Dr. Evin McGovern
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Chemistry all at Sea! ….. Monitoring the changing chemistry of our marine environment
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Dr. Evin McGovern
- 1. CASI Dublin City University 15th April 2016. All at Sea?? Marine Chemistry: Sound data for Ocean Governance Evin McGovern, Triona McGrath, Brendan McHugh, Conor Duffy Marine Institute
- 2. 1. Ocean Services and marine chemistry 2. A brief history of salt NEW DIRECTIONS CASE STUDIES 3. Ocean Carbon and acidification 4. Monitoring Hazardous Substances 5. Safe to eat!! Shellfish toxins
- 3. EEA 2015
- 4. Understanding the Oceans and processes Oceans under pressure - Human Driven changes Socio-economic – ecosystem services Ocean Tracers e.g. CFCs Biogeochemical Processes – C, N, P, metals Climate Change – Carbon/ ocean acidification, nutrients Pollution – Pesticides, hydrocarbons, nutrients, metals, industrial substances, plastics, pharma, EDCs Seafood safety– natural toxins, contaminants Bioactives- natural ocean products Mitigation– e.g. iron fertilisation
- 5. • 71 % surface of the earth • >97% of the water on the planet • 90% between 0 and 12.6°C and 3.43 and 3.51% salinity Image Credit: NASA Earth Observatory image by Jesse Allen, using VIIRS data from the Suomi National Polar-orbiting Partnership. Caption Credit: Michael Carlowicz. Instrument: Suomi NPP - VIIRS
- 6. Robert Boyle - The Sceptical Chymist Father of Marine Chemistry 1674 International Council of the Exploration of the Sea 1902 “Copenhagen Seawater” (Knudsen)
- 7. Courtesy of Ruth Curry, WHOI
- 8. PERPETUAL OCEAN Gulf Stream Sea Surface Currents and Temperatures NASA/MIT Visualisation http://svs.gsfc.nasa.gov/cgi-bin/details.cgi?aid=3913
- 9. Extended Continental Shelf– Real Map of Ireland!!! EEZ
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Nutrients and Ocean Acidification (OA) 0 10 20 30 TOxN uM 33 34 35 36 Salinity M6 M6 M6 M6 M6 M6M6M6 M6 M6 M6 M6 M6 M6 M6 L6 L6 M6 L6 K6 L6 K6 L6 K6 L6L6 K6 L6 L6 L6 L6 L6 L6 L6 L6 L6 L6 L6 L6 K6L6 L6 K6 L6 L6 L6 L6 L6 K6 L6 L6 L6 L6 L6 K6 K6 K6K6 K6 K6 K6 K6K6 K6K6 K6 K6 K6 K6K6 K6 K6 K6 K6 K6 K6 K6 K6 K6K6 K6K6 M6 M6 M6 L6 L6 L6 K6 K6 K6 K6 K6K6 K6 L6L6L6 K6 K6K6K6 M6 K6 M6 K6 K6 L6 L6 L6 L6 L6 L6L6 L6 M6 M6 M7 M6 M6 N6 N6 N6 N6 L6 L6 L6 L6L6 L6 N6 N6 L6L6 L6L6 L6 L6 L6 L6L6 L6 L6 L6 L6 L6 L6 L6 L6L6L6L6L6L6L6 L6L6L6 L6 L6 L6 L6 M6 L6 M6 M6 M6 M6M6 M6 M6 M6 M6 M6 M6 M6M6 M6M6 M6M6M6 M6 M6 M6 M6 M6M6M6 M6M6 M6 M7 M6 M6 L6 L6 M6M6M6 K6 K6 K6 K6K6K6 K6 K6 K6 K6 K6K6K6 K6 K6 K6K6 K6 K6 K6K6K6 K6K6 K6 K6K6 K6 K6 K6 L6 L6 L6 L6L6 L6 L6L6 L6 L6L6 L6 L6 L6 L6 L6 L6 L6 L6 L6 L6 L6 L6 L6 L6 L6L6 L6 L6L6 L6 L6 L6 L6 L6 M6 M6 M6 M6 M6 M6 M6M6 M6 M6 M6 M6 M6 M6 M6 M6 M6 M6 M6M6M6 M6 M6 M6 M6 M6 M6 L6 L6 L6 L6 M6 M6M6 K6 K6 K6K6 K6 K6 K6 K6 K6K6 K6 K6K6 K6 K6 K6 K6 K6K6K6 K6 K6 K6 K6 K6 K6 L6 L6 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- 13. The marine inorganic carbon system 25% of CO2 emitted is taken up by oceans, preindustrial pH8.2 ->8.1 Described by four variables: the partial pressure of carbon dioxide (pCO2), dissolved inorganic carbon (DIC), total alkalinity (TA) and pH. Knowledge of any 2 of these parameters allows for the determination of the entire inorganic carbonate system (along with other parameters – temperature, salinity, pressure, nutrients) pH reduction ~0.02 units/decade ; decreasing CaCO3 saturation states DIC with TA tend to be reference method to achieve precision (CRMs) pCO2 in situ
- 14. Effects of OA on marine ecosystems Ecosystem response will depend on the ability of species to adapt to an unprecedented rapid change in ocean chemistry Calcifying organisms are mostly are risk; calcifying phytoplankton (coccolithophores), planktonic foraminifera and pteropods, tropical and cold water corals, coralline algae including maërl, bivalves and gastropod molluscs (e.g. mussels, oysters, clams) and echinoderms (e.g. star fish, sea urchins) Other effects including fish behaviour Prediction of marine ecosystem response to OA => Proxies, experimental manipulation, paleo- Ni Longphuirt et al 2010 Raven et al 2005
- 15. MI- NUIGalway McGrath et al. 2012
- 16. The Future…. Integration and Expansion of Capabilities and Infrastructures
- 17. EMSO Fixed Station Observatories 4 test sites active (3 cabled) presently 11 nodes 9 operating nodes (cabled and autonomous) Koljö Fjord OBSEA MeDON Molène SmartBay
- 18. Marine Pollution – Hazardous substances Challenges and Direction in Monitoring • Spatial? • Getting better /worse? • Biological effects? • Compliance?
- 19. Contaminants in the marine Environment _ Sources Persistent, bioaccumulative &toxic or equal level of concern •Trace metals: e.g. Mercury, Lead, Cadmium •Persistent Organic Pollutants e.g. dioxins, DDTs, PCBs, flame retardants, PFAS •Oil pollution and hydrocarbons •Endocrine disrupting substances (e.g TBT) Synthetic e.g. PCBs Human activities add to natural loads in the marine environment e.g. metals
- 20. OSPAR Convention Assessments -Trends, spatial: Example lead in biota Comparability – Agreed • Sampling methodology • Analytical guidelines • Quality Control and Proficiency testing • Data reporting • Assessment approach including thresholds/criteria
- 21. PBDEs in mussels around the Irish coast
- 22. Cadmium in mussels around the Irish coast
- 23. Water Framework & Marine Strategy Directives Lower limit of target state High Good Moderate Poor Bad Good Ecological Status WFD MSFDUnimpacted state Unacceptable degree of impact Destroyed/ irrecoverable Not GEnS Not GEcS Good Environmental Status Deviation from unimpacted Good Chemical Status (<EQS) Not Good Chemical Status (>EQS) Biological Quality Elements, Physico-chemical, other pollutants Priority Substances, EQS in Water and Biota, QC Directive Compliance No Deterioration
- 24. Water Framework Directive - EQS • OSPAR: Trends and spatial selecting best matrices for measurement - biota or sediment • WFD: Environmental Quality Standards (EQS) based on toxicological derivation (EC Tech Guidance 27) • Application of EQS to wider marine environment???? • EQS Water – dissolved phase concentrations for metals; Total water organic substances (Little marine data) • Water is a challenging matrix – snap shot, multiple samples-costly, v. low target concentrations • EQS biota for certain substances - secondary poisoning top predators (whole fish) or human health (fish muscle)
- 25. EQSbiota Biomagnification model Moermond et al Int Env Assess and Man Vol 9: #1 pp 87- 97 (2012) 𝑩𝑪𝑭𝒍𝒂𝒃𝒐𝒓𝒂𝒕𝒐𝒓𝒚 = 𝑪 𝒐𝒓𝒈𝒂𝒏𝒊𝒔𝒎 𝑪 𝒘𝒂𝒕𝒆𝒓 𝑩𝑴𝑭 𝟏 = 𝑪 𝒑𝒓𝒆𝒅𝒂𝒕𝒐𝒓 𝑪 𝒑𝒓𝒆𝒚 Marine top predator Marine Predator (TL=5) Freshwater Predator (TL=5) Large Fish Trophic Level=4 QS biota, secpois QS biota, hh Human Fish Consumption BMF2 BMF1 BAF BCF Water Small Fish (mussels!) (TL=1-3) May not have samples at TL=4 `=>Trophic level adjustment
- 26. http://www.spc.int/oceanfish/en/ofpsection/ema/biological-research/trophic-dynamic-sampling Trophic level assignation and Stable Isotopes: ConcTL-adj = Concmeas*TMF (4-TL(x)) *default dry wt / actual dry wt: Uncertainty TMF, TL
- 27. Passive Sampling Advantages • Target analyte in situ • Time integrated (TWA) • High detection capability • Truly dissolved (bioavailable) • Contaminants not metabolised • Extracts used in bioassays Disadvantages • Rate limiting step dependent on: • Type/properties of membrane • Properties of analyte • Environmental factors • Legislative constraints Kinetic or Equilibrium Passive Samplers Free flow of analyte molecules from seawater sampler receiving phase POCIS PDMS
- 28. Overview of main components proposed for an integrated monitoring programme for effects of contaminants. Solid-lined boxes, prioritized core components; bold text, components in CEMP; broken-lined boxes, additional optional components proposed. ECOSYTEM INTEGRATION
- 29. Test system and contaminant coverage Scale of Organisation EDC + Pharm + BOD + Metal PAH Chemical Eutroph Ecosystem Population Individual Organ Cell Sensitivity Controlof Timescale Biocomplexity HIGH LOW LONG SHORT LOW HIGH Fish pathology, sediment toxicity Imposex, Intersex Vitellogen MTinduction EROD Lysosome stability Reproduction, SFG COX, peroxisome DNA strand breaks Benthic indicators Giltrap et al 2014
- 30. Assessment of contaminants, exposure and effects for eight locations in Irish marine waters
- 31. Safe to eat…….!! • contaminants in seafood • residues in farmed fish • algal toxins in shellfish
- 32. Toxin Group Paralytic Shellfish Poisoning PSP Amnesic Shellfish Poisoning ASP Diarrhetic Shellfish Poisoning DSP Azaspiracid Shellfish Poisoning AZP Yessotoxin YTX Pectenotoxin PTX Neurotoxic Shellfish Poisoning (NSP) Cyclic Imine Group – Spirolides, Gymnodimines, Pinnatoxins, Pteriatoxins, Prorocentrolides. }Most relevant to Irish Industry
- 33. AZP- Azaspiracid Shellfish Poisoning Lipophilic Toxin Group • Causative Organism: Azadinium Spinosum. • Toxin Present: Azaspiracid. 30+ analogues • First Reported: 1995 in Killary harbour. • Effect: Diarrhoea, nausea, vomiting and abdominal pain. • Regulatory Limit: 0.16ug/g • Method of Analysis: MBA, LCMSMS, Elisa. • No. of samples tested per year: 1600 • Major cause of closures of shellfish growing areas.
- 34. DSP toxins AZP toxins 5 min 2010 2012 AZA-1 AZA-1 AZA-2 AZA-2 AZA-3 AZA-3 Free Oa Free Oa Free DTX1 Free DTX1 Free DTX2 Free DTX2 Total Oa Total DTX1 Total DTX2 PTX1 PTX2 YTX Homo YTX 45-Homo-YTX 45-OH -YTX •Faster Analysis •Improved turnaround times •Multi-residue - Increased No. of analytes per sample •Meets regulatory requirements •Allows for the move away from MBA •MI – AZA Standards •Proficiency testing 16 min LCMSMS – New official method replaced mouse bioassay.
- 35. Conclusions Good Quality marine chemistry data is fundamental to understanding the physical and ecosystem processes in the oceans especially in the context of changes driven by human activities New monitoring platforms offer new paradigms….but sensitive, robust, high precision sensors are necessary that will withstand long term offshore deployment There are issues in translating freshwater approaches for monitoring hazardous substances to the marine environment. Areas of development include use of passive samplers and biological effects/ ecosystem assessment Seafood – new developments for ensuring seafood is safe to eat supports consumers and industry
- 36. Acknowledgements: MI Chemistry group, Shellfish Safety group and project partners in NUI Galway, DCU, DIT, GMIT,TCD, SFPA, FSAI and EPA. Thank You
Hinweis der Redaktion
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- The Gulf Stream is a powerful ocean current found in the Atlantic Ocean that transports warm water from the Gulf of Mexico along the South Atlantic Seaboard, subsequently influencing local weather patterns and climate—especially in Florida. The current then turns northeastward crossing the Atlantic, where it exerts a warming influences on the climate of Western and Northern Europe, making these areas warmer then they would otherwise be. This visualization shows the warm-water Gulf Stream and its associated temperatures as it stretches across the Atlantic generating smaller currents and ocean eddies along the way. Model output from the Estimating the Circulation and Climate of the Ocean, Phase II (ECCO2) project were used to create this visualization. The project used a general circulation model to synthesize satellite and in situ data of the global ocean at resolutions that resolve ocean eddies and other narrow current systems, like the Gulf Stream, that transport heat in the oceans and impact Earth’s climate.
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- Illustrative slide – map shows data in database over a ~20 year period of RV based winter surveys (oceanography, nutrients and other surveys) Top graph is total oxidised nitrogen vs salinity showing different TOxN concentrations across shelf showing decreasing concentrations away from the shelf break Bottom graph shows decline in pH associated with increasing CO2 in surface waters of the Rockall trough. Our data are compared with 1990s WOCE data. Measured decline is (one of the few such datasets globally). We also see reductions to pH in deep water (Labrador Sea Water)
- Illustrative slide – map shows data in database over a ~20 year period of RV based winter surveys (oceanography, nutrients and other surveys) Top graph is total oxidised nitrogen vs salinity showing different TOxN concentrations across shelf showing decreasing concentrations away from the shelf break Bottom graph shows decline in pH associated with increasing CO2 in surface waters of the Rockall trough. Our data are compared with 1990s WOCE data. Measured decline is (one of the few such datasets globally). We also see reductions to pH in deep water (Labrador Sea Water)
- This slide highlights many of the different types of platforms in use in ocean observation - particularly in the coastal zone.
- 15 nodes in total in European Water includes deepwater and shallow sites.
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- Is a sample suitable…..
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- The first report of human intoxication was in the Netherlands in 1961. Often mistaken for e colic or Norovirus contamination which has similar symptoms. Also shown to be a tumor promoting substance in animal tests.
- First reported in 1995 after 8 people got sick after eating mussels originating from Ireland.
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