Release of algal organic matter from cyanobacteria following application of USEPA-registered chemical algaecides.

Increased occurrence of harmful algal blooms significantly impedes uses of freshwater resources, especially as potable water supply. Rapid mitigation using algaecides is common; however, the potential release of algal organic matter (AOM) and cyanotoxins poses challenges due to the difficulty of removal with conventional water treatment and negative health impacts. This study evaluated four USEPA-registered algaecides for their efficacy against Microcystis aeruginosa growth and AOM and cyanotoxin release. Successful inhibition of cell growth was achieved in both unialgal and mixed culture samples at concentrations of 0.2 mg Cu/L for copper-based algaecides and 6 mg H2O2/L for peroxide-based algaecides. At 12 h after treatment (HAT), a significant increase in dissolved phycocyanin was observed, which was more pronounced with copper-based algaecides. Microbial byproduct-related and simple aromatic proteins were measured in the unialgal culture, while microbial byproduct-related proteins and humic-like substances were dominant in the mixed culture samples. In both unialgal and mixed-culture experiments, 0.2 mg Cu/L application of copper-based algaecides was the minimum dosage for cyanobacterial cell inhibition and the lowest release of AOM and cyanotoxins, with Oximycin P5 at 6 mg H2O2/L yielding similar results among peroxide-based algaecides. These results help inform water supply managers on algaecide use toward maintaining integrity of drinking water quality.

Most treatments to control freshwater algal blooms are not effective: Meta-analysis of field experiments.

Harmful algal blooms negatively impact freshwater, estuarine, and marine systems worldwide, including those used for drinking water, recreation, and aquaculture, through the production of toxic and nontoxic secondary metabolites as well as hypoxic events that occur when algal blooms degrade. Consequently, water resource managers often utilize chemical, bacterial, physical, and/or plant-based treatments to control algal blooms and improve water quality. However, awareness of available treatments may be limited, and there is ambiguity among the effects of algal bloom treatments across studies. Such variation within the literature and lack of knowledge of other tested treatments leave uncertainty for water resource managers when deciding what treatments are best to control algal blooms and improve water quality. Our primary objective was to synthesize data from 39 published and unpublished studies that used one of 28 chemical, bacterial, physical, and/or plant-based treatments in field experiments on various water quality measurements, including phytoplankton pigments and cell density, cyanobacterial toxins (microcystin), and common off-flavors (i.e., taste and odor compounds; geosmin and 2-methylisoborneol). We hypothesized that treatments would improve water quality. Across all studies and treatment types (227 effect sizes), water quality improvements were observed when measured at the time of greatest decline following treatment or at the end of the experiment. However, these findings were primarily mediated by only four chemicals, namely copper sulfate, hydrogen peroxide, peracetic acid, and simazine. None of the bacterial, physical, or plant-based treatments were shown to significantly improve water quality by themselves. Results from this synthesis quantitatively showed that most treatments fail to improve water quality in the field and highlight the need for more research on existing and alternative treatments.

Comparative assessment of algaecide performance on freshwater phytoplankton: Understanding differential sensitivities to frame cyanobacteria management.

Cyanobacterial bloom represent a growing threat to global water security. With fast proliferation, they raise great concern due to potential health and socioeconomic concerns. Algaecides are commonly employed as a mitigative measure to suppress and manage cyanobacteria. However, recent research on algaecides has a limited phycological focus, concentrated predominately on cyanobacteria and chlorophytes. Without considering phycological diversity, generalizations crafted from these algaecide comparisons present a biased perpective. To limit the collateral impacts of algaecide interventions on phytoplankton communities it is critical to understand differential phycological sensitivities for establishing optimal dosage and tolerance thresholds. This research attempts to fill this knowledge gap and provide effective guidelines to frame cyanobacterial management. We investigate the effect of two common algaecides, copper sulfate (CuSO4) and hydrogen peroxide (H2O2), on four major phycological divisions (chlorophytes, cyanobacteria, diatoms, and mixotrophs). All phycological divisions exhibited greater sensitivity to copper sulfate, except chlorophytes. Mixotrophs and cyanobacteria displayed the highest sensitivity to both algaecides with the highest to lowest sensitivity being observed as follows: mixotrophs, cyanobacteria, diatoms, and chlorophytes. Our results suggest that H2O2 represents a comparable alternative to CuSO4 for cyanobacterial control. However, some eukaryotic divisions such as mixotrophs and diatoms mirrored cyanobacteria sensitivity, challenging the assumption that H2O2 is a selective cyanocide. Our findings suggest that optimizing algaecide treatments to suppress cyanobacteria while minimizing potential adverse effects on other phycological members is unattainable. An apparent trade-off between effective cyanobacterial management and conserving non-targeted phycological divisions is expected and should be a prime consideration of lake management.

Effect of three commercial algaecides on cyanobacteria and microcystin-LR: implications for drinking water treatment using activated carbon.

Toxic cyanobacterial blooms in aquatic ecosystems are associated to both public health and environmental concerns worldwide. Depending on the treatment technologies used, the removal capacity of cyanotoxins by drinking water treatment plants (DWTPs) is not sufficient to reach safe levels in drinking water. Likewise, controlling these blooms with algaecide may impair the efficiency of DWTPs due to the possible lysis of cyanobacterial cells and consequent release of cyanotoxins. We investigated the effects of three commercial algaecides (cationic polymer, copper sulfate, and hydrogen peroxide) on the growth parameters of the cyanobacterium Microcystis aeruginosa and the release of microcystin-LR (MC-LR). The potential interference of each algaecide on the MC-LR removal by adsorption on activated carbon (AC) was also tested through adsorption isotherms and kinetics experiments. Most algaecides significantly decreased the cell density and biovolume of M. aeruginosa, as well as increased the release of MC-LR. Interestingly, the presence of the algaecides in binary mixtures with MC-LR affected the adsorption of the cyanotoxin. Relevant adsorption parameters (e.g., maximum adsorption capacity, adsorption intensity, and affinity between MC-LR and AC) were altered when the algaecides were present, especially in the case of the cationic polymer. Also, the algaecides influenced the kinetics (e.g., by shifting the initial adsorption and the desorption constant), which may directly affect the design and operation of DWTPs. Our study indicated that algaecides can significantly impact the fate and the removal of MC-LR in DWTPs when the adsorption process is employed, with important implications for the management and performance of such facilities.

New is not always better: Toxicity of novel copper based algaecides to Daphnia magna.

In this study, the effects of traditional copper (CuSO4.5H2O) and novel copper algaecides (Captain XTR, SeClear and Lake Guard Blue) were tested on Daphnia magna under acute (48 h) and chronic (21 d) exposure scenarios. The EC50 values calculated in the acute tests were between 0.5 and 0.6 mg Cu L-1 for all four compounds. Lake Guard Blue and CuSO4.5 H2O were more toxic than SeClear and Captain XTR. During the chronic test, the effects of SeClear (EC50: 0.274 mg Cu L-1) on reproduction and body length were larger than the effects of the other three copper-based algaecides (EC50: 0.436 mg Cu L-1 for CuSO4.5 H2O, 0.498 mg Cu L-1 for Captain XTR, and 0.295 mg Cu L-1 for Lake Guard Blue). Captain XTR had the strongest negative effect on body weight, whereas body weight was affected the least by CuSO4.5 H2O. The four copper compounds affected the age at first brood significantly, which was delayed by 1.8, 2.0, 2.3 and 3.2 days for Captain XTR, CuSO4.5H2O, Lake Guard Blue and SeClear, respectively. Intrinsic rate of population increase was lowest (0.145 d-1) at the highest dosage in the SeClear treatments. Chemical equilibrium modelling revealed that most copper was chelated with EDTA present in the artificial medium used. These combined results indicate that the toxicity of the novel copper algaecide SeClear to D. magna is greater than that of traditional copper algaecide. Prior to each Cu application, tests on the effects of Cu compounds on the organisms being targeted should be done, taking into consideration the water chemistry.

Innovative method of utilising hydrogen peroxide for source water management of cyanobacteria.

The treatment and control of cyanobacterial blooms using copper-based algaecides in water reservoirs have historically been used; however, due to the adverse impact of copper on the environment, water authorities have been researching and studying new and innovative ways to control cyanobacterial blooms. Hydrogen peroxide has been investigated as an environmentally friendly alternative, and this research aims to determine the impact of water quality on its effectiveness based on the decay characteristics in different water samples. Natural water samples from South Australian reservoirs and river were used to evaluate hydrogen peroxide decomposition and provide a better strategy for water operators in using it as an algaecide. Our experiments show the dependency of hydrogen peroxide decomposition not only on water quality but also on the initial hydrogen peroxide dose. A higher initial hydrogen peroxide dose can trigger the increase of pH, leading to increased consumption of hydrogen peroxide. In addition, the hydrogen peroxide decomposition is significantly accelerated with the rise of copper concentration in water samples. Moreover, it is found that UV light can also affect the decomposition rate of hydrogen peroxide. The hydrogen peroxide decay is more significant under UV light for the samples with lower hydrogen peroxide concentrations. Our study also shows the impact of dissolved organic carbon (DOC) on hydrogen peroxide decomposition is not substantial. The study also presents a modelling method to optimise hydrogen peroxide application based on water quality characteristics. Our findings can provide knowledge for the water industry to produce a suitable model which can be used to optimise the application of hydrogen peroxide for the control of cyanobacteria.

A critical review on operation and performance of source water control strategies for cyanobacterial blooms: Part I-chemical control methods.

Cyanobacterial blooms produce nuisance metabolites (e.g., cyanotoxins and T&O compounds) thereby posing water quality management issues for aquatic sources used for potable water production, aquaculture, and recreation. A variety of in-lake/reservoir control measures are implemented to reduce the abundance of nuisance cyanobacteria biomass or decrease the amount of available phosphorous (P). This paper critically reviews the chemical control strategies implemented for in-lake/reservoir management of cyanobacterial blooms, i.e., algaecides and nutrient sequestering coagulants/flocculants, by highlighting (i) their mode of action, (ii) cases of successful and unsuccessful treatment, (iii) and factors influencing performance (e.g., water quality, process control techniques, source water characteristics, etc.). Algaecides generally result in immediate improvements in water quality and offer selective cyanobacterial control when peroxide-based alagecides are used. However, they have a range of limitations: causing cell lysis and release of cyanotoxins, posing negative impacts on aquatic plants and animals, leaving behind environmentally relevant treatment residuals (e.g., Cu in water and sediments), and offering only short-term bloom control characterized by cyanobacterial rebound. Coagulants/flocculants (alum, iron, calcium, and lanthanum bentonite) offer long-term internal nutrient control when external nutrient loading is controlled. Treatment performance is often influenced by background water quality conditions, and source water characteristics (e.g., surface area, depth, mixing regimes, and residence time). The reviewed case studies highlight that external nutrient load reduction is the most fundamental aspect of cyanobacterial control. None of the reviewed control strategies provide a comprehensive solution to cyanobacterial blooms.

Laboratory-scale evaluation of algaecide effectiveness for control of microcystin-producing cyanobacteria from Lake Okeechobee, Florida (USA).

Growth of microcystin-producing cyanobacteria in Lake Okeechobee (Florida, USA) and surrounding waters has resulted in adverse health impacts for humans and endangered species, as well as significant economic losses. As these issues worsen, there is growing pressure for efficacious solutions to rapidly mitigate harmful algal blooms (HABs) and protect critical freshwater resources. Applications of USEPA-registered algaecides as management tactics meet many decision-making criteria often required by water resource managers (e.g., effective, scalable, selective), but have not yet been evaluated on a large scale within the Lake Okeechobee waterway. This study was conducted to bolster the peer-reviewed database for available management tactics against microcystin-producing cyanobacteria in waters of this region. Laboratory-scale experiments can be conducted first to minimize uncertainty at larger scales and improve confidence in decision-making. In this study, samples containing microcystin-producing cyanobacteria collected from Lake Okeechobee were exposed to several USEPA-registered algaecides in laboratory toxicity experiments. Responses of target cyanobacteria were measured 3 days after treatment (DAT) in terms of cell density, chlorophyll-a concentrations, and phycocyanin concentrations. Based on responses of the cyanobacteria, minimum effective exposure concentrations were identified for each algaecide. Microcystin release (i.e. proportion of total microcystins in the aqueous phase) was measured and compared 1 DAT among effective exposures. Total microcystin concentrations were measured in effective treatments at 1, 4, and 9 DAT to discern potential for microcystin persistence following exposures to the effective formulations and exposure concentrations. Overall, several formulations including GreenClean Liquid® 5.0, GreenClean Liquid® 5.0 combined with Hydrothol® 191, and the copper-based algaecides evaluated (Algimycin® PWF, Argos, Captain® XTR, Cutrine® Ultra, and SeClear®) achieved significant and similar effects on target cyanobacteria. The chelated copper-based formulations (Algimycin® PWF, Argos, Captain® XTR, and Cutrine® Ultra) resulted in relatively less microcystin release 1 DAT and lesser total microcystin concentrations 4 DAT. At 9 DAT, total microcystin concentrations were significantly lower than in untreated controls in all treatments evaluated. These results provide the necessary comparative performance data for preliminary decision-making and designing additional studies at larger scales. Importantly, the comparative toxicity data and approach provided in this study demonstrate the initial steps for development of site-specific management strategies for Lake Okeechobee and other areas impacted by harmful algal blooms with large spatial and temporal scales.

Copper concentration data for water, sediments, and vegetation of urban stormwater ponds treated with copper sulfate algaecide.

We characterized copper (Cu) concentrations in the water, sediments, and shoreline plants of stormwater ponds in the urban Tampa, Florida area. We selected 6 urban residential stormwater ponds that receive summer wet season (May to September) Cu sulfate applications at least twice a month. We collected triplicate water and sediment samples from each pond and analyzed for Cu, as well as nutrient pools (inorganic N and P) and a suite of other physicochemical properties (e.g., water temperature, pH, conductivity, alkalinity, etc.). We analyzed shoreline plant tissue samples for Cu. The raw dataset provides values for Cu concentrations in water, sediments and plant tissue, and other measured parameters in water and sediments. This dataset is important for characterizing the fate and potential mobility of Cu in freshwater ponds treated with Cu sulfate algaecides. This applied research data will provide baseline understanding of Cu concentrations in water, sediments, and select plant tissue samples, providing insights on potential toxicity of Cu and any threats that Cu sulfate algaecides may pose to aquatic organisms and downstream waters. This dataset can also inform future research designs aimed at elucidating the effects of Cu on denitrifying bacteria and N removal in stormwater pond ecosystems. Finally, the plant tissue data shows variable Cu concentrations among plant species, and this data can inform future phytoremediation experiments.

Use of an integrated metabolomics platform for mechanistic investigations of three commonly used algaecides on cyanobacterium, Microcystis aeruginosa.

Algal blooms are a global environmental and public health problem. Copper Sulfate (CuSO4), Hydrogen Peroxide (H2O2) and Sodium Carbonate Peroxide (SCP) are commonly used algaecides for algal bloom control. However, their efficacy and mechanisms of interaction with algae have not been well studied. This study aimed to compare their capability, and concurrently elucidate the metabolic responses of a common cyanobacterium, Microcystis aeruginosa. Algal responses were measured by cell density, chlorophyll a, toxin release and an integrated GC- and LC- Mass Spectrometry-Time of Flight metabolomics platform. CuSO4 was observed to kill the algae cells rapidly at relative low concentration, compared with the other two algaecides. However, it led to severe secondary contamination, with substantial release of various microcystins. Metabolomics data showed that a total of 32 metabolites were significantly changed compared with the controls. Most of the metabolites identified in CuSO4 treated algae were significantly reduced, whereas metabolites in algae treated with H2O2 and SCP were found to increase, and were of similar types. Although most of the metabolites identified for the three algaecides are associated to oxidative stress, the pathways affected appear to be different.

The presence of algae mitigates the toxicity of copper-based algaecides to a nontarget organism.

Copper-based algaecides are routinely applied to target noxious algal blooms in freshwaters. Standard toxicity testing data with copper suggest that typical concentrations used to control algae can cause deleterious acute impacts to nontarget organisms. These "clean" water experiments lack algae, which are specifically targeted in field applications of algaecides and contain competing ligands. The present research measured the influence of algae on algaecide exposure and subsequent response of the nontarget species Daphnia magna to copper sulfate and an ethanolamine-chelated copper algaecide (Captain®). Significant shifts (p < 0.05) in D. magna 48-h median lethal concentration (LC50) values were found when algae were present in exposures along with a copper salt or a chelated copper formulation. Copper sulfate 48-h LC50 values shifted from 75.3 to 317.8 and 517.8 µg Cu/L, whereas Captain increased from 353.8 to 414.2 and 588.5 µg Cu/L in no algae, 5 × 105 , and 5 × 106 cells/mL algae treatments, respectively. Larger shifts were measured with copper sulfate exposures, although Captain was less toxic to D. magna in all corresponding treatments. Captain was more effective at controlling Scenedesmus dimorphus at most concentrations, and control was inversely proportional to toxicity to D. magna. Overall, incorporating target competing ligands (i.e., algae) into standard toxicity testing is important for accurate risk assessment, and copper formulation can significantly alter algaecidal efficacy and risks to nontarget organisms. Environ Toxicol Chem 2018;37:2132-2142. © 2018 SETAC.

Relationship among aqueous copper half-lives and responses of Pimephales promelas to a series of copper sulfate pentahydrate concentrations.

Copper algaecide exposures in situ are often of shorter duration than exposures for static toxicity experiments because aqueous concentrations in situ dissipate as a function of site-specific fate processes. Consequently, responses of organisms to static copper exposures may overestimate effects following in situ exposures. To understand the role of exposure duration for altering responses, Pimephales promelas survival was compared following static (96 h) and pulse (1.5, 4, 8, and 15 h half-lives) exposures of CuSO4•5H2O. Copper concentrations sorbed by fry indicated a consequence of different exposures. Responses of P. promelas to static exposures resulted in 96 h LC50s of 166 µgCu/L (95% confidence interval [CI], 142-189 µgCu/L) as soluble copper and 162 µgCu/L (CI, 140-183 µgCu/L) as acid soluble copper. Relative to static 96 h LC50s, exposures with half-lives of 1.5, 4 and 8 h resulted in LC50s 10, 3 and 2 times greater, respectively, for responses measured 96 h after exposure initiation. Copper concentrations extracted from fry exposed for 1.5, 4 and 8 h half-lives were less than the static experiment. However, copper sorbed by fry in the 15 h half-life experiment was not different than the static experiment. The relationship between 96 h LC50 and 1/half-life was expressed using the equations y = 116 + 1360 × (R2 = 0.97) for soluble copper and y = 147 + 1620 × (R2 = 0.98) for acid soluble copper. Incorporation of exposure duration for predictions of P. promelas responses to copper pulse exposures increases prediction accuracy by an order of magnitude.

Influence of CuSO4 and chelated copper algaecide exposures on biodegradation of microcystin-LR.

Copper exposures from algaecide applications in aquatic systems are hypothesized to impede bacterial degradation of microcystin (MC), a cyanobacterial produced hepatotoxin. Despite regulatory implications of this hypothesis, limited data exist on influences of copper-exposures on MC-degrading bacteria and consequent MC-degradation. In this study, influences of copper-algaecide concentrations and formulations on bacterial composition and microcystin-LR (MCLR) degradation were investigated. Microcystis aeruginosa was exposed to four concentrations (0-5.0 mg Cu L-1) of three copper-algaecide formulations, and rates and extents of MCLR degradation were measured. In untreated controls and following exposures of 0.1, 0.5, and 1.0 mg Cu L-1, MCLR concentrations decreased at a rate of ∼41-53 µg MCLR/L d-1. Following exposure to 5.0 mg Cu L-1 MCLR degradation rates decreased an order of magnitude to ∼3-7 µg MCLR/L d-1. Bacterial diversity decreased following copper-exposures greater than 0.1 mg Cu L-1 for all formulations. Relative abundance of certain groups of MC-degrading bacteria identified in treatments increased with increasing copper concentration, suggesting they may be less sensitive to copper exposures than other, MCLR and non MC-degrading heterotrophic bacteria present in the assemblage. Results from this study revealed that copper concentration can influence degradation rates of MCLR, however this influence was not significant within copper concentrations currently registered for use (≤1.0 mg Cu L-1) of the tested algaecides. Copper formulation did not significantly alter degradation rates or bacterial composition. These data augment our understanding of the influences of copper algaecide-exposures on MCLR degradation, and can be used to inform more accurate risk evaluations and use of copper-algaecides for management of MCLR-producing cyanobacteria.

Cellular and aqueous microcystin-LR following laboratory exposures of Microcystis aeruginosa to copper algaecides.

Microcystin release from algal cells influences use of copper-algaecides in water resources. Accurate data regarding relationships between copper-algaecide exposures and responses of microcystin-producing algae are needed to make informed management decisions. Responses of Microcystis aeruginosa were measured in terms of cellular microcystin-LR (MC-LR), aqueous MC-LR, and chlorophyll-a following exposure to CuSO4 and copper-ethanolamine. Comparisons were made between treated and untreated samples, and copper formulations. EC50s and slopes for M. aeruginosa responses to copper exposures were calculated. Algal responses followed a sigmoidal exposure-response relationship, and cellular MC-LR and chlorophyll-a were negatively related to copper concentrations. Aqueous MC-LR increased with copper concentrations, although the increase in aqueous MC-LR was not proportional to decreases in cellular MC-LR and chlorophyll-a. Cellular MC-LR and chlorophyll a declined at a greater rate than aqueous MC-LR increased. Total MC-LR was less than untreated controls following copper exposure. Differences were measured between copper formulations in terms of aqueous and total MC-LR concentrations at concentrations of 0.5 and 1.0 mg Cu L-1. Aqueous and total MC-LR were greater (10-20%) following exposure to CuSO4 compared to copper-ethanolamine one day following exposure. The positive relationship between copper concentration and aqueous MC-LR at 0.07-1.0 mg Cu L-1 demonstrates that lower copper concentrations were as effective as higher concentrations in controlling M. aeruginosa while decreasing the total amount of MC-LR, and minimizing the proportion of MC-LR released to the aqueous-phase. Results serve to support more accurate risk evaluations of MC-LR concentrations when M. aeruginosa is exposed to copper-algaecides and when it is untreated.

Responses of Lyngbya wollei to algaecide exposures and a risk characterization associated with their use.

To make informed decisions regarding management of noxious algal growths, water resource managers require information on responses of target and non-target species to algaecide exposures. Periodic treatments of Phycomycin®-SCP (sodium carbonate peroxyhydrate) followed by Algimycin®-PWF (gluconate and citrate chelated copper) to control Lyngbya wollei growths for ten years provided an opportunity for a risk evaluation of treated coves in Lay Lake, AL. Abiotic sediment characteristics (acid soluble copper concentrations, acid volatile sulfides, percent organic matter and cation exchange capacity) and survival of Hyalella azteca and Chironomus dilutus were measured in sediment samples from treated and untreated coves to assess the bioavailability of potential copper-residuals. In laboratory studies to seek a more effective approach for managing the growth of Lyngbya, six algaecide treatments consisting of combinations of copper-based algaecides (Cutrine®-Ultra, Clearigate® and Algimycin®- PWF), a hydrogen peroxide based algaecide (Phycomycin®-SCP) and an adjuvant (Cide-Kick II) were assessed for efficacy in controlling L. wollei sampled from Lay Lake. The most efficient algaecide treatment was determined based on post-treatment algal wet weight and visual observations of responses to exposures. To estimate the margin of safety for non-target organisms, Pimephales promelas was exposed to the most efficacious treatment and a treatment of Phycomycin®-SCP followed by Algimycin®-PWF. Results from sediment experiments demonstrated that there were no measureable copper residuals and no adverse effects on H. azteca and C. dilutus from sediments following ten years of copper-based algaecide treatments. Based on the laboratory results, a treatment of Phycomycin®-SCP at 10.1 mg H2O2/L followed by Cide-Kick II at 0.2 mg/L and Algimycin®- PWF at 0.26 mg Cu/L could control the growth of Lyngbya wollei from Lay Lake, AL and enhance the margin of safety for non-target species (e.g. P. promelas).