Chemical oceanography
Introduction
Chemical oceanography is the study about the chemistry of the ocean based on
the distribution and dynamics of elements, isotopes, atoms and molecules. This
ranges from fundamental physical, thermodynamic and kinetic chemistry to
two-way interactions of ocean chemistry with biological, geological and
physical processes. It encompasses both inorganic and organic chemistry, and
includes studies of atmospheric and terrestrial processes as well.
Chemical oceanography includes processes that occur on a wide range of spatial
scales; from global to regional to local to microscopic dimensions, and temporal
scales; from geological epochs to glacial-interglacial to millennial, decadal,
inter annual, seasonal, diurnal and all the way to microsecond time scales. The
field by its own nature is very much an interdisciplinary field.
Fig. 1: Different processes occurs in ocean and atmosphere
The advantages of the chemical perspective include:
(a) Huge information potential due to large number of elements (93), isotopes
(260), naturally occurring radioisotopes (78) and compounds (innumerable)
present in the ocean.
(b) Chemical measurements in the ocean are highly representative, reproducible
and predictable (statistically meaningful). One drop of water is about 1/20th of a
milliliter or 0.05 g, this is 2.8 x 10-3 moles or 1.7 x 1021 molecules.
(c) Quantitative treatments are possible (stoichiometry, balances, predictions of
reaction rates and extents).
(d) We can learn about processes from chemical changes. Seawater composition
integrates multiple previous events, this is important because most of the ocean
is inaccessible to direct observation.
Definition of Marine Chemistry
Ocean chemistry, also known as marine chemistry, studies on the chemical
composition, the distribution and the chemical properties of substances and
chemical processes in each part of the ocean, as well as the chemistry questions
about the development and utilization of marine resources.
Marine chemistry is the study of the chemical composition and chemical
processes of the world’s oceans. Some of the key processes studied are the
cycling of: inorganic and organic carbon; nutrients, such as nitrogen and
phosphorus; and trace elements, such as iron.
Marine Chemistry deals with the following area of ocean chemistry:
Ocean circulation and mixing based on chemical and isotopic tracers
Marine organic and natural products chemistry
Geochemical interactions of sediments with seawater and interstitial
waters
Geochemistry of volcanic and geothermal phenomena
Chemical exchanges between the ocean and the atmosphere
Geochemical cycles of carbon, oxygen, sulfur, nitrogen, and other
elements
Isotopic geochemistry of the solid earth and meteorites
Atmospheric trace gas chemistry
Pale atmospheric composition recorded in polar ice cores, corals and
sediments
Chemistry of lakes and other freshwater systems
The physical and inorganic chemistry of seawater
How and why is This Field Relevant?
We are all aware of the CO2 and other greenhouse gases increase in the
atmosphere since the beginning of the industrial revolution. This is seen in the
classic data from C.D. Keeling (1976) showing the seasonal oscillations and the
steady annual increase of CO2 at the Mauna Loa Observatory. Most experts
conclude that we are already witnessing the impact of this as global warming,
and the signal is expected to become increasingly more pronounced.
Fig. 2: CO2 concentration changes during the years
The inventory of dissolved inorganic C in the oceans is 50-60 times greater than
that in the atmosphere, so a small perturbation of the ocean carbon cycle can
result in a substantial change in the concentration of CO2 in the atmosphere.
The ocean carbon cycle influences atmospheric CO2 via changes in the net air-
sea CO2 flux that are driven by differences in the partial pressure of CO2
between the surface ocean and atmosphere. This exchange process is dominated
by two interdependent “carbon pumps” that deplete the surface ocean of total
CO2 relative to deep water. Because the solubility of CO2 increases with
decreasing temperature, the solubility pump transfers CO2 to the deep sea
during formation of cold deep water at high latitudes.
This is a link of the ocean carbon cycle to physical processes (circulation). At
the same time the biological pump removes carbon from surface waters by
settling of organic and inorganic carbon derived from biological production to
the deep sea. This is a link of the ocean carbon cycle to biological processes.
Understanding the natural processes that affect the global carbon cycle is an
important requisite for correctly predicting the effects of global warming. For
this we need a sound descriptive and quantitative background in all aspects of
chemical oceanography and a good understanding of the coupling between
chemical oceanography, tectonics, climate, and physical, and biological
oceanography. As illustrated in the figure below the oceans are in continues
contact with the atmosphere, lithosphere and biosphere.
Figure shows that oceans are in continues contact with the atmosphere,
lithosphere and biosphere.
In addition to the major role the ocean plays in the global carbon cycle the
world’s ocean is also a resource for minerals, energy (gas and petroleum),
fisheries, and is the ultimate water source.
Overview of Ocean Chemistry
Chemical Oceanography is the most interdisciplinary of all the sub-disciplines
of ocean sciences. The above figure illustrates some of the interactions between
the oceans (hydrosphere), lithosphere, atmosphere and biosphere.
*Chemical components of the ocean influence the density of seawater and thus
effect its circulation.
*Biological processes in the ocean are controlled by the chemistry (nutrient
availability). At the same time biological processes are an important control on
chemical distributions. The synergy between biology and chemistry has led to a
whole new thriving sub-discipline called biogeochemistry
*Chemical components are tracers of physical, biological, geological and
chemical processes. Understanding what controls chemical distributions helps
us understand ocean dynamics.
*Oceanic-Crustal coupling control the distribution of many ions in seawater on
time scales of 104 to 106 years. Thus, we can learn from ocean chemistry about
weathering, hydrothermal activity, and other crustal processes.
*Chemical components of marine sediments provide clues necessary to unravel
the history of past ocean chemistry and ocean-atmosphere dynamics.
Understanding the past should help us predict the future.
History of Marine Chemistry or Chemical oceanography
Much of the early history of oceanography was descriptive and chemical
oceanography was considered part of biological oceanography until the 1960's.
The stature of chemical oceanography grew as it was realized that chemical
tracers had the power to answer problems in all disciplines of oceanography. By
the 1970's the basic distribution of most elements in seawater had been fairly
well understood. At that time the sub-discipline of marine chemistry emerged.
These chemists focused their efforts on understanding chemical reactions and
mechanisms in the ocean and at its boundaries.
Some especially noteworthy events include:
-1772 Lavoisier produced the first respectable analyses of seawater and
attempted to isolate some of its constituent salts.
-1836 Gay-Lussac showed that the total salt content of the ocean was
remarkably constant throughout the Atlantic. He suggested that the small
differences that did exist were due to variations in river runoff as well as
evaporation and precipitation
-1819 Marcet analyzed seawater from several different locations and determined
that there was a constant proportion between the major elements. We now refer
to this fundamental concept as the Marcet's Principle or the Principle of
Constant Proportions.
-1865 Forchhammer presented the first definition of salinity
-1884 Dittmar completed the first systematic analyses of the major ions in
seawater. He used samples collected during the HMS Challenger Expedition
(1873-1876)
-1930s Rockefeller Foundation provided support to strengthen oceanographic
programs at Scripps Institution of Oceanography, the Woods Hole
Oceanographic Institution and the University of Washington.
-1940s World War II, which led to the building of the ocean research
establishment. Congress created the Office of Naval Research (ONR) in 1946.
-1970s International Decade of Ocean Exploration (IDOE) funding of major
oceanographic programs (GEOSECS, MANOP, CLIMAP)
-1990s Global Change Research Program (GCRP) funding of major programs
related to global change (JGOFS, WOCE, TOGA, GLOBEC, RIDGE)
Scope of Chemical Oceanography: Fundamental Questions
Here are a few examples of some of the key questions addressed in chemical
oceanography.
-Why is the ocean salty and what controls its salt content? Does evaporation of
river water make seawater? The answer is no. Evaporation of river water makes
an alkaline lake with pH values ~10 and very low concentrations of calcium and
magnesium.
-What are the different forms of chemicals in the oceans and how can we
calculate their concentrations using a systematic chemical approach? Copper is
toxic to phytoplankton like Thalassiosira pseudonana.
The growth rate of this organism decreases with increasing total concentration
of Cu, but with much scatter in the data (left figure below). When the speciation
of copper is taken into account and the activity of the free Cu2+ ion is calculated,
the scatter is removed (Sunda and Guillard, 1976). The conclusion is that the
activity of Cu2+ and not the concentration is the main determinant of the toxicity.
-What are the chemical controls on biological production and food web
structure of the ocean? In some ocean areas iron limits phytoplankton growth.
Martin (1991) conducted experiments where he added iron to samples and
showed that adding iron stimulated growth rate and also stimulated diatom
production.
Pattern of Iron and Chlorophyll contains
-In what ways do biological processes control the distributions of chemicals in
the ocean? Photosynthesis and respiration control the distribution of many
elements in seawater.
-What controls the distribution of clay minerals and biogenic phases like calcite
(CaCO3), opal (SiO2) and organic carbon in marine sediments? CaCO3 is
enriched in shallow sediments and almost totally absent in deep sediments. A
balance between the production of CaCO3 by organisms in the upper water
column and dissolution in deeper waters, which is a function of temperature and
pressure, controls CaCO3 distribution.
-What can chemical tracers (specific elements and compounds as well as stable
and radioactive isotopes) tell us about physical, biological and geological
processes and their rates in the ocean? For example, the distribution of 14C and
CFCs in seawater can tell as when a water mass was last in contact with the
atmosphere thus, the “age” of that water mass and circulation rates.
-How important is the ocean as a sink for fossil fuel CO2 and other greenhouse
gases? Brewer (1978) calculated the pCO2 in samples from the core of the
salinity minimum of the Antarctic Intermediate Water. The youngest samples
from further south have highest pCO2 reflecting the increase in atmospheric
CO2.
-How much has atmospheric CO2 varied in the geological past and what were
the controls? Martin (1991) shows the distribution of iron and CO2 versus age
(0 to 160,000 years BP) in the Vostok ice core in Antarctica. Martin argued that
there was increased atmospheric input of dust rich in iron during the last glacial.
This stimulated biological production in the ocean and lowered atmospheric
CO2.
