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Trace metal cycling in the ocean
Julia MiddletonWoods Hole Oceanographic Institution
Prepared for:
Coastal Ocean Environment Summer School09 August 2019
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Why study trace elements in the ocean?
• Some trace elements are essential for marine life.
• Some trace elements are toxic to marine life.
• Some trace elements reveal anthropogenic impacts on the ocean.
• Some trace elements can be used to understand important processes in the ocean.
• Some trace elements might influence climate change.
• Some trace elements can be used to study the geological history of the ocean.
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Why study trace elements in the ocean?
• Some trace elements are essential for marine life.
• Some trace elements are toxic to marine life.
• Some trace elements reveal anthropogenic impacts on the ocean.
• Some trace elements can be used to trace important processes in the ocean.
• Some trace elements might influence climate change.
• Some trace elements can be used to study the geological history of the ocean.
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Some trace metals are essential building blocks of life
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Dissolved inorganic carbon (DIC)Nitrate Phosphate
These are the basic building blocks of all life
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Chlorophyll a
Lots of nutrients (nitrogen, phosphorous)
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High Nutrient Low Chlorophyll regions (HNLCs)
Lots of nutrients, but not much primary productivity
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Karl Turekian, on the field of Marine Trace Metal Chemistry (1930-1980)
Quoted in L-G. Daniellson’s Ph.D thesis “Trace metals in marine waters: analytical investigations on Cadmium, Cobalt, Copper, Iron, Lead, Nickel and Zinc
"Indeed one has the feeling that the whole field of trace metal marine geochemistry would have been a completely dull one over the past fifty years if it weren't for analytical errors.”
NOTE: “analytical errors” includes both errors in laboratory handling and measurement methods and contamination during sampling and analysis.
Slide courtesy of Ed Boyle11
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Karl Turekian, on the field of Marine Trace Metal Chemistry (1930-1980)
Quoted in L-G. Daniellson’s Ph.D thesis “Trace metals in marine waters: analytical investigations on Cadmium, Cobalt, Copper, Iron, Lead, Nickel and Zinc
"Indeed one has the feeling that the whole field of trace metal marine geochemistry would have been a completely dull one over the past fifty years if it weren't for analytical errors.”
NOTE: “analytical errors” includes both errors in laboratory handling and measurement methods and contamination during sampling and analysis.
Metal
Metal
Metal
Metal
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Karl Turekian, on the field of Marine Trace Metal Chemistry (1930-1980)
Quoted in L-G. Daniellson’s Ph.D thesis “Trace metals in marine waters: analytical investigations on Cadmium, Cobalt, Copper, Iron, Lead, Nickel and Zinc
"Indeed one has the feeling that the whole field of trace metal marine geochemistry would have been a completely dull one over the past fifty years if it weren't for analytical errors.”
NOTE: “analytical errors” includes both errors in laboratory handling and measurement methods and contamination during sampling and analysis.
Metal
Metal
Metal
Metal
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Trace metals were notoriously difficult to measure because…
• Ships are painted with marine paints that contain metals (e.g. copper, lead, tin)
• Ships pump out bilge water and let off exhaust, contaminating the water near the ship
• Old sampling techniques used bottles either made entirely of metal or using metal joints
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Towed FISH (1974)Working toward better sampling techniques in the surface
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MIT pole (1978)Working toward better sampling techniques in the surface
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Working toward better sampling techniques through the water column
MIT Vanes sampler (1983-1995)
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Working toward better sampling techniques through the water column
Niskin-X Vane Sampler (2015)
Zhang (2015) Mar. Chem. 177: 653 18
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Current gold-standard sampling techniques
Kevlar conducting cable deployed, polyurethane powder-coated carousel, teflon-coated Niskin bottles with no internal metal.
Sampling is done while moving up through the water column to avoid CTD contamination.
GEOTRACES GOFlo Carousel
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Must process samples in a clean lab to prevent contamination
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Dissolved Iron
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Lots of nutrients (nitrogen, phosphorous)
Dissolved Iron
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Electron export chain in plants
• Generates energy for life
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Electron export chain in plants
• Generates energy for life
Photosystem I• must have iron to function
properly and generate energy 24
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Cadmium carbonic anhydrase Nickel super oxide dismutase• Catalyzes the conversion of
CO2(aq) to HCO3-(aq)• Catalyzes the conversion of
Superoxide to oxygen or peroxide
Iron nitrogenase• Catalyzes the reduction of N2
to NH3 , allowing nitrification in the oceans
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Why study trace elements in the ocean?
• Some trace elements are essential for marine life.
• Some trace elements are toxic to marine life.
• Some trace elements reveal anthropogenic impacts on the ocean.
• Some trace elements can be used to trace important processes in the ocean.
• Some trace elements might influence climate change.
• Some trace elements can be used to study the geological history of the ocean.
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Some trace metals are anthropogenic pollutants
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Rise of industrialization and the advent of leaded gasoline
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Petrol burning by cars and industry
Fuel burning for industrial activity
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Tetraethyl leadPros• Increases engine efficiency
• Increases vehicle performance
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Input of lead into the surface ocean (10-9 g/cm2)
20oS Central South Pacific
15oNCentral North Pacific
33oN Central North Pacific
34oN West North Atlantic
Flegal et al. (1983) EPSL 64:19 31
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Tetraethyl leadPros• Increases engine efficiency
• Increases vehicle performance
Cons• Found to be highly toxic to many
forms of life (including humans) • Brain swelling• Pulmonary edema • Hallucinations• Coma• Death
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1996
2002
2000
2000
2002
2002
1989
1986
Bans/phase-outs of leaded gasoline
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For the US population, during and after the leaded gasoline bans, the average blood lead level dropped from 16 μg/dLin 1976 to only 3 μg/dL in 1991.
Pirkle, Brody, et. al. (1994) National Bureau of Economic Research
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Metal level measurements are important to track the degree of anthropogenic pollutants reaching the environment
Other common heavy metal pollutants:
• Mercury• Arsenic• Chromium• Cadmium
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