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15 The influence of redox chemistry on groundwater vulnerability

4.15 The influence of redox chemistry

on groundwater vulnerability
4.15.1 Background
Reduction and oxidation processes exert an
important control on the distribution of dissolved
groundwater. They also play a major role in
aquifer pollution problems such as nitrate from
fertilizers. Indeed, problems in aquifers often
concern the addition of an oxidant, like oxygen
or nitrate, to an aquifer system containing a
reductant, like a sulphide mineral or organic
carbon (Appelo & Postma 1999).
In assessing the vulnerability of an aquifer to
nitrate contamination, it may be quite useful to
consider the redox chemistry of the groundwater.
The same is true of data on the ability of the
subsurface sediments to chemically reduce

4.15.2 Sediment chemistry

The thickness and distribution of suitable clay
cover layers above an aquifer plays a most
important part in protecting the aquifer, as they
form a physical barrier which to some degree
prevents polluted groundwater from reaching the
Clay cover layers, and indeed most other
sediments likely to be encountered above
aquifers in Northwest Europe, also provide a
varying degree of chemical protection of aquifers.
The reason for this is that they, with the
exception of coarse-grained or monomineralical
deposits such as gravel or quartz sand, contain
various amounts of minerals and organic matter
reductants capable of reacting chemically with
nitrate in the groundwater and, in effect, break it
Minerals such as pyrite (iron sulphide FeS2) as
well as organic matter occur in varying but
appreciable amounts in the subsurface. For
example, a pyrite content of 0.11 % is quite
common in many types of Pleistocene and
Miocene sediments in north-western Europe.

When groundwater with dissolved nitrate is

moving through subsurface sediments containing
pyrite, bacterially assisted chemical reactions
break down the nitrate and pyrite into free
nitrogen + iron + sulphate + water. With organic
matter as reductant in stead of pyrite, a similar
type of reaction produces carbon dioxide and
bicarbonate ions in addition to free nitrogen and
The nitrate reduction capacity of a given
sediment volume can be calculated from
chemical analyses of their pyrite, organic carbon
and ferrous iron content. When this is combined
with data on nitrate-supply via the infiltrating
groundwater, the number of years it takes to use
up the reduction capacity of one metre of
sediment in a given area may then be calculated.
The finer grained sediments the clays appear
to offer the highest nitrate reduction capacity. As
water passes very slowly through clay layers,
there is ample time for the chemical reactions to
use up the available reagents. Some clays have
nitrate reduction capacities running into
hundreds or even a thousand years per metre the
redoxcline is pushed (Ringkjbing Amt 2006), at
a constant agricultural-level nitrate infiltration
rate. The redoxcline is the depth where
conditions change from oxidising to reducing, see
Section 4.15.3.
However, the major part of aquifer recharge will
happen where a more coarse-grained lithology
dominates the subsoil, favouring the infiltration
of groundwater to deeper levels. The nitrate
reduction capacities of silts and fine- to middlegrained sands appear to be significantly lower
than for clays, but even these coarser sediments
can have effective reduction capacities up to a
hundred or two-hundred years per metre the
redoxcline is pushed (Ringkjbing Amt 2002,

4.15.3 Water chemistry

Depending on its source and transport through
the atmosphere, rainwater will contain a number
of ions in solution prior to hitting the surface of
the earth. Typical components of rainwater will
be chloride and sodium from natural seawater
and also anthropogenic nitrates and sulphates



from industrialised areas, ultimately responsible

for the acid rain phenomenon.
The chemical composition of groundwater starts
out with the rainwater chemistry. Its final
composition results from the chemical action the
water has been exposed to on its way from the
surface to the aquifer. The water interacts with
the sediments through which it passes during the
infiltration from surface to aquifer. Various
elements can be taken up by the water from
sources such as organic matter and minerals in
the subsurface sediments.
The agricultural application of fertilizers and
manure can add high concentrations of nitrate to
the infiltrating groundwater. This may reach
deeper-seated aquifers, if these aquifers are
vulnerable towards nitrate, i.e. are open to the
introduction of an oxidised environment where
nitrate is stable.
A redox-based chemical classification system for
groundwater is useful for assessing the
vulnerability and age of groundwater. The
classification set up below is a simplified version
of the one used by the Danish EPA (Danish EPA
2000). It is based on the waters content of
redox-sensitive elements like oxygen, nitrate,
iron, sulphate and methane. The system has four
basic water classes ranging from the most
oxidised to the most reduced:

A. The Oxygen zone. Recently formed

groundwater, only a few years old at the
most. It contains considerable amounts
oxygen as well as nitrate and sulphate.
Vulnerable in relation to nitrate.

A continuing supply of nitrate-containing

groundwater will push the redoxcline along
the direction of the groundwater flow, thus
making nitrate stable in larger and larger
groundwater volumes as the nitrate
reduction capacity of the subsurface
sediments is used up. Eventually the oxidised
chemical conditions may reach the aquifer
used for drinking water supply.
High sulphate content in the nitrate zone
water is a sign of possible nitrate reduction
with pyrite in the sediment, as this reaction
among other things produces sulphate. The
reaction may also lead to an increase in the
content of nickel or arsenic in the water,
because these unwanted metals can be part
of the pyrite mineral structure. As nitrate and
pyrite reacts with each other, this breakdown
process will release eventual metals to the
groundwater. In some areas, including
buried valleys, serious problems with high
concentrations of nickel or arsenic in the
groundwater may arise.
Nitrate zone groundwater is vulnerable with
respect to nitrate and relatively young,
usually less than 50 years.

C. The Iron-sulphate zone. Moderately reduced

conditions with little or no nitrate, oxygen
and methane. High content of dissolved iron.
The sulphate content may be as high as in
the oxygen and nitrate zones. The
groundwater is relatively old, typically more
than 50 years. As a rule, the groundwater is
not vulnerable and pollution is rare.
Increasing sulphate contents accompanied by
a decrease of the bicarbonate ( HCO3 ) ion in
the water indicates pressure on the zone in
the form of a sliding redoxcline.

B. The Nitrate zone. Characterised by its nitrate

content but has little or no oxygen. The
development of this zone is controlled by the
presence of nitrate reducing substances like
sulphide minerals, iron and organic matter in
the subsurface.
The depth/limit to which the nitrate-zone
water has progressed is called the nitrate
front or Redoxcline. In the subsurface
sediments the redoxcline is usually
accompanied by a change in colour from
grey and green (reduced) colours to yellow
and red (oxidised) colours.


D. The Methane zone. A strongly reduced

chemical environment where methane
occurs. There is no free oxygen or nitrate.
The sulphate content is low, less than 20
Brown water containing dissolved organic
material or elevated chloride concentrations may
occur. The water is not very vulnerable, and the
risk of pollution is low. More than fifty and up to
hundreds of years old or more.

4.15 The influence of redox chemistry on groundwater vulnerability

Fig. 4.15.1:

Depth of redoxcline, example of Tarm, Ringkjbing County.

Common to the zones B, C and D, an

inappropriately large water extraction can pull
an overlying zone or elements of this downwards
and initiate a slide in the water chemistry to a
more oxidised and thereby more vulnerable water
type. Even in the short term this can cause
problems with nitrate and perhaps nickel or
pesticide metabolites like BAM in an aquifer.
This process may be accelerated if the aquifer in
question is situated near-surface or in a sanddominated buried valley, without suitable clay
cover layers or any significant nitrate reduction
capacity in the subsurface. Here, the redoxcline
will likely be pulled down in a matter of years,
causing a waterwork extracting groundwater
from this particular aquifer to experience nitrate
and perhaps nickel problems.

Figure 4.15.1 shows a typical example. It is a

contoured map of the depth to the redoxcline in
an area near the small town of Tarm, Ringkjbing
County, Denmark. The map is based on sediment
colour-changes recorded in well descriptions. A
complex buried valley system runs through the
area. The waterworks of the nearby town has its
wells situated within this valley system, the infill
of which is strongly sand-dominated in this area.
Outside the limits of the buried valley system
Miocene clays provide excellent cover layers, and
they, as well as the sands of similar age found
here, contain appreciable amounts of pyrite and
organic material. These Miocene sediments are
found very close to the surface, and here the
redoxcline lies only a short distance below the



Inside the valley the redoxcline is clearly pulled

down around the waterwork well field, which
contains several wells extracting about 800,000
cubic metres of groundwater per year. Indeed,
nitrate and the pesticide metabolite BAM is
found in wells at depths up to 100 m below
Another pulldown in the redox-cline surface is
seen to the southeast, situated across the border
of the buried valley system. This is due to
pumping at a large landfill site situated here.

4.15.4 Conclusion
In addition to the physical protection of aquifers
accorded by clay layers, the level of chemical
protection may also be important. Groundwater
and sediment chemistry investigations can be
used to assess susceptibility of aquifers to nitrate
pollution, and form an important part of the
vulnerability mapping process.

4.15.5 References
Appelo CAJ, Postma D (1999): Geochemistry,
groundwater and pollution: 239290.
Balkema, Rotterdam.
Danish EPA (2000): Groundwater zoning. Guide
nr. 3, 2000. Danish EPA , Ministry of
Environment, Copenhagen. In Danish.
Ringkjbing County (2002): Hydrogeological
mapping at Brande. Ringkjbing County,
Department of Environment & Infrastructure.
In Danish.
Ringkjbing Amt (2006): Action planning in
mapping in Skjern and Egvad municipalities,
September 2006. Ringkjbing County
Department of Environment & Infrastructure.
In Danish.