Chapter 2

Literature Review

2.1 Ground Water

Ground water is a product of rain, snow, sleet and hail that sink into the ground. The water
moves into the ground due to gravity, passing between particles of clay, sand gravel, or rock,
until it reaches a depth where the ground is filled, or saturated with water (WISA, 2004).

There is an increasing concern in many countries about contamination of aquifer, which may
seriously inhibit their use as water sources. A major problem in some areas is the presence of
high nitrate levels in ground waters due to increased drainage and heavy fertiliser application,
which tend to occur because of intensive farming practices. The use of soakaways for the
disposal of domestic industrial wastewaters and for the removal of surface run-off can
produce major ground water quality problems (Tebbutt et. al., 1998).

2.2 The Origin of Nitrate

Nitrates accumulate naturally in ground water under certain conditions. Along the western
and south-western edge of the Kalahari and the springbok for instance, elevated nitrates are
derived from natural soil nitrogen (WW, 2005). In the semi-arid to arid parts of Southern
African subcontinent, and else where in the world, there are large tracts of land extending
over hundreds o f kilometres, where groundwater has high nitrate concentrations (Tredoux,
2004). Tredoux continued to specify that not all of these are considered to be related to
pollution, but rather to natural accumulation of nitrate in the groundwater. A full
understanding of this process is required for designing a complete ground water protection
strategy.

However, the greatest nitrate contribution is through human activities. In rural areas,
pollution can be caused by the high concentration of livestock at watering points, near
boreholes, and by inappropriate on-site sanitation. In Delmas, Mpumalanga, many people
still make use of the bucket sanitation system. While the causes of the current typhoid

6
outbreak are still under investigation, research into a similar outbreak twelve years ago
showed that nitrates in the groundwater was due to pollution.
In the southern Africa region, excessive nitrate levels are usually caused through point source
pollution. This includes sewage sludge; drying beds, land application of sludge, and
irrigation of partly treated wastewater. Groundwater pollution of this nature usually occurs
around urban centres.

On site sanitation has also been identified as a cause of high nitrate levels such as in the
village of Ramotswana in Botswana located south of Gaborone. The problem is usually
compounded by the fact that surface waste disposal practices, for example, manure, waste
water and refuse disposal, usually occur in the close vicinity of the water source and all
jointly increase the likelihood of pollution ( Tredoux, 2004).

2.3 Inorganic Combination of Nitrates and Nitrogen Compounds

In inorganic combined form, nitrogen occurs in soils as nitrous oxide (N 2O), nitric oxide
(NO), nitrogen oxide (NO2), ammonia (NH4+), nitrite (NO2-), and Nitrate (NO3-). The first
four of these are gasses and ordinarily are not present in concentrations large enough to be
detected. The last three are ionic forms found in the soil solution. Nitrite and nitrate occur
exclusively or almost exclusively as freely diffusable ions in the soil solution.

Ordinarily the ammonium in exchangeable and soil-solution forms and the nitrite and nitrate
collectively constitute less than 2% of the total nitrogen in soils. The fact that some soils
have the property of retaining the ammonium in non-exchangeable form against extraction
with potassium chloride or other salts has been known for many years, but little consideration
was given to the possibility that substantial amounts of non-exchangeable ammonium may
exist in soils (Black, 1967).

2.4 Occurrence of Nitrates in Municipal Waste Water

Nitrogen present in fresh wastewater is primarily combined in protenaceous matter and urea.
Decomposition by bacteria readily changes the form to ammonia. The age of wastewater is
indicated by the relative amount of ammonia that is present. In an aerobic environment,
bacteria can oxidise the ammonia nitrogen to nitrates and nitrites. The predominance of

7
nitrate nitrogen in wastewater indicates that the waste has been stabilised with respect to
oxygen demand. Death and decomposition of the plant and animal protein by bacteria again
yield ammonia (Metcalf & Eddy, 1991).

Ammonia present in waste water is oxidised to nitrate in the waste treatment possess by a
bacteria known as nitrosomonous, according to Metcalf & Eddy another bacteria known as
the nitro-bacteria converts the nitrate to the nitrites. Aisleby sewerage treatment works
receives both industrial and domestic wastes for treatment.The industrial wastewater contains
high concentrations of chloride and sulphates and does not contain organic matter (Water SA,
2003).
Nitrate nitrogen is the most highly oxidised form of nitrogen compound found in wastewater.
According to Metcalf & Eddy a typical range is from 15 to 20mg/L as N.

2.5 Laws and By-Laws Governing Water Use and Pollution

2.5.1 Water Act 1999 (Chapter 20:24)

The new Water Act, although gazetted in 1999, has been in effect from 1 January 2000. The
Act makes provision for a National Water Authority (ZINWA) with considerable powers to
control the pollution of both surface and ground water.

Clause 68 makes it an offence to discharge any water into a public stream, surface or ground
water that contains any organic or inorganic matter; raw sewage fits this definition. The law
allows the imposition of a heavy fine or imprisonment or both. Mitigation may be allowed if
it can be proved that reasonable steps were taken to prevent the discharge.

The (then) Ministry of Water Development issued Guidelines for the Disposal of Sewage
during wet weather in 1978 and these are still applicable. The key points of these guidelines
are summarized below: -
 Enforcement action will be taken where frequent discharges occur due to blockages or
malfunctions.
 Legal action will not normally be initiated where accidental or infrequent discharges of
raw sewage occur provided that it is not due to:

8
 - Negligence, poor design, poor workmanship or poor maintenance.
- The fault is cleared as quickly as possible.
- The discharge is thoroughly investigated by the operating authority and reported to
the Provincial Water Engineer.
- Immediate steps are taken to abate the hazard.
 Discharges resulting from extreme storm conditions will be accepted providing the sewer
or pumping system meets certain criteria set out in the Guidelines.

2.5.2 Public Health Act

Clause 83 of the Public Health Act places a general duty on Local Authorities to take all
reasonable and practical measures to keep their district in a clean and sanitary condition and
from preventing the occurrence of any condition liable to the injurious or dangerous to
health.

2.5.3 Urban Councils Act

Clause 168 of the Urban Councils Act relates to the Water Act in requiring the Council not to
discharge any sewage in contravention of the Water Act.

2.5.4 Water (Waste and Effluent Disposal) Regulations, 2000

These were issued in October 2000 and Clause 13 requires a permit holder to report orally
and in writing any accidental discharge of waste or effluent and supply such information as is
necessary for the Pollution Control Officer to assess the impact on the environment. All
Drainage Authorities are required to be permit holders.

2.6 Nitrates Accumulation Processes

A number of site related factors control nitrate generation in the soil, leaching to the
subsurface and accumulation in ground water. Under natural conditions, nitrate generation is
primarily dependent on the availability of organic nitrogen in the soil. This nitrogen pool is
maintained through nitrogen fixation by specific plant species (e.g. the legume species). At
the same time uptake of nutrients by plants as well as natural de-nitrification serves to
balance nitrate generation. Vegetation is therefore a prerequisite to the whole sequence.

9
Plant growth is dependent on the number of factors of which climatic conditions and
particularly rainfall (quality and distribution) is of overriding importance. In high rainfall
areas, the natural vegetation cover is dense and interception by root systems of the plant
cover is sparser. Further, the high variability of rainfall leads to a periodic die-off of plants
and thus a variation of the leaching of nitrate, therefore, it is expected to be at least it is
highest at the start at the rainy season (Tredoux, 2004).

2.7 Contribution of Septic Tanks to Ground Water Nitrates Accumulation

A septic tank is a watertight settling tank to which wastes are carried by water flushing down
a short sewer. A septic tank does not dispose of its wastes; it only helps to separate and digest
the solid matter. The liquid effluent flowing out of the tank remains to be disposed of,
normally by a soakage pit or drain field, and this sludge accumulating in the tank must be
periodically removed (Zama, 2005).

In many tropical cities it is common to see septic tank effluents overflowing from overloaded
soakaways and discharging to storm water drains, often open and frequently blocked
(Cairncross & Feachem, 2000).

The water content of the septic tank’s effluent travel into the soil giving a high risk of
contamination (Isaah, 2005). Domestic sewage has got a content of ammonium compounds
mainly from urea excreta. The urea that is later transformed to nitrates in the ground water.

10
Chemical Strong(ppm) Medium(ppm) Weak(ppm)
Total nitrogen 85 50 25
Organic nitrogen 35 20 10
Free ammonia 50 30 15
Nitrites 0.10 0.05 0
Nitrates 0.40 0.20 0.10
Chlorides 175 100 15
Alkalinity (as CaCO3) 200 100 50
Dissolved oxygen 0 0 0
(Adopted from Singh, 1986)
Table 2.1: Typical sanitary chemical analysis of a septic tank effluent to neighbouring
ground, ppm

2.8 Removal of Nitrates in Waste Water

There are three main methods of removing nitrates from wastewater: ion exchange, reverse
osmosis and biological denitrification. The most versatile and widely used technology is
biological denitrification (Matefy et. al., 1992). The bacterium responsible for the
denitrification is classified as facultative heterotrophes and it is able to use nitrate as an
acceptor of electrons, transforms it into nitrogen gas. During the process, electrons are
transferred from a donor, normally an organic substrate, to an acceptor, nitrate or nitrite.
Practically any organic compound that can be biologically degraded under aerobic conditions
can be used for denitrification (Carrera et. al. 2003). In order to treat industrial waste waster
with a low COD/N it is necessary to add an external organic carbon source. Different
external carbon sources can be used for denitrification e.g. glucose (Chevron et. al., 1997).

1. The removal of nitrate by the conversion to nitrogen gas can be accomplished

biologically under “anoxic” (without O2) conditions. The process is known as
denitrification (Metcalf & Eddy, 1997).

11
2. The first step starts with the conversion of nitrate to nitrite, this stage is followed by
production of nitric oxide, nitrous oxides and nitrogen gas.
NO3 NO2 NO N2O N2

(Source: Peter O’neill, 1993)

Figure 2.1: Energy requirements for various conversions between nitrogenous
compounds.

12
2.9 Assimilation
Microbes present in the treatment processes will assimilate ammonia-nitrogen and evaporate
it into cell mass. A portion of this ammonia – nitrogen will be returned to the wastewater on
the death and lisps of the cells (Metcalf & Eddy, 1997).

Organic Nitrogen

Ammonia nitrogen Organic nitrogen Organic nitrogen

(bacteria cells) (net growth)
Lysis and Antooxidation
O2
Nitrate (NO2-)

O2

Nitrate (NO3-) Denitrification Nitrogen gas (N2)

Organic Carbon
(Source: Metcalf & Eddy, 1997)

2.10 The nitrogen Cycle

In 1972, Rutherford described the properties of the gas that remains when all of the
atmospheric oxygen is removed from air, when this gas was later shown to be an element that
was also a constituent of the mineral nitre, it was called nitrogen (Ebbing & Wrighton,1984)
Nitrogen is fixed by bacteria, lightning, and industrial synthesis of ammonia. Fixed nitrogen
is used by plants and enters the food chain of animals. Later plants and animal waste
decomposes. Denitrifying bacteria complete the cycle by producing free nitrogen again
(Ebbing & Wrighton, 1984). The nitrogen cycle is shown overleaf.

13
(Source: Peter O’neill, 1993)
Fig 2.2: The Nitrogen Cycle

2.11 Nitrates in Water Supplies

Drinking water should not contain more the 10mgNO-3-Nl-1 (EPA, 1993). The toxicity of
nitrates to humans is attributable to its reduction to nitrite (WHO, 1998). Generally an
excess of nitrates in water is related to public health diseases like methameglobinaemia and
carcinogenesis (Carrera & Vicete, 2003). Because of the possibility of the simultaneous
occurrence of nitrite and nitrate in drinking water, the sum of their concentration (C) of each
to its guideline value (GV) should not exceed 1:
Cnitrite + C nitrate < 1 (WHO, 1998).
GV nitrite GV nitrate

14
2.12 Variation of Nitrates and Nitrogenous Compounds with Annual Temperature and
Water Supply in the Soil
The classical investigation of the relationships between climate and soil nitrate content shows
that there is a marked decrease in soil nitrogen content with increase in annual temperature
from 0 to 200C (Jenny, 1930).

Jenny considered that the effect of temperature on microbial activity was primarily
responsible for the various conversions in the nitrogen cycle. Other factors remaining the
same, the content of nitrogen in the soil increases with the water supply. Where the water
supply exceeds the amount corresponding to the maximum rate of production of vegetation,
however the further increase that occurs in the soil nitrogen is probably attributable to the
effect of water supply decreasing the rate of decomposition (Black, 1967).

Jenny expressed the combined effects of temperature and water supply on the variation of
nitrates by the equation below:

N=0.55e-0.08T(1-e-0.005H)
where
N is the nitrogen percentage of the surface soil.
e is the base of natural logarithms.
T is the mean annual temperature in degrees centigrade.
H is the humidity factor; it is the ratio of mean annual precipitation in millimetres to the
absolute water vapour saturation deficit of the air in millimetres of mercury.

Black investigated the relationships between nitrogen nitrates and annual temperature for
soils developed under different conditions of climate and vegetation in the United States and
came up with the graph figure 4.3 over leaf.

15
(Source: C.A. Black, 1967)
Fig 2.3: Graph showing the variation of nitrogen nitrates with mean annual temperature.

2.13 Variation of Nitrates and Nitrogen Content with Depth below the Ground
The maximum nitrates content occurs in the surface layer of all soils, the distribution with
depth differs among soils. Weller silt loams, developed under forest vegetation, have a
greater relative concentration of nitrates near the surface than do the other loam soils.

The depth of accumulation of nitrogen varies in accordance with the accumulation of organic
matter. In soils where depth of penetration of water is shallow, the depth of organic matter is
shallow and nitrates accumulation is shallow. The figure overleaf illustrates a typical
variation of nitrates with depth.

16
.

(Source: Pearson &Simonson, 1939)

Fig 2.4: Graph showing the variation of nitrogen nitrates with depth.

2.14 Hazards of nitrates to Health

Excessive nitrate levels (above 50mg/l) can be dangerous to human health. Nitrate itself has a
low toxicity (Rohmamann & Sontheimer, 1985) when it is reduced to nitrite it becomes an
oxidising agent, capable of converting haemoglobin in the blood to methaemoglobin. A
reaction of nitrite with amides and amines form N-nitroso compounds, (e.g. nitrosamine and
nitrosamide) some of which are known to have carcinogenic properties (Rohmann &
Sontheimer, 1985).
The first symptoms of ‘cyanosis’ are generally noticeable when the concentration of
methaemoglobin in the blood is between 5 and 10 percent, while death results at levels of 50
percent and higher (Terblanche, 1991). Following a literature survey, Walton (1951)

17
concluded that 10mg/l (NO3- N) was a safe limit for drinking water. When bottle-fed infants
digest water containing a high concentration of nitrate, this nitrate, when converted to nitrite
in the infants’ body interferes with the oxygen carrying capacity of the Child’s blood (it
replaces the oxygen on the red blood cells).

Children with methameglobinaemia, as it is known, will show signs of blueness around the
mouth, hands and feet, hence the common name ‘blue baby syndrome’. These children may
also have trouble breathing as well as vomiting and diarrhoea. In extreme cases, there is a
marked legathy, an increase in the production of saliva, loss of consciousness and seizures.
Some cases may be fatal (W.W, 2005).

In most areas of Botswana there are high nitrates –N concentration, sometimes exceeding
500mg/l leading to a phenomenon of spontaneous abortion known as the still birth.
Anecdotal reports say that there were many cases of stillbirth, though it was not yet
confirmed (Tredoux, 2004). The abortion or still birth was also reported in livestock.
The risk of livestock loss through nitrate poisons is largely known among the local
population except in Namibia. No statistics are available and information is mostly anecdotal.
One of the recently recorded incidents of livestock losses in Southern Africa occurred in year
2000 on Ghanzi River in the Ghanzi-Karakubis area in Botswana. At least 356 heads of cattle
died as a result of nitrate poisoning (W.W, 2004). Stock losses due to nitrate poisoning have
occurred in neighbouring Namibia (Anonymous, 1974). In 2002 a further incident of
livestock loss occurred at Kautsha, north of Ghanzi where 28 heads of cattle died.

In Thabambi, Limpopo 60 heads of cattle died in 2001. However, it would seem that chronic
toxicity occurs only at higher nitrate levels. Accordingly, nitrate limits for stock watering is
set at 110mg/L (DWA Namibia, 1977). In South Africa 90.3mg/L is used as a guideline
value for the watering of dairy cows (Baard, 1992). According to Davison et al. (1964) cattle
ingesting nitrates have a reduced life span, inhibition of growth and increased incidences of
abortion and related infertility.

Hypertension and Hotdog headache has been described in literature and has been related to
nitrites used in the curing of meat to give it uniform colour (Johnson & Goldfinger, 1982).

18
The nitrates are also vaso- dilators, so that some people find that soon after eating such meat
products, they develop flushing of the face and headache (Talma, 1991).
2.15 Effects of Nitrates in treated Wastewater in Crop Growth
The nitrates in reclaimed wastewater provider fertiliser when applied to the soil for crop
production. However these nutrients can cause problems in certain instances, when they are
in excess of plant needs.
The nitrogen in reclaimed wastewater can replace an equal amount of commercial fertiliser
during the early to mid-season crop growing period. Excessive nitrogen in the later part of
the growing season may be detrimental to many crops, causing excessive vegetable growth,
delayed or uneven maturity or reduced crop quantity (Metcalf & Eddy, 1997).

19
Component Concentration (mgL-1)
LOD 0
N-NO3- 700-900
N-NH4+ 0-10
F-1 10-20
CL 1000-1500
SO42- 5000-10000
(Source: Carrera, 2003)
Table2.2: General constituent of industrial waste after the nitrification ready for irrigation.

2.16 Occurrence of Nitrates in Soils

Non-ionic and non-polar organic pollutants are normally absorbed on soil humic material.
Since most soil organic matter is found in the surface horizon, there is a tendency of these
pollutants to be concentrated in the topsoil (Alloway and Ayres, 1997). The flow chart
below shows the transport processes undergone by nitrates as pollutants in the soil.

Fig 2.6: Movement processes of nitrate pollutant.

20
2.17 Nitrate Transport Processes in Ground Water
To model the transport of nitrates in ground water there is need to view the nitrates as if they
do not change i.e. they are a conservative species. The nitrates are considered as stable,
removal mechanisms such as volatilisation, adsorption, fixation, biological denitrification,
incorporation into cell tissue and removal by vegetable are also not considered (Dakes at al.,
1980).

The transport mechanism is by the bulk ground water movement by processes of advection,
dispersion and diffusion. This is mainly due to the concentration energy gradients and
random molecular movements (Dakes at al., 1984)
Nitrates can be considered to move through the porous medium without interacting with the
porous matrix or ground chemical or biotic transformations (Gumede, 2005). Basic
understanding of the natural paths and rates of ground water movement is the starting point
for evaluating problems of ground water contamination. In many cases of contamination of
ground water with nitrates, the movement of nitrates has been altered by man’s activities,
such as pumping of wells or addition of liquids to the ground. Knowledge or inferences about
earlier conditions may guide decisions about remedial action on some nitrate contamination
problems and may help responsibility for injustices in some cases (Strobbe, 1971).

Interdependent considerations controlling natural movement of ground water are geologic

framework, climate, and topography. Brief, useful generalisations about geologic framework
are difficult to make, but we should be constantly reminded that nitrates in ground water
flows with the ground water under the influence of gravity, following the most direct route
from points of higher potential to points of lower potential, and producing the steepest
pressure gradient and greatest rate of flow; to the extent that it can take preferential paths,
water tends to flow through permeable materials and relatively impermeable materials
(Mcguiness, 1963).

2.17.1 Advection as a Transport Mechanism for Nitrates

In this mechanism the nitrates are transported in the bulk movement of water (Mutsvangwa,
2005). The nitrates are transported with the mean velocity of water as it flows through the

21
porous media. The advection mass vector is proportional to the medium hydraulic
conductivity which is also proportional to the energy gradient (Mutsvangwa, 2005) i.e.
JAdvection = kiC = qC
( i- hydraulic gradient, C- concentration, K- conductivity & q is the velocity)

2.17.1 Dispersion as a Transport Mechanism for Nitrates

Dispersion refers to both the mechanical mixing during fluid advection and molecular
diffusion. Dispersion flux is proportional to the concentration gradient i.e.

JDispersion = -DAC  Where:

------Porosity of the media

D------Longitudinal dispersion coefficient

C ---Concentration gradient

2.18 Measurement of Nitrate Levels in Samples

The nitrate method that involves the reduction of nitrates that are determined by a diazonim
reaction to form a reddish dye is used. Nitratest tablet and nitratest powder to catalyse
flocculation in the reduction period in the nitrate’s tube.
The nitrate resulting from the reduction stage is determined by reaction with sulphuric acid in
the presence of M-(1-naphthy 1) ethylene diamine to form a reddish dye. The reagent is
provided in a single nitrocol tablet, which is simply added to the test solution. The intensity
of the colour produced in the test is proportional to the nitrate concentration and is measured
using the photometer (Gumede, 2005).

2.19 Contribution of Waste Water Streams to Ground Nitrates Accumulation

2.19.1 Matsheumhlope and Mazai Waste Water Streams

Matsheumhlope stream is a stream that passes through Matsheumhlope and then runs close to
some industries in the western side of the town the where it probably gets most of its
pollution eventually meets with Mazai stream. Mazai stream also passes through some
industries, Renkini, Makokoba and eventually joins with other streams and pass through the
region of Aisleby. Industries discharge some toxic chemicals to these streams especially at
22
night when no one is awatch. Some chemical tests carried out by the Trade Waste section of
Bulawayo reveals that the waste consists of high levels of ammonium compounds (Isaiah,
2006).

The Bulawayo City Council under its Trade Waste Section (TWS) carries out spot checks on
the industrial water of the stream after every fortnight. The TWS sample many parts of the
streams to try and detect any harmful pollutants in the streams. The environment inspector
also carries out company checks to find out any company that discharges polluted industrial
water. If any firm/organisation is found guilty, they are charged with contravention of the
Water Act 1976 (Sibanda, 2000).

Clement carried out various chemical tests on these two streams during the year of 2003 in
the region of Aisleby farm and came out with the following results.

Fluoride Sulphates Phosphates Ammonia Nitrates P.V

(mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)

Sample 25 10 25 25 10 100
size
April 4.5 2.9 2.2 6.3 1.29 9.6
May 5.1 2.2 3.0 6.7 1.35 9.8
June 4.7 2.3 3.1 6.7 1.37 10.1
July 4.9 2.7 3.0 6.6 1.30 10.0
Ave. value 4.8 2.5 2.8 6.6 1.34 9.8
Table 2.3: Chemical Test Results for Mazai Stream during the year 2003.

23
 Fluoride Sulphates Phosphates Ammonia Nitrates P.V
(mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)
Sample size 25 10 25 25 10 100
April 9.3 1.8 2.4 5.2 0.27 11.3
May 9.0 1.8 2.2 5.0 0.15 10.7
June 7.8 1.6 2.2 4.9 0.2 10.5
July 10.6 2.0 2.4 4.7 0.5 11.5
Ave. value 9.2 1.8 2.3 5.2 0.25
Table 2.4: Chemical Test Results for Matsheumhlope Stream during the year 2003.

Na K Fe Mn Zn Cr Cd Ni Cu
Mazai 52.4 8.2 0.35 0.25 0.06 0.09 0.01 0.06 0.01
Matsh 54.4 8.5 0.39 0.28 0.04 0.05 .0.01 0.07 0.01
Table 2.5: Chemical Test Results for Metals Measured in Mazai & Matsheumhlope Streams
for the Year 2003

There is a high possibility of ground water pollution in the region of Aisleby farm due to
leaching of these chemicals flowing along these streams. Three sampling points along Mazai
river (BC4, BC4.2, BC5) were sampled for a period from 1995 to 1999 and the levels of
ammonia (nitrate), pH, conductivity and dissolved oxygen are as shown below.

24
Year Sampling Point pH NH3 Conductivity DO
BC4 7.3 7.2 207.0 2.6
1995 BC4.2 7.2 0.5 215.0 3.2
BC5 7.3 0.9 185.0 3.1
BC4 7.2 1.2 146.8 2.3
1996 BC4.2 7.3 2.4 420 1.3
BC5 7.1 0.2 292 2.2
BC4 7.0 1.6 - 1.95
1997 BC4.2 7.1 3.4 - 1.3
BC5 7.0 3.7 - 1.42
BC4 7.3 8.6 276 4.3
1998 BC4.2 7.5 7.0 302.2 0.9
BC5 7.4 3.7 249.0 4.1
BC4 8.7 2.2 178 7.3
1999 BC4.2 8.1 6.3 268 1.2
BC5
Table 2.6: Results in terms of the yearly average for the BCC Sampling Points along
Streams passing through Aisleby Region

25
2.20 Chemical Analysis of Water to Assess Portability
Boreholes in the surroundings of Aisleby supply several residents and livestock with
domestic and consumption water. The local authority gives a standard of the chemicals from
the boreholes to be suitable for drinking.
Chemical Max Recommended Max Allowable Unit
Nitrate 6 10
Ammonia 1 2
Flouride 1 1.5
pH 6-9 5.5-9.5
Turbidity 1 5
Conductivity 70 300
PV
Sulphate 200 650
Phosphate
(Source:BCC, 2005)
Table 2.7: BCC Standard Chemical levels for borehole water.

2.21 Wastewater Irrigation and Standard for Irrigation Water

Irrigation water must, above all, be free from toxic or radioactive substances, hydrocarbons
and greases. Excess salinity destroys the structure of the soil. Some products may impair the
test of certain vegetables and fruits on the other hand; the presence of certain organic content
may have a nutrient value for plants (Sacramento, 1951). Nitrogen compounds are useful for
plant growth. However, excess amounts of nitrates may lead excessive growth and delayed
or late maturity with little production.
Excessive nitrates without enough water may lead to stunted growth of plants (Ngulube,
1998). Possibly one of the only advantages of mildly nitrogenous groundwater is that it can
be applied fruitfully for irrigation of certain crops during part of the growth cycle. In their
report of nitrates in ground water of Central Australia, Murray and Siebert (1962) suggested
that the fixation of atmospheric nitrogen by legumes could account for areas giving rise to
moderately and highly nitrated waters.

26
The build up of nitrates in groundwater in areas where wastewater irrigation takes place has
been subject of much research (Montgomery et al, 1984, Kayser, 1988; Jinyan Chen et al
2002) in the environmental effects of wastewater irrigation.

The levels of nitrate in treated or untreated wastewater is usually low since most of the
nitrogen is in ammonical form, which is later converted into nitrites and nitrates by aerobic
bacteria in the soil. The nitrate concentration in the effluent used for irrigation at a farm
north of Braunschweig in Germany is around 1.1 mg/1 and the ammonical nitrogen is
26.9mg/1, the levels of the same chemicals were noted in groundwater and observed to be
1.6mg/1 and 25.2mg/1 respectively (Kayser, 1988).
The nitrate removal capacity of the soil is enhanced if a primary settled effluent instead of
the secondary effluent is applied because it contains organics, which are used in the
denitrification of nitrates into nitrogen that is eventually lost to the air. By the application of
primary effluents at a chalk site in Winchester (UK) and secondary effluents from trickling
filters at other smaller sites Montgomery et al (1984) showed that if primary effluent is used
for irrigation up to 90% of residual ammonia is removed with the remaining portion being
converted to nitrates.
This was much better than the observed 100% residual ammonia conversion into nitrates in
areas where secondary effluents were used. A carbon to nitrogen ratio of at least 2:1 is
necessary for maximum nitrogen removal (Metcalf and Eddy, 1991). A flooding and drying
sequence is also recommended for maximum nitrate removal, lab and field studies show that
to achieve high nitrogen removal percentages the amount of ammonium nitrogen applied
during flooding must be balanced against the amount of oxygen entering the soil during
drying (Bouwer et al 1974; 1980).

The findings on the enhanced removal of nitrogen in primary settled effluents do not in any
way exonerate these effluents from causing high nitrate levels in groundwater. Nitrate levels
as high as 124mg/L as nitrate were observed (Jinyao Chen et al, 2002) in wells near an
untreated wastewater irrigation canal is the Hebei province of North China. Stable isotopes
0-18 and N-15 were used as tracers to identify the source of pollution as wastewater
irrigation. It was observed that the nitrate levels generally decreased with distance from the
canal.

27
In Mexico City where untreated wastewater has been used for decades for crop irrigation
nitrate levels in boreholes near the sites were observed to be between 47 and 69mg/L as
nitrate (Downs et al, 1999). Primary treatment does not improve the carbon content of the
effluent but infact removes the settleable organic matter these results of using untreated
effluents can be used to assess the effect of primary effluent on the nitrate levels in the
groundwater. It is clear from these and many other findings that the threat posed on
groundwater quality cannot be properly predicted by considering the level of treatment of the
applied wastewater. Many other factors like the depth to groundwater and the soil
characteristics are required in predicting the nitrate pollution levels.

In slow rate systems plant uptake is the principal nitrogen removal mechanism. This
nitrogen uptake only takes place near the root zone. To maximise the nitrogen removal of
the system the vegetation must be harvested and removed from the system or else the
nitrogen in the vegetation will be recycled and will re-enter the system as organic nitrogen.
Experiments carried out in Cyprus by the Agricultural Research Institute (1984) using cotton
as the test crop and analysing soil samples to a depth of 120cm have shown that as the
nitrates in irrigation water increases, the nitrates begin to accumulate in the soil. This
accumulation of nitrates at greater depths poses a great groundwater pollution hazard hence it
is necessary to ensure that the nitrogen in the irrigation water is above the uptake capacity of
the crops under irrigation.

2.22 Chemical Analysis of Industrial Effluent

The quantities and compounds of nitrates in ground water is also affected by the nitrogen
nitrates that enters the sewerage works from either industrial or domestic raw waste water.
There are allowable levels for nitrogen nitrates on the fresh wastewater given by the local
authority and Zimbabwe Water Authority. These standards are given mainly to avoid
overloading the STW and also to reduce the changes of the final effluent from being too high
in chemicals of concern. The table below gives some of the standard levels of chemicals
allowed for industries to dispose into municipal sewers as raw wastewater.

28
Parameter Conc, mg/L
Nitrates
PH 6-12
Conductivity 300
Suspended solids 600
Chlorides
Fluorides
Temp 45C
COD 2000
Table 2.8: BCC Standards for Industrial Waste

In a case of an industry disposing wastewater into municipal sewers with chemical levels that
are out of given range, the particular industry is charged with a penalty.

2.23 Ground Water Nutrients

2.23.1 pH
Acidic solutions are characterised by the presence of the hydronium ion. In fact, it is the
hydronium ion that is responsible for the acidic properties of such solutions. Some solutions
have high concentrations of the hydronium ion and some have low concentrations. In any
sample of water or water solution, hydronium ion and hydroxide ion are in equilibrium with
water.
H2O + H2O H3O+ + OH-
In pure water or neutral aqueous solution, that is, a solution not containing an acid or base,
the concentrations of hydronium ion and hydroxide ion are equal. However the possible
concentrations cover a very wide range, a special scale has been devised to express
hydronium ion concentrations in aqueous solutions. This is called the pH scale and is based
on the following definition:
- pH is the negative logarithm of the hydronium ion concentration:
pH = -Log [H3O+]. The autotrophic ammonium-oxidising organisms are sensitive
also to the combination of high concentrations of ammonium and high pH values
developed in soil by anhydrous ammonia, urea, and other fertilisers that contain or
and produce ammonium hydroxide. Because of this inhibition, there is a tendency
29
 for oxidation to proceed most rapidly in peripheral locates around the fertiliser zones
where ammonium concentrates and pH values decrease, and the soil may become
strongly acidic. The central part of the fertiliser zone is the last to become acidic.
- As the annual rainfall increases, the depth of carbonates increases where the annual
rainfall is 35-50mm many soils contain carbonates within the surface 50cm. At a
rainfall 90-100mm, the soils are free of carbonates. Where leaching is absent or
limited, practically all carbonic acid is volatilised because chemical equilibrium soon
limit the accumulation of carbonic acid and bicarbonates in soil. Mangore (2002)
monitored the ground pH in residential areas of Bulawayo and came up with the
variations below for the year 2002.

(Source: Mangore, 2002)

Fig 2.7: Variation of pH in residential areas of Bulawayo through the year 2002

2.23.2 Chlorides
Chlorides exist mainly in a pale, greenish yellow gaseous form. It never occurs as the free
element in nature, but it can be obtained from the many compounds in which it is found.
Combined chlorine is found in various minerals called chlorides, the most notable of which is

30
salt or sodium chloride. Vast salt deposits are found native and as dissolved salts found in
abundance in seawater. Elemental chlorine can kill bacteria so it is used to treat drinking
water and swimming pool water. It is also used to make household bleach. In ground water
it can also be combined with nitrogen compounds. Wastewater can also contain notable
quantities of chlorides. High chloride levels are expected to exist where high nitrate levels
are present (Dickson, 1987). Mangore (2002) monitored the variation of chlorides in ground
water in the greater Bulawayo in residential locations and came up with the results below.

(Source: Mangore, 2002)

Fig 2.8: Variation of Chlorides in residential areas of Bulawayo through the year 2002

2.23.3 Phosphates
Organic wastes not only deplete wastewater of oxygen, but also produce inorganic ions such
as nitrate, NO3-, and phosphate, PO43-, as a result of bacteria/degradation. These ions also
find their way into surface waters from agricultural run-off (fertilisers) and from household
detergents. A part of these ions is leached to ground water being plant nutrients, these ions

31
over fertilise the growth of algae in lakes. Large mats of algae die and sink to the bottom of
the leke, where they decay, using up the oxygen. Existence of phosphates is an indication of
the possibility of the presence of nitrates, however phosphate and nitrates can exist
independently (Ebbing, 1984). In wastewater phosphorus, exist mainly in the form of
orthosphates. Varied findings on the removal of phosphates in the soil exists but it is clear
that the degree of removal depends on the degree of contact of wastewater and the soil matrix
(Chikanya, 2005).

(Source: Mangore, 2002)

Fig 2.9: Variation of Phosphates in residential areas of Bulawayo through the year 2002

2.23.4 Turbidity
The appearance of water can be a significant factor in consumer satisfaction case of drinking
water. Turbidity in water is caused by the presence of colloidal and suspended matter (such
as clay, silt, finely divided organic matter, plantation, and other microscope organisms)
(Letterman, 1999).
Turbidity is measured using an instrument called a turbidimeter, or nephelometer, it detects
the intensity of light scattered at one or more angles to an incident beam of light. Turbidity
measurements were just used to maintain the aesthetic quality of treated water. In 1974, after

32
the passage of the Safe Drinking Water Act, the USEPA lowered the limit for filtered water
to the nephelometric turbidity unit (INTU) with the explanation that particles causing
turbidity can interfere with the disinfection process by enmeshing and therefore, protecting
microbiological contaminants from chemical disinfectants such as chlorine. Mangore (2002)
monitored the variations of turbidity in residential areas of Bulawayo and presented the
results below.

(Source: Mangore, 2002)

Fig2.10: Variation of turbidity in residential areas of Bulawayo through the year 2002

2.23.5 Nitrite
Nitrite does not typically occur in natural waters at significant levels, except under reducing
conditions. It can also occur if water when sufficient ammonia is treated with permanganate.
Sodium nitrite is widely used for cured meats, pickling and beer. Nitrite, or nitrate converted
to nitrite in the body, causes two chemical reactions that can cause adverse health effects.
Induction of methameglobin especially in infants less than one year of age.
Nitrite is formed by a reaction of nitrate with saliva, but infants under one year of age have
relatively alkaline conditions in their stomach which allows bacteria to form nitrite. Ground
33
water nitrites can be demonstrated to vary with time during the year, mainly due to seasonal
changes of rainfall. Mangore (2002) monitored the variations through the year and came up
with the results in the graph 4.6.

(Source: Mangore, 2002)

Fig 2.11: Variation of Nitrites in residential areas of Bulawayo through the year 2002

2.23.6 Total Hardness

Total hardness represents the sum of multivalent metallic ions that are normally considered
to be only calcium and magnesium. Generally, chemical analysis are performed to determine
the total hardness and calcium hardness present in the water in Magnesium hardness is then
computed as the difference between total hardness and calcium hardness.
Originally, the hardness of water was understood to be a measure of the capacity of the water
for precipitating soap. It is this aspect of hard water that is the most perceptible to
consumers. Hardness is expressed as an equivalent quantity of calcium carbonate (CaCO 3).
Waters having less than 75mg/l CaCO 3 are generally considered soft. Those between 150-
300mg/l CaCO3 are classified as very hard.

34
Fig 2.12: Variation in solubility of CaCO3 complex ion with temperature

Fig 2.13: Variation of Calcium Hardness in residential areas of Bulawayo through the year
2002

35
2.23.7 Chemical Oxygen Demand (COD)
This is a chemical test done by using boiling dichromate and concentrated sulphuric acid. It
gives no indication of what proportion of the organic material is biodegradable, but has been
developed to the point where separate degradable and non-degradable fractions can be
measured by additional tests. As a result, COD is now used as the basis of STW design, and
solids production in activated sludge STW can be calculated from the COD.
Within the same method the COD test has precision, though different COD analytical
procedures show significant variations in the results. Nuisance organic compounds such as
oil, fat and grease are totally oxidised (Chikanya, 2005)
The COD test requires careful technician skills and takes about 2 hours to carryout.
Simplified and miniaturised equipment is available to allow large batches of COD tests to be
carried out at the same time.

2.23.8 Permanganate Value (PV)

PV is defined as the oxygen absorbed from acid potassium permanganate in 4 hours at 27C.
It is also referred to as the oxygen absorbed (OA) test. It is the oldest test in use, simple and
requiring little skill. However, it is highly empirical and measures only organic matter
oxidised by acid permanganate. It also gives no indication of whether organic matter can be
metabolised biologically.

Some organic compounds including tertiary alcohol and similar do not react at all with
permanganate. PV test results can vary over a wide range depending on the size of the
sample, and severe distortions of the PV are experienced when inorganic oxidising agents are
present. PV tests do not yield information usable for STW design purposes.

2.23.9 Biochemical Oxygen Demand (BOD)

BOD is defined as the amount of dissolved oxygen used by bacteria in stabilising organic
matter in 5 days at 20C and represents appropriately 60% of the theoretical ultimate BOD.

36
BOD is a time consuming test and it is not easy to obtain reliable results especially in the
presence of certain compounds. The BOD value has meaning only in countries that have not
yet adopted the international COD-based models for design of biological treatment systems.

2.24 Data Analysis

2.24.1 Statistics Method

The spearman rank correlation coefficient is a method that allows to test for correlation
between two sets of data. The test statistic is a measure of association. As such, it is strictly
speaking a measure of the degree of correspondence between the rates of the sample
observations rather than between the observations themselves. It is however, thought of as a
measure of the strength of the relationship between the sample X and Y values and as an
estimate of the strength of relationship between X and Y in the sampled population.
Unfortunately the exact measure of the strength that rs is estimating is difficult to interpret.
(Danniel, 1990).

When the rank of X is the same as the rate of Y for every pair of observations (perfect direct
relationship), all the differences di will be equal to zero, and rs will be equal to +1. Kendall

(T3) has shown that in general rs = -1 when the rate of are variable within each pair of
observations (Xi; Yi) is the reverse of the other (perfect inverse relationship).
Thus if
[R(x) = 1, R (Y) = n]
[Rx = 2, R (Y) = n-1], …, [R(X) = n, R (Y) = 1] for a pairs of observations,
rx = -1.
The assumptions of the test statistic are: -
A. The data consists of a random sample of n pairs of numeric or non-numeric
observations.
B. Each pair of observations represents two measurements taken on the subject or
individual, called the unit of association.

In preparation for a computing the spearman rank correlation, coefficient data is subjected to
the following procedures: -
37
1. If the data consists of observations from a bivariate population, it is designated into n
pairs of observations (X1, Y1), (X2,Y2),… (Xn, Yn).
2. Each X is ranked relative to all other observed values of Y, from smallest to largest in
order of magnitude. The rank of the ith value of Y is denoted by R (Yi), and R (Yi) =
1 if Yi is the smallest observed value of Y.
3. If this occur among the X is or among the Y’s each tied value is assigned the mean of
the rank positions for which it is tied.
4. If the data consists of non-numeric observations, they must be capable of being
ranked as described.

2.24.2 Hypothesis
It may be defined as a statement about one or more populations (Danniel, 1990). A research
hypothesis is frequently the result of a hunch or suspicion based on extended observations by
the potential investigator is usually not a statistician.
There are two for statistical hypothesis:
The null hypothesis (which is designated H 0) and the alternative hypothesis (which is
designated H1). The null hypothesis is the hypothesis tested. The null hypothesis is always a
statement of no difference in the level of concentration of nitrates.

38