyi populations founded by single or multiple clones to increased concentrations of CO2. Around 500 asexual generations later we assessed their fitness. Compared with populations kept at ambient CO2 partial pressure, those selected at increased partial pressure exhibited higher growth rates, in both the single- and multiclone experiment, when tested under ocean acidification conditions. Calcification was partly restored: rates were lower under increased CO2 conditions in all cultures, but were up to 50% higher in adapted compared with non-adapted cultures. We suggest that contemporary evolution could help to maintain the functionality of microbial processes at the base of marine food webs in the face of global change.

Elaboração de uma unidade de ensino potencialmente significativa em Química para abordar a temática água

The evidence of the water theme in news reports is configured as an important topic of interest to contextualize, problematize and/or generate meaning in the midst of discussion of a content from different levels of education and/or disciplines of basic education. The possibilities to use this theme in classroom is also highlighted in Brazilian official documents that guide the practice of teachers of all Brazilian curricular components of this educational level. So, the theme water can be used as subsidy to teach chemistry, since contextualises the teaching of this discipline aiding in the discussion of different chemical concepts. In this perspective, the meaningful learning theory, developed by David Ausubel, has constructivist nature and says that an individual learns significantly when he can relate new information with a specific knowledge structure that integrates the prior knowledge of its structure. In this sense, the use of water as a theme for the approach prior knowledge of chemical concepts has already been characterized as an important topic that can give meaning to the content of education in chemistry. In this dissertation, a teaching unit potentially significant (TUPS) is presented based on meaningful learning theory of David Ausubel approaching the theme water. approaching the theme water. The unit was used in a class of thirty-five students of the 2nd year of high school, a public school in the city of Extremoz-RN, metropolitan region of Natal / RN. Through it was possible to discuss an issue of interest to students of the school to address the chemical contents, such as solutions, physicochemical aspects and stages of water treatment. At first, an initial questionnaire was used to identify the students' previous ideas on the topic under study to the concept of chemical solutions. It was subsequently developed and implemented a series of activities based on students' ideas. To subsidize the sequence, it was prepared four booklets that worked the content of chemical solutions, contextualizing the theme water. The results of this work showed that the alternative conceptions that students have about concepts related to the chemical solutions are similar to the ideas of other students presented in the literature and that the development of the TUPS, allied to the contextualization strategy with the theme water, not only motivated the students for the teaching of chemical content, as yet provided the learning of chemical concepts not in isolation, but making a connection between their ideas and experiences with scientific knowledge. To this, beyond of dialogued lectures, were also used strategies as experimental activities, problem solving, group discussions and construction of concept maps. The final evaluation of the unit was conducted by a questionnaire based on the Likert scale, answered individually by students, who approved the unit as conducive to teaching and learning of chemistry process