- 3.8.

-
GROUNDWATER POLLUTION AND
MONITORING

1
3.8. GROUNDWATER POLLUTION
AND MONITORING
Dr. Jan Willem Foppen (and Peter Kelderman)

UNESCO-IHE Institute for Water Education

(see Chapter 9, Chapman)

Online Module Water Quality Assessment

2
 Course objectives

1. Groundwater concepts
2. What are sources and fate of groundwater pollution?
3. Groundwater monitoring: why, how, what, how often?
4. Case studies

3
 GROUNDWATER MONITORING

Objectives groundwater monitoring:

• To assess/understand general groundwater quality of the

groundwater (ambient + operational monitoring)

• Finding major pollution sources (ambient/effluent monitoring)

• Compliance with regulations/ standards (effluent monitoring)

• Impact of an accidental pollution (early warning monitoring).

4
Also here follow the monitoring cycle, starting with a
survey, designing the network (parameters, stations,
frequency); data analysis, etc. Make use of results to
improve the network, if necessary.
5
 GROUNDWATER POLLUTION

• Input of untreated domestic wastewater (BOD,

Suspended solids, nutrients, bacteria and viruses, etc.)

• Industrial spills; mining (BOD, SS, micropollutants)

• Agriculture (NO3- , pesticides, Cl- ....)

• Pit latrines and other on-site sanitation systems

• Waste dumps (domestic and hazardous wastes)

Treatment: slow, difficult and very expensive --> prevention!

6
Groundwater-surface water relationships

7
 GROUNDWATER FLOWS

• May take decades-millenia between recharge  discharge

• In arid/semi arid zones often poor quality, e.g. high salinity
8
SOME CONCEPTS IN GROUNDWATER
MONITORING

9
The unsaturated zone (above the water table)

Contains network of plant roots; usually < 2m thick;

Absent in humid areas, but with large thickness in arid areas;

Zone directly above groundwater table; water pressure is less

than atmospheric (tension). Thickness ranges from 1-50 cm,
dependent on rock type.

Zone with (saturated) groundwater. Pressure at the

groundwater table is atmospheric.

10
Processes in the unsaturated zone

Water in unsaturated zone is prone to

evapotranspiration and/or downward flow or
‘groundwater recharge from precipitation’.

Assuming a precipitation event with

groundwater recharge, then after the event
stopped, downward flow will continue until
field capacity is reached (curve 1). At field
capacity, gravity forces acting on water equal
surface tensions exterted by the pore
structure, and downward flow terminates.
Field capacity depends on type of soil. The
one shown here is typical for silty loam.

During dry periods, when there is no

downward flow, there may be upward flow or
capillary flow. When wilting point is reached,
roots are not able to extract sufficient
moisture for plant survival. Curve 2 shows
wilting point conditions for a silty loam.

11
 The structure of rocks: porosity
Porosity of rock is the ratio of the volume of open space in the rock and the
total volume of rock (including the open space):

V n rock porosity
n O
VT VO volume of the open space (m3)
VT total volume of the rock including open space (m3)

In consolidated rocks,
openings are primarily present
at fractures, joints, bedding
planes, and solution holes. This
type of porosity is referred to as
secondary porosity.

In unconsolidated rocks,
openings or pores are present
between individual grains. This
type of porosity is referred to as
primary porosity.
12
 Rock type Range of
The structure of rocks: porosity porosities
Unconsolidated
In unconsolidated rock 0.2-0.4
Gravel 0.2-0.5
rocks, (total) porosity Sand 0.3-0.5
ranges from 0.2-0.7. Silt..clay 0.3.. -0.7>0.95

Porosity in this case relates to the

packing, sorting, and shape of grains:

Porosity of sediment with cubic packing,

well-sorted, well-rounded =  0.48

Porosity of similar sediment, but

rhombohedrally packed =  0.26

When sorting is poor, and grains are not

rounded, porosity decreases further.

13
 The structure of rocks  permeability

Permeability is defined as the capacity of a rock to

transmit groundwater (common unit: m/day, but also other
units are used, like m/s, ft/m, ft/s, etc.).

There is no fundamental law or correspondence

between permeability and porosity.

It is possible to have very high porosity without having

any permeability at all, as in the case of clays and
shales. The reverse of high permeability with a low
porosity might also be true, such as in microfractured
carbonates, and also in sand.

14
Relative classification of geological formations in a groundwater basin
based on their hydraulic properties (rock permeability):
• Aquifer: geological formation or unit with a relatively large permeability.
Able to transmit water. Examples: sand, karstic limestone
• Aquitard: geological formation or unit with a relatively low permeability.
Still able to transmit water. Examples: silts, clays
• Aquiclude: geological formation or unit with a relatively very low
permeability. Not able to transmit water.
• Aquifuge: geological formation or unit with a relatively very low
permeability and porosity. Does not contain water: Solid rock

•Don’t take too absolute; it’s all relative !

15
Aquifer classification: based on the position of the water level
in the aquifer.
Unconfined (phreatic) aquifers are in direct contact with the
atmosphere (or: the unsaturated zone). At the groundwater
table, pressure is atmospheric.
Semi-confined (leaky) aquifers are overlain and/or underlain
by aquitards. Groundwater levels or ‘piezometric levels’ are
usually above the top of the aquifer.
Confined aquifers are overlain and/or underlain by aquicludes
or aquifuges. There is no vertical flow component.
Groundwater levels or the piezometric level are above the top
of the aquifer.
Perched water: not connected with other aquifers.
16
 Classifying aquifers: a quite complicated example
From left to right, aquifer B is phreatic, confined, leaky, confined, and finally, leaky
again. Please note that, when the piezometric surface is above ground surface, the
aquifer is called ‘artesian’.

17
 Regional flow and groundwater head contour maps

Equipotential plane: a plane where the hydraulic head is

constant. For isotropic conditions, flow is perpendicular to
these equipotential planes.
So in an aquifer (where flow is horizontal; “Dupuit
Forchheimer assumption”), equipotential planes have
vertical directions.
In an aquitard, where flow is vertical, equipotential planes
have horizontal directions.

Observe the case of Zhengzhou city (next slide).

18
 Regional flow and groundwater head contour maps
For shallow aquifer:
flow towards river.

For lower aquifer:

flow towards the
city. Here, a cone of
depression is
present, caused by
excessive pumping
below the city.

There is also flow

from the upper to
the lower aquifer
through the
aquitard.
Left figure: upper aquifer; right figure: lower aquifer (separating aquitard is not shown)
19
Modelling Natural flow line pattern (MODFLOW)

20
21
Groundwater sampling/ analysis
Piezometer nests
in Exfiltration area

Peat

Holocene Cover
Clay

Peat

Clay

Sand

Pleistocene 1st aquifer

22
Groundwater sampling/analysis

Sampling a 60 m deep groundwater well in

Karst spring, Mount Hermon area, Syria
Limburg, The Netherlands

Dug well in Yemen highland

Hidden in the little hill, a public supply

Groundwater seep (with very low
drinking water well, Brixen, Italy
electrical conductivity!!)
Artesian well, Strijbeekse beek,
South-Pare mountains, Tanzania
The Netherlands
Groundwater sampling/analysis
Maps (GPS)
Field book
Bottles: acidified, non-acidified
Syringe with filter holder and filter paper
EC meter
pH meter
Alkalinity set

24
Variables to be determined

General:
Electrical conductivity
pH
Temperature

Cations: Anions:
Ca2+ Alkalinity (or HCO3-)
Mg2+ Cl-
Na+ SO42-
K+ NO3-

“Others” like micropollutants

25
Types of groundwater pollutants

26
 Natural inorganic constituents

Arsenic, fluoride, selenium, radon and uranium are examples of health-

relevant naturally occurring groundwater constituents.

Their concentrations in groundwater are strongly dependent on

hydrogeological conditions.

Parameter Guideline Value

Arsenic 10 µg/l
Fluoride 1.5 mg/l
Selenium 0.01 mg/l
Radon 100 Bg/l
Uranium 15 µg/l
Nitrate (as NO3) 50 mg/l
Nitrite (as NO2) 3 mg/l
27
 Fluoride, Selenium

Fluoride:
 > 1.5 mg/L staining of tooth enamel, brittle teeth (dental fluorosis),
 Skeletal fluorosis at prolonged intake of more than 15 mg/day;

 Guideline: 1.5 mg/L;

 In areas with acidic volcanic rocks (Sudan, Ethiopia, Kenya, Tanzania); fluorite,..

 Especially when [Ca

2+] is low (effective precipitation CaF )
2

Selenium:
 Essential trace element (1 µg per kg body weight and day for adults);
 Too much Se can cause loss of hair and finger nails, finger deformities, skin lesions,

tooth decay and neurological disorders;

 Guideline: 0.01 mg/L;

 Co-precipitatation with pyrite: FeS2

28
 Arsenic
Health aspects:
 Skin cancer, internal cancers (lung, bladder, kidney); blackfoot disease;
 Guideline: 10 ug/L;

Occurrence:
 Geothermal fluids and areas of active volcanism
 Sulphide minerals (principally arsenopyrite)

 Co-precipitation with hydrous iron oxides (anaerobic environment);

Radioactivity: Radon and Uranium

 Radon: emits alpha particles that can damage lung tissue; guideline: 100 Bq/L;
 Half life 3.8 days;

 Uranium: Long term exposure can lead to kidney problems;

 3 isotopes: 234, 235, 238

 Guideline: 15 ug/L;

29
 Aromatic hydrocarbons: BTEX
Health aspects:
 benzene = highly carcinogenic!!

Occurrence:
 Primary contaminants of concern associated with point sources of fuels and fuel
related contamination from petroleum production;

Transport and attenuation:

 Most petroleum products are LNAPLs;
 Natural attenuation of BTEX is highly significant due to biodegradation;

Parameter (BTEX) Guideline Value

Benzene 10 µg/l
Toluene 700 µg/l
Ethylbenzene 300 µg/l
Xylene 500 µg/l
30
Classical contaminant conceptual model

31
LNAPL (light non-aqueous phase liquid; e.g. petrol, benzene)

32
DNAPL (Dense non-aqueous phase liquid, e.g. heavy oils)

33
 FATE OF POLLUTANTS IN GROUNDWATER
Groundwater flow cm’s/day (much less in clay)

• Adsorption/precipitation (but for e.g. NO3- unhindered flows)

• Microbiological degradation (e.g. BOD; also die-off of bacteria)
• Complexation, redox reactions, etc. (e.g. Fe2+  Fe3+Fe(OH)3↓)
34
 EXAMPLE

Bacteria and virus die-off proceeds via an exponential function:

Ntt = N0 x 10-kt

N0 , Nt : number of bacteria, viruses at t= 0, t

k : decay rate constant (day-1)

For a decay rate of 0.1 day-1, to reach 99.9999%

reduction (“6 log-reductions”):
Nt/N0 = 10-6

10 log (N0/Nt) = 6 = kt  t = 6/0.1 = 60 days.

35
So, under these conditions, it will take 60 days to reach
99.9999% reduction in bacteria/viruses.

For a (reasonable) groundwater flow of 20 cm/day,

a travel time of 60 days would mean a distance of 12 m

So at short distance already relatively “safe” groundwater

quality (however larger distances needed for higher
velocities (sand; high permeability!) and “short-
circuiting”).
36
Main stages in the operation
of a monitoring network
(Broers, 2002)
1. Information analysis 5. Network exploitation
- system properties - data collection
- monitoring objectives - chemical analysis

2. Preliminary survey 6. Data analysis and reporting

- overview of chemical status
- changes in time
3. Design and installation
- sample size
- locations 7. Evaluation
- depths
- screen lengths
- monitoring frequency 8. Optimization
- measured chemical components
- data analysis protocols

4. Set up of procedures
- sampling
- chemical analysis
- QA-QC
37
 1. Information analysis
- monitoring objectives

Example of monitoring objectives (country wide efforts):

General policy information goals: To determine the effects of excessive
infiltration of wastewater to groundwater resources.
Monitoring information goals: To determine the concentrations of
nutrients and contaminants in sandy areas with urban land use in the
first 25 m of the subsurface.

38
 1. Information analysis
- monitoring objectives

Example of monitoring objectives (local plume):

1. Validate the conclusions of a remedial investigation or feasibility study;
2. Determine if contamination is migrating off site;
3. Determine if contamination will reach a receptor (such as a drinking water
supply well);
4. Track contaminants exceeding some standard;
5. Track the changes in shape, size, or position of a contaminant plume;
6. Assess the performance of a remedial system (including monitored
natural attenuation);
7. Assess the practicability of achieving complete remediation; or
8. Satisfy regulatory requirements (such as those for a landfill closure).

39
 3. Design and installation
- sample size
- locations

Risk concept (example: Dutch and Polish regional networks):

Pollution loading Aquifer vulnerability

Land use Soil type Geohydrological situation

Risk for contamination of shallow

and deep groundwater

Vulnerability reflects the subsurface sensitivity to the leaching of

contaminants to deeper groundwater

The risk concept is a combination of pollution loading and vulnerability

40
 3. Design and installation
- sample size
- locations

Local spill:

Monitoring wells should be placed:

- so that you can obtain background levels of contaminants of concern
(COCs).
- (and screened) to bound the horizontal and vertical extent of contaminant
plumes.
- so that bulk movement of the plume can be assessed (sampling frequency).
- in locations that provide feedback on performance of both active and
passive remedial measures.

41
3. Design and installation
- sample size
- locations

Local plume of
pollutant(s)

42
 3. Design and installation
- sample size
- locations

Local spill:

Monitoring wells should be placed:

- so that you can obtain background levels of contaminants of concern
(COCs).
- (and screened) to bound the horizontal and vertical extent of contaminant
plumes.
- so that bulk movement of the plume can be assessed (sampling frequency).
- in locations that provide feedback on performance of both active and
passive remedial measures.

43
 NUMBER, LOCATIONS, FREQUENCY...

• Number of stations much dependent on objectives; in The

Netherlands: ca. 1 per 100 km2 (near drinking water extractions)
• In many (large and/or less developed) countries: much lower
density.
• Location of stations: After surveys. Look at groundwater
flows and directions; geology, etc. Often special boreholes
have to be constructed.

Piezometers installed in a
drillhole

44
 NUMBER, LOCATIONS, FREQUENCY...

• Sampling frequency: about 1-4 times per year; much more for:
• Specific research (see figure hereunder)
• Rapid groundwater flows; high permeability (sand)

45
46
SOME CASE STUDIES

47
GROUNDWATER WELLS PROTECTION THE NETHERLANDS

Zone of restrictions close to extraction

wells:
• First 30-150 m: only water
abstraction activities
• 1000-2000 m: still strong restrictions
• Outer zone: less restrictions

In many parts of the world similar policies. Use is thus made of

natural degradation of pollutants in the groundwater
48
 Example: Gaza strip

• Limited water resources, leading to over-abstraction

 sea water intrusion giving soil salinization (chloride
values up to 1500 mg/L!)

• Much use of fertilizers  nitrate (10 x WHO standard)

• Much (waste) water reuse in irrigation  high nitrate,
pesticides and pathogens levels)

Rapid contamination due to high groundwater flows (sandy soil)

49
 Bermuda
(Chapman, p. 444)

Correlation of high nitrate concentration with densely populated areas in

Bermuda with unsewered sanitation (WHO guideline NO3-N = 11 mg/L)
50
 Industrial spill: Nassau County, USA
(Chapman, p. 447)

Ground water pollution since 1940, by metal plating industry:

Cr6+ and Cd2+.

• Pollution plume(1990s): 1300 m long; 300 m wide; 21 m thick

• > 10 mg Cr6+/L (WHO guideline drinking water: 0.05 mg/L)

• > 10 mg Cd2+/L (WHO guideline: 0.005 mg/L)

51
 CASE STUDY GERMANY*
Responsibility at the provincial (“State”) level
• Monitoring stations: total about 2,000
of which 800 in “General Monitoring Network”

Three types of stations:

• Basic stations: for general trend detection, impacts, etc.
• Operational stations (especially for drinking water
extraction)
• Special emission stations (agriculture, waste dumps etc.)

* See MTM-II, p. 65; MTM-III, p.277

52
 CASE STUDY GERMANY (Cont’d)

• Parameters: see GEMS programme discussed before. If

necessary extra components are added, or left out
• Frequency of monitoring: normally 2-4 times per year.
Higher in case of large variations. Lower in e.g. clay layers.

Example: State of Bavaria (70,000km2)

• 280 basic monitoring stations
• Construction cost 25,000 €; running cost 3,500 € /station.year
Annual cost (without data processing): about 1 million €/year

53
 Example: Nitrate in groundwater

(WHO standard: 50 mg NO3-/L)

54
 WASTE DUMP, CANADA*
• Period: 1940-1976; municipal and industrial solid waste
• Pollution plume in groundwater: about 700 m.
Contamination “closed off” from aquifer by clay layer.

• Cl- was used as “tracer” for transport rate of pollutants;

detailed studies were done within polluted zone.

* See Chapman,
p.486

55
For more details on groundwater quality & monitoring:

• Book Chapman - Ch. 9

• See MTM-articles
• See EU-WFD (Additional material Course 3.2.)
• UNEP (1996) – Environment Library no 15: “Groundwater, a
threatened resource”
(http://new.unep.org/publications/search/pub_details_s.asp?ID=2884)

56