Rita K. Henderson

Fluorescence as a potential monitoring tool for recycled water systems: a review.

A rapid, highly sensitive and selective detector is urgently required to detect contamination events in recycled water systems - for example, cross-connection events in dual reticulation pipes that recycle advanced treated sewage effluent - as existing technologies, including total organic carbon and conductivity monitoring, cannot always provide the sensitivity required. Fluorescence spectroscopy has been suggested as a potential monitoring tool given its high sensitivity and selectivity. A review of recent literature demonstrates that by monitoring the fluorescence of dissolved organic matter (DOM), the ratios of humic-like (Peak C) and protein-like (Peak T) fluorescence peaks can be used to identify trace sewage contamination in river waters and estuaries, a situation analogous to contamination detection in recycled water systems. Additionally, strong correlations have been shown between Peak T and biochemical oxygen demand (BOD) in rivers, which is indicative of water impacted by microbial activity and therefore of sewage impacted systems. Hence, this review concludes that the sensitive detection of contamination events in recycled water systems may be achieved by monitoring Peak T and/or Peak C fluorescence. However, in such systems, effluent is treated to a high standard resulting in much lower DOM concentrations and the impact of these advanced treatment processes on Peaks T and C fluorescence is largely unknown and requires investigation. This review has highlighted that further work is also required to determine (a) the stability and distinctiveness of recycled water fluorescence in relation to the treatment processes utilised, (b) the impact of matrix effects, particularly the impact of oxidation, (c) calibration issues for online monitoring, and (d) the advanced data analytical techniques required, if any, to improve detection of contamination events.

Characterisation of algogenic organic matter extracted from cyanobacteria, green algae and diatoms

Algogenic organic matter (AOM) can interfere with drinking water treatment processes and comprehensive characterisation of AOM will be informative with respect to treatability. This paper characterises the AOM originating from four algae species (Chlorella vulgaris, Microcystis aeruginosa, Asterionella formosa and Melosira sp.) using techniques including dissolved organic carbon (DOC), specific UV absorbance (SUVA), zeta potential, charge density, hydrophobicity, protein and carbohydrate content, molecular weight and fluorescence. All AOM was predominantly hydrophilic with a low SUVA. AOM had negative zeta potential values in the range pH 2-10. The stationary phase charge density of AOM from C. vulgaris was greatest at 3.2 meq g(-1) while that of M. aeruginosa and Melosira sp. was negligible. Lower charge density was related to higher hydrophobicity, while it was related in turn to increasing proteins >500 kDa:carbohydrate ratio. This demonstrates that AOM is of a very different character to natural organic matter (NOM).

The impact of algal properties and pre-oxidation on solid–liquid separation of algae

Algae are traditionally classified according to biological descriptors which do not give information on surface characteristics that are important with respect to removal by water treatment processes. This review examines the character of freshwater algal populations from a water treatment perspective and evaluates the impact of their varying properties and the use of pre-oxidation on their removal by solid-liquid separation processes.. The characteristics shown to impact on treatment were morphology, motility, surface charge, cell density and the extracellular organic matter (EOM) composition and concentration. With the exception of density, these are not phyla specific. It was also shown that dissolved air flotation (DAF) was the most robust clarification method, where up to 99.8% removal was achieved compared to 94% for sedimentation when using metal coagulants. However, successful clarification relied heavily on the optimisation of preceding coagulation and flocculation and coagulant demand was important in this respect. Comparison of all available data reveals a relationship between cell surface area and coagulant demand. It is thus suggested that cell surface area would provide a basis for regrouping algae such that the classification is informative with respect to water treatment. However, the absolute coagulant demand is a result of both surface area and EOM influences. The latter are relatively poorly understood in comparison to natural organic matter (NOM) systems and this remains a limit in current knowledge.

Organic matter fluorescence in municipal water recycling schemes: Toward a unified PARAFAC model

Organic matter (OM) is a ubiquitous constituent of natural waters quantifiable at very low levels using fluorescence spectroscopy. This technique has recognized potential in a range of applications where the ability to monitor water quality in real time is desirable, such as in water treatment systems. This study used PARAFAC to characterize a large (n=1479) and diverse excitation emission matrix (EEM) data set from six recycled water treatment plants in Australia, for which sources of variability included geography, season, treatment processes, pH and fluorometer settings. Five components were identified independently in four or more plants, none of which were generated during the treatment process nor were typically entirely removed. PARAFAC scores could be obtained from EEMs by simple regression. The results have important implications for online monitoring of OM fluorescence in treatment plants, affecting choices regarding experimental design, instrumentation and the optimal wavelengths for tracking fluorescent organic matter through the treatment process. While the multimodel comparisons provide a compelling demonstration of PARAFACs ability to distill chemical information from EEMs, deficiencies identified through this process have broad implications for interpreting and reusing (D)OM-PARAFAC models.

The impact of differing cell and algogenic organic matter (AOM) characteristics on the coagulation and flotation of algae.

The aim of this study was to compare the coagulation and flotation of different algae species with varying morphology and algogenic organic matter (AOM) composition in order to link physical and chemical algae characteristics to treatment. Microcystis aeruginosa (cyanobacteria), Chlorella vulgaris (green algae), Asterionella formosa and Melosira sp. (diatoms) were treated by coagulation with aluminium sulphate and flotation. The AOM was extracted and treated separately. Analyses included cell counts, dissolved organic carbon, aluminium residual and zeta potential. Removal efficiencies in the range 94-99% were obtained for each species. Cells, AOM and aluminium were concurrently removed at a coagulant dose that was related on a log-log basis to both cell surface area and total charge density, although the relationship was much stronger for the latter. This was attributed to a significant proportion of the coagulant demand being generated by the AOM. The implications of such findings are that relatively simple charge measurements can be used to understand and control coagulation and flotation of algae.

Water extractable organic carbon in untreated and chemical treated biochars.

Biochar, as a soil amendment, can increase concentrations of soil organic matter, especially water-extractable organic carbon (WEOC). This can affect the adsorption-desorption equilibrium between the dissolved solid phases in soil organic matter. Dissolved organic carbon (DOC) represents a small proportion of soil organic matter, but is of significant importance in the soil ecosystem due to its mobility and reactivity. Here, water extracts obtained from twelve non-herbaceous biochars (before, and after, chemical treatment with either H(3)PO(4) or KOH), were tested by Liquid Chromatography - Organic Carbon Detection (LC-OCD) to identify the effects of both pyrolysis conditions and chemical treatments on WEOC content. LC-OCD has the capacity to provide a fingerprint of WEOC, which allows analysis of the various fractions present. WEOC content was affected by both the pyrolysis temperature and the feedstock used. High mineral ash contents deriving from the feedstock can prompt thermochemical reactions of lignocelluloses to produce a relatively high WEOC content, which includes low molecular weight neutrals and humic acids as dominant components. A significant change in WEOC occurred during pyrolysis due to secondary reactions which resulted in a much lower WEOC in the high temperature biochars where fractions of low molecular weight acids and neutrals are dominant. Chemical treatments with H(3)PO(4) or KOH increased WEOC concentration, possibly by promoting hydrolysis reactions on biochar surfaces. These observations assist in assessing the contribution of biochar additions to the soil ecosystem and demonstrate the utility of LC-OCD in providing an understanding of how biochar additions to soil can alter DOC.

Successful Removal of Algae through the Control of Zeta Potential

Abstract Algae can interfere with treatment processes at a water treatment works. Coagulation control is critical to reduce the impact of algae on downstream processes. This paper investigates the coagulation and flotation of four species of algae – Asterionella formosa, Melosira sp., Microcystis aeruginosa, and Chlorella vulgaris. The zeta potential at optimum removal was measured and it was observed that when the zeta potential was reduced to between −8 mV and +2 mV, removal of algae and associated organic material was optimized, irrespective of the coagulant dose or pH. Process control using zeta potential is therefore a viable tool for algae removal.

Fluorescence monitoring at a recycled water treatment plant and associated dual distribution system--implications for cross-connection detection.

Dual distribution systems are becoming increasingly common in greenfield housing developments in Australia for the redistribution of recycled water to households for non-potable use. Within such schemes there exists the potential for cross-connections between recycled and drinking water systems. Due to the high level of recycled water treatment, these events are unlikely to lead to outbreaks of illness in the community. Nonetheless, they do represent a breach of the recycled water risk management strategy and therefore an elevated level of risk to consumers. Furthermore, cross-connection events have the potential to undermine public confidence in these types of water recycling. A rapid, highly sensitive method of cross-connection detection may therefore provide an additional level of confidence in these schemes. The aim of this research was to determine the potential for using fluorescence spectroscopy as a monitoring tool in water treatment plants and dual distribution systems. Samples from both the water recycling plant and dual distribution system were collected on a weekly basis over 12 weeks. Fluorescence excitation-emission matrix (EEM) spectra and water quality parameters including dissolved organic carbon, UV(254), pH, conductivity, free chlorine and turbidity were obtained for each sample. The fluorescence EEM spectra of recycled and drinking water were distinctly different and exhibited low variability throughout the course of the sampling program, indicating a degree of stability of the fluorescent components within the organic matter. A ten-fold difference in mean fluorescence intensity was observed for recycled water compared to drinking water, which was greater than the difference observed for the other measured water quality parameters. Probabilistic analysis was used to determine the reliable detection limit of recycled water contamination of drinking water. Accounting for the inherent variability of both recycled water and drinking water, a 45% contamination of recycled water in drinking water could be detected with a signal-to-noise ratio greater than 3 for more than 95% of individual random sample pairs. Greater sensitivity can be assured by averaging numerous samples. In comparison, a 70% contamination of recycled water in drinking water was required for the same detection using conductivity.

The Potential for Using Bubble Modification Chemicals in Dissolved Air Flotation for Algae Removal

Abstract This paper investigates the potential for using surface modified bubbles in the treatment of algae using dissolved air flotation (DAF) instead of upstream coagulation and flocculation. Bubble modification is attempted by adding either metal coagulant, surfactant or polymers direct to the saturator. In this way, the chemical characteristics most suitable for removing small algae cells using this technique are examined. Optimum removal using metal coagulant, aluminium sulphate, was 60%; however, both a decrease in the magnitude of the zeta potential and microfloc generation occurred concurrently, thus accounting for the improved removal. In contrast, there was no change in system zeta potential and no microfloc generation when using cationic surfactant cetyltrimethyl-ammonium bromide (CTAB), for which 63% removal was achieved. An average of 95% removal was achieved using the cationic polymer, PolyDADMAC, with no change to system zeta potential. The results therefore confirm that there is a potential for adapting the conventional DAF process to operate without upstream coagulation and flocculation. A chemical with both a hydrophobic component in addition to a high molecular weight, hydrophilic, highly charge component is advised for the process.

Examination of the physical properties of Microcystis aeruginosa flocs produced on coagulation with metal salts.

Coagulation-flocculation (C-F) is a key barrier to cyanobacterial and algal cell infiltration in water treatment plants during seasonal blooms. However, the resultant cell floc properties, in terms of size, strength and density, which dominate under different coagulation conditions and govern cell removal, are not well understood. This paper investigated the floc properties produced during C-F of the cyanobacterium, Microcystis aeruginosa, under low and high doses of aluminium sulphate and ferric chloride coagulants and at different pH values, so as to promote charge neutralisation (CN) and sweep flocculation (SF) dominant conditions (or a combination of these). It was demonstrated that application of ferric chloride produced larger flocs that resulted in higher cell removal during jar testing. These flocs were also larger than those observed for natural organic matter (NOM) and kaolin, suggesting a role of algogenic organic matter (AOM) as an inherent bioflocculant. Under SF conditions, stronger flocs were produced; however, these had lower capacity for size recovery after exposure to high shear. Analysis of particle size distribution demonstrated that large scale fragmentation followed by erosion dominated for CN while erosion dominated under SF conditions. Overall, marked differences were observed dependent on the coagulation regime imposed that have implications for improving robustness of cell removal by downstream separation processes. While the cyanobacterium, M. aeruginosa, appeared to share general floc characteristics commonly observed for NOM and kaolin flocs, there were distinct differences in terms of size and strength, which may be attributed to AOM.