Mussels chromatogram

One of the first applications of the HPLC method was the investigation of differences in toxin profiles between shellfish species from various localities ( ). It became apparent immediately that there were vast differences in these toxin profiles even among shellfish from the same beach. There were subtle differences between the various shellfish species, and butter clams had a completely different suite of toxins than the other clams and mussels. It was presumed that all of the shellfish fed on the same dinoflagellate population, so there must have been other factors influencing toxin profiles such as differences in toxin uptake, release, or metabolism. These presumptions were strengthened when toxin profiles in the littleneck clam (Prototheca Staminea) were examined. It was found that, in this species, none of the toxin peaks in the HPLC chromatogram had retention times that matched the normal PSP toxins. It was evident that some alteration in toxin structure had occurred that was unique in this particular shellfish species. 

Figure 8.3 GC-MS comparison of ion chromatograms of extracts from mussels Mytilus edulis) and SPMDs, Corio Bay Australia. Peaks labeled ISTD are internal standards. Reprinted with permission from the American Petroleum Institute, copyright 2002 (Huckins et al., 2002).

Figure 6. A-Chromatogram of toxic butter clam extract showing the presence of the PSP toxins. B-Chromatogram of extract from non-toxic (bioassay) mussels showing the presence of a trace of GTX II, GTX III, and C. Conditions as in Table I with gradient shown in Figure 4.

Figure 12.3. LC-MS chromatogram for OA group toxins in mussel hepatopancreas. o = acyl-OA d = acyl-CTX2 X = interfering signal from isotype peak of lower molecular weight compound = unknown compound. (Source ...

The composition of the chlorobiphenyl mixtures present In the surface sediment, particulate matter In the water column, filtrate from water column samples, and mussels reflect a combination of Aroclor 1242 and 1254 mixtures of chlorobiphenyls although there are distinct differences In each sample type. The chlorobiphenyl composition of water column samples (gas chromatograms not shown) resembles that of the mussels and surface sediments, although further measurements of a larger set of samples may reveal small but significant differences In composition. 

Examination of the gas chromatograms of PCBs In the samples of lobster and crab reveals the marked contrast In composition of PCBs In these types of biota samples and the composition of PCBs In water, sediment, bivalves and Aroclor mixtures. For example, the chlorobiphenyl composition of the lobsters are dominated by lUPAC chlorobiphenyl (CB) numbers 118, 153 and 138 while numbers 118 and 153 dominate the composition In the crab (Figure 2). Several more chlorobiphenyls, e.g. 28, 52, 44, 70, 95, 101, 110, are present In the mussel and sediment samples In addition to 118, 153 and 138 (Figure 2). PCBs In flesh of flounder species (L. maculata and P. amerlcanus) were Intermediate In composition between the lobsters and the mussels based upon examination of the gas chromatograms (not shown), I.e. 118, 153 and 138 predominate but not as much as In the lobsters. The possible reasons for these differences will be discussed below. 

Figure 3. High resolution gas chromatograms of PCBs In lobster tall and claw mussel tissue and whole green crab (N. taxons). Also see legend Figure 2.

Figure 11.10 HILIC-MS/MS analyses (MRM mode) of an extract of (left side) a plankton sample (Alexandrium tamarense) and (right side) of tissue from contaminated mussels (Mytilus edulis), each containing several PSP toxins. HILIC conditions were the same as those used with analytical standards to obtain Figure 11.9. Some SRM chromatograms are plotted with expanded scales as indicated. Reproduced from Dell Aversano, /. Chromatogr. A, 1081, 190 (2005), cop)rtght (2005) with permission from Elsevier.

Figure 8.16 GC—ICP-MS chromatogram of the spike and reference isotopes of mercury, lead, and tin in different elemental species fractions of an isotope-diluted mussel tissue sample. Reproduced with permission from [86],...

Some studies have found that creosote-treated timber can be a source of PAHs to marine organisms. Tissue of mussels Mytilus edulis) around creosote-treated piers contained elevated concentrations of benzo[a]pyrene, which declined with distance from the pilings (Dunn and Stich 1976b). The authors examined the gas chromatographic profiles of PAHs in mussels and nearby creosote-treated wood and found remarkably similar patterns in the chromatograms, indicating that the creosote-treated wood was probably the source in mussels. Dunn and Fee (1979) found that commercial lobsters Homarus americanus) accumulated PAHs when kept in an impoundment area that was constructed with creosote-coated timbers. After 3 mon, the tail muscle of the animals in the pound facility contained from 3 times more phenanthrene to 482 times more benzo[k]fluoranthene than in control lobsters. Most of the HPAHs were 100-300 times more abundant in the impounded animals compared to control animals. 

For quality assurance the standard reference material Lake Michigan Fish Tissue, SRM 1947, mussel tissue, SRM 1974b, fresh fish from the retail market, and fish feed were used. The fish feed used was composed of fish meal (48.8%), fish oil (5.7%), wheat (17.4%), wheat by-products (8.8%), soya (13.4%) and other components (5.9%). Typical chromatograms of the target contaminants in retail market samples are shown in Figures 4.108-4.110. 

Fig. 9.10. GC-DCP chromatogram for an extract of shellfish (mussel) from Maryland, USA, with tributyltin p>eak as indicated. Specific conditions megabore 1 /tm DB-17 column, 30 m X 0.53 mm, operated at 150°C, injection port 180 C, column flow rate 35 ml min argon, DCP at 303.41 nm, gain setting 40, PMT 9, sleeve pressure 50 psi (345 kla), active diagnostic mode, recorder chart speed 0.5 in min (1.3 cm min", 10 mV FSD). (Reprinted with permission of the copyright owner, Longman Group, UK and Journal of Applied Organometallic Chemistry [53].)...

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