Removal of microcystins from a waste stabilisation lagoon: Evaluation of a packed-bed continuous flow TiO2 reactor.

Photocatalysis has been shown to successfully remove microcystins (MC) in laboratory experiments. Most research to date has been performed under ideal conditions in pure or ultrapure water. In this investigation the efficiency of photocatalysis using titanium dioxide was examined in a complex matrix (waste stabilisation lagoon water). A flow-through photocatalytic reactor was used for the photocatalytic removal of four commonly occurring microcystin analogues (MC-YR, MC-RR, MC-LR, and MC-LA). Up to 51% removal for single MC analogues in waste lagoon water was observed. Similar removal rates were observed when a mixture of all four MC analogues was treated. Although treatment of MC-containing cyanobacterial cells of Microcystis aeruginosa resulted in no decline in cell numbers or viability with the current reactor design and treatment regime, the photocatalytic treatment did improve the overall quality of waste lagoon water. This study demonstrates that despite the presence of natural organic matter the microcystins could be successfully degraded in a complex environmental matrix.

Diagnosing water treatment critical control points for cyanobacterial removal: Exploring benefits of combined microscopy, next-generation sequencing, and cell integrity methods.

A wide range of cyanobacterial species and their harmful metabolites are increasingly detected in water bodies worldwide, exacerbated by climate change and human activities. The resulting bloom conditions represent significant challenges to production of safe drinking water and cost effective water reuse, therefore their removal is a priority to ensure public safety. While current microscopic taxonomy identification methods provide valuable information about cell numbers during treatment, these methods are incapable of providing information about the fate of cells during treatment. The objectives of this study were to (1) identify the critical control points for breakthrough and accumulation of cells by investigating the fate of cells during treatment processes using a combination of taxonomy, cell integrity and next-generation sequencing (NGS), and (2) assess the impact of pre-treatment processes on breakthrough prevention at critical control points, and the benefits of cell integrity and NGS analysis for improved management purposes. This paper presents the results of an unprecedented cyanobacterial monitoring program conducted in four full scale water treatment plants located in three different climate zones. Cyanobacterial cell integrity and accumulation during operation process were assessed for the first time using next generation of gene sequencing methods. NGS analysis led to detection of cyanobacterial and melainabacteria orders in water samples that were not identified by microscopy. 80 ±â€¯5% of cells were completely lysed post pre-oxidation (for both ozone and potassium permanganate). However unlike pre-ozonation, the remaining cells were undamaged cells with the potential to accumulate and grow within the plants post-KMnO4 treatment, particularly in clarifier sludge. To effectively monitor water quality, this study presents a synergistic approach coupling new and traditional analytical methods and demonstrates the importance of identifying critical points for managing accumulation of cyanobacteria within plants.

Treatment challenge of a cyanobacterium Romeria elegans bloom in a South Australian wastewater treatment plant - a case study.

A bloom of the non-toxic cyanobacterium Romeria elegans in waste stabilisation ponds (WSPs) within Angaston waste water treatment plant (WWTP) has posed an unprecedented treatment challenge for the local water utility. The water from the WSPs is chlorinated for safety prior to reuse on nearby farmland. Cyanobacteria concentrations of approximately 1.2 × 106 cells mL-1 increased the chlorine demand dramatically. Operators continuously increased the disinfectant dose up to 50 mg L-1 to achieve operational guideline values for combined chlorine (0.5-1.0 mg L-1) prior to reuse. Despite this, attempts to achieve targeted combined chlorine residual (CCR) failed. In this study, samples from the waste stabilisation pond at Angaston WWTP were chlorinated over a range of doses. Combined chlorine, disinfection by-product formation, cyanobacteria cell concentration, Escherichia coli inactivation, as well as dissolved organic carbon and free ammonia were monitored. This study shows that, in the occurrence of cyanobacterial blooms, CCR does not directly suggest pathogen removal efficiency and is therefore not an ideal parameter to evaluate the effectiveness of disinfection process in WWTP. Instead, E. coli removal is a more direct and practical parameter for the determination of the efficiency of the disinfection process.

Fate of cyanobacteria in drinking water treatment plant lagoon supernatant and sludge.

In conventional water treatment processes, where the coagulation and flocculation steps are designed to remove particles from drinking water, cyanobacteria are also concentrated into the resultant sludge. As a consequence, cyanobacteria-laden sludge can act as a reservoir for metabolites such as taste and odour compounds and cyanotoxins. This can pose a significant risk to water quality where supernatant from the sludge treatment facility is returned to the inlet to the plant. In this study the complex processes that can take place in a sludge treatment lagoon were investigated. It was shown that cyanobacteria can proliferate in the conditions manifest in a sludge treatment lagoon, and that cyanobacteria can survive and produce metabolites for at least 10days in sludge. The major processes of metabolite release and degradation are very dependent on the physical, chemical and biological environment in the sludge treatment facility and it was not possible to accurately model the net effect. For the first time evidence is provided to suggest that there is a greater risk associated with recycling sludge supernatant than can be estimated from the raw water quality, as metabolite concentrations increased by up to 500% over several days after coagulation, attributed to increased metabolite production and/or cell proliferation in the sludge.

Impact of UV-H2O2 Advanced Oxidation and Aging Processes on GAC Capacity for the Removal of Cyanobacterial Taste and Odor Compounds.

Cyanobacteria and their taste and odor (T&O) compounds are a growing concern in water sources globally. Geosmin and 2-methylisoborneol (MIB) are the most commonly detected T&O compounds associated with cyanobacterial presence in drinking water sources. The use of ultraviolet and hydrogen peroxide (H2O2) as an advanced oxidation treatment for T&O control is an emerging technology. However, residual H2O2 (>80% of the initial dose) has to be removed from water prior final disinfection. Recently, granular activated carbon (GAC) is used to remove H2O2 residual. The objective of this study is to assess the impact of H2O2 quenching and aging processes on GAC capacity for the removal of geosmin and MIB. Pilot columns with different types of GAC and presence/absence of H2O2 have been used for this study. H2O2 removal for the operational period of 6 months has no significant impact on GAC capacity to remove the geosmin and MIB from water.

Fate of geosmin and 2-methylisoborneol in full-scale water treatment plants.

The increasing frequency and intensity of taste and odour (T&O) producing cyanobacteria in water sources is a growing global issue. Geosmin and 2-methylisoborneol (MIB) are the main cyanobacterial T&O compounds and can cause complaints from consumers at levels as low as 10 ng/L. However, literature concerning the performance of full-scale treatment processes for geosmin and MIB removal is rare. Hence, the objectives of this study were to: 1) estimate the accumulation and breakthrough of geosmin and MIB inside full-scale water treatment plants; 2) verify the potential impact of sludge recycling practice on performance of plants; and, 3) assess the effectiveness of aged GAC for the removal of these compounds. Sampling after full-scale treatment processes and GAC pilot assays were conducted to achieve these goals. Geosmin and MIB monitoring in full-scale plants provided the opportunity to rank the performance of studied treatment processes with filtration and granular activated carbon providing the best barriers for removal of total and extracellular compounds, correspondingly. Geosmin was removed to a greater extent than MIB using GAC. Geosmin and MIB residuals in water post GAC contactors after two years of operation was 20% and 40% of initial concentrations, correspondingly. Biological activity on the GAC surface enhanced the removal of T&O compounds. These observations demonstrated that a multi-barrier treatment approach is required to ensure cyanobacteria and their T&O compounds are effectively removed from drinking water.

Extraction method for total microcystins in cyanobacteria-laden sludge.

Cyanobacteria in water treatment sludge pose a health risk as they continue to be viable, multiply, and produce potentially harmful secondary metabolites. To date, little research has focused on accurately determining cell bound microcystin (MC) concentrations of cyanobacterial cells in water treatment sludge. Three extraction methods (freeze-thaw, lyophilisation, direct methanolic extraction) with three different pre-treatments (homogenisation, (ultra)sonication, combination of both, and controls) were investigated for their MC extraction recovery. It was found that lyophilisation with prior sonication achieved the highest toxin recovery across the two MC analogues (MC-LR, MC-LA) tested. The method was able to extract 69 and 56% of MC-LR and MC-LA, respectively with good reproducibility. Comparable results were also obtained with direct methanolic extraction, with poor reproducibility. The least efficient method was freeze-thawing which achieved poor recoveries and was less reproducible. This study highlights a rapid, efficient, low-cost extraction method for determining total microcystins in cyanobacterial-laden sludge.

Fate of cyanobacteria and their metabolites during water treatment sludge management processes.

Cyanobacteria and their metabolites are an issue for water authorities; however, little is known as to the fate of coagulated cyanobacterial-laden sludge during waste management processes in water treatment plants (WTPs). This paper provides information on the cell integrity of Anabaena circinalis and Cylindrospermopsis raciborskii during: laboratory-scale coagulation/sedimentation processes; direct filtration and backwashing procedures; and cyanobacterial-laden sludge management practices. In addition, the metabolites produced by A. circinalis (geosmin and saxitoxins) and C. raciborskii (cylindrospermopsin) were investigated with respect to their release (and possible degradation) during each of the studied processes. Where sedimentation was used, coagulation effectively removed cyanobacteria (and intracellular metabolites) without any considerable exertion on coagulant demand. During direct filtration experiments, cyanobacteria released intracellular metabolites through a stagnation period, suggesting that more frequent backwashing of filters may be required to prevent floc build-up and metabolite release. Cyanobacteria appeared to be protected within the flocs, with minimal damage during backwashing of the filters. Within coagulant sludge, cyanobacteria released intracellular metabolites into the supernatant after 3d, even though cells remained viable up to 7d. This work has improved the understanding of cyanobacterial metabolite risks associated with management of backwash water and sludge and is likely to facilitate improvements at WTPs, including increased monitoring and the application of treatment strategies and operational practices, with respect to cyanobacterial-laden sludge and/or supernatant recycle management.

Removal of cyanobacterial metabolites through wastewater treatment plant filters.

Wastewaters have the potential to proliferate excessive numbers of cyanobacteria due to high nutrient levels. This could translate to the production of metabolites, such as the saxitoxins, geosmin and 2-methylisoborneol (MIB), which can impair the quality of wastewater destined for re-use. Biological sand filtration was assessed for its ability to remove these metabolites from a wastewater. Results indicated that the sand filter was incapable of effectively removing the saxitoxins and in some instances, the effluent of the sand filter displayed greater toxicity than the influent. Conversely, the sand filter was able to effectively remove geosmin and MIB, with removal attributed to biodegradation. Granular activated carbon was employed as an alternative filter medium to remove the saxitoxins. Results showed similar removals to previous drinking water studies, where efficient removals were initially observed, followed by a decrease in the removal; a consequence of the presence of competing organics which reduced adsorption of the saxitoxins.

Biological treatment options for cyanobacteria metabolite removal--a review.

The treatment of cyanobacterial metabolites can consume many resources for water authorities which can be problematic especially with the recent shift away from chemical- and energy-intensive processes towards carbon and climate neutrality. In recent times, there has been a renaissance in biological treatment, in particular, biological filtration processes, for cyanobacteria metabolite removal. This in part, is due to the advances in molecular microbiology which has assisted in further understanding the biodegradation processes of specific cyanobacteria metabolites. However, there is currently no concise portfolio which captures all the pertinent information for the biological treatment of a range of cyanobacterial metabolites. This review encapsulates all the relevant information to date in one document and provides insights into how biological treatment options can be implemented in treatment plants for optimum cyanobacterial metabolite removal.

Fate of toxic cyanobacterial cells and disinfection by-products formation after chlorination.

Drinking water sources in many regions are subject to proliferation of toxic cyanobacteria (CB). Chlorination of source water containing toxic cyanobacterial cells for diverse treatment purposes might cause cell damage, toxin release and disinfection by-products (DBP) formation. There is limited information available on chlorination of different toxic CB cells and DBP formation potentials. This work: (1) determines the extent of lysis and toxins/taste and odor compound release in chlorinated natural water from CB cells (Anabaena circinalis, Microcystis aeruginosa, Cylindrospermopsis raciborskii, and Aphanizomenon issatsckenka) from laboratory cultures and natural blooms; (2) assesses the rates of oxidation of toxins by free chlorine under environmental conditions; (3) studies the DBP formation associated with the chlorination of CB cell suspensions. With chlorine exposure (CT) value of <4.0 mg min/L >60% cells lost viability causing toxin release. Cell membrane damage occurred faster than oxidation of released toxins. Kinetic analysis of the oxidation of toxins in natural water revealed significant differences in their susceptibility to chlorine, saxitoxins being the easiest to oxidize, followed by cylindrospermopsin and microcystin-LR. Furthermore, concentrations of trihalomethanes and haloacetic acids (<40 µg/L) and N-nitrosodimethylamine (<10 ng/L) as chlorination by-products were lower than the guideline values even at the highest CT value (220 mg min/L). However, the DBP concentrations in environmental bloom conditions with very high cell numbers were over the guideline values.

Assessing granular media filtration for the removal of chemical contaminants from wastewater.

Granular media filtration was evaluated for the removal of a suite of chemical contaminants that can be found in wastewater. Laboratory- and pilot-scale sand and granular activated carbon (GAC) filters were trialled for their ability to remove atrazine, estrone (E1), 17α-ethynylestradiol (EE2), N-nitrosodimethylamine (NDMA), N-nitrosomorpholine (NMOR) and N-nitrosodiethylamine (NDEA). In general, sand filtration was ineffective in removing the contaminants from a tertiary treated wastewater, with the exception of E1 and EE2, where efficient removals were observed after approximately 150 d. Batch degradation experiments confirmed that the removal of E1 was through biological activity, with a pseudo-first-order degradation rate constant of 7.4 × 10(-3) h(-1). GAC filtration was initially able to effectively remove all contaminants; although removals decreased over time due to competition with other organics present in the water. The only exception was atrazine where removal remained consistently high throughout the experiment. Previously unreported differences were observed in the adsorption of the three nitrosamines, with the ease of removal following the trend, NDEA > NMOR > NDMA, consistent with their hydrophobic character. In most instances the removals from the pilot-scale filters were generally in agreement with the laboratory-scale filter, suggesting that there is potential in using laboratory-scale filters as monitoring tools to evaluate the performance of pilot- and possibly full-scale sand and GAC filters at wastewater treatment plants.

Application of powdered activated carbon for the adsorption of cylindrospermopsin and microcystin toxins from drinking water supplies.

Cylindrospermopsin (CYN) and microcystin are two potent toxins that can be produced by cyanobacteria in drinking water supplies. This study investigated the application of powdered activated carbon (PAC) for the removal of these toxins under conditions that could be experienced in a water treatment plant. Two different PACs were evaluated for their ability to remove CYN and four microcystin variants from various drinking water supplies. The removal of natural organic material by the PACs was also determined by measuring the levels of dissolved organic carbon and UV absorbance (at 254 nm). The PACs effectively removed CYN and the microcystins from each of the waters studied, with one of the PACs shown to be more effective, possibly due to its smaller particle diameter. No difference in removal of the toxins was observed using PAC contact times of 30, 45 and 60 min. Furthermore, the effect of water quality on the removal of the toxins was minimal. The microcystin variants were adsorbed in the order: MCRR > MCYR > MCLR > MCLA. CYN was found to be adsorbed similarly to MCRR.

Removal of cyanobacterial metabolites by nanofiltration from two treated waters.

Cyanobacterial metabolites, both toxic and non-toxic, are a major problem for the water industry. Nanofiltration (NF) may be an effective treatment option for removing organic micropollutants, such as cyanobacterial metabolites, from drinking water due to its size exclusion properties. A rapid bench scale membrane test (RBSMT) unit was utilised to trial four NF membranes to remove the cyanobacterial metabolites, microcystin, cylindrospermopsin (CYN), 2-methylisoborneol (MIB) and geosmin (GSM) in two treated waters sourced from the Palmer and Myponga water treatment plants. Membrane fouling was observed for both treated waters; however, only minor differences were observed between feed waters of differing natural organic matter (NOM) concentration. Low molecular weight cut-off (MWCO), or 'tight' NF, membranes afforded average removals above 90% for CYN, while removal by higher MWCO, or 'loose' NF membranes was lower. MIB and GSM were removed effectively (above 75%) by tight NF but less effectively by loose NF. Microcystin variants (MCRR, MCYR, MCLR, MCLA) were removed to above 90% by tight NF membranes; however, removal using loose NF membranes depended on the hydrophobicity and charge of the variant. Different NOM concentration in the treated waters had no effect on the removal of cyanobacterial metabolites.

A coagulation-powdered activated carbon-ultrafiltration--multiple barrier approach for removing toxins from two Australian cyanobacterial blooms.

Cyanobacteria are a major problem for the world wide water industry as they can produce metabolites toxic to humans in addition to taste and odour compounds that make drinking water aesthetically displeasing. Removal of cyanobacterial toxins from drinking water is important to avoid serious illness in consumers. This objective can be confidently achieved through the application of the multiple barrier approach to drinking water quality and safety. In this study the use of a multiple barrier approach incorporating coagulation, powdered activated carbon (PAC) and ultrafiltration (UF) was investigated for the removal of intracellular and extracellular cyanobacterial toxins from two naturally occurring blooms in South Australia. Also investigated was the impact of these treatments on the UF flux. In this multibarrier approach, coagulation was used to remove the cells and thus the intracellular toxin while PAC was used for extracellular toxin adsorption and finally the UF was used for floc, PAC and cell removal. Cyanobacterial cells were completely removed using the UF membrane alone and when used in conjunction with coagulation. Extracellular toxins were removed to varying degrees by PAC addition. UF flux deteriorated dramatically during a trial with a very high cell concentration; however, the flux was improved by coagulation and PAC addition.

Release and oxidation of cell-bound saxitoxins during chlorination of Anabaena circinalis cells.

Surface water sources are increasingly subject to proliferation of toxic cyanobacteria. Direct chlorination of source water containing toxic cyanobacterial cells for different treatment purposes might cause cell damage and toxin release. There is limited information available on chlorination of saxitoxins (STXs: saxitoxin, C-toxins, and gonyautoxins) produced by Anabaena circinalis. This work: (1) investigated the impact of chlorination on cell lysis and toxin/odor compound release in natural waters; (2) assessed the rates of chlorination of total STXs, and (3) estimated apparent rate constants for STX oxidation in ultrapure and natural waters. With a chlorine exposure (CT) value of 7.0 mg x min/L all cells lost viability causing toxin release. Cell-membrane damage occurred faster than released STXs oxidation. All saxitoxin and more than 95% of other STX analogues were subsequently oxidized. Kinetic analysis of the oxidation of STX analogues revealed significant differences in the susceptibility to chlorine, saxitoxin being the easiest to oxidize. Also, concentrations of trihalomethanes, haloacetic acids, and N-nitrosodimethylamine as chlorination byproducts were respectively <50 µg/L and 11 ng/L even at the highest CT value (50.3 mg x min/L).

Determining the fate of Microcystis aeruginosa cells and microcystin toxins following chloramination.

The cyanobacterium Microcystis aeruginosa can produce potent toxins known as microcystins. While many studies have focussed on the chlorination of microcystin toxins, little work has been conducted with respect to the chloramination of the microcystins. In addition, no studies have been reported on the effect of chloramination on intact Microcystis cells. This study was conducted to determine the fate of M. aeruginosa cells and microcystin toxins following chloramination of a drinking water source. Results indicate that monochloramine could effectively oxidise dissolved microcystin-LR (MCLR) provided high CT values were employed, typically greater than 30,000 mg min L(-1). The decay of MCLR was demonstrated to be a pseudo first-order reaction with rate constants ranging from 9.3x10(-7) to 1.1x10(-5) s(-1) at pH 8.5. However, in the presence of Microcystis cells, monochloramine was ineffective in oxidising microcystin toxins due to the cells exerting a demand on the oxidant. The doses of monochloramine applied (2.8 and 3.5 mg L(-1)) were shown to rapidly release intracellular microcystins into the dissolved state. Flow cytometric analysis of the cells determined that the lower monochloramine dose did not compromise the cell membrane integrity, even though microcystins were rapidly released from the cells. In contrast the higher monochloramine dose resulted in cell membrane disruption with up to 90% of the cells shown to be non-viable after the high dose was applied.

Investigations into the biodegradation of microcystin-LR in wastewaters.

Microcystins are potent hepatotoxins that can be produced by cyanobacteria. These organisms can proliferate in wastewaters due to a number of factors including high concentrations of nutrients for growth. As treated wastewaters are now being considered as supplementary drinking water sources, in addition to their frequent use for irrigated agriculture, it is imperative that these wastewaters are free of toxins such as microcystins. This study investigated the potential for biodegradation of microcystin-LR (MCLR) in wastewaters through a biological sand filtration experiment and in static batch reactor experiments. MCLR was effectively removed at a range of concentrations and at various temperatures, with degradation attributed to the action of microorganisms indigenous to the wastewaters. No hepatotoxic by-products were detected following the degradation of MCLR as determined by a protein phosphatase inhibition assay. Using TaqMan polymerase chain reaction, the first gene involved in bacterial degradation of MCLR (mlrA) was detected and the responsible bacteria shown to increase with the amount of MCLR being degraded. This finding suggested that the degradation of MCLR was dependent upon the abundance of MCLR-degrading organisms present within the wastewater, and that MCLR may provide bacteria with a significant carbon source for proliferation; in turn increasing MCLR removal.

Optimising water treatment practices for the removal of Anabaena circinalis and its associated metabolites, geosmin and saxitoxins.

The cyanobacterium Anabaena circinalis has the ability to co-produce geosmin and saxitoxins, compounds which can compromise the quality of drinking water. This study provides pertinent information in optimising water treatment practices for the removal of geosmin and saxitoxins. In particular, it demonstrates that pre-oxidation using potassium permanganate could be applied at the head of water treatment plants without releasing intracellular geosmin and saxitoxins from A. circinalis. Furthermore, powdered activated carbon (PAC) was shown to be an effective treatment barrier for the removal of extracellular (dissolved) geosmin and saxitoxins, with similar adsorption trends of both compounds. The relative removal of the saxitoxins compared with geosmin was determined to be 0.84 +/- 0.27, which implies that saxitoxin removal with PAC can be estimated to be approximately 60 to 100% of the removal of geosmin under equivalent conditions. Chlorine was shown to be effective for the oxidation of the saxitoxins with CT values of approximately 30 mg min l(-1) required for greater than 90% destruction of the saxitoxins.