Bernd Krock
1, Urban Tillmann
1, Tilman Alpermann
2, Rafael Salas
3Allan D. Cembella
1Alfred-Wegener-Institut für Polar- und Meeresforschung in der Helmholtz-Gemeinschaft www.awi.de
1) Alfred Wegener Institute 2) LOEWE Biodiversity and Climate Reasearch Centre (BiK-F) 3) Marine Institute
Am Handelshafen 12 Senckenberganlage 25 Rineville, Oranmore
27570 Bremerhaven, Germany 60325 Frankfurt a.M., Germany Galway, Ireland
A Multi-Year Comparison of Spirolide Profiles in Planktonic Field Samples from the North Sea and Adjacent Waters
Known structural variants of spirolides
Abundance of spirolides in the 20-50 µm size fraction of 20 m vertical net tows; A) FS Poseidon PO 356 cruise, June – July 2007; B) FK Uthörn cruise, July 2008; C) FS Heincke HE 302 cruise, April – May 2009
20-Methyl G is the most abundant spirolide in the North Sea
Alexandrium ostenfeldii isolates from distinct geographical locations showed almost identical profiles, primarily consisting of 20- methyl spirolide G (20-meG). Whereas the Scottish isolate produces only this variant, the Irish isolate additionally yields slight amounts of 13-desmethyl spirolide C (13-desmeC).
These profiles were also reflected in the field data, where 20-meG was the most abundant spirolide throughout all samples and years.
Even though 13-desmeC was also detected in the North Sea, the highest 13-desmeC/20- meG ratios were found in the southern Irish and the western Celtic Sea (HE 302, stns. 46- 51). Spirolide A was barely detected in 2007 and 2008, in contrast to relatively high concentrations found in 2009 in the North Sea and western Scottish waters, but not along the Irish coast. There is no known source of spirolide A in Europe, but field surveys based upon LC-MS/MS profiling provide a plausible means of identifying new toxin sources and their biogeographical distribution.
References:
1) Cembella, A. D., N. I. Lewis, and M. A. Quilliam. 2000. Phycologia 39:67-74.
2) Hu, T., I. W. Burton, A. D. Cembella, J. M. Curtis, M. A. Quilliam, J. A.
Walter, and J. L. C. Wright. 2001. J. Nat. Prod. 64:308-312.
3) Hu, T., J. M. Curtis, Y. Oshima, M. A. Quilliam, J. A. Walter, W. M. Watson- Whright, and J. L. C. Wright. 1995. J. Chem. Soc. Chem. Commun.:2159- 2161.
4) Aasen, J., S. L. MacKinnon, P. LeBlanc, J. A. Walter, P. Hovgaard, T. Aune, and M. A. Quilliam. 2005. Chem. Res. Toxicol. 18:509-515.
Time series Clim. & Anthr.
0 2000 4000 6000 8000 10000 12000
2 3 3-6 4 5 6 DK01 DK02 DK03 DK04 DK05 DK06 DK07 DK08 DK09 DK10 DK11 DK12 DK13 DK14 DK15 DK16 DK17 DK18 DK19 DK20 DK21 DK22 DK23 DK24 DK25
Station
pg/net tow
0 20000 40000 60000 80000 100000 120000 140000 160000 180000 200000
2345 678910 1112131415 1617181920 212223242526 27282930 3132333435 363738394041 42434445 464748495051 52535455 5657585960
Station
pg/net tow
O O O N
O O
O H
R2 R3 OH R1
23 13 31
19
O O N
O O
R2 R3 OH R1
23
13 32
20
O O H 17
691.5 705.5
√
√ H CH3 H H CH3 CH3 G 20-Me-G
691.5 693.5 705.5 691.5 677.5 707.5 693.5
√ -
√
√
√ - - CH3 CH3 CH3 CH3 H CH3 CH3 CH3 CH3 CH3 H H CH3
H H H CH3 CH3 CH3 CH3 CH3 A B C 13-desMe-C 13,19-didesMe-C
D 13-desMe-D
[g/mol]MW
∆2,3 R3 R2 R1 Spirolide
691.5 705.5
√
√ H CH3 H H CH3 CH3 G 20-Me-G
691.5 693.5 705.5 691.5 677.5 707.5 693.5
√ -
√
√
√ - - CH3 CH3 CH3 CH3 H CH3 CH3 CH3 CH3 CH3 H H CH3
H H H CH3 CH3 CH3 CH3 CH3 A B C 13-desMe-C 13,19-didesMe-C
D 13-desMe-D
[g/mol]MW
∆2,3 R3 R2 R1 Spirolide
0 10000 20000 30000 40000 50000 60000 70000 80000 90000
374 375 376 377 378 379 380 381 383 384 385 386 387 388 389 390 391 392 393 394 395 396 398 399 400 415 416 417 418 419 420 421 424 425 426 427 428 429 430 431 432 433 434 435 436 447 458 459 460
Station spirolide [pg/NT] 13-desMe C
20-Me G PO 356 (2007)
UTH (2008)
13-desMe C 20-Me G
HE 302 (2009)
13-desMe C 20-Me G spirolide A spirolide C
Introduction
Spirolides are „fast acting“ lipophilic cyclo imine toxins, which are produced by the marine dinoflagellate Alexandrium ostenfeldii1. Most spirolides were identified in isolates from the Canadian east coast and structurally belong to the A – D type2,3. Recently G-type spirolides were identified in shellfish and plankton from Skjer (Sognefjord, Norway)4.
415
420
430
374 376
386
390
400 382
2 10 30 21
40
50
A
B
C
Spirolide profiles of two isolates of A. ostenfeldii
2 4 6 8 10 12 14 16 18 20 22 24 26 28
20-Me-G A. ostenfeldii 1065 (Bantry Bay, SW Ireland)
2 4 6 8 10 12 14 16 18 20 22 24 26 28
20-Me-G A. ostenfeldii S6_P12_E11 (Scotland, North Sea) 13-desMe-C
Acknowledgements:
This work was financed by the HGF through the research programmes MARCOLPOLI and PACES and is part of the GEOHAB CORE research project on HABs in Fjords and Coastal Embayments.
