Harmful algae bloom (HAB) forecasting has developed rapidly over recent decades, but predicting harmful levels of marine biotoxins in shellfish is still a challenge. New discoveries suggest that predator‐prey interactions may be an important driver in the formation of HABs. Key species of harmful algae respond to copepod infochemicals with increased toxin production. In addition, copepods feed selectively on less defended prey, which may further promote harmful taxa. Here we explore if eavesdropping on predator‐prey dynamics by monitoring zooplankton can improve HAB forecasting. We first examine an 8‐yr time series including copepod biomass, harmful algae cells (Dinophysis spp.), and diarrhetic shellfish toxins in blue mussels (Mytilus edulis) using generalized additive models. Models including copepod biomass more accurately predicted okadaic acid in mussels than phytoplankton alone. We then apply this connection more narrowly by analyzing the specific copepod exudates known to induce toxin production, copepodamides, from the mussels sampled in biotoxin monitoring. Adding copepodamide data from shellfish extracts increased model performance compared to copepod biomass. Results suggest that including grazing effects through copepodamide measurements may provide a cost‐efficient way to improve accuracy and lead time for predicting the accumulation of microalgal toxins in shellfish.

Domoic acid produced by toxigenic Pseudo-nitzschia species is the main toxin threat from harmful algal blooms in Monterey Bay and the larger California Current region on the West Coast of the United States. Toxin monitoring in Monterey Bay includes a long-running time series of weekly measurements of domoic acid from water samples, sentinel mussels, and solid phase adsorption toxin tracking (SPATT) at the Santa Cruz Municipal Wharf (SCW). The SCW sampling site is unusual because of its position in the Monterey Bay upwelling shadow in the north bay. The upwelling shadow circulation pattern has been previously characterized as a bloom incubator for dinoflagellates, but it has not yet been analyzed in the context of long-term monitoring methods. In data collected from the SCW from 2012 - 2020, domoic acid from water samples and sentinel mussels had a different temporal distribution than domoic acid from SPATT. Here we explore the discrepancy through a seasonal and non-seasonal analysis including physical oceanography of the region. Results show that domoic acid from water samples and sentinel mussels are related to seasonal upwelling and Pseudo-nitzschia blooms. Domoic acid monitored by SPATT, on the other hand, is correlated to anomalous upwelling and warmer than usual temperatures during the relaxation season. This work builds on previous analyses of the SCW time series and contributes to understanding of the circulation of dissolved toxin in the environment. Results lend rationale for the continuation of rigorous domoic acid monitoring in Monterey Bay and encourage stakeholders to consider local physical dynamics when interpreting toxin monitoring data.

Chemical signaling is ubiquitous in the marine environment. Plankton rely on chemical signals to find mates, hunt prey, and respond to threats, and these small‐scale interactions can propagate into community‐wide cascades and large‐scale ecological changes. The chemical signaling exchange in the open ocean is poorly understood, and fundamental information about concentrations and spatiotemporal variability is lacking. Passive sampling has been used to monitor a wide range of dissolved chemicals, including anthropogenic pollutants and harmful algal toxins, but it is not generally applied to the study of marine chemical ecology. Here we test the compatibility of two resins commonly used for passive sampling via solid phase adsorption toxin tracking (SPATT), Diaion® HP20 and Sepabeads® SP207, with copepodamides, a group of polar lipid signaling compounds produced by copepods. We developed extraction and analysis methods that align with current SPATT practices for algal toxins and show the first measurements of copepodamides from Monterey Bay in California. In lab trials, mean copepodamide recovery from HP20 resin was approximately 240% greater than SP207. In addition, copepodamides were found to have a mean half‐life of 34 h in seawater. Adsorption to HP20 stabilized dissolved copepodamides, increasing the mean recovery after 168 h from 0.62% in seawater to 65.2% from SPATT. Results suggest that SPATT is a sensitive and effective tool for obtaining integrated copepodamide concentrations, spotlighting a novel method to include information from copepod mesozooplankton in time series and field studies.

Domoic acid (DA) produced by toxigenic species of the diatom genus Pseudo-nitzschia during harmful algal blooms (HABs) bioaccumulates in filter feeders, bait fish, and commercial seafood products, posing a threat to marine organisms and public health. Copepodamides, a group of polar lipids exuded by copepods, are known to induce DA production in multiple species of Pseudo-nitzschia . However, copepodamides are not currently considered in HAB monitoring and prediction, in part because of challenges associated with measuring ambient concentrations of dilute and labile compounds. Here we employ solid phase adsorption toxin tracking (SPATT) to measure natural concentrations of copepodamides over 28 mo in Monterey Bay, California, a known hotspot for HAB events. Copepodamides were significantly correlated to copepod biovolume, confirming utility as a zooplankton proxy. In generalized linear models, copepodamides from SPATT provided greater accuracy and lead time for predicting Pseudo-nitzschia abundance and DA concentration in sentinel mussels than DA from SPATT. Field experiments in the Northeast Atlantic assessed sampling methodology, and lab experiments demonstrated DA induction in Pseudo-nitzschia multiseries isolated from Monterey Bay. Results show potential for copepodamides to improve HAB predictions and encourage development of novel approaches to include top-down information in HAB monitoring systems.

Domoic acid (DA), produced by Pseudo-nitzschia diatoms, is the one of the major toxin threats from harmful algal blooms (HABs) on the west coast of the United States. DA events vary in magnitude, timing, and duration, and elucidating drivers for individual events is a persistent challenge. Monterey Bay experiences near-annual DA events and hosts long-term HAB monitoring at the Santa Cruz Municipal Wharf (SCW). Here we characterize two toxin events, occurring in May 2023 and March 2024. The events were similar in magnitude and duration, but an exploration of physical, biological, and chemical dynamics revealed distinct environmental drivers. These differences resulted in a significant deviation in cellular DA (cDA) within the same species of Pseudo-nitzschia. In addition, opportunistic solid-phase adsorption toxin tracking (SPATT) was used for environmental metabolomics. The novel application of SPATT revealed 159 metabolites that were strongly correlated with DA in both events and produced a spectral match to a new marine natural product using Global Natural Products Social Molecular Networking (GNPS). This work takes a multivariable approach to understanding toxin drivers and lends proof of concept for the integration of environmental metabolomics in HAB monitoring.

Domoic acid (DA), produced by Pseudo-nitzschia diatoms, is the one of the major toxin threats from harmful algal blooms (HABs) on the west coast of the United States. DA events vary in magnitude, timing, and duration, and understanding drivers for indi-vidual events is a persistent challenge. Monterey Bay experiences near-annual DA events and hosts long-term HAB monitoring at the Santa Cruz Municipal Wharf (SCW). Here we characterize two toxin events, occurring in May 2023 and March 2024. The events were similar in magnitude and duration, but an exploration of physical, biological, and chemical dynamics revealed distinct environmental drivers. These differences resulted in a significant deviation in cellular DA (cDA) within the same species of Pseudo-nitzschia. We also include a novel application of solid phase adsorption toxin tracking (SPATT) for environmental metabolomics. Opportunistic SPATT samples showed 159 metabolites that were strongly correlated with DA in both events and produced a spectral match to a new marine natural product using Global Natural Products Social Molecular Networking (GNPS). This work takes a multivariable approach to understanding toxin drivers and lends proof of concept for the integration of environmental metabolomics in HAB monitoring.