Widespread, low concentration microcystin detection in a subtropical Louisiana estuary.

Spatiotemporal patterns and drivers of hepatotoxic microcystins (MC) were investigated in the Atchafalaya-Vermilion Bay System (AVBS), a subtropical, river-dominated estuary in Louisiana. Along with environmental data, monthly particulate MC (pMC) samples were examined over a two-year period (2016-2018), and biweekly pMC and dissolved MC (dMC) samples were examined over a five-month period in 2020. Solid phase adsorption toxin tracking (SPATT) samplers used to quantify time-integrated dMC concentrations were also deployed in 2020. Low, but detectable concentrations of pMC (≤0.033 µg L-1) and dMC (≤0.190 µg L-1) were found throughout the AVBS in 37.8 and 21.2 % of samples, respectively. Time integrative SPATT samplers detected dMC in nearly 100 % of the deployments, compared to dMC detections in 30.8 % of the discrete samples. This study documents widespread MC presence throughout the AVBS and while concentrations were low, knowledge gaps remain regarding the potential long-term impacts of sublethal MC exposure to estuarine organisms.

Using solid phase adsorption toxin tracking and extended local similarity analysis to monitor lipophilic shellfish toxins in a mussel culture ranch in the Yangtze River Estuary.

Harmful algal blooms (HABs) and their associated phycotoxins are increasing globally, posing great threats to local coastal ecosystems and human health. Nutrients have been carried by the freshwater Yangtze River and have entered the estuary, which was reported to be a biodiversity-rich but HAB-frequent region. Here, in situ solid phase adsorption toxin tracking (SPATT) was used to monitor lipophilic shellfish toxins (LSTs) in seawaters, and extended local similarity analysis (eLSA) was conducted to trace the temporal and special regions of those LSTs in a one-year trail in a mussel culture ranch in the Yangtze River Estuary. Nine analogs of LSTs, including okadaic acid (OA), dinophysistoxin-1 (DTX1), yessotoxin (YTX), homoyessotoxin (homoYTX), 45-OH-homoYTX, pectenotoxin-2 (PTX2), 7-epi-PTX2 seco acid (7-epi-PTX2sa), gymnodimine (GYM) and azaspiracids-3 (AZA3), were detected in seawater (SPATT) or rope farmed mussels. The concentrations of OA + DTX1 and homoYTX in mussels were positively correlated with those in SPATT samplers (Pearson test, p < 0.05), indicating that SPATT (with resin HP20) would be a good monitoring tool and potential indicator for OA + DTX1 and homoYTX in mussel Mytilus coruscus. The eLSA results indicated that late summer and early autumn were the most phycotoxin-contaminated seasons in the Yangtze River Estuary. OA + DTX1, homoYTX, PTX2 and GYM were most likely driven by the local growing HAB species in spring and summer, while Yangtze River diluted water may impact the accumulation of HAB species, causing potential phycotoxin contamination in the Yangtze River Estuary in autumn and winter. Together, the results showed that the mussel harvesting season, late summer and early autumn, would be the season with the greatest phycotoxin risk and would be the most contaminated by local growing toxic algae. Routine monitoring sites should be set up close to the local seawaters.

Seasonal Single-Site Sampling Reveals Large Diversity of Marine Algal Toxins in Coastal Waters and Shellfish of New Caledonia (Southwestern Pacific).

Algal toxins pose a serious threat to human and coastal ecosystem health, even if their potential impacts are poorly documented in New Caledonia (NC). In this survey, bivalves and seawater (concentrated through passive samplers) from bays surrounding Noumea, NC, collected during the warm and cold seasons were analyzed for algal toxins using a multi-toxin screening approach. Several groups of marine microalgal toxins were detected for the first time in NC. Okadaic acid (OA), azaspiracid-2 (AZA2), pectenotoxin-2 (PTX2), pinnatoxin-G (PnTX-G), and homo-yessotoxin (homo-YTX) were detected in seawater at higher levels during the summer. A more diversified toxin profile was found in shellfish with brevetoxin-3 (BTX3), gymnodimine-A (GYM-A), and 13-desmethyl spirolide-C (SPX1), being confirmed in addition to the five toxin groups also found in seawater. Diarrhetic and neurotoxic toxins did not exceed regulatory limits, but PnTX-G was present at up to the limit of the threshold recommended by the French Food Safety Authority (ANSES, 23 µg kg-1). In the present study, internationally regulated toxins of the AZA-, BTX-, and OA-groups by the Codex Alimentarius were detected in addition to five emerging toxin groups, indicating that algal toxins pose a potential risk for the consumers in NC or shellfish export.

What happens in the shadows - Influence of seasonal and non-seasonal dynamics on domoic acid monitoring in the Monterey Bay upwelling shadow.

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.

A Review of In Situ Methods-Solid Phase Adsorption Toxin Tracking (SPATT) and Polar Organic Chemical Integrative Sampler (POCIS) for the Collection and Concentration of Marine Biotoxins and Pharmaceuticals in Environmental Waters.

Solid Phase Adsorption Toxin Tracking (SPATT) and Polar Organic Chemical Integrative Sampler (POCIS) are in situ methods that have been applied to pre-concentrate a range of marine toxins, pesticides and pharmaceutical compounds that occur at low levels in marine and environmental waters. Recent research has identified the widespread distribution of biotoxins and pharmaceuticals in environmental waters (marine, brackish and freshwater) highlighting the need for the development of effective techniques to generate accurate quantitative water system profiles. In this manuscript, we reviewed in situ methods known as Solid Phase Adsorption Toxin Tracking (SPATT) and Polar Organic Chemical Integrative Sampler (POCIS) for the collection and concentration of marine biotoxins, freshwater cyanotoxins and pharmaceuticals in environmental waters since the 1980s to present. Twelve different adsorption substrates in SPATT and 18 different sorbents in POCIS were reviewed for their ability to absorb a range of lipophilic and hydrophilic marine biotoxins, pharmaceuticals, pesticides, antibiotics and microcystins in marine water, freshwater and wastewater. This review suggests the gaps in reported studies, outlines future research possibilities and guides researchers who wish to work on water contaminates using Solid Phase Adsorption Toxin Tracking (SPATT) and Polar Organic Chemical Integrative Sampler (POCIS) technologies.

In situ use of bivalves and passive samplers to reveal water contamination by microcystins along a freshwater-marine continuum in France.

Cyanobacteria are a potential threat to aquatic ecosystems and human health because of their ability to produce cyanotoxins, such as microcystins (MCs). MCs are regularly monitored in fresh waters, but rarely in estuarine and marine waters despite the possibility of their downstream export. Over a period of two years, we monthly analyzed intracellular (in phytoplankton) and extracellular (dissolved in water) MCs at five stations along a river continuum from a freshwater reservoir with ongoing cyanobacterial blooms to the coast of Brittany, France. MCs were quantified using two integrative samplers placed at each site: solid phase adsorption toxin tracking (SPATT) samplers for collecting extracellular MCs and caged mussels (Anodonta anatina and Mytilus edulis) filter-feeding on MC-producing cyanobacteria. The MC transfer was demonstrated each year during five months at estuarine sites and sporadically at the marine outlet. SPATT samplers integrated extracellular MCs, notably at low environmental concentrations (0.2 µg/L) and with the same variant profile as in water. The mussel A. anatina highlighted the presence of MCs including at intracellular concentrations below 1 µg/L. M. edulis more efficiently revealed the MC transfer at estuarine sites than water samplings. Bivalves showed the same MC variant profile as phytoplankton samples, but with differential accumulation capacities between the variants and the two species. Using SPATT or bivalves can give a more accurate assessment of the contamination level of a freshwater-marine continuum, in which the MC transfer can be episodic. MC content in M. edulis represents a potent threat to human health if considering updated French guideline values, and particularly the total (free and protein-bound) MC content, highlighting the necessity to include cyanotoxins in the monitoring of seafood originating from estuarine areas.

Adsorption of marine phycotoxin okadaic acid on a covalent organic framework.

Phycotoxins, compounds produced by some marine microalgal species, can reach high concentrations in the sea when a massive proliferation occurs, the so-called harmful algal bloom. These compounds are especially dangerous to human health when concentrated in the digestive glands of seafood. In order to generate an early warning system to alert for approaching toxic outbreaks, it is very important to improve monitoring methods of phycotoxins in aquatic ecosystems. Solid-phase adsorption toxin tracking devices reported thus far based on polymeric resins have not been able to provide an efficient harmful algal bloom prediction system due to their low adsorption capabilities. In this work, a water-stable covalent organic framework (COF) was evaluated as adsorbent for the hydrophobic toxin okadaic acid, one of the most relevant marine toxins and the parental compound of the most common group of toxins responsible for the diarrhetic shellfish poisoning. Adsorption kinetics of okadaic acid onto the COF in seawater showed that equilibrium concentration was reached in only 60min, with a maximum experimental adsorption of 61mgg-1. Desorption of okadaic acid from the COF was successful with both 70% ethanol and acetonitrile as solvent, and the COF material could be reused with minor losses in adsorption capacity for three cycles. The results demonstrate that COF materials are promising candidates for solid-phase adsorption in water monitoring devices.

Occurrence and variation of lipophilic shellfish toxins in phytoplankton, shellfish and seawater samples from the aquaculture zone in the Yellow Sea, China.

Lipophilic shellfish toxins (LSTs) produced by diverse microalgae have become a potential threat to the marine aquaculture industry in coastal regions throughout the world. In this study, phytoplankton, scallop, and seawater samples were collected and monitored in the aquaculture zone of Liuqing Bay located in the coast of Qingdao, Yellow Sea, in 2014 and 2015. Dissolved LSTs in seawater were adsorbed by solid phase adsorption toxin tracking (SPATT) bags and solid phase extraction (SPE) cartridges, respectively. PTX2 was found to be the predominant LSTs, while OA and DTX1 were detected at trace levels in the three species of Dinophysis and Phalacroma genera picked from the investigation zone. The highest quota of PTX2 occurred in D. fortii (0.28 pg cell-1), followed by D. acuminata complex (0.08 pg cell-1) and P. rotundatum (=D. rotundata) (0.02 pg cell-1). PTX2 (nd∼5.7 µg kg-1), OA (nd∼2.8 µg kg-1) and DTX1 (nd∼1.6 µg kg-1) were also observed in cultivated scallops, but in addition to the former, PTX2sa, 7-epi-PTX2sa and an isobaric form of DTX1 suspected as DTX1b were also found in the SPATT bags. The isobaric compound of DTX1 only appeared in the SPATT bags deployed in field samples of seawater. A significant higher quantity of OA was adsorbed by SPATT bags compared to DTX1, although similar concentrations of both toxins were adsorbed by SPE cartridges from the aquaculture zone. AZA2 was also found in the concentrated phytoplankton cells, which demonstrated that AZA-producing microalgae were present in this investigated area. The variation in concentrations of PTX2 adsorbed by SPATT bags could reflect the change of Dinophysis density in seawater, but there was a time lag behind the peaks of Dinophysis density. Comparative results did not support the SPATT technology as a useful warning tool for toxic algal blooms and toxin accumulation in bivalves. The data suggest that the contamination of LSTs was prevalent in the coast of Qingdao and the environmental behavior of LSTs should be explored further.

Recent Application of Solid Phase Based Techniques for Extraction and Preconcentration of Cyanotoxins in Environmental Matrices.

Cyanotoxins are toxic and are found in eutrophic, municipal, and residential water supplies. For this reason, their occurrence in drinking water systems has become a global concern. Therefore, monitoring, control, risk assessment, and prevention of these contaminants in the environmental bodies are important subjects associated with public health. Thus, rapid, sensitive, selective, simple, and accurate analytical methods for the identification and determination of cyanotoxins are required. In this paper, the sampling methodologies and applications of solid phase-based sample preparation methods for the determination of cyanotoxins in environmental matrices are reviewed. The sample preparation techniques mainly include solid phase micro-extraction (SPME), solid phase extraction (SPE), and solid phase adsorption toxin tracking technology (SPATT). In addition, advantages and disadvantages and future prospects of these methods have been discussed.

Effect of seawater salinity on pore-size distribution on a poly(styrene)-based HP20 resin and its adsorption of diarrhetic shellfish toxins.

In the present study, okadaic acid (OA) and dinophysistoxin-1 (DTX1) were spiked into artificial seawater at low, medium and high estuarine salinities (9‰, 13.5‰ and 27‰). Passive samplers (HP20 resin) used for solid phase adsorption toxin tracking (SPATT) technology were exposed in these seawaters for 12-h periods. Adsorption curves well fitted a pseudo-secondary kinetics model. The highest initial sorption rates of both toxins occurred in the seawater of medium salinity, followed by seawater of low and high estuarine salinity. Pore volumes of micropores (<2 nm) and small mesopores (2 nm

Mechanism and application of solid phase adsorption toxin tracking for monitoring microcystins.

The production of toxic microcystins by cyanobacteria is an important safety issue in terms of ecological food chains and drinking water supplies. Studies were carried out to demonstrate the applicability of solid phase adsorption toxin tracking (SPATT) to the monitoring of microcystins in fresh water. Work focused on the distribution of the intra- and extra-cellular toxins MC-LR and [Dha(7)] MC-LR produced by Microcystis aeruginosa (FACHB 905). The dynamic adsorption and desorption behavior of both toxins on aromatic resins HP20 and SP700 was examined, and the use of SPATT bags for monitoring microcystins in cyanobacterial cultures is discussed. It was shown that intracellular MC-LR and [Dha(7)] MC-LR are released continuously during batch incubation. The adsorption capacity of the SP700 resin was higher than that of the HP20 resin, while the opposite was true for desorption efficiency. The highest desorption efficiency of HP20 was 91.5±4.6% and 89.0±7.1% for MC-LR and [Dha(7)] MC-LR, respectively; accordingly, that of SP700 was 78.1±4.1% and 72.3±2.1%, respectively. Taking both adsorption and desorption behavior into consideration, HP20 is recommended as an adsorbent for SPATT monitoring of microcystins in freshwater bodies.