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Inorganic Water Quality Parameters Nitratespdf

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Water Quality Fact Sheet:

Nitrate

WHO guideline value for nitrate (recommended limit): 50 mg/l (short term exposure)
WHO guideline value for nitrite (recommended limit): 3 mg/l (short term exposure)
WHO guideline value for nitrite (recommended limit): 0.2 mg/l (long-term exposure)
WHO guideline value for combined nitrate plus nitrite (recommended limit): the sum of the
ratios of the concentration of each to its guideline value should not exceed 1
Typical range in groundwater: 0 – 100 mg/l

This is one of a series of information sheets prepared for a limited number of inorganic constituents of
significant health concern that are commonly found in groundwater. The sheets aim to explain the nature of
the health risk for each constituent, the origin and occurrence in groundwater, the means of testing and
available methods of mitigation. The purpose of the sheets is to provide guidance to WaterAid Country
Office staff on targeting efforts for water-quality testing and to encourage further thinking in the
organisation on water-quality issues.

Health effects The weight of evidence is strongly against there


being an association between nitrite and nitrate
The primary health concern regarding nitrate and exposure in humans and the risk of cancer (WHO,
nitrite is the formation of methaemoglobinaemia, so- 1998).
called ‘blue-baby syndrome’. Nitrate is reduced to
nitrite in the stomach of infants, and nitrite is able to Occurrence in groundwater
oxidize haemoglobin (Hb) to methaemoglobin
(metHb), which is unable to transport oxygen Nitrate is one of the most commonly identified
around the body. This reduced oxygen transport groundwater contaminants. Nitrate (NO3-) is the
becomes clinically manifest when metHb main form in which nitrogen occurs in groundwater,
concentrations reach 10% or more of normal Hb although dissolved nitrogen may also be present as
concentrations; the condition, called methaemo- nitrite (NO2-), ammonium (NH4+), nitrous oxide
globinaemia, causes cyanosis and, at higher (N2O) and organic nitrogen. The concentration,
concentrations, asphyxia. form and behaviour of nitrogen in water are
governed by the chemical and biological processes
The Hb of young infants is more susceptible to forming the nitrogen cycle. In this cycle, atmospheric
metHb formation than that of older children and nitrogen gas is converted to organic nitrogen
adults; this is believed to be the result of the large compounds by nitrogen fixers such as blue-green
proportion of foetal Hb, which is more easily algae and some bacteria, such as those in the root
oxidized to metHb, still present in the blood of nodules of leguminous plants. Nitrogen in organic
infants. In addition, there is a deficiency in infants of form and ammonium can be converted by bacteria
metHb reductase, the enzyme responsible for the in aerobic conditions into nitrite and nitrate, a
reduction of metHb to Hb. The reduction of nitrate process termed ‘nitrification’. Nitrate in anaerobic
to nitrite by gastric bacteria is also higher in infants systems can be reduced by other strains of bacteria
because of low gastric acidity. The level of nitrate in to nitrous oxide or nitrogen gas, by ‘denitrification’.
breast milk is relatively low; when bottle-fed,
however, these young infants are at risk because of Nitrate speciation in the aqueous environment is
the potential for exposure to nitrate/nitrite in therefore redox controlled. In aerobic water nitrogen
drinking-water and the relatively high intake of water occurs as nitrate or nitrite ions. Nitrate is stable over
in relation to body weight. The higher reduction of a considerable range of conditions and is very mobile
nitrate to nitrite in young infants is not very well in water. Ammonium and organic forms are unstable
quantified, but it appears that gastrointestinal and are generally considered to be indicators of
infections exacerbate the conversion from nitrate to pollution. In confined aquifers, where conditions
nitrite.
1
are anaerobic, nitrate is converted to nitrogen gas by Crop type
Groundwater
nitrate (mg/l)
denitrification but nitrite or ammonium may persist.
Horticulture 1
The nitrate concentration in groundwater is normally Wheat 2
low but can reach very high levels as a result of Grassland 3 >50
leaching or runoff from agricultural land together Sugarcane 4
with contamination from human or animal wastes,
(Laftouhi et al. 2003). Coffee 5 25-50

Orchard
Sources of nitrate pollution in groundwater Paddy
6
<25
7
Agriculture 50 200 500

Large increases in food production in developing Nitrate fertiliser application (kg/ha/year)


countries have resulted from the highest rates of
increase in nitrogen fertiliser use during recent years Figure 1. Anticipated groundwater nitrate
and rates have tripled since 1975. In Asia a quarter concentrations for a range of crop types (circled
of the growth in rice production has been attributed numbers correspond to text examples).
to increased fertiliser use (BGS et al. 1996).
A wide variation in nitrate leaching losses from 2. Increasingly intensive cultivation of cereals in
agriculture occurs, resulting from differences in soil temperate European regions has produced
and crop types, fertiliser application rates and average nitrogen leaching in the range 40-70
irrigation practices. High rates of nitrogen leaching kg/ha from annual applications of 150-200
from the soil can be anticipated in areas where soils kg/ha, as determined from unsaturated zone
are permeable and aerobic, and nitrogen applications nitrate concentrations of 50-80 mg/l in
are made to relatively short duration crops, e.g. infiltrating recharge (Foster et al. 1982).
vegetables or wheat. The nitrogen loading will be
3. Similar unsaturated zone profiling techniques
greatest where cultivation is intensive and double or
have confirmed that unfertilised and ungrazed
triple cropping is practised. Especially high nitrogen
grassland produces negligible nitrate leaching.
leaching can occur from soils where irrigation is
However, applications to intensive grassland of
excessive and not carefully controlled (BGS et al.
150 kg N/ha/yr produce leaching losses in the
1996).
same range as drinking water standards, and the
The amount of annual recharge from precipitation considerably higher applications sometimes
will influence the amounts of nitrate in groundwater encountered produce correspondingly greater
through dilution effects so that in arid or semi-arid losses (Chilton and Foster, 1991).
regions concentrations will be proportionately
4. The continuous crop cover and strong root
greater than for an equivalent environment in a
development of sugar cane plantations
humid region.
combined with limited irrigation contributes to
Continuous crop cover e.g. sugar cane, citrus groves moderate nitrate leaching to groundwater from
or coffee plantations, tends to reduce nitrogen yearly nitrogen applications of some 130 kg/ha
leaching loss. Losses beneath paddy cultivation are (Chilton et al. 1995).
likely to be low as a result of volatile losses and
5. High coffee yields in Costa Rica are coupled to
denitrification in the waterlogged, anaerobic soil.
large additions of nitrogen from chemical
Figure 1 shows the nitrate concentrations in fertilisers. High rates of nitrogen uptake by both
groundwater that could be anticipated from a range coffee and shade trees, if present, coupled with
of typical crops, illustrating the results from case soil denitrification reduce overall leaching to
studies: groundwater to 3-8% of the applied nitrogen
(Babbar and Zak, 1995)
1. Intensive cultivation of two crops per year of
onions and chillies on a shallow coastal sand 6. Coconut plantations with low nutrient inputs
aquifer in Sri Lanka produced concentrations of and leaching to groundwater were the traditional
up to 220 mg/l of nitrate in groundwater, crop in areas of Sri Lanka. (Morris et al, 2003)
equivalent to 70% of the applied nitrogen, after
7. Little leaching of nitrate from paddy soils in
taking into account recycling in irrigation water
India and China was found despite high
pumped from shallow on-the-plot irrigation
application rates and 2 – 3 crops per year (BGS
wells (Mubarak et al, 1992; Morris et al. 2003).
el al. 1996; Ghosh and Bhat, 1998: Zhu et al,
2003). Plant uptake, volatile losses of ammonia
2
Table 1. Groundwater nitrate concentrations beneath selected urban areas
City/ Population Disposal systems Aquifer type Groundwater Reference
suburb during study nitrate
(millions) concentration
range (mg/L)
Lucknow, 1.1 Septic tanks, latrines Alluvium (0 – 100 m) 10 – 600 BGS et al.
India and soakaways (1996)
Hat Yai, 0.14 On-site sanitation and Semi-confined coastal alluvium <5 (N present as Lawrence et al.
Thailand canal NH4+) (2000)
Yogyakarta, Septic tanks Volcanic deposits (0 – 45 m) 30 - 180 Smith et al.
Indonesia (1999)
Taejon, 1.3 Piped sewerage, septic Alluvium and weathered granitic 0 - 170 Jeong (2001)
Korea tanks and latrines rocks (0 – 50 m)
Yeumbeul, 0.007 Latrines Shallow coastal sand 40 - 370 Tandia et al.
Dakar, Semi-confined infrabasalt (1999)
Senegal
Cotonou, 0.7 Coastal sands and alluvium 5 - 130 Boukari et al.
Benin Confined sands and clays 10 - 120 (1996)

Merida, 0.5 Septic tanks, soakaways Shallow karst limestone 20 - 130 Morris et al.
Mexico and cesspits (1994)
Santa Cruz, 0.7 On-site sanitation Shallow alluvial outwash plain 50 – 180 Morris et al.
Bolivia deposits (0 – 50 m) (1994)
Deep semiconfined (>50 m)

and denitrification are the predominant likely to develop from the infiltration of effluent to
processes. underlying aquifers except where water use is high
and population density is low. In vulnerable karstic
Livestock environments, such as the Yucatan, Mexico, all
Nitrogen leaching from ungrazed grassland is nitrogen deposited in sanitation systems may be
normally low since grass provides continuous leached and oxidised. Especially high concentrations
ground cover. However leaching from intensively are also likely to occur in those arid regions with low
grazed land can be a problem since 80% of the per capita water usage (Morris et al. 1994).
nitrogen consumed by grazing animals is returned to Surveys of groundwater quality in a range of cities
the soil as urine or dung. Ryden et al (1984) with incomplete or no piped drainage out of the city
demonstrated that, for the same chalk soils, leaching have shown that nitrate concentrations can reach
losses were five times greater for grazed grassland very high levels, such as those found under Lucknow
than for an equivalent cut grassland. (Table 1). The work at Hat Yai, however, has
Discharge of effluent from areas of livestock demonstrated that nitrate may not give problems
concentration can also be a common source of where the aquifer is confined and the nitrogen is not
groundwater pollution (Cho et al. 2000). Leachate oxidised.
from manure heaps, leaking slurry storage pits and In many cities, especially those on low-lying coastal
slurry or manure spreading can also be a major alluvial plains which are underlain by a shallow water
source of nitrogen in groundwater. table, disposal of excreta to the ground is not
Urban unsewered sanitation possible, particularly in areas affected by the
monsoon because of surfacing of the water table
Nitrogen is present in sewage in a range of reduced during periods of heavy rainfall. Thus wastes are
and organic forms, such as ammonia and urea. These discharged directly or indirectly into surface water
can be oxidised in aerobic groundwater systems to courses which can themselves become major line
nitrate, although there is uncertainty about the sources of groundwater pollution.
proportion of nitrogen which is leached and
oxidised. There is major concern with the subsurface Urban wastewater disposal and reuse
contaminant load associated with unsewered The expanding demands on groundwater and greater
sanitation units such as septic tanks, cesspits and problems of wastewater disposal have led to the
latrines. Troublesome nitrate concentrations are
3
greater recognition of the value of wastewater as an the aquifer became anaerobic and nitrate was only
important resource. There are now many examples detected at a few points (Morris et al. 2003).
of schemes which use wastewater, with varying
degrees of treatment, for agricultural irrigation. Natural sources

Methods for reuse of water range from localised, It is important to recognise that other sources of
peri-urban, often informal irrigation of small gardens groundwater nitrate exist (Edmunds and Gaye,
by collected but untreated wastewater, through large 1997). These include:
canal commanded irrigation schemes still using • geological sources, such as the saltpetre deposits
untreated water to highly sophisticated, heavily of Northern Chile;
controlled and managed soil aquifer treatment in
which the reabstracted, fully treated effluent can be • naturally high baseline concentrations in semi-
used to grow unrestricted types of crop. arid areas, thought to be derived from nitrogen
fixing indigenous plants, such as the acacia
The largest and longest established of these schemes
species found in areas of the Sahara/Sahel
pipes the wastewater produced by Mexico City into
region of North Africa;
the adjacent valley where it is used to produce a large
area of crops without any pre-treatment (CNA et al. • atmospheric deposition.
1998). This has resulted in some 30% of local public
supply boreholes containing nitrate at >50 mg/l with Distinguishing sources of nitrate
maximum concentrations of 70 – 80 mg/l. This
Due to the large number of nitrogen sources it can
only represents a fraction of the total nitrogen
be difficult to determine the origin of nitrate in
loading in the incoming water since a large fraction is
groundwater. The simplest indication can come from
utilised by the crops.
looking at the ratio of concentrations with other
Nitrogen concentration in the irrigation water can waste components, such as chloride. The ratio of
also be reduced by impounding the wastewater in a chloride to nitrogen in groundwater beneath
series of basins using flooding and drying cycles. unsewered sanitation is often about 2:1. If the waste
These promote oxidation to nitrate and subsequent has been subject to a process which removes
denitrification to nitrogen gas (Bouwer, 1985). nitrogen for example application to agricultural land
Problems can also arise from infiltration directly the ratio is increased (Figure 2).
from such stabilisation ponds, for example from the
The use of other species present appears an
Es-Samra ponds, serving Amman, Jordan (Al-
attractive method for distinguishing between sources
Kharabsheh, 1999).
of nitrate. This requires the indicator to be present
Solid waste disposal in only one recharge source and detectable in
groundwater. Such indicators are rare and have
Leachate arising from solid waste disposal is a highly included:
mineralised mixture of inorganic and organic
compounds. In humid tropical conditions leachate • boron or optical brighteners from laundry
can be generated in relatively large volumes detergents in domestic sources;
potentially leading to extensive groundwater plumes.
Leachate is generally anaerobic and may contain a
high concentration of ammoniacal nitrogen. Such
nitrogen is readily absorbed to clay minerals in the 30
aquifer and may not migrate for large distances, but Irrigation well
Supply borehole
it can also be oxidised in the aquifer giving rise to 25
Nitrate-N concentration (mg/l)

Wastewater
high concentrations of nitrate. City
20
Wastewater
Groundwater in drinking water wells in two suburbs irrigation area
15
of Ibadan and Lagos were found to have very poor
water quality, including unacceptable concentrations 10
of nitrate and ammonia, ascribed to local waste
disposal sites (Ikem et al., 2002). Down gradient 5
wells were particularly heavily affected. Wastewater
0
A study at Chiang Mai, Thailand found that even ten 0 200 400 600 800
years after an open waste dump had been closed and Chloride concentration (mg/l)
covered with soil, there was still evidence for pulses
of contaminants, included nitrate, moving away from Figure 2 Groundwater nitrogen and chloride from
the site in the rainy season. During the dry season Leon, Mexico
4
• coliform bacteria from sewage; These options will achieve the desired results for
limited number of major abstraction sites, although
• specific compounds, such as silver from at often great expense, but it is difficult to envisage
photographic industry or zinc from metal their implementation for large number of relatively
working. small abstractions in rural areas.
The potential sources of nitrate contamination are In these circumstances effective control of rising
characterised by unique ranges of the δ15N isotopic nitrate concentrations means reducing the inputs by
signature. This can be used to distinguish between cutting losses from the surface. For agricultural
nitrogen derived from inorganic fertilisers and nitrate this means restrictions on the timing and
animal or sewage wastes (Girard and Hillaire-Marcel, amounts of fertiliser application, and using improved
1997). Determination of nitrogen stable isotopes is crop strains, cultivation practices and irrigation
very expensive and this limits its potential methods to promote more effective use of nutrients
application. (Bijay-Singh et al, 1995; Cuttle and Scholefield, 1995;
Schepers et al, 1995; Shrestha and Ladha, 2002). If
Testing for nitrate such improvements are insufficient then the only
Test strips are available for use in field-testing which approach is to consider radical changes in land use in
give semi-quantitative results. These cover the designated vulnerable zones around abstraction
sensitivity range 0-50 mg/l for NO3 and 0-3 mg/l points, introducing land uses from which nitrate
for NO2. losses are small. Any such agricultural control
measures may have serious economic consequences
Nitrate can be determined in the field using an ion- for the farmers involved, and may be difficult to
selective electrode. This has a limit of detection of monitor and enforce.
about 0.2 mg/l. Chloride and bicarbonate interfere
when present in ratios of > 10 and may be removed For some urban areas abandoning a shallow aquifer
by precipitation with silver sulphate or acidification due to progressive contamination is not an option in
to pH4 by addition of a suitable buffer solution. social or economic terms, because low income and
socially deprived districts may be dependent on the
Nitrate and nitrite are normally measured by underlying shallow aquifer for handpumps and
formation of the red-purple azo dye produced by public standpipes. In such situations the demands of
diazotised sulphanilic acid and N- (1-naphthyl)- supply and waste disposal have to be balanced and
ethylene diamine dihydrochloride. Nitrite reacts there is no easy prescriptive solution. One possible
with the reagent directly. Total oxidised nitrogen is measure could be to use urban housing density
determined separately after a reduction step in which controls to limit contaminant loading.
nitrate is reduced to nitrite and nitrate is determined
by difference. In the field the colour is measured Water treatment
using a commercial colour comparator kit. In the
Nitrate can be removed from drinking water by ion-
laboratory a spectrophometer is used. This method
exchange. Units for point of supply operation
can be automated and is usually carried out in
comprise a pressure vessel containing anion-
modern laboratories by flow injection analysis.
exchange resin, distribution and collection systems,
Nitrate and nitrite can also be determined together and effluent storage tanks. In the exchange process,
with other anions by ion chromatography. nitrate ions are retained on the resin and replaced in
the water by chloride. When the capacity of the
Control measures resin is exhausted and nitrate starts to break through
into the processed water, the resin can be
The options for control can be divided into those regenerated, normally using salt. The disadvantage
implemented at the point of abstraction and those of this technique is the need for disposal of saline
designed to control the amount of nitrogen entering effluent from regeneration.
the aquifer. The former include:
Other treatment techniques include chemical
• blending low and high nitrate water from reduction, biological denitrification, reverse osmosis
different supplies; and electrodialysis. Of these, reverse osmosis has
• closure of supplies and development of proved to be effective but is relatively expensive.
alternatives;
Data sources
• treatment to remove nitrate; Al-Kharabsheh, A. 1999. Groundwater deterioration in
arid areas: a case study of the Zerqa river basin as
• drilling deeper to draw on low-nitrate water. influenced by Khirbet Es-Samra wastewater (Jordan).
Journal of Arid Environments, 43, 2 227-239
5
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agrosystems in Costa Rica: Leaching and denitrification in Air and Soil Pollution, 140, 1-4, 307-333.
the presence and absence of shade trees. Journal of
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hydrochemistry and contamination of groundwater from
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Fertilizer-N use efficiency and nitrate pollution of
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Hydrology, 20, 167-184. Aboufirassi, M, Bahir, M and Persoons, E. 2003.
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