Sea Water Chemistry

Chapter 7
 Sea Water Chemistry
 determine many important oceanographic
phenomena including :
 Global patterns of oceanic and atmospheric
circulation, and the growth and distribution
of marine organisms.
 Life on earth probably evolved in
water
 Most animals are 50-65% water
 water exists in all three physical
states of matter: solid, liquid, and
gas
 71% of the Earth Surface - Sea
Water
 regulates the climate, dilute waste
 major habitat for living creatures
 polarity of water molecules results
in hydrogen bonding

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 Characteristics of H20

 1. has cohesive behavior

 2. resists changes in temperature
 3. has a high heat of vaporization
and cools surfaces as it evaporates
 4. expands when it freezes
 5. is a versatile solvent

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 1. Surface tension
– measure of how difficult it is to
stretch or break the surface of a liquid

– water has a greater surface tension

than most liquids

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 2-3. Water's high heat of
vaporization:
 moderates the earth's climate.
 solar heat absorbed by tropical
seas dissipates when surface water
evaporates

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 4. Oceans and lakes don't freeze
 because of hydrogen bonding,
water is less dense as a solid than
it is as a liquid.
 consequently, ice floats.

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 5. water is a versatile solvent
owing it to the polarity of the
water molecule
 ionic compounds dissolve in water

02/05/24 Prepared by: Prof. Rodriguez 13

 Major Components of Seawater

 dissolved salts - hydrated anions and

cations (Table 7.1;, f. 7.3)
 dissolved gases - nitrogen, oxygen, carbon
dioxide
 organic and inorganic - dissolved organic
materials suspended particulate matter
 Major Ions in Typical Seawater

 Ion Parts per thousand by weight ‰ (ppt)(Table

7.1)
 Cl- 18.98
 SO4-2 2.649
 HCO3- 0.140
 Na+ 10.556
 Mg2+ 1.272
 Ca+ 0.400
 K+ 0.380
 On average, concentration of dissolved salts,
i.e., the salinity, in seawater is 3.5% or
35‰.
 The relative abundances of the ions listed
above does not change, even though salinity
does; are said to be conservative.
 Relative abundances of minor and trace
constituents do vary
 Determining Salinity
 Evaporation of water to weight the salt is an
imprecise method
 Because of the constancy of composition if
we measure one component we can get a
more precise measurement
 Salinity ppt = 1.80655 x Chlorinity in ppt
 If chlorinity is 19.2 ppt, what is the salinity of
sea water?
 34.7 ppt = 35 ppt
 Sources of Salt
 Rivers (winds and glaciers are a less
important, indirect source)
 Weathering of oceanic crust
 Hydrothermal Vents associated with
Mid-ocean ridges and other submarine
volcanoes
 Sinks
 Biologic activity
 Interaction with Particulate matter: clays
and organic matter absorb dissolved
metals
 Direct Precipitation
 Hydrothermal Activity: (fig. 7.4)
 Reaction between seawater and new
oceanic crust
 Minerals like magnesium is incorporated
into deposits
 Calcium is added to sea water
 Physical and Chemical
Properties of Water

 Heat Capacity - energy added to raise

temperature of 1 gram of substance by °C
 adding energy breaks H-bonds, increases
fraction of free water
 important in thermal buffering and heat
transport to higher latitudes
 Latent Heats and Evaporation

 heat input or release associated with phase

changes (ice - liquid, liquid - vapor)
 changes in water structure, H-bonding with
phase changes
 important in thermal buffering, heat
transport and heat exchange with
atmosphere
 Density - mass per unit volume (grams/cm3)
 density of water phases (ice, liquid, vapor)
due to structural changes at molecular level
 density maximum at °C in pure water
 Major role in deep ocean circulation and
water column structure and stability
 Light Transmission

 transparent in visible part of spectrum

 Absorbed as is goes deeper in the water
column
 strongly absorbs infrared (heat) and
ultraviolet (prevents damage to DNA)
 Dissolving Power

 hydration of solutes - interactions between

solutes and free water
 decreases H-bonding, increases order of
free water, increases density
 exclusion of solutes on freezing and
evaporation
 other effects of solutes: freezing point
depression, boiling point elevation
 pH (acidity or alkalinity)

 measure of the dissociation of water into

ions (H+, OH), (fig. 7.9)
 pH = - log [H+]
 pH effects on biological and geochemical
reactions
Conservative vs. Non Conservative
Properties

 Conservative Properties of Seawater

 those properties that can only be altered at
the sea surface: temperature, salinity, inert
gases
 properties not altered by biological or
geochemical reactions
 importance in water mass identification,
tracing and mixing
 Nonconservative Properties of Seawater
 those properties that can be altered
anywhere in the water column
 properties altered by biological and
geochemical reactions
 Dissolved Gases
 The proportions of gases in the atmosphere is not
the same as their proportions in seawater, (Table
7.4)
 There is less N2 (nitrogen gas) in the ocean than in
the atmosphere,
 much more oxygen,
 and even more CO2.
 All this CO2 in the oceans keeps CO2 from being
in the atmosphere and causing global warming.
 The colder the water, the more gas can
dissolve in it.
 When you leave your can of coke in the car
in the sun, then open it, what happens?
 Coke sprays all over you.
 That's because the gas has exsolved (come
out of solution); a lot has accumulated in
the little space at the top of the can.
 Very active fish, such as trout and salmon, require
very cold water to live in because they have high
oxygen requirements.
 They literally suffocate when the water gets too
warm, and the oxygen levels drop.
 This explain why these fish don't live down south.
 'Thermal pollution' occurs when electric plants put
warm water into streams, lowering the oxygen
level.
 CO2 is important because it is needed by
plants so they can photosynthesize.
 O2 is important because animals need it for
respiration.

Photosynthesis:
 CO2 + H2O + energy [from the sun]  O2 +
sugar (organic matter)

Respiration (the reverse of photosynthesis):

 O2 + sugar CO2 + H2O + energy
 Dissolved Oxygen

 seawater\atmosphere exchange at air water

interface only (fig.7.8)
 biological processes that affect O2
concentration: photosynthesis and
respiration
 typical distribution of O2 in water column
and processes that control this distribution
 Phytoplankton Nutrients

 inorganic sources of N, P, S and other

atoms required for phytoplankton growth
 photosynthesis and respiration contributes
in nutrient distribution
 Especially important, because so much is
needed, are N (nitrogen) and P (phosphorus).
 Si (silica) is also important for all the siliceous
organisms we‘ll discuss: diatoms, radiolarians,
and siliceous sponges.
 N is necessary to make proteins.
 P is necessary to make new cells (it's part of the
cell wall), and also genetic material, DNA and
RNA.
 N is useful for plants only in these forms:
 NO3- nitrate
 NO2- nitrite
 NH4+ ammonium
 N2, the gas, is not usable by most plants.
 Only a few bacteria can break this very strong
molecule apart and turn it into nitrate.
 These are 'nitrogen-fixing bacteria'.
 P is useful in the form of phosphate, PO43-
 Thus weathering, sedimentation, and
ocean chemistry are all closely linked.
 Other ions in seawater, such as Cl – and
SO4 , are not derived from weathering,
but from volcanic degassing.
 The Carbonate System in
Seawater

 CO2 in seawater is controlled by: ( f.7-

10-11)
 Exchange with the atmosphere
 Photosynthesis/Respiration:
 6CO2 + 6H2 O  C6 H12 O6 + 6O2
 The Carbonate Buffer
 Carbon Dioxide: CO2 ,
 Carbonic Acid: H2CO3 ,
 Bicarbonate: HCO3 ,
 Carbonate: CO32-
 CO2 + H2O  H2CO3 .
 H2CO3  HCO3 + H+2.
 HCO3  CO32-+ H +3.
 Another important reaction is the dissolution
and precipitation of calcium carbonate:
 CO3 + Ca+2  CaCO34..
 Importance of these reactions:
 Maintain constant pH (seawater is said to be
buffered).
 Few marine organisms can tolerate a pH very
different from 8.
 Biological Productivity
 In general, shells of organisms are likely
to be preserved where their production
rate is high,
 Siliceous shells are preserved only
where the production rate is high.
 Siliceous oozes occur where
productivity rate is high and terrigenous
sedimentation rate low.
 Carbonate shells: the oceans are
supersaturated with respect to CaCO3 at the
surface and become increasingly
undersaturated with depth.
 Shells more likely to be preserved at shallow
depth.
 Lysocline: depth at which rapid dissolution of
CaCO3 begins.
 This is deeper than the depth where ocean
becomes undersaturated.
 CCD
 Carbonate Compensation Depth (or
‘snow line’):
 depth where dissolution>supply of
CaCO3 and
 below which CaCO3 shells are not
preserved in sediment.