Marine Chemistry I

Outline
Part I

Physical Properties of Water

Salinity

Part 2

Geochemical Cycles

Conservative Constituents

Non-Conservative Constituents

Physical Properties of
Water

The Molecular Structure of Water

Water is a Highly Polar Molecule
-

non-bonding
electrons

Oxygen
Hydrogen

Hydrogen

polar covalent bonds

Dissolving Power of Water

1. Highest of any substance known

2. Solvation effects must consider the molecular interactions
between water (solvent) and dissolved substances (solutes)

Simple case: NaClsolid Na+solvated + Cl-solvated

Cl-

Na+

Relatively Weak (but highly important) Hydrogen Bonding

-

+
+

Hydrogen Bond
an electrostatic attraction between
partial + and charges on separate
polar molecules

Three States (Phases) of Water

solid, liquid and gas
Two opposing forces determine the structure of water in its three phases:

H-bonds

relatively weak bond energy holding adjacent water molecules together

unchanging strength

!

Thermal (kinetic) Energy

pushes/breaks adjacent molecules apart

increases with increasing temperature

Three States (Phases) of Water

Solid Ice
Low Temperature Limit:
EH-bond > Ethermal
1. Maximum number of H-bonds

2. Maximum order, low thermal motion

3. Regular lattice structure of ice
ice (solid)

Three States (Phases) of Water

Liquid Water
The Intermediate Case:
EH-bond Ethermal
1. Clusters of H-bonded water
(structural water)

2. Interspersed non-H-bonded water
(free water)
liquid water

Three States (Phases) of Water

Water Vapor (gas)
High Temperature Limit:
EH-bond < Ethermal

1. minimum number of H-bonds

2. minimum order, rapid thermal motion

3. independent, non-interacting gas
molecules

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water vapor (gas)

Amount of heat energy need to change phase and

temperature of water
1. Latent Heat of Fusion

Amount of heat required to convert 1 gram of solid ice to liquid water
(80 calories per gram)

2. Specific Heat Capacity

Amount of heat required to raise 1 gram of liquid water by one degree
celsius (1 calorie per gram per deg C). This is among the highest of
any substance on earth

3. Latent Heat of Vaporization

Amount of heat required to convert 1 gram of liquid water to water
vapor (540 calories per gram)

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An Important Consequence of Waters Exceptionally High

Specific Heat Capacity...
1. The exceptionally high specific heat capacity of water means that it takes an
exceptionally large amount of heat energy to change ocean temperatures

2. Conversely, relatively small observed changes in ocean temperature represent
very large changes in heat content

3. All things being equal, if you have more heat energy coming into the earth than
leaving the earth, then you should observed a steady rise in global temperature.

However, if you had the same amount of excess heat coming into the earth,
but you shifted more of the excess heat to the ocean versus the atmosphere (or
land), then the rise in temperature would not be as great (since the same
excess heat added to water does not change the water temperature all that
much because of waters high specific heat capacity)

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Evaporation Moves Latent Heat From the Ocean to the

Atmosphere

2. Condensation: Latent Heat released

into the atmosphere by condensation of
water vapor to form clouds and rain

1. Evaporation: Latent Heat removed from

the ocean and stored in the atmosphere
in the form of water vapor

13

Conclusions: Molecular Properties of Water

1. Strong polar nature of the water molecule makes it a very good solvent for ionic
constituents (salt ions) i.e., it can dissolve a lot of salt

2. Hydrogen bonds are weak, but below 100 oC they are strong enough to allow
individual water molecules to bond temporarily with other water molecules to form
liquid water. Below 0 oC they are strong enough to hold/lock all water molecules into
solid crystalline ice.

3. High specific heat capacity means a given heat addition does not change ocean
temperatures as much as would occur if the same amount of heat was added to the
atmosphere (or land)

4. High latent heat of vaporization allows large amounts of heat to be removed from the
ocean, stored at latent heat in the form of water vapor and then transported by winds
to other parts of planet where it can then be released to the atmosphere as sensible heat
upon precipitation

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Salinity of Seawater

15

Definition: Salinity
Salinity is a measure of the salt concentration (total weight of salt) in a seawater
sample. It is often expressed as the number of grams of salt contained in a
thousand grams of seawater and expressed as parts per thousand and denoted by
the symbol . 35 grams of salt in 1000 grams of seawater has a salinity of 35

Side Note: A more modern unit of salinity is used in official oceanographic research called the practical
salinity unit (psu), that is based on electrical conductivity measurements rather than the mass of salt
measurements. Both methods give essentially the same numerical values (i.e., 35 35 psu).

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The Total Amount of Salt Contained in the Entire Ocean is Essentially Constant
Input: Weathering of continental rock, and subsequent transport by rivers, constantly
brings new salt ions to the ocean each year

Output: Mineral precipitation (e.g., calcium carbonate CaCO3 shell formation and
deposition into sediments) within the ocean constantly removes salt ions from solution
each year

The magnitude of the input and output rates have been roughly equal for millions of
year - i.e. steady state conditions have been achieved

NOTE: While the total amount of salt in the ocean does not vary, the unequal
addition/removal of freshwater over the global oceans surface creates large regional
differences in surface ocean salt concentration (i.e., in surface ocean salinity)

17

Salinity (total mass of salt in a kilogram of seawater) can vary greatly

across different ocean regions, but the relative proportion of ions
making up the salt mass remains unchanged everywhere in the ocean!
Relative Contribution of Ions in Seawater (by weight)

Cl- (chloride)

Na+ (sodium)



SO4-(sulfate)



Mg2+ (magnesium)


Ca2+ (calcium)



K+
(potassium)


HCO3-(bicarbonate)

All other ions

55%





31%





8%


4%




1%





1%

0.4%





<1%

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Variation in Surface Salinity

1. All salinities in the ocean (deep ocean included!) are/were set at
the air-sea interface

2. Evaporation at the ocean surface removes only freshwater and
leaves behind salt - thus increasing surface ocean salinity

3. Atmospheric precipitation adds freshwater to the surface ocean thus reducing surface ocean salinity

4. Overall, salinity is a direct function of evaporation minus
precipitation

19

Global Pattern of Precipitation and

Evaporation

20

Question
Given that surface salinity is a function of evaporation and precipitation, and given the
basic Hadley Circulation pattern (below), what do you expect the surface salinity to be
in the subtropical gyres?

subtropical gyre

a) salinity is relatively low in the subtropics

b) salinity is relatively high in the subtropics
The correct answer is (b) - dry winds produce high evaporation and low precipitation

21

Idealized Hadley Circulation

High SLP

Low SLP

High SLP

Low SLP

1. Moist surface air at the equator warms and rises aloft. Air aloft spreads north/south and
becomes more dense as it cools and dries (due to precipitation) and then sinks at about 30
latitude.

2. Dry air aloft descends and warms and spreads out over the sea surface at 30 to the north and
south. The surface air picks up moisture and by 60 latitude it has warmed and moistened to the
point where it rises, cools, precipitates and spreads out aloft north/south.

3. Near the poles the dry air aloft becomes very cold and very dense so it sinks over the poles and
spreads out toward the equator

22

Annual Average Precipitation Pattern

Millimeters Per Day

Hadley circulation produces upward convection and high precipitation

along the equator and also at about 60 Latitude

23

Idealized Hadley Circulation

High SLP

Low SLP

High SLP

Low SLP

1. Moist surface air at the equator warms and rises aloft. Air aloft spreads north/south and becomes
more dense as it cools and dries (due to precipitation) and then sinks at about 30 latitude.

2. Dry air aloft descends and warms and spreads out over the sea surface at 30 to the north and
south. The surface air picks up moisture and by 60 latitude it has warmed and moistened to the
point where it rises, cools, precipitates and spreads out aloft north/south.

3. Near the poles the dry air aloft becomes very cold and very dense so it sinks over the poles and
spreads out toward the equator

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Annual Average Evaporation Pattern

Millimeters Per Day

Hadley circulation at around 30 latitude is where cold dry air aloft descends and warms and spreads out
north/south (and is turned by Coriolis) over the earths surface.

The warm and dry surface winds are conducive to strong evaporation in the subtropics regions centered
at 30 latitude.

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Ocean Surface Salinity

Parts per Thousand

26

Vertical Distribution of
Salinity

27

Atlantic Ocean Salinity

The salinity of seawater in the ocean interior is set at the ocean surface in the regions of deep water
formation (North Atlantic and Antarctica) by the combined effects of precipitation and evaporation in
these regions. Once removed from the surface the salinity remains constant unless it mixes with
other water masses.

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Pacific Ocean Salinity

29

Indian Ocean Salinity

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Surface Salinity Variation Summary

1. Surface salinity varies widely and is a function of evaporation minus precipitation

High latitudes have low surface salinity

High precipitation

Low evaporation

Tropics have high surface salinity

High evaporation

Low precipitation

Equator has a dip in surface salinity

High precipitation offsets high evaporation

2. While salinity may vary considerably in different regions, the relative proportion of one
ion to another does not vary.

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Marine Chemistry II

32

Outline
1. Spatial patterns of conservative constituents

2. Spatial patterns of non-conservative constituents

33

Geochemical Cycles
Keeping Track of Elemental Inputs, Chemical Transformations and Outputs

34

Spatial Distribution of Conservative and

Non-Conservative Constituents in Seawater

35

Conservative and Non-conservative Properties

Conservative Constituents of seawater are those that are only varied by
physical exchange processes at the sea surface (or else mixing at depth).
Once the water leaves the surface, these properties are conserved.
1. salinity ()

2. temperature

3. inert gas concentration (e.g., Argon)

Non-conservative Constituents of seawater are those that are varied by

processes (other than mixing) that occur anywhere in the water
column. For example:
1. biological processes (e.g. nutrient uptake and remineralization)

2. geochemical processes (e.g., radioactive decay)

36

Phytoplankton Nutrients

(Nonconservative Constituents)
Nutrients - elements or compounds required by phytoplankton to
grow and reproduce

nitrogen

NO3- (nitrate), NH4+ (ammonium)

phosphorus
PO43- (phosphate)

silicon

SiO42- (silicate)

trace metals
Fe, Zn, Mo, Cu, Co, etc

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Non-conservative Constituents: Plant Nutrients

1. Low in surface layer because of rapid uptake by phytoplankton in the presence of sunlight

2. High at depth because of respiration/remineralization and no uptake by phytoplankton in
the dark
[Nutrient Conc.]

sea surface

dissolved nutrient
photosynthesis

Particulate Organics

depth

deep water

thermocline
sinking

dissolved nutrient
respiration

Particulate Organics
burial
sediments

dissolved nutrient = NO3 or PO4 or SiO2

38

Atlantic Ocean Nitrate

While plant nutrients like nitrate and phosphate and silica are low in most of the
surface ocean (except in the iron-limited Southern Ocean), the generally higher
deep nutrient concentrations can vary greatly due to horizontal advection. Note
the high southern ocean nitrate moving with Antarctic Intermediate Water
northward under the south and north subtropical gyres.

39

Global Pattern of Nutrient Concentration

in the Deep Ocean

40

Conveyor Belt Circulation

41

Phosphate at 4000 Meters

42

Pattern of Oxygen Concentration

in the Ocean

43

Dissolved O2

(Non-conservative Constituent)
Biological Sources and Sinks
1. Photosynthesis produces oxygen

2. Respiration consumes oxygen
CO2 + H2O

inorganic N (NO3-, NH4+)

inorganic P (PO43-)

photosynthesis

organic

materials

+ O2

respiration

Physical Sources and Sinks

1. Vertical diffusion across the air sea interface

2. Horizontal advection from nearby regions

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Non-conservative Constituent: Dissolved O2

O2

[O2]

atmosphere

O2

particulate organics

O2
deep water

Photosynthesis produces O2

Thermocline
particulate organics
respiration consumes O2

depth

mixed
layer

sea surface

Little respiration occurs at depth due to low organics needed to

fuel O2 consumption combined with horizontal advection of
high O2 water from other locations

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oxygen
minimum

Atlantic Ocean Oxygen

Notice the southward movement of high O2 water within the North

Atlantic Deep Water (NADW).

46

Global warming is expected to increase the strength of the thermocline and

thereby reduced vertical mixing and diffusion across this boundary and make
the oxygen minimum zone even lower

depth

strong

diffusion/mixing
weak

thermocline

oxygen
minimum

[O2]

Today
Weak
Thermocline

relatively easy
mixing and diffusion
(thick red arrow) of
oxygen down into
the oxygen minimum
zone to moderate
the extent of the
minimum

weak

diffusion/mixing
strong

thermocline

depth

[O2]

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oxygen
minimum

Future
Strong
Thermocline

relatively difficult
mixing and
diffusion (thin red
arrow) of oxygen
down into the
oxygen minimum
zone so minimum is
made even stronger

Conveyor Belt Circulation

48

Oxygen at 4000 Meters

49

Carbon Dioxide

(Non-conservative Constituent)
1. Photosynthesis Consumes CO2

2. Respiration Produces CO2
CO2 + H2O

inorganic N (NO3-, NH4+)

inorganic P (PO43-)

photosynthesis

respiration

organic

materials

+ O2

3 Diffusion Across the Air-Sea Interface

4. Chemical Reaction With Water Makes Hydrogen Ions:
CO2 + H2O H2CO3 carbonic acid

H2CO3 H+ + HCO3- bicarbonate

HCO3- H+ + CO3-2 carbonate
CO2 + H2O H2CO3 H+ + HCO3- H+ + CO3-2

carbonic acid

bicarbonate

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carbonate

Non-conservative Constituent: CO2

CO2gas diffusion across air/sea interface
photosynthesis takes up (consumes) some CO2 and makes organic carbon and thereby
lowers CO2 in the upper ocean
below the euphotic zone (the sun lit zone of surface ocean) the respiration by bacteria that
degrade dead organic carbon produces CO2 and thereby increases CO2 at depth

respiration -->

reaction of CO2 with water --------------------------------------->

organic C

CO2 + H2O

H2CO3

HCO3- + H+

organic C deposition

sediments

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CO32- + H+

Non-conservative Constituent: CO2

Photosynthesis Consumes CO2 in
the surface ocean to form
particulate organic carbon

Respiration Produces CO2 in the

deep ocean

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ocean

Pacific Meridional Section of Inorganic Carbon Species

53

Carbon Dioxide in the Deep Ocean (below the thermocline) is by Far the
Largest Active/Mobile Reservoir of Carbon Dioxide on Earth.

54

Bringing deep ocean water that is rich in CO2 into contact with the atmosphere
causes CO2 to flux out of the ocean note the equatorial upwelling region

1. Red and Yellow are regions where CO2 fluxes out of the ocean

2. Purple and Blue are regions where CO2 fluxes into the ocean

55

pH of the Ocean Surface Layer

1.Purple and Blue are regions that are more acidic

2.Red and Yellow are regions that are less acidic

56

Coastal Upwelling brings deep water that is cold and rich in CO2 (and
therefore more acidic) up to the surface in coastal regions...

<---- Offshore

Onshore --->

57

Conclusions
1. The field of chemical oceanography is concerned with the geochemical
(i.e., global-scale elemental) cycles that take place at least in part within
the ocean.

2. A main approach to identifying geochemical cycles is to identify a
particular elements principal sources into the ocean, its major avenues of
removal from the ocean and any significant chemical reactions that it
participates in while in the ocean.

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Conclusions
1. Conservative Properties (e.g., temperature and salinity) do not change
value once the water leaves the surface ocean (except when different water
masses mix together at great depth)

2. Non-Conservative Properties (e.g., nitrate, phosphate, oxygen, carbon
dioxide) can change value after the water leaves the surface ocean.

3. The Conveyor Belt Circulation explains why nitrate and phosphate get
more concentrated as the deep water moves from the Deep North
Atlantic and gradually into the Deep Pacific - organic matter rains down into
the deep water, and it is remineralized to nitrate and phosphate, as the deep water
slowly moves toward the Pacific

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Conclusions
1. Oxygen in the deep ocean become lower as the deep circulation slowly carries
water from the North Atlantic to the Pacific because the remineralization process,
that caused nitrate and phosphate to increase along the way, consumes oxygen.

2. Carbon Dioxide that enters the ocean by diffusion across the air-sea interface, or
from biological respiration, undergoes a chemical reaction with water to form
other inorganic carbon compounds (e.g., carbonate and bicarbonate) and this
reaction needs to be considered when examining the overall cycling of carbon
dioxide in the ocean - for this class, the details of the reactions are not important,
just knowing that other reactions need to be considered is enough - you do,
however, need to know that increases in CO2 leads to more acidic ocean

3. Sinking organic carbon and biogenic/mineral precipitation produces a strong
vertical gradient of CO2 in the ocean.

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