Five Years Monitoring the Emergence of Unregulated Toxins in Shellfish in France (EMERGTOX 2018–2022)

Abstract

Shellfish accumulate microalgal toxins, which can make them unsafe for human consumption. In France, in accordance with EU regulations, three groups of marine toxins are currently under official monitoring: lipophilic toxins, saxitoxins, and domoic acid. Other unregulated toxin groups are also present in European shellfish, including emerging lipophilic and hydrophilic marine toxins (e.g., pinnatoxins, brevetoxins) and the neurotoxin β-N-methylamino-L-alanine (BMAA). To acquire data on emerging toxins in France, the monitoring program EMERGTOX was set up along the French coasts in 2018. Three new broad-spectrum LC-MS/MS methods were developed to quantify regulated and unregulated lipophilic and hydrophilic toxins and the BMAA group in shellfish (bivalve mollusks and gastropods). A single-laboratory validation of each of these methods was performed. Additionally, these specific, reliable, and sensitive operating procedures allowed the detection of groups of EU unregulated toxins in shellfish samples from French coasts: spirolides (SPX-13-DesMeC, SPX-DesMeD), pinnatoxins (PnTX-G, PnTX-A), gymnodimines (GYM-A), brevetoxins (BTX-2, BTX-3), microcystins (dmMC-RR, MC-RR), anatoxin, cylindrospermopsin and BMAA/DAB. Here, we present essentially the results of the unregulated toxins obtained from the French EMERGTOX monitoring plan during the past five years (2018–2022). Based on our findings, we outline future needs for monitoring to protect consumers from emerging unregulated toxins.

Analytical Methods for Anatoxin-a Determination: A Review

“…However, concentrations of up to 33.00 μg/g of this toxin have been detected in dietary supplements containing cyanobacteria [ 22 ]. In relation to seafood, in addition to the study by Biré et al [ 21 ] mentioned above, Amzil et al [ 23 ] detected, for the first time, the presence of this neurotoxin in mussels in France. Moreover, interestingly, different studies have investigated the potential bioaccumulation of ATX-a in fish.…”

A Review of Cyclic Imines in Shellfish: Worldwide Occurrence, Toxicity and Assessment of the Risk to Consumers

“…In addition to New Zealand, shellfish contaminated with GYMs have been detected in shellfish collected from Bosnia and Herzegovina [ 25 ], Croatia [ 25 , 26 ], France [ 27 ], Italy [ 28 ], Morocco [ 29 ], South Africa [ 30 ], Australia [ 31 ], China [ 32 , 33 , 34 ], Lebanon [ 35 ], Tunisia [ 36 ], Spain [ 37 ], New Caledonia [ 38 ] and Greece [ 39 ]. GYM A has been the dominant compound observed ( Figure 1 ), but GYM B has been detected in shellfish from Lebanon and GYM D has been detected in shellfish originating from Spain.…”

“…As observed for other CI classes, fatty acid esters of SPXs were detected [ 54 ]. SPXs were found in shellfish from Argentina [ 55 ], Croatia [ 26 ], France [ 39 ], Italy [ 28 ], Norway [ 56 ], Portugal [ 57 ], Slovenia [ 58 ], Spain [ 59 ], China [ 60 ], Lebanon [ 35 ], New Zealand [ 61 ], Greece [ 39 ] and the Netherlands [ 15 ]. The dominant SPX detected was 13-desmethyl SPX C, but SPX A, 13-desmethyl SPX D, 13,19-didesmethyl SPX C, SPX C, isoSPX C, 20-methyl SPX G, SPX D, 13,19-didesmethyl SPX C and iso13,19-desmethyl SPX C were also found.…”

“…In this case, it was fatty acid esters of PnTXs A and G [ 71 ]. PnTXs have been found to contaminate shellfish from Canada [ 71 ], Chile [ 72 ], Croatia [ 26 ], France [ 73 ], Ireland [ 58 ], Netherlands [ 58 ], New Caledonia [ 38 ] Norway [ 74 ], Spain [ 75 ], Mozambique [ 76 ], New Zealand [ 61 ], Slovenia [ 58 ], Italy [ 58 ] and Greece [ 39 ]. PnTX G is the most abundant analogue observed, but PnTXs A, D, E and F have also been detected in shellfish ( Section 4 ).…”

The Temporal Distribution of Cyclic Imines in Shellfish in the Bays of Fangar and Alfacs, Northwestern Mediterranean Region

“…SPXs are polyether compounds that contain a spiro group attached to tricyclic ethers and are mainly produced by Alexandrium ostenfeldii, a thecate dinoflagellate that was first isolated in Iceland and described by Paulsen in 1904 [ 14 , 15 , 16 ]. They were identified, for the first time, in mussels off the coast of Nova Scotia (Canada, 1995) [ 17 ], although they are currently found in countries such as Spain, France, Italy, Scotland, Norway, Denmark, Mozambique, Chile, and Asia–Pacific countries [ 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 ]. The reference compound for this group is 13-desmethyl SPX-C (SPX-1) [ 26 ], which, together with SPX-C and 20-methyl SPX-G, is the most toxic compound [ 8 ].…”