Nutrient cycles and

distribution
CH311
Marine Chemistry
Dr. M. Maata

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Classification of elements
3 major categories of elements in seawater based on their
involvement in biological processes

1. Bio-limiting
2. Bio-intermediate
3. Bio-unlimited

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Bio-limiting
almost totally depleted in surface waters
e.g., N (nitrate) , P (phosphate), Si (silica)

Figure 1: Bio-limiting profile

3
Bio-intermediate
partially depleted in surface waters
e.g., Ba, Ca, C & Ra

Figure 2: Bio-intermediate
profile

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Bio-unlimited
show no measurable depletion in surface waters (constant
ratio of concn. to total salinity)
e.g., B, Br, Cs, Cl, F, Mg, K, Rb, Na, Sr, S

Figure 3: Bio-unlimited profile

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Typical Concentration-Depth Profiles

Figure 4: Concentration-depth profiles for three seawater constituents.

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Nutrient Cycles and Distribution
Recycled Elements (bio-limiting)
Nutrients [NO3-, PO43-, {Si(OH)4 - referred
to as SiO2 for brevity}] from particulate OM
progressively move downward out of the photic zone.

most heavily utilized in the photic zone

their availability can limit production
remineralization returns them to solution
source is from biogenic materials that fall from
surface water into deep water (organic tissue, calcium
carbonate & opaline silica)

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Typical Concentration-Depth profiles for
Nutrients

Figure 5: Typical concentration-depth profiles for (a) phosphate, (b) nitrate,

(c) silica.

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NO3- and PO43- profiles reach maxima at ~1km depth while
silica is somewhat deeper. Explain?

Reason for decrease in conc’n. below maxima at mid-depth:

Slow upward mixing from the deep water masses formed at

the surface in polar regions.

These are relatively depleted in nutrients as a consequence

of biological production occurring there.

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Chemical composition of soft organic tissue in terms of N:P
is 15:1
Ratio of N to P in the oceans is remarkably close also to 15:1
Question:
Why should N & P occur in SW in the same ratio that
organisms require them?
Did organisms evolve to use the ratio because it was there
or have marine organisms themselves established the ratio
through time?
Whatever the answer, we can say to a first approximation,
the amounts of N & P in different parcels of SW will
depend on the extent to which organisms have removed
or added these elements in the ratio 15:1.

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Vertical Movement of dissolved Constituents
The Two-Box Model
Marine chemists model the oceans as a layered series of
well-mixed reservoirs (boxes)
model consists of 2 boxes:
(i) surface ocean - thinner & warmer
(ii) deep ocean - thicker & colder
the lower box is some 20x bigger than the upper box
other components include:
- the boundary in between which is the base of the mixed
surface layer (100-200m depth), and

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Figure 6: Simple two-box model for the oceans.
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- the permanent thermocline below, that extends 500-
1000m over most of the world’s oceans
- the intermediate & deep water masses further down
although only a model, it is still usable to:
(i) quantify basic processes occurring in oceans to a
1st approximation

(ii) estimate the rates at which different

constituents move through the system

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Assumptions accompanying the model:
i) rivers are the only source or origin of the dissolved
constituents; ignore all other sources
ii) the removal of dissolved constituents is by organic
particles (biogenic) falling to the sea-floor
iii) the ocean is in a steady-state i.e., rates of input &
loss of any dissolved constituents have remained
constant over long periods thus concns. at any
point do not change with time
It follows from the above assumptions that:
dissolved material added by the rivers (source) to the sea must
be removed at the same rate, by preservation in sediments
(sink) after being mixed & cycled within the oceans

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The 2-box model & phosphate
input from rivers
- some 3.75x1016 kg water are added annually to
oceans from rivers
- mean [PO43-] in river water is ~0.5x10-6 molkg-1
-  annual input of PO43-
= (3.75x1016) kg x 0.5x10-6 PO43-)molkg-1
= 18.75x109 mol PO43-

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Figure 7: The two-box model for use with the
Phosphate
exercise. 16
for a steady-state condition, input from rivers must
equal amount preserved in sediments
= 18.75x109 mol PO43-
Upwelling (UW) flux of SW (14C age-dating technique)
~20x the river flux
and UW = DW (downwelling)  can determine the
amount of water being exchanged b/w the surface &
deep oceans each year
-river flux=3.75x1016 kgyr-1;  UW=DW =7.5x1017
kgyr-1 (20x3.75x1016)
concns. of bio-limiting recycled constituents are very
much less at the surface than in the deep ocean
-for PO43-, it is of the order of 0.1x10-6 molkg-1 (surface)
& 2.5x10-6 molkg-1 (bottom)
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 PO43- fluxes:
DW=7.5x1017 kgx0.1x10-6 mol
PO43- kg-1=75x109 molPO43-

UW:
7.5x1017x2.5x10-6
= 1875x109 mol PO43-
if the low concn. at the surface is to be maintained,
then the huge diff. b/w UW & DW waters must be
balanced
PO43- from rivers & welled from the deep is fixed by
organisms

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on death, PO43- is released & becomes part of the
falling particles

PO43- (particles)

= PO43-(UW) + PO43-(rivers) - PO43-(DW)

=1875x109+18.75x109 -75x109
=1818.75x109 mol PO43-

remaining calculation is for the redissolved and

recycled PO43- in the deep ocean

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= diff. b/w amt. carried down by falling particles & amt.
preserved in sediments
=1818.75x109-18.75x109 mol PO43-
= 1800x109 mol PO43-

Check!!
PO43-(UW)=PO43-(RR)+PO43-(DW)
1875x109 1800x109 75x109

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most nutrient recycling takes place in the
mixed surface area (due to primary production
in the photic zone)

below this layer, consumption & decomposition

of organic matter (mineralization) occur which
eventually release the nutrients back into
solution

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Horizontal Variation in Deep Oceans

The 2-box model emphasizes vertical fluxes but does not

address horizontal or lateral variations.
e.g., model might give the impression that the small
proportion of PO43- that leaves the cycle & gets preserved
in sediments each year is uniformly distributed through
out the oceans as a whole.
No, this is not the case.

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 Consider variation of PO43- in the deep oceans (Figure
8).

minimum in North Atlantic

increases southwards round
S. Africa
continues to increase eastwards & northwards
towards the Indian & the Pacific Oceans
highest in the Pacific Ocean

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Table 1 shows the average ratios for biologically
important elements in the Atlantic & Pacific

-the ratio uses the difference between deep & surface

concentrations in each ocean,  this is a measure of
the lateral enrichment of each element in the deep
waters of the two oceans
Table 1: Approximate average ratios for biologically important elements
in the deep parts of the Atlantic and the Pacific [C=concentration]

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Figure 8: Distribution of phosphate in the oceans at 2000m
depth.
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i.e., as one goes from the Atlantic towards the Pacific ,
there is horizontal or lateral enrichment

What mechanism could be in operation?

Consider Figure 9 for mechanism.

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Figure 9 (a)
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Figure 9 (a):

• Generalized map of deep water flow (dark blue) &

surface water return (mid-blue) in the oceans.

• Large ellipses designate sources of North Atlantic Deep

Water (NADW) & Antarctic Bottom Water (AABW);

• small mid-blue circles indicate areas of localized

upwelling

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Figure 9 (b) 29
Figure 9 (b):

• Generalized cross-section from the North Atlantic to the

North Pacific, showing:
- major advective flow patterns (thin pale blue lines), &

- rain of particles (wavy arrows)

• AABW is not shown in this picture

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So what happens…

NADW (nutrient poor), flows southward

steadily enriched with nutrients from POM sinking

from the surface & re-dissolving in the deep

continues flowing round S. Africa then Indian &

Pacific Oceans

in southern Atlantic, joined by AABW which is more

nutrient rich (upwelling)

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• in Indian & Pacific Oceans, continues to be enriched
by sinking POM

• thus oldest & most nutrient rich waters are in deep

Pacific Ocean

• localized upwelling spots at intermediate depths 

are not truly ‘deep water’

• these all suggest that DW in some parts are much

older than the average 500yrs

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radiocarbon studies in deep Indian & Pacific Oceans
yielded values >1000yrs
in general, the older the DW, the richer it is in
elements of the nutrient-type or recycled
concentration-depth profiles
this explains the ratio shown in the summary (>1)

Summary for overall distribution for the 5 biologically

most important dissolved constituents in SW
See Figure 10.

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Figure 10: Diagram showing changes in nutrient & skeleton
- building elements in the oceans as a result of biological
activity.

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N:P ratio constant throughout the range; molar N:P ratio
for organic tissue also close to 15:1(Redfield ratio)
so when all the dissolved NO3- in surface waters is used up,
so has all, or nearly all, the dissolved PO 43- & vice versa
Qn: Why is it that N & P appear in seawater at the same
ratio that organisms require them?
It is not known whether:
(i) 15:1 was there at the beginning of time & organisms
adapted to it, or
(ii) whether the organisms have established the ratio
over time
How do you explain the vast difference in concentrations of
the biologically important elements at the opposite ends of the
dark band? By using the explanations given for figures 8 and 9.

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