Contamination of shellfish with lipophilic marine biotoxins (LMB), pectenotoxins (PTXs), yessotoxins (YTXs) and okadaic acid (OA) toxin groups in southern Chile is a constant challenge for the development of miticulture considering the high incidence of toxic episodes that tend to occur. This research is focused on using methodologies for assessing the decrease in toxins of natural resources in Chile with high value, without altering the organoleptic properties of the shellfish. The species were processed through steaming (1 min at 121°C) and subsequent canning (5 min at 121°C). Changes in the profiles of toxins and total toxicity levels of LMB in endemic bivalves and gastropods were determined using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The total reduction of toxicity (≈ 15%) was not related to the destruction of the toxin, but rather to the loss of LMB on removing the shells and packing media of canned products (***p < 0.001). Industrial processing of shellfish reduces LMB contents by up to 15% of the total initial contents, concomitant only with the interconversion of PTX-group toxins into PTX-2sa. In soft bottom-dwelling species with toxicities beyond the standard for safe human consumption (≥ 160 μg OA-eq kg), toxicity can be reduced to safe levels through industrial preparation procedures.
Saxitoxin (STX) group toxins consist of a set of analogues which are produced by harmful algal blooms (HABs). During a HAB, filter-feeding marine organisms accumulate the dinoflagellates and concentrate the toxins in the tissues. In this study, we analyze the changes in antioxidant enzymes and oxidative damage in the bivalves Mytilus chilensis and Ameghinomya antiqua, and the gastropod Concholepas concholepas during a bloom of Alexandrium pacificum. The results show that during the exponential phase of the bloom bivalves show an increase in toxicity and activity of antioxidant enzymes (superoxide dismutase, catalase, glutathione peroxidase, and glutathinoe reductase, p < 0.05), while in the gastropods, increased activity of antioxidant enzymes was associated with the bioaccumulation of toxins through the diet. At the end of the bloom, decreased activity of antioxidant enzymes in the visceral and non-visceral tissues was detected in the bivalves, with an increase in oxidative damage (p < 0.05), in which the latter is correlated with the detection of the most toxic analogues of the STX-group (r = 0.988). In conclusion, in areas with high incidence of blooms, shellfish show a high activity of antioxidants, however, during the stages involving the distribution and bioconversion of toxins, there is decreased activity of antioxidant enzymes resulting in oxidative damage.
Lipophilic marine toxins (LMTs) are a group of marine toxins which in recent years have been consistently identified in the vast majority of shellfish worldwide. One of their main characteristics is having a latitudinal variability and an assimilation/retention specific for each species. LMTs consist of four important groups: okadaic acid group (OA-group), pectenotoxin group (PTX-group), azaspiracid group (AZA-group) and yessotoxin group (YTX-group). These groups have different chemical structures, which has generated an important challenge to establish analytical techniques to identify all toxic analogues from the same toxic matrix. Likewise, in the aquatic environment, shellfish represent the best bio-indicator model that allows for the establishment of levels of toxicities related to LMTs. In this chapter, the evolution for detection of LMTs from mouse bioassay (MBA), enzymatic assays (PP2a), and analytical techniques, such as liquid chromatography tandem-mass spectrometry (LC-MS/MS), are described. These analytical advances have allowed us to determine and identify the characteristic profiles of LMTs produced by marine microalgae, including the prevalence and biotransformation of LMTs in the different endemic species. It is worth mentioning that these techniques have favoured the updating of numerous sanitary standards and the definition of the most appropriate technique for the detection of LMTs in shellfish and endemic species.
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