Copper-based Algaecides Research Articles

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.

Laboratory evaluation of copper-based algaecides for control of the invasive macroalga starry stonewort (Nitellopsis obtusa)

Laboratory evaluation of copper-based algaecides for control of the invasive macroalga starry stonewort (Nitellopsis obtusa)

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 riverwere 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.

Characterization of Dissolved Organic Matter from Wildfire-induced Microcystis aeruginosa Blooms controlled by Copper Sulfate as Disinfection Byproduct Precursors Using APPI(-) and ESI(-) FT-ICR MS

Copper-based algaecides are usually used for controlling algae bloom triggered by the elevated levels of nutrients after wildfires, resulting in the promoted reactivity of dissolved organic matter (DOM) in forming disinfectant byproducts (DBPs). To identify the best strategy for handling this source water, we employed Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to characterize the DBPs precursors after 4-d Microcystis aeruginosa bloom cultured with black (BE) and white (WE) ash water extracts under 0, 0.5, and 1.0 mg-Cu/L. The disappeared DOM during disinfections, primarily composed of O1-14, N1O1-14 and N2O1-14, had a higher average molecular weight (MW) and double-bond equivalent (DBE), relative to DOM after incubation, regardless of disinfects and Cu2+. This result suggests assigned features with larger MW and more double bonds/rings as preferable DBP precursors. We observed a larger number of disappeared assigned features with low DBE of 1-10 in control without Cu2+ addition, possibly explaining lower DOM chlorine reactivity in forming carbonaceous and oxygenated DBPs, relative to the treatments with Cu2+ addition. We found a larger number of O1-14 and N1O1-14 with DBE=5-16 in the treatments, potentially explaining higher DOM chloramine reactivity in forming N-nitrosodimethylamine (NDMA), compared to the control. Our study suggests removing oxygen- and nitrogen-containing organic compounds with more double bonds/aromatic rings as a preferable strategy for handling source water after controlling post-fire algae blooms with copper sulfate.

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.

FurA-Dependent Microcystin Synthesis under Copper Stress in Microcystis aeruginosa.

Massive blooms of cyanobacteria frequently occur with microcystin (MC) production. Cyanobacteria are exposed to copper stresses such as copper algaecides which are often used to remove cyanobacterial blooms. However, copper increased the MC production of cyanobacteria, and the underlying mechanism remains unclear. The present study investigated the relationship between copper exposure (0.5 and 3 µM) and MC synthesis in Microcystis aeruginosa PCC 7806. The study concluded that the content of intracellular MCs increased by nearly two times both in 0.5 and 3 µM copper. High-throughput RNA sequencing (RNA-seq) provided evidence that copper mainly attacked Fe–S clusters, with evidence of changes in iron, sulfur, iron uptake regulators (fur), glutaredoxins and dehydratase genes. The transcription of numbers of genes implicated in iron uptake, MC synthesis and furA was also evaluated with quantitative real-time PCR (qRT-PCR). In these three Cu treatment groups, the amount of MCs increased as copper elevated. As the expression of mcyD gene was directly regulated by FurA and copper ions affected the expression of the FurA-related genes, we believed that MC synthesis genes were controlled by copper. This study has made a further understanding of the mechanism of the increase in MC synthesis of M. aeruginosa PCC 7806 treated with copper-based algaecides. We aimed to understand the mechanism of copper ion influencing the synthesis of MCs.

Biomass of the Cyanobacterium Lyngbya wollei Alters Copper Algaecide Exposure and Risks to a Non-target Organism.

Nuisance algal infestations are increasing globally in distribution and frequency. Copper-based algaecides are routinely applied to control these infestations, though there is an ever-present concern of risks to non-target species. This research evaluated risks associated with a commonly applied chelated copper algaecide (Captain® XTR; SePRO Corporation) to a sentinel non-target species (Daphnia magna) and further assessed alteration of the exposure and toxicity when a nuisance mat-forming cyanobacterium, Lyngbya wollei, was present in exposures. Aqueous copper concentrations in treatments with algae significantly decreased within 1 h after treatment and averaged 57.5% of nominal amended Cu through the experiment duration. The 48 h LC50 values were 371 µg Cu/L with no algae present in exposures and increased significantly to 531 µg Cu/L when L. wollei was simultaneously exposed. This research provides information on the short-term fate of copper and hazard assessment by incorporating targeted binding ligands, as present in operational treatments.

Evaluating the treatment effectiveness of copper-based algaecides on toxic algae Microcystis aeruginosa using single cell-inductively coupled plasma-mass spectrometry

Single cell-inductively coupled plasma-mass spectrometry (SC-ICP-MS) is an emerging technology. In this work, we have developed a novel SC-ICP-MS method to quantify metal ions in individual cells of a toxic cyanobacterial species, Microcystis aeruginosa (M. aeruginosa), without complicated post-dosing sample preparation, and applied this method to study the treatment effectiveness of copper-based algaecides (cupric sulfate and EarthTec®) on the toxic algae M. aeruginosa. The developed SC-ICP-MS method uses new intrinsic metal element magnesium to determine real transport efficiency and cell concentration. The cell viability and microcystin-LR release by algaecide treatment were studied by flow cytometry and ultra-fast liquid chromatography-tandem mass spectrometry, respectively. The results showed that this novel method was very rapid, highly sensitive (detection limits of intracellular copper and magnesium were 65 ag/cell and 98 ag/cell, respectively), and reproducible (relative standard deviation within 12%). The algaecide effectiveness study further demonstrated that copper in the forms of cupric sulfate and copper-based algaecide EarthTec® successfully diminished M. aeruginosa populations. The higher the copper concentration used to treat the cells, the faster the speeds of copper uptake and cell lysis in the copper concentrations ranged from 0 to 200 μg/L of copper-based algaecide. The cells exhibit obvious heterogeneity in copper uptake. The result suggests that M. aeruginosa cells uptake and cumulate copper followed by cellular lysis and microcystin-LR release. These novel results indicated that though the copper-based algaecides could control this type of harmful algal bloom, further treatment to remove the released algal toxin from the treated water would be needed.Graphical abstract

Comparison of Partitioning and Efficacy Between Copper Algaecide Formulations: Refining the Critical Burden Concept

Filamentous mat-forming algae are increasingly impairing freshwater resources. To restore water utility, reactive management programs often involve application of copper-based algaecides. Copper algaecide formulations can differ significantly, and this research outlined an advanced approach to evaluate formulation efficiency for controlling filamentous algae. Two common algal species (Lyngbya wollei, Pithophora varia) were used to assess copper internalization and adsorption as well as relation to control among copper formulations. Captain® XTR achieved control (7-day EC85) of L. wollei with internal copper concentrations of 0.78 and 0.76 mg Cu/g based on chlorophyll a content or filament viability, respectively. Cutrine® Ultra achieved control of L. wollei based on filament viability only at 0.85 mg Cu/g. Internalized copper concentrations required for control following Captain XTR exposures were similar for P. varia, 0.81 and 0.95 mg Cu/g, whereas Cutrine Ultra and copper sulfate did not elicit control nor attain the critical internal copper threshold. The relationship between internalized copper and responses, among all formulations, was significant (P < 0.0001) with R2 values of 0.920 and 0.935 for L. wollei and 0.807 and 0.826 for P. varia based on filament viability and chlorophyll a content, respectively. Formulation efficiency, internalized copper versus total amended, was greatest with Captain XTR (average 0.17), followed by Cutrine Ultra (0.13), and copper sulfate (0.09). By measuring the efficiency of a specific algaecide and the corresponding amount required to achieve control of targeted algal biomass, management objectives can be achieved while decreasing environmental loads of copper, number of treatments, and operational costs.

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.

Assessing Copper Adsorption, Internalization, and Desorption Following Algaecide Application to Control Lyngbya wollei from Lake Gaston, NC/VA, USA

Application of copper-based algaecide formulations is commonly conducted to control nuisance cyanobacterial blooms. Most field application scenarios have a rapid decline in external aqueous copper concentrations. Copper partitioned to algae can remain bound in external state, transition into the cell, or desorb back into solution. Understanding short-term fate of applied copper-based algaecides is critical in risk assessment for non-target species as well as achieving desired efficacy of target nuisance algae. This research assessed the ability of copper from different algaecide formulations to partition to Lyngbya wollei and the subsequent internalization and desorption of copper following cessation of the aqueous exposure. Following a 6-h exposure, there were no significant differences in total partitioned copper between copper sulfate and an ethanolamine chelated copper formulation (Captain® XTR). Four days after cessation of the aqueous copper exposure, all chelated copper and copper sulfate (except 2 mg Cu/L) exposures had significantly decreased adsorbed copper to L. wollei. However, chelated copper had significantly more internalized copper (P < 0.05) at the 0.5, 1, and 2 mg Cu/L treatments compared with the 6-h measurements and higher internalized copper than copper sulfate at the 2 and 4 mg Cu/L treatments. Average desorbed copper was lower in most chelated copper treatments compared with copper sulfate, although no statistically significant differences were measured between formulations. This information will allow water resource managers to select the most efficient algaecide formulation for desired algal control, with a better understanding of depuration potential, offsite movement, and risks to non-target organisms.

Microcystin-LR Degradation Following Copper-Based Algaecide Exposures

When copper-based algaecides are used in aquatic systems to decrease cyanobacteria densities, endotoxin fate is a concern, due to the potential for human health and ecological risks. Pulse exposures of algaecides can result in episodic low dissolved oxygen (DO) concentrations (< 2 mg L−1), due to oxygen consumed via microbial oxidation of algal detritus. Research objectives of this study were to determine the influence of declining DO levels on microcystin-LR (MC-LR) degradation and changes in resident bacterial assemblages. It was hypothesized that cyanobacteria cell densities would be positively correlated with rates and extents of DO decline based on the oxygen required for bacteria to degrade cyanobacteria detritus following exposure to copper-based algaecides. In addition, it was hypothesized that total MC-LR concentrations would increase proportionally with increasing cyanobacteria cell densities. Mesocosm experiments were conducted in a pond in Anderson, SC, that frequently experiences cyanobacteria blooms. Three densities of a cyanobacteria assemblage were exposed to a copper ethanolamine algaecide. DO and total MC-LR concentrations were measured with time following algaecide exposures to determine rates and extents of declines. As anticipated, DO concentrations had the highest rate of decline in the highest cell density treatment, followed by medium and low cell densities. MC-LR degradation occurred at similar rates (half-lives 1 to 1.9 days) among cell densities. Acinetobacter and Aeromonas were dominant in treatments following copper exposures. The relationship between cyanobacteria densities and MC-LR half-lives demonstrates the benefits of managing cyanobacteria in early growth stages to minimize MC concentrations.

Cell density dependence of Microcystis aeruginosa responses to copper algaecide concentrations: Implications for microcystin-LR release

Along with mechanistic models, predictions of exposure-response relationships for copper are often derived from laboratory toxicity experiments with standardized experimental exposures and conditions. For predictions of copper toxicity to algae, cell density is a critical factor often overlooked. For pulse exposures of copper-based algaecides in aquatic systems, cell density can significantly influence copper sorbed by the algal population, and consequent responses. A cyanobacterium, Microcystis aeruginosa, was exposed to a copper-based algaecide over a range of cell densities to model the density-dependence of exposures, and effects on microcystin-LR (MC-LR) release. Copper exposure concentrations were arrayed to result in a gradient of MC-LR release, and masses of copper sorbed to algal populations were measured following exposures. While copper exposure concentrations eliciting comparable MC-LR release ranged an order of magnitude (24-h EC50s 0.03–0.3mg Cu/L) among cell densities of 106 through 107 cells/mL, copper doses (mg Cu/mg algae) were similar (24-h EC50s 0.005–0.006mg Cu/mg algae). Comparisons of MC-LR release as a function of copper exposure concentrations and doses provided a metric of the density dependence of algal responses in the context of copper-based algaecide applications. Combined with estimates of other site-specific factors (e.g. water characteristics) and fate processes (e.g. dilution and dispersion, sorption to organic matter and sediments), measuring exposure-response relationships for specific cell densities can refine predictions for in situ exposures and algal responses. These measurements can in turn decrease the likelihood of amending unnecessary copper concentrations to aquatic systems, and minimize risks for non-target aquatic organisms.

Management of Target Algae by Using Copper-Based Algaecides: Effects of Algal Cell Density and Sensitivity to Copper

Public concerns regarding the use of copper-based algaecide for controlling problematic algae may arise due to the risks it creates to non-target algae. To examine this concern, a series of comparative algal toxicity experiments were conducted to study effects of prokaryotic and eukaryotic algal cell densities on their responses to exposures of copper sulfate and copper-ethanolamine (Cu-EA). Microcystis aeruginosa and Pseudokirchneriella subcapitata were cultured separately in BG 11 medium to three initial cell densities (5 × 104, 5 × 105, and 5 × 106 cells/mL). The 96-h EC50 values of copper sulfate for M. aeruginosa at the three cell densities were 9, 63, and 112 μg Cu/L, respectively; and were 192, 1873, and 4619 μg Cu/L for P. subcapitata. The 96-h EC50 values of Cu-EA were 101 and 2579 μg Cu/L for M. aeruginosa and P. subcapitata at 106 cells/mL. The margin of safety (MOS) for P. subcapitata at 104 cells/mL was 1.3, 0.9, and 0.8 when M. aeruginosa cell density was 104, 105, and 106 cells/mL. This laboratory study suggests that applying copper-based algaecides to control problematic algae at a relatively low cell density would inhibit their growth with minimum impacts on non-target algae; risks to non-target algae would increase with increases of problematic algal cell density.

Sediment Copper Concentrations, In Situ Benthic Invertebrate Abundance, and Sediment Toxicity: Comparison of Treated and Untreated Coves in a Southern Reservoir

Copper-based algaecides are used to control algae that compromise uses of lakes and reservoirs. However, there are concerns regarding potential adverse effects to benthic macroinvertebrates following long-term, repeated applications. Multiple lines-of-evidence are useful for evaluating potential ecological risks. These lines-of-evidence are encompassed in the sediment quality triad (SQT) and include sediment copper concentrations, in situ benthic invertebrate abundance, and sediment toxicity testing. The objective of this study was to measure potential ecological risks associated with long-term applications of copper algaecides in coves in Lay Lake, Alabama. Sediments from three coves treated for 7, 10, and 20 years were compared to sediments from three untreated coves in terms of copper concentrations, in situ benthic macroinvertebrate total abundance, and survival of Hyalella azteca and Chironomus dilutus in laboratory sediment toxicity tests. Sediment copper concentrations were not different between treated and untreated coves, with the exception of one treated cove (PC-1S) that contained elevated sediment copper concentrations compared to all other coves. However, the copper was not bioavailable to organisms based on in situ macroinvertebrate abundance and laboratory toxicity tests. In situ benthic invertebrate abundance was not different between treated and untreated coves. In all sediments tested, there were no measurable adverse effects to H. azteca and there were no significant differences in survival of C. dilutus between treated and untreated coves. Based on the weight-of-evidence approach utilized in this study, long-term copper use in three Lay Lake coves has not resulted in adverse effects to benthic invertebrates compared to untreated coves.

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 10.1mg H2O2/L followed by Cide-Kick II at 0.2mg/L and Algimycin®- PWF at 0.26mg 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).

Responses of Planktothrix agardhii and Pseudokirchneriella subcapitata to Copper Sulfate (CuSO4 · 5H2O) and a Chelated Copper Compound (Cutrine®-Ultra)

Reliable viability measures are needed to predict responses of algae to phytotoxic exposures. Non-axenic laboratory cultures of Planktothrix agardhii and Pseudokirchneriella subcapitata were exposed to a series of concentrations of CuSO4 · 5H2O (0.1–0.5 and 1.0–8.0 mg Cu/L) and a chelated copper compound with an adjuvant, Cutrine®-Ultra (0.05–0.25 and 1.0–8.0 mg Cu/L) in 7-day static laboratory experiments. Algal viability measures in terms of cell density, uptake of mortal stain (erythrosin b), chlorophyll a concentration, pheophytin a concentration, and respiration (measured as 2-(p-iodophenyl)-3-(p-nitrophenyl)-5-phenyl tetrazolium formazan absorbance (INT)) were discerned daily. The time and concentration required to achieve algal control, 96-h EC50s, potency slopes, and doubling times were calculated from algal responses if algal viability measures were accurate and precise. Cell densities and erythrosin b-stained cells had sufficient accuracy and precision to differentiate responses of P. agardhii and P. subcapitata from resident algae while chlorophyll a concentrations and INT formazan absorbances did not discriminate. In this study, pheophytin a concentrations lack precision and accuracy. P. agardhii was an order of magnitude more sensitive than P. subcapitata, and Cutrine®-Ultra was more than twice as potent as CuSO4 · 5H2O. This laboratory study corroborates previous laboratory and field studies suggesting that chelated copper-based algaecides when applied in the field can selectively control specific target algae at a lower copper concentration than CuSO4 · 5H2O. Individual algal viability measures such as cell density and erythrosin b staining can measure the relevant change in algal assemblage as a result of exposure.

Responses of Lyngbya wollei to Exposures of Copper-Based Algaecides: The Critical Burden Concept

The formulation of a specific algaecide can greatly influence the bioavailability, uptake, and consequent control of the targeted alga. In this research, three copper-based algaecide formulations were evaluated in terms of copper sorption to a specific problematic alga and amount of copper required to achieve control. The objectives of this study were (1) to compare the masses of copper required to achieve control of Lyngbya wollei using the algaecide formulations Algimycin-PWF, Clearigate, and copper sulfate pentahydrate in laboratory toxicity experiments; (2) to relate the responses of L. wollei to the masses of copper adsorbed and absorbed (i.e., dose) as well as the concentrations of copper in the exposure water; and (3) to discern the relation between the mass of copper required to achieve control of a certain mass of L. wollei among different algaecide formulations. The critical burden of copper (i.e., threshold algaecide concentration that must be absorbed or adsorbed to achieve control) for L. wollei averaged 3.3 and 1.9mg Cu/g algae for Algimycin-PWF and Clearigate, respectively, in experiments with a series of aqueous copper concentrations, water volumes, and masses of algae. With reasonable exposures in these experiments, control was not achieved with single applications of copper sulfate despite copper sorption >13mg Cu/g algae in one experiment. Factors governing the critical burden of copper required for control of problematic cyanobacteria include algaecide formulation and concentration, volume of water, and mass of algae. By measuring the critical burden of copper from an algaecide formulation necessary to achieve control of the targeted algae, selection of an effective product and treatment rate can be calculated at a given field site.