Krock, Bernd

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Red Tides and Phycotoxins:the Problems arein the DetailsXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockChile is prone to HAB events, e.g. 2016 IntroductionXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockFebruary/March 2016, Regíon de Los Lagos: massive bloom ofPseudochattonella cf. verruculosaInforme Final, Comisión Marea Rojahttps://www.economia.gob.cl/wp-content/uploads/2016/11/InfoFinal_ComisionMareaRoja_24Nov2016-1.compressed.pdfIntroductionXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockInforme Final, Comisión Marea Rojahttps://www.economia.gob.cl/wp-content/uploads/2016/11/InfoFinal_ComisionMareaRoja_24Nov2016-1.compressed.pdfhttps://www.mundoacuicola.cl/new/mortalidad-de-salmones-por-fans-no-aceptemos-los-mismos-errores/April/May 2016, Región de Los Lagos: massive bloom event ofAlexandrium catenellaIntroductionXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. Krockhttps://www.mundoacuicola.cl/new/mortalidad-de-salmones-por-fans-no-aceptemos-los-mismos-errores/Both blooms were almost coinciding in time and space and caused massmortality of marine life, especially in salmon aquacultureMechanistically both blooms were differrent:Pseudochattonella cf. verriculosa: IchthyotoxicAlexandrium catenella:PSP Toxin producerhttps://alchetron.com/Pseudochattonella20µmU. TillmannIntroductionXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockVariabilityKarlotoxins: 20+ known variantsPrymnesins: 100+ variantsOther ichthyotoxic species:Alexandrium spp.Chattonella spp.Chrysocromulina spp.Fibrocapsa japonicaHeterosigma akashiwoProtoceratium reticulatumPseudochattonella cf. verruculosaIchthyotoxins:Unknown !!Amphidinols: 20+ known variantsOOOOHOOOOOOO OOOONH2ClCl OHOOOHHOOHHOHOOHOOHOOOHHOHOOHOHHOHOOHOHOHHOH HH HHOHHClHHHOOHHH H HHH HHHHHHHHHHOCl OOHOHHOOHOHOHOHOOHOHOHOHOHOHOHOHOHOHOHOHOHOHHOIchthyotoxinsXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockCl OOHOHHOOHOHOHOHOOHOHOHOHOHOHOHOHOHOHOHOHOHOHHOOOOOHOOOOOOO OOOONH2ClCl OHOOOHHOOHHOHOOHOOHOOOHHOHOOHOHHOHOOHOHOHHOH HH HHOHHClHHHOOHHH H HHH HHHHHHHHHHOPRM-1Lipophilic partHydrophilic partKmTx-2Known IchthyotoxinsIchthyotoxinsXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockLong et al. (2021) Toxins 13(12): 905.IchthyotoxinsMode of actionXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. Krock10µm20µmAlexandrium catenella  strain 2 (Alex2)Rhodomonas salinaLytic EffectVideo: U. TillmannRhodomonas salina exposed to A. catenella supernatant (cell free)IchthyotoxinsXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockChemical compound Ecological FunctionOrganismAlexandriumspp.PSP-ToxinsNN NHHNNH2OHOHOH2NR1R2R3R4?Pseudochattonellacf. verriculosa(Alexandrium spp.)Defense against PredatorsElimination of Competitors?OONOOOOHHO233113SpirolidesIchthyotoxinsXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockCurrent Hypothesis:Lytic compounds of marine protists are weapons of chemical warfare among protists Ichthyotoxicity is a collateral damage of protistan allelochemistry XIchthyotoxinsXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. Krockhttps://www.mundoacuicola.cl/new/mortalidad-de-salmones-por-fans-no-aceptemos-los-mismos-errores/Both blooms were almost coinciding in time and space and caused massmortality of marine life, especially in salmon aquacultureMechanistically both blooms were differrent:Pseudochattonella cf. verriculosa: IchthyotoxicAlexandrium catenella:PSP Toxin producerhttps://alchetron.com/Pseudochattonella20µmU. TillmannXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockNeed of monitoring for seafood safetyVariability of phycotoxinsHigh variability of phycotoxin cassesXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockMouse Bioassay (MBA)Variability of phycotoxinsLiquid chromatography coupled to tandemmass spectrometry (LC-MS/MS)MBA is banned in the United States and the European Union XLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockProblems of MBA:• Poor reproducibility• Low sensivity• Low specifity• Ethical concernsVariability of phycotoxinsProblems of LC-MS/MS:• High cost• Need of trained staff• Only targeted analysisXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockThe EFSA Journal (2009) 1306, 1-23Variability of phycotoxins                    1 2 3 4 5 6 7 8 9 10 11 12 13 14Ti  i 11,70Scottish strain 3D9 (2007)AZA-1AZA-2Me-AZA-1                   1 2 3 4 5 6 7 8 9 10 11 12 13 14 15  12,31Danish strain UTH E2 (2008)AZA-1AZA-2Me-AZA-15 µmm/z 842>824m/z 856>838Azadinium as AZA producerRetention timeRetention timeA. spinosumKrock, B., et al. (2009) Harmful Algae 8, 254-263. Krock, B., et al. (2013) J. Plankt. Res. 35, 1093-1108. XLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockVariability of phycotoxinsNHOOOOOOOOOHOOHHOHHHHHHHR5ABCDEFGHI1101314212628323740R3R1R2R498U. TillmannXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockVariability of phycotoxinsNHOOOOOOHHOHHHHR5EF283237R2R4HOOAZA-33NHOOOOOOOOOOHHOHHHHHHHR5ABCDEFGHI101314212628323740OHR1R2R487AZA-34/35NHOOOOOOOOOHOOHHOHHHHHHHR5ABCDEFGHI1101314212628323740R3R1R2R498Toxin R1 R2 R3 R4 R5 Δ7,8 [M+H]+AZA-1 H CH3 H H CH3 √ 842AZA-2 CH3 CH3 H H CH3 √ 856AZA-3 H H H H CH3 √ 828AZA-4 H H OH H CH3 √ 844AZA-5 H H H OH CH3 √ 844AZA-6 CH3 H H H CH3 √ 842AZA-7 H CH3 OH H CH3 √ 858AZA-8 H CH3 H OH CH3 √ 858AZA-9 CH3 H OH H CH3 √ 858AZA-10 CH3 H H OH CH3 √ 858AZA-11 CH3 CH3 OH H CH3 √ 872AZA-33 - CH3 H H CH3 - 716AZA-34 H CH3 - H CH3 √ 816AZA-35 CH3 CH3 - H CH3 √ 830AZA-36 CH3 CH3 OH H H √ 858AZA-37 H CH3 OH H H - 846AZA-38 nd nd nd nd H nd 830AZA-39 nd nd nd nd H nd 816AZA-40 CH3 CH3 H H H √ 842XLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockVariability of phycotoxinsXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. Krock# AZA m/z [M+H]+ m/z group 4 fragment m/z group 5 fragment Producer Reference1 AZA-1 842 362 262 A. spinosum Krock et al. 20092 AZA-2 856 362 262 A. spinosumA. poporumAm. languidaKrock et al. 2009Krock et al. 2014Tillmann et al. 20173 epi-AZA-7 858 362 262 A. dexteroporum Rossi et al. 20174 AZA-11 872 362 262 A. poporum Krock et al. 20145 AZA-33 716 362 262 A. spinosum Kilcoyne et al. 20146 AZA-34 816 362 262 A. spinosum {Kilcoyne et al. 20147 AZA-35 830 362 262 A. spinosumA. dexteroporumKilcoyne et al. 2014Rossi et al. 20178 AZA-36 858 348 248 A. poporum Krock et al. 20159 AZA-37 846 348 248 A. poporum Krock et al. 201510 AZA-38 830 348 248 Am. languida Krock et al. 201211 AZA-39 816 348 248 Am. languida Krock et al. 201212 AZA-40 842 348 248 A. poporum Krock et al. 201413 AZA-41 854 360 260 A. poporum Krock et al. 201414 AZA-42 870 360 260 A. poporum Krock et al. under review15 AZA-43 828 360 260 Am. languida Tillmann et al. 201716 AZA-50 842 348 262 A. spinosum Tillmann et al. 201817 AZA-51 858 348 262 A. spinosum Tillmann et al. 201818 AZA-52 830 348 248 Am. languida Tillmann et al. 201819 AZA-53 830 348 248 Am. languida Tillmann et al. 201820 AZA-54 870 362 262 A. dexteroporum Rossi et al. 201721 AZA-55 868 360 260 A. dexteroporum Rossi et al. 201722 AZA-56 884 362 262 A. dexteroporum Rossi et al. 201723 AZA-57 844 362 262 A. dexteroporum Rossi et al. 201724 AZA-58 828 362 262 A. dexteroporum Rossi et al. 201725 AZA-59 860 362 262 A. poporum Kim et al. 201726 AZA-62 870 362 262 A. poporum Krock et al. 2019Currently62 published AZAsAnd at least additional10 known AZAs26 AZAs fromplanktonic originVariability of phycotoxinsCurrently Known AZA from Dinoflagellate (Algal) OriginAZA-1 AZA-41AZA-2 AZA-42epi-AZA-7 AZA-43AZA-11 AZA-50AZA-33 AZA-51AZA-34 AZA-52AZA-35 AZA-53AZA-36 AZA-54AZA-37 AZA-55AZA-38 AZA-56AZA-39 AZA-57AZA-40 AZA-58AZA-59 AZA-62AZA-3 AZA-14 AZA-25 AZA-47AZA-4 AZA-15 AZA-26 AZA-48AZA-5 AZA-16 AZA-27 AZA-49AZA-6 AZA-17 AZA-28 AZA-60AZA-7 AZA-18 AZA-29 AZA-61AZA-8 AZA-19 AZA-30AZA-9 AZA-20 AZA-31AZA-10 AZA-21 AZA-32AZA-11 AZA-22 AZA-44AZA-12 AZA-23 AZA-45AZA-13 AZA-24 AZA-46AZAs produced by algae AZA shellfish metabolites of AZA-1 and -2Two AZAs of phytoplankton origin result in38 shellfish metabolites! Azaspiracids - VariantsKrock, B., et al. (2019) Harmful Algae 82, 1-8.XLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockVariability of phycotoxinsToxin AZA-1 Analog m/z [M+H]+ m/z [M+H-H2O]+ Retentiontime [min]AZA-59 AZA-1/2 860 842 10,6AZA-59-A AZA-3/6 846 828 10,1AZA-59-B AZA-8/12 876 858 9,6AZA-59-C AZA-17/19 890 872 9,9AZA-59-D ? 890 872 10,3AZA-59-E No analog 892 874 9,0AZA-59-F No analog 878 860 9,65Kilcoyne, J., et al. (2018) J. Nat. Prod. 81(4), 885-893.Azaspiracids – Metabolism in BivalvesXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockVariability of phycotoxins                   1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 10,0 11,0 12,0 13,0 14,0 15,0 16,0 17,0 18,0Time min0,05,0e41,0e51,5e52,0e52,5e53,0e53,5e54,0e54,5e55,0e55,5e56,0e56,5e56,9e5Intensity, cps11,49XLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockAzadinium poporumstrain 1D5 isolated near Chañaral, Northern ChileTillmann et al. (2017) J. Plankt. Res 39(2): 350-367)m/z 872>854AZA-11Variability of phycotoxinsAZA-1,-2,-33AZA-2,-43AZA-59AZA-2AZA-39,-52,-53AZA-11,-50,-51AZA-38,-39AZA-11, 62AZA-2,-11,-40,-41,-42AZA-36AZA-7,-35,-54,-55,-56,-57,-58Azaspiracids – Geographic distributionAZA-2, -11, -40, -59AZA-37XLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockVariability of phycotoxinsToxin distribution in the Última Esperanza Province (Southeast Pacific, Chile) during the PROFAN expedition November 2019XLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. Krock© Diego Nahuelhuén, IDEALStudy areaPto. EdénPto. MonttXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockPROFAN expedition (November 2019)1. PSP-toxin – relative profilesQuellónSto. DomingoIsla OvaladaCanal CostaIsla CaillínIsla San PedroBahía AsasaoAysénIsla JorgeIsla QuemadaPF1Isla LuzPF5PF3PF12PF11PF8PF7PF6PF18PF17 PF14PF13Varela et al. 2012Aguilera-Belmonte et al. 2011PF22004 2009B1 (GTX 5) B2 (GTX 6)XLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockPROFAN expedition (November 2019)Puerto EdénPF11PF12PF18PF5PF8PF14PF1PF2PF3PF6PF71. PSP-toxins – geographic distribution of profilesCanal MessierCanal WildeCanal TrinidadXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockPROFAN expedition (November 2019)1. PSP-toxins – species contributions?Puerto EdénVarela et al. 2012Alexandrium ostenfeldiiAlexandrium catenellaIsla VergaraSalgado et al. 2015PF14PF3???Cultured strainsPlanktonic field samplesXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockPROFAN expedition (November 2019)2. Lipophilic toxins – qualitative profilesDA only at inner stationsCoincidence of YTX, homo-YTX and OH-homo-YTX Presence of PTX-2sa in planktonPresence of 20-Me SPX G almostexclusively at inner stations; firstreport of 20-Me SPX G in ChileAZA-2 only at outer stationsXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockPROFAN expedition (November 2019)SPATT = Solid Phase Adsorption Toxin Tracking• Water is pumped through a porous synthetic resin passively adsorbing toxins• Pros:• Time-integrating sampling Toxin dynamics• Low-cost; easy sampling Potential as an early warning system• Cons:• Lack of calibration • Monitoring of dissolved toxins only  no iformation on the current plankton presence3. SPATT samplingXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockPROFAN expedition (November 2019)3. SPATT samplingToxin abundance higher in channels and fjords than in the open PacificOA/DTX-1 were detetcedduring the entire trackand were not restrictedto Aysén RegionAZA-2 was presentduring the entire trackat low abundancesFirst report ofpinnatoxin G in Chile XLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockPROFAN expedition (November 2019)Möller et al. (2022) Prog. Oceanogr., in revisionMain results1. Phycotoxins were detected at all stations except for station 4 (Eyre Gulf, Pio XI Glaciar)7. Pinnatoxin G (PnTx G) was detected for the first time in Chilean waters and stonglyindicates the presence of Vulcanodinium rugosum6. AZA-2 was detected in low concentrations in water samples during the entire cruise transect and seems to be the prevalent AZA variant in southern Chile5. Even though no OA/DTX-1 were detected in plankton samples, these toxins were presentin water samples during the entire cruise transect and indicate the presence ofDinophysis acuta also in the Magallanes Region4. Presence of homo-YTXs indicates the presence of other YTX-producing species thanProtoceratium reticulatum3. DA, PTXs and YTXs were most abundant lipophilic toxins2. Greographically discinct distribution of PSP toxin profiles in Úlima Esperanza ProvinceXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockPROFAN expedition (November 2019)M179FjordFluxXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockFurther information:https://m.dw.com/es/una-ventana-al-futuro-desde-la-patagonia-la-campaña-trilateral-fjord-flux/a-60584473XLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockFjordFlux expedition (January/February 2022)XLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockFjordFlux expedition (January/February 2022)12341 Almirantazgo Bay4 Garibaldi Fjord2 Cockburn/Ballenero Channel3 Beagle ChannelXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockFjordFlux expedition (January/February 2022)XLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockFjordFlux expedition (January/February 2022)30./31. Jan.10./11. Feb.Beagle ChannelGaribaldi FjordXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockFjordFlux expedition (January/February 2022)Transmission (%)65707580859095Transmission (%) Temperature (°C)23456789Temp. (°C)Stations1 s2 s3 s4 s5 s7 s8 s9 s10 s11 s12 s13 s14 s15 s16 s17 s18 s19 s20 s21 s22 s23 s25 s26 s28 s29 s31 s32 s33 s35 s36 s37 s38 s40 s41 s42 s43 s44 s45 s46 s47 s48 s49Chlorophyll (ug L-1)01234567Green Algae Bluegreen DiatomsCryptophytaAlmitantazgo BayCockburn ChannelBallenero ChannelBeagle ChannelDrake Passage Beagle ChannelGaribaldi FjordBallenero Channel, Cockburn Channel, Magellan StraitData: Ricardo Giesecke, IDEALFunctional plankton groupsXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. Krock0500100015002000250030001 2 3 4 5 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 25 26 28 29 31 32 33 35 36 37 38 40 41 42 43 44 45 46 GS 47 48 49 50 51DA DTX1 PTX2 SPX1 20 methyl SPX G YTX YTX-1047 YTX-1131 YTX-1143Drake PassageBeagle ChannelGaribaldi FjordBallenero Channel, CockburnChannel, Magellan StraitAlmirantazgo BayCockburnChannel Ballenero ChannelBeagle ChannelLipophilictoxins[ng/NT]FjordFlux expedition (January/February 2022)XLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. Krock01020304050607080901001 2 3 4 5 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 25 26 28 29 31 32 33 35 36 37 38 40 41 42 43 44 45 46 GS 47 48 49 50 51YTX YTX-1047 YTX-1131 YTX-1143Drake PassageBeagle ChannelGaribaldi FjordBallenero Channel, CockburnChannel, Magellan StraitAlmirantazgo BayCockburnChannel, Ballenero ChannelBeagle ChannelYTXs [ng/NT]FjordFlux expedition (January/February 2022)2. Phycotoxin variability of known toxin classes is high and yet not fully explored, especially in hard to access coastal areas in Southern ChileXLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. KrockConclusions1. Ichthyotoxins are rarely characterized, but pose an increasingthreat to increasing aquacultural activities3. Phycotoxin profiles tend to be geographically relatively stable4. Locally occurring phycotoxin variants should be included in chemical monitoring efforts in addition to officially regulatedtoxinsThanks forYour Attention!AnyQuestions?XLI Congreso Chileno de Ciencias del Mar, UCSC, Concepción, 23-27 Mayo 2022, B. Krock

Red Tides and Phycotoxins: the Problems are in the Details

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Red Tides and Phycotoxins: the Problems are in the Details

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