Algal blooms plague freshwaters across the globe, as increased nutrient loads lead to eutrophication of inland waters and the presence of potentially harmful cyanobacteria. In this context, remote sensing is a valuable approach to monitor water quality over broad temporal and spatial scales. However, there remain several challenges to the accurate retrieval of water quality parameters, and the research in this thesis investigates these in an optically complex lake (Lake Balaton, Hungary). This study found that bulk and specific inherent optical properties [(S)IOPs] showed significant spatial variability over the trophic gradient in Lake Balaton. The relationships between (S)IOPs and biogeochemical parameters differed from those reported in ocean and coastal waters due to the high proportion of particulate inorganic matter (PIM). Furthermore, wind-driven resuspension of mineral sediments attributed a high proportion of total attenuation to particulate scattering and increased the mean refractive index (n̅p) of the particle assemblage. Phytoplankton pigment concentrations [chlorophyll-a (Chl-a) and phycocyanin (PC)] were also accurately retrieved from a times series of satellite data over Lake Balaton using semi-analytical algorithms. Conincident (S)IOP data allowed for investigation of the errors within these algorithms, indicating overestimation of phytoplankton absorption [aph(665)] and underestimation of the Chl-a specific absorption coefficient [a*ph(665)]. Finally, Chl-a concentrations were accurately retrieved in a multiscale remote sensing study using the Normalized Difference Chlorophyll Index (NDCI), indicating hyperspectral data is not necessary to retrieve accurate pigment concentrations but does capture the subtle heterogeneity of phytoplankton spatial distribution. The results of this thesis provide a positive outlook for the future of inland water remote sensing, particularly in light of contemporary satellite instruments with continued or improved radiometric, spectral, spatial and temporal coverage. Furthermore, the value of coincident (S)IOP data is highlighted and contributes towards the improvement of remote sensing pigment retrieval in optically complex waters.

Algal infestation in water bodies causes the release of soluble organic compounds that impact negatively on the taste and odour of the water. With increasing pollution in water bodies and increasing nutrient loading from agricultural activities, most water reservoirs in South Africa and around the world have become affected by this problem. In this study, an advanced oxidation process (AOP), namely, photocatalysis was evaluated for its potential to degrade aromatic compounds; and taste and odour causing bi-cyclic compounds originating from algae. Semiconductor photocatalysis is an environmentally friendly technology requiring no chemical inputs which is capable of completely mineralising organic pollutants to CO2 and H2O thereby eliminating production of unwanted by-products. Although processes involved in the photo-degradation have been reported for a wide range of pollutants, the degradative pathway in this process has not been fully established. In this study, compounds including phenol, 2-chlorophenol, 4-chlorophenol and nitrophenol were successfully eliminated from simulated wastewater. Degradation of geosmin at an environmentally significant initial concentration of 220 ng/L to levels below the lowest detectable concentration was achieved with an optimum catalyst concentration of 60 mg/L at a rate of 14.78 ng/L/min. Higher catalysts loading above 60 mg/L resulted in a decrease in degradation rates. An increase in initial geosmin concentration resulted in a decrease in rates. Ionic species commonly found in surface waters (HCO3 -, and SO4 2-) significantly reduced the efficiency of geosmin degradation. Degradation of geosmin produced acyclic intermediates from ring fission tentatively identified as 3,5-dimethylhex-1-ene, 2,4-dimethylpentan-3-one, 2-methylethylpropanoate and 2-heptanal. The results obtained indicate that the degradation of organic pollutants in aqueous solution is as a result of synergic action from hydroxyl radicals, positive holes and direct photolysis by UV radiation, though the predominant pathway of degradation is via hydroxyl radicals in solution. Major aromatic intermediates of phenol degradation include catechol, resorcinol and hydroquinone produced in the order catechol > resorcinol > hydroquinone. All three are produced within 2 minutes of photocatalytic reaction of phenol and remain in solution until all phenol is degraded in aerated systems. Production of resorcinol in non-aerated systems is transient, further supporting the hydroxyl radical dominant reaction pathway. / Thesis (PhD)--University of Pretoria, 2014. / gm2014 / Chemical Engineering / unrestricted

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published_or_final_version / Civil Engineering / Master / Master of Philosophy

This study investigated the role of grazing as a possible cause for the upper limit of distribution of algae on a typical South African south coast.

As cyanobacteria (also known as blue green algae) produce a range of cyclic peptides which are highly toxic, capillary electrophoresis and associated techniques have been investigated to assess their applicability for toxin monitoring in the water bodies of kwaZulu Natal, South Africa. Capillary electrophoresis (CE) is a technique in which charged molecules can be efficiently separated in a buffer solution within a capillary tube under the influence of a strong electric field. Two CE modes, namely capillary zone electrophoresis (CZE) and micellar electrokinetic capillary chromatography (MECC) were initially evaluated using a laboratory-built CE instrument. The former mode lacked selectivity due to the similar charge to size ratio of the algal toxins. However, with the latter mode, incorporation of a surfactant (sodium dodecyl sulphate) into the buffer, produced sufficient resolution between components. Parameters including surfactant concentration, buffer ionic strength, buffer pH and operating voltage were systematically optimized to separate the four algal toxins under investigation (microcystin YR, microcystin LR, microcystin RR and nodularin). The optimum separation conditions were: 30 mM borax, 9 mM sodium dodecyl sulphate, pH 9.18, 30 kV applied voltage, 10 s hydrodynamic injection, 70 cm x 50 Ilm Ld. bare fused silica capillary (LEFF 40 cm) and UV detection at 238 nm. Under these conditions, typical detection limits were in the low ng/IlL range (14.13 ng/IlL for microcystin LR to 29.85 ng/ILL for nodularin). The MECC method was evaluated in terms of migration time precision, efficiency and resolution, peak area and normalised peak area precision. Standard deviation values for retention times acquired using replicate electrokinetic injections ranged from 0.018 to 0.054 and 0.069 to 0.148 for hydrodynamic injections. Normalised peak area precision for replicate hydrodynamic injections were in the range 84 to 97 % RSD, while improved % RSD values of 11.5 to 18.7 were achieved for electrokinetic injections. Due to poor precision resulting from the lack of automation on the laboratory built CE system, poor correlation between increasing concentration and a corresponding change in normalised peak areas were achieved. The MECC method developed was applied to the analysis of an algal scum extract to illustrate the technique. A general problem with CE is that it suffers from poor detection sensitivity. Hence in this study, alternative injection modes, sample concentration strategies and alternative detection techniques were investigated in an attempt to improve detection limits for algal toxins. Using optimized electrokinetic injection conditions, detection limits were five to ten times better than those obtained with hydrodynamic injections. On-line sample concentration methods were partially successful. Field amplified back and forth MECC in which analyte injected in the entire column volume and subsequently focused in a narrow band by manipulating the electric field, resulted in an enormous sensitivity enhancement that ranged from 197 times for microcystin RR to 777 times for microcystin YR when compared to hydrodynamic injections. Field amplified sample stacking (FASI) was ineffective for toxin preconcentration, while electro-extraction produced detection limits ranging from 0.27 ng/J.tL for microcystin YR to 1.08 ng/J.tL for microcystin RR. Solid phase extraction, in which analytes are first trapped and concentrated on HPLC material in a cartridge and then eluted in a more concentrated form for injection, was found to be practical only in the offline mode. A concentration detection limit of less than 0.002 ng/J.tL was obtained. Attempts with on-line solid phase extraction failed due to problems associated with coupling the cartridge with the separation capillary. Finally, laser induced fluorescence (LIF) detection was investigated as an alternative to UV detection. Unfortunately, the algal toxins were not amenable to LIF detection because tagging with the fluorescent moiety, fluorescein isothiocyanate (FITC), was prevented by the stereochemistry of these cyclic peptides. A comparative study between HPLC and MECC revealed that the former displayed poor efficiency peaks and long analysis times for toxin analysis. However HPLC was superior in terms of retention time precision (0.12 to 0.64 % RSD) and area precision (1.78 to 2.86 % RSD). Mass detection limits for MECC (0.0142 to 0.0603 ng) were far superior to those achieved by HPLC (0.55 to 1.025 ng). In addition to HPLC and MECC, a preliminary investigation of micro-high performance liquid chromatography (J.tHPLC) and capillary electrochromatography (CEC) for the analysis of algal toxins was made using 50 J.tm Ld. capillary columns packed in-house, with reverse phase HPLC packing material. / Thesis (M.Sc.)-University of Natal, 1997.

<em>Cladophora glomerata</em> is a filamentous green alga that currently forms extensive blooms in nearshore areas of Lake Ontario, eastern Lake Erie, Lake Michigan, and isolated locations in Lake Huron. The biomass, areal coverage, algal bed characteristics, and tissue phosphorus concentrations of <em>Cladophora glomerata</em> were measured at 24 nearshore rocky sites along the northern shoreline of Lake Erie?s eastern basin between 1995-2002. Midsummer areal coverage at shallow depths (&le;5m) ranged from 4-100 %, with a median value of 96%. Peak seasonal biomass ranged from <1 to 940 g m^-2 dry mass (DM), with a median value of 171 g m^-2 DM. Tissue phosphorus varied seasonally, with initial high values in early May (0. 15 to 0. 27 % DM; median 0. 23 % DM) to midsummer seasonal low values during peak biomass (0. 03 to 0. 23 % DM; median 0. 06 % DM). A numerical <em>Cladophora</em> growth model (CGM) was revised and field-tested at 5 sites in eastern Lake Erie during 2002. The CGM is useful for: 1) Predicting <em>Cladophora</em> growth, biomass, and tissue phosphorus concentrations under non-point source P loading with no depth restrictions; 2) providing estimates of the timing and magnitude of the midsummer sloughing phenomenon; 3) determining the contribution of <em>Dreissena</em> invasion to the resurgence of <em>Cladophora</em> in eastern Lake Erie; and 4) developing management strategies for <em>Cladophora</em> abatement. The CGM was applied to investigate how the spatial and temporal patterns of <em>Cladophora</em> growth were influenced by the natural variability in environmental parameters in eastern Lake Erie. Seasonal patterns in <em>Cladophora</em> growth were strongly influenced by temperature, and peak depth-integrated biomass was strongly influenced by both available light and phosphorus. The photosynthetic capacity of field collected <em>Cladophora</em> was a poor predictor of the mid-summer sloughing phenomenon. The CGM, however, predicted that self-shading within the dense <em>Cladophora</em> mats would have caused negative growth rates at the base of the dense mats for 14 days prior to the sloughing event. The metabolic imbalances at the base of the <em>Cladophora</em> mats were driven primarily by the availability of light and were exacerbated by intermediate water temperatures (~23??C). The excellent agreement between model simulations and field data illustrates the ability of the CGM to predict tissue P and growth over a range of sites and depths in eastern Lake Erie and suggests potential for the model to be successfully applied in other systems.

This work investigates, for the first time, the Pseudo-nitzschia (PN) dynamics in the western English Channel (L4) and the environmental factors impacting on domoic acid (DA) production in these waters. This is combined with laboratory studies examining key environmental factors and the multifactorial impact of multiple macronutrient and micronutrient availability on PN growth and DA production. An LC-MS method was established, optimised, and compared with ELISA for the accurate and reproducible extraction and determination of particulate and dissolved DA. The method was used to measure the seasonal variation in DA at L4 during 2009 and this was compared to PN seasonal abundance and diversity. Three groups a P. delicatissima-group, a P. seriata-group, and a P. pungens/multiseries-group were identified and were found to have different ecological distributions with the latter two groups significantly correlating with DA concentration. Macronutrients, in combination with other environmental factors, were found to influence PN populations at L4. Multifactorial laboratory culture experiments investigating the availability of nitrate, phosphate, and silicate, confirmed that the interrelatedness of all these nutrients significantly affected the growth, decline, and DA production of P. multiseries, and highlight the importance of both phosphate and silicate availability for DA production. When the impacts of both macronutrient (phosphate and silicate) and micronutrient (iron and copper) availability were investigated, limited growth and DA production was observed in P. multiseries cultures. Results revealed the complexity and interrelationship of factors affecting both PN growth and DA production. Furthermore, molecular methods were developed to elucidate the PN species present from 2009 Lugol’s-preserved L4 samples. DNA was successfully extracted and amplified from these samples which had been stored for up to 2 years. Initial sequence analysis identified the rbcL DNA marker as an informative site for future work with a number of L4 sequences closely relating to different Pseudo-nitzschia spp.

With the global rise in frequency of harmful algal blooms in estuarine environments comes an increase in prevalence of toxic metabolites, such as microcystin (MC), that some of the cyanobacteria involved will produce. At high concentrations, MC may accumulate in consumer tissues and have deleterious effects on organisms; however impacts of the toxin on aquatic living resources at ecologically relevant concentrations have not been widely documented. We analyzed the effects of MC on juveniles of five fish species from the James River, Virginia to determine if MC has the potential to impede growth. Using three separate experimental approaches, it was shown that exposure to concentrations of the toxin currently observed in the James River estuary do not appear to significantly impact the growth or survivorship of tested fish species. Extraneous factors in parts of the study led to an inability to draw clear conclusions on mortality or growth impacts; however it is evident from the experiments that at least some of the fish species have biological mechanisms in place that allow them to effectively eliminate the toxin from their systems. An ability to extricate the toxin suggests the possibility for fishes to withstand MC exposures and sustain few negative health impacts at low MC concentrations.