Week 8 Nutrient cycles and distribution

Learning Outcomes

At the end of this topic, students should be able to:

 Classify elements on the basis of their involvement in biological processes and
concentration depth profiles
 Discuss vertical movement of nutrients using the two-box model
 Explain how horizontal variation in the oceans occur with reference to phosphate
 Briefly explain the Redfield ratio

Classification of elements
There are three major categories of elements in seawater based on their involvement in
biological processes. These are:

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

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

Figure 8.1 Concentration-depth profile of bio-limiting nutrients

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

Figure 8.2 Concentration-depth profile of bio-intermediate nutrients

Bio-unlimited or Bio-inert
-elements which show no vertical gradient due to biological processes (constant ratio of
concentration to total salinity)
e.g., B, Br, Cs, Cl, F, Mg, K, Rb, Na, Sr, S

Figure 8.3 Concentration-depth profile for bio-unlimited nutrients

Figure 8.4 Concentration-depth profiles for three seawater constituents.

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)

Self-Test 8.1
What is the photic zone and what important process occurs in it?
 Typical Concentration-Depth profiles for Nutrients

Figure 8.5 Typical concentration-depth profiles for (a) phosphate, (b) nitrate, (c) silica.

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

Reason for the decrease in concentration below maxima at mid-depth:

Due to the slow upward mixing from the deep water masses which are formed at the surface in
the polar region. These water masses are relatively depleted in nutrients as a consequence of
biological production occurring there.

Chemical composition of soft organic tissue in terms of N:P is 15:1

Ratio of N to Pin 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.

Self-Test 8.2
What is the Redfield ratio for C:N:P?

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

Figure 8.6 Simple two-box model for the oceans

 other components include:

o the boundary in between which is the base of the mixed surface layer (100-200m
depth), and
o the permanent thermocline below, that extends 500-1000m over most of the
world’s oceans
o the intermediate & deep water masses further down
 although only a model, it is still usable to:
(i) quantify basic processes occurring in the oceans to a 1st approximation
(ii) estimate the rates at which different constituents move through the system

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 concentrations 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
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-

Figure 8.7: The two-box model for use with the phosphate exercise.

 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 (down-welling)  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)
 concentrations 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)
 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
 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 re-dissolved and recycled PO43- in the deep ocean

= 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
 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

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 throughout the oceans as a
whole.
No, this is not the case.
Consider variation of PO43- in the deep oceans (Figure 8.8).

Figure 8.8 Distribution of phosphate in the oceans at 2000m depth.

 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
 Table 8.1 shows the average ratios for biologically important elements in the Atlantic &
Pacific
-the ratio uses the difference between the 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 8.1: Approximate average ratios for biologically important elements

in the deep parts of the Atlantic and the Pacific [C=concentration]
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 8.9 for mechanism.

Figure 8.9 (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
 Figure 8.9 (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

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)
 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
 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 8.10.
Figure 8.10 Diagram showing changes in nutrient & skeleton
- building elements in the oceans as a result of biological
activity

Self-Test 8.3
(a) Give the concentrations of total dissolved carbon, nitrate and nitrate for mean ocean
water.

(b) Does it follow the Redfield ratio?

 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 PO43- & 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? Use explanations given for figures 8.8 and
8.9.
Summary

At the end of this topic, you have learnt that:

 Nutrients in seawater can be classified based on how they are used biologically as bio-
limiting, bio-intermediate and bio-unlimiting
 The two-box model comprising of a surface ocean and the deep ocean can be used to
illustrate vertical movement of nutrients
 Horizontal or lateral movement is not accounted for by the two-box model
 Horizontal movement can be explained through consideration of flow of shallow and
deep water masses
 The Redfield ratio for N:P of 15:1 is seen in seawater as well as in organic tissue
Recommended Readings and Video Links

1. Biogeochemical Cycling
https://www.youtube.com/watch?v=09_sWPxQymA
2. Oceans May Absorb More Carbon Dioxide: Redfield Ratio
ttp://www.scientificamerican.com/article/oceans-may-absorb-more-carbon-dioxide/