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Geochemistry
Applied Geochemistry 20 (2005) 5568
www.elsevier.com/locate/apgeochem
a,*
Water and Environmental Sanitation Section, UNICEF Pakistan, Saudi Pak Tower, Islamabad, Pakistan
b
Geological Sciences, University College London, Gower Street, London WC1E 6BT, UK
c
Department of Geology, Royal Holloway University of London, Egham, Surrey TW20 0EX, UK
Received 11 April 2003; accepted 5 June 2004
Editorial handling by R. Fuge
Abstract
In 49 samples of groundwater, sampled in Muzaargarh District of south-western Punjab, central Pakistan, concentrations of As exceeded the World Health Organisation provisional guideline value, and United States Environmental
Protection Agency (USEPA) Maximum Contaminant Level (MCL), of 10 lg L1 in 58% of samples and reached up to
906 lg L1. In this semi-arid region canal irrigation has lead to widespread water-logging, and evaporative concentration of salts has the potential to raise As concentrations in shallow groundwater well above 10 lg L1. In fact, in rural
areas, concentrations stay below 25 lg L1 because As in the oxic shallow groundwater, and in recharging water, is
sorbed to aquifer sediments. In some urban areas, however, shallow groundwater is found to contain elevated levels
of As. The spatial distribution of As-rich shallow groundwater indicates either direct contamination with industrial
or agricultural chemicals, or some other anthropogenic inuence. Geochemical evidence suggests that pollutant organics from unconned sewage and other sources drives reduction of hydrous ferric oxide (HFO) releasing sorbed As to
shallow groundwater. The situation is slightly less clear for seven wells sampled which tap deeper groundwater, all of
which were found with >50 lg L1 As. Here As concentrations seem to increase with depth and diering geochemical
signatures are seen, suggesting that As concentrations in older groundwater may be governed by dierent processes.
Other data on parameters of potential concern in drinking water are discussed briey at the end of the paper.
2004 Elsevier Ltd. All rights reserved.
1. Introduction
It is estimated that approximately one third of the
worlds population use groundwater for drinking
0883-2927/$ - see front matter 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apgeochem.2004.06.004
56
57
Fig. 1. Location of the District and town of Muzaargarh, south-western Punjab, Pakistan, showing location of sample sites. Large
inset to the right shows location of study area in Pakistan. Smaller inset at the foot of the gure shows detail of wells sampled in
Muzaargarh Town.
3. Methods
Water from the Chenab River, Taunsa Panjnad
Link Canal, and wells, was collected in July 2001
(Fig. 1; Table 1). Of the 49 wells sampled in the study
area, 42 tap water at <30 m depth, of which ve were
electrically pumped water-supply wells, and 37 were
hand-pumped tubewells. The other seven tap water of
>30 m depth, all of which were electrically pumped
water-supply wells. One sample was also collected of
58
Table 1
Sample location and hydrochemical data
59
Table 1 (continued )
Note. SDPW is Small diameter electrically-pumped well, LDPW is Large diameter electrically-pumped well and HP is Handpumped well.
60
4. Results
5. Discussion
Decades of natural recharge and evaporation, induced irrigation recharge and evaporative concentration
due to water-logging, have concentrated dissolved constituents in groundwaters in the Muzzafargarh area.
Conservative behaviour of Na, Cl, and SO4 are apparent
(Fig. 2), with samples plotting along evaporative trends
from end-members represented by either Chenab River
or the Taunsa Panjnad Link Canal (TPLC hereinafter;
Fig. 2). Calcium concentrations are less than those predicted by evaporative trends (Fig. 2). This can be explained by precipitation of calcite on evaporation:
samples highest in HCO3 are amongst the lowest in
Ca. Small departures from the evaporation trends may
also be accounted for by mineral weathering, gain or
loss of less soluble salts (gypsum) and ion-exchange
reactions: e.g. Well 36, with 8 mg L1 of Cl, has a lower
Ca/Cl and a higher Na/Cl than the Taunsa Panjnad Link
61
1000
10000
100
Ca mg L
Na mg L
-1
-1
1000
100
10
10
1
1
10
100
1000
Cl mg L
(a)
10000
-1
10
1000
100
Cl mg L
(b)
1000
10000
1000
10000
-1
10000
SO4 mg L-1
Mg mg L-1
1000
100
10
100
10
1
1
10
100
1000
10000
Cl mg L-1
(c)
10
500
(d)
100
Cl mg L-1
60
1000
NO3 mg L
HCO3 mg L
-1
-1
50
30
20
10
0
100
1
(e)
40
10
100
Cl mg L
-1
1000
10000
(f)
1000
Cl mg L
1500
2000
-1
Fig. 2. Evaporative trends in the major ion composition of groundwater from Muzaargarh District. Open symbols are wells less than
30 m depth, closed symbols are wells >30 m depth. Circles are samples from the rural area including and to the north of samples 15 and
31, triangles are samples from the Muzaargarh area, squares are samples from Multan. Large open circle for Chenab River water
(sample 28) and double circle for sample 20, which is taken to be representative of the water recharging from the Taunsa Panjnad Link
Canal.
62
1000
As g L-1
100
10
0
1
10
100
Cl mg L-1
1000
10000
Fig. 4. Concentrations of As in Muzaargarh District and its relation to wells, rivers and irrigation canals.
63
300
200
100
As g L-1
As g L
-1
1000
100
10
0
0
20
40
60
-1
NO 3 mg L
Fig. 5. Relation of NO3 to As in groundwaters from Muzaffargarh District. Symbols as for previous gures. Plot excludes
well 8, which is an outlier aected by hydrocarbon pollution
and contains zero NO3 and 905 lg L1 of As.
0.1
6
pH
Fig. 6. Relation of pH to As in groundwaters from Muzaargarh District. Symbols as for previous gures.
64
As g L
-1
300
200
100
0
0
100
200
300
-1
PO 4 g L
Fig. 7. Relation of PO4 to As in groundwaters from Muzaffargarh District. Symbols as for previous gures. Plot excludes
well 8, which is an outlier aected by hydrocarbon pollution
and contains zero NO3 and 905 lg L1 of As.
20
20
40
40
40
80
60
80
100
100
120
1000
Cl mg L
1500
-1
2000
40
NO 3 mg L
60
-1
(c)
0
20
20
20
40
40
40
60
80
100
100
100
200
As g L
300
-1
80
Fe mg L
-1
(f)
20
20
20
40
40
40
60
80
100
100
120
120
0
NH 4 mg L-1
Depth, m
Depth, m
80
100
200
PO 4 g L 1
300
400
60
80
100
120
(h)
1500
60
60
1000
SO 4 mg L-1
120
0
(e)
500
100
120
120
(d)
Depth, m
80
Depth, m
20
60
(g)
80
120
0
(b)
Depth, m
Depth, m
500
60
100
120
0
(a)
Depth, m
0
20
Depth, m
Depth, m
60
65
50
100
150
Ca mg L-1
200
250
(i)
0.0
0.5
1.0
1.5
2.0
B mg L-1
Fig. 8. Depth relation of As and other constituents in groundwater from Muzaargarh District wells. Symbols as in Fig. 2.
2.5
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Table 2
As concentrations in shallow and deep well water at three localities
Location
Shallow well
Muzaargarh Centre,
UC City 35
Alipur Jhanubi Village
Chowk Sharwar
Shaheed Town
Deep well
1
Sample no.
As (lg L )
Sample no.
11
4.9
44
88
167
50
8.8
2.2
26
36
30
107
61
170
20
20
27
37
9
7.5
-1
10
B mg L
0.1
0.01
1
10
Lateral
distance (m)
45
1
100
-1
1000
As (lg L )
6. Conclusions
In groundwater of the shallow Quaternary alluvial
sediments of Thal Doab, Punjab, As enrichment of shallow aquifers occurs in urban areas where pollutant
organics promote reduction of HFO, which releases
its sorbed As to groundwater. In rural areas, which
are not impacted by such pollution, As concentrations
naturally remain 25 lg L1 despite strong evaporative
concentration of groundwater because of strong sorption of As from the oxic groundwater to aquifer sediments: potential concentrations of As up to 1500
lg L1 are therefore avoided. This sorption keeps the
oxic shallow aquifer As free in the absence of human
pollution. For the deep (>30 m) aquifer, the data would
seem to suggest that reduction of HFO by naturally-occurring organic matter is an important process and may
lead to concentrations of As up to 170 lg L1. This conclusion is tentative because all of the deep wells were in
urban areas and the possibility remains that HFO reduction is pollutant-driven. Arsenic concentrations appear
to increase with depth so it must be investigated whether
an increase in As with depth is conned to Muzaargarh
District, or whether it is a general trend in the alluvial
aquifers of Pakistan, in order that long-term planning
of water resources can be undertaken.
The nature and extent of the human impact on As
pollution will have a profound inuence on how national surveys for As (Nickson, 2001; Shrestha, 2002)
are interpreted. The knowledge that aquifer sediments
have a long-term capacity to sorb As and so remove it
from groundwater will also impact such interpretations.
Quantication of sorptive loss of As to aquifer sediments needs to be undertaken. Where As enrichment is
found in urban areas it is particularly important to
determine the nature of the pollutant organic matter
that drives HFO reduction: whether it is from unsewered
sanitation, waste dumps, or spilled hydrocarbon fuels
and, if a mixture, which has most impact where.
10000
Cl mg L
Acknowledgements
We thank Dr. Michael Wood, Department of Geography, Aberdeen University for assistance with digitising
basemaps of Muzaargarh and for the use of the Universitys equipment for this purpose. Miss. Kieren Smith
and Mr. Rick Gard assisted greatly with this process.
Mr. A. Osborn is thanked for undertaking much of
the water analysis, using the facilities of the Wolfson
laboratory of the Department of Geological Sciences,
UCL, with permission of the Director, K. Hudson-Edwards. Cation analysis was done by JMMcA using the
NERC ICP-AES Facility at RHUL, with permission
of the Director, Dr. J.N. Walsh. We acknowledge the
invaluable assistance, under adverse eld conditions, of
Mr. Tariq Kamran, of UNICEF Pakistan. Mr. Rana
Altaf Hussain, the Assistant Director Local Government, Muzaargarh District greatly assisted the work
as did Mr. Ghulam Shabir and Mr. Safdar Bukhari.
We thank Dr. Nasreen Elahi, Project Ocer of UNICEF Lahore, for her logistical support. Dr. George
Breit (USGS) provided invaluable satellite images, maps
and geological reports about Pakistan. Finally we thank
Dr. Karen Johannesson of the University of Texas at
Arlington and one anonymous reviewer for their accurate and constructive comments on the original
manuscript.
References
Ahmann, D., Krumholz, L.R., Hemond, H.H., Lovley, D.R.,
Morel, F.M.M., 1997. Microbial mobilization of arsenic
from sediments of the Aberjona watershed. Environ. Sci.
Technol. 31, 29232930.
Baneld, J.F., Nealson, K.H., Lovley, D.R., 1998. Geomicrobiology: interactions between microbes and minerals. Science 5360 (280), 5455.
Bhattacharya, P., Chatterjee, D., Jacks, G., 1997. Occurrence of
arsenic-contaminated groundwater in alluvial aquifers from
the Delta Plain, Eastern India: options for a safe drinking
water supply. Water Resour. Dev. 13, 7992.
Chapelle, F.H., 2000. The signicance of microbial processes in
hydrogeology and geochemistry. Hydrogeol. J. 8, 4146.
Cullen, W.R., Reimer, K.J., 1989. Arsenic speciation in the
environment. Chem. Rev. 89, 713764.
Dowdle, P.R., Laverman, A.M., Oremland, R.S., 1996. Bacterial dissimilatory reduction of arsenic (V) to arsenic (III) in
anoxic sediments. Appl. Environ. Microbiol. 62, 16641669.
Goldberg, S., Forster, H.S., Heick, E.L., 1993. Boron adsorption mechanisms on metal oxides, clay-minerals, and soils
inferred from ionic-strength eects. Soil Sci. Soc. Am. 57,
704708.
Greenman, D.W., Swarzenski, W.V., Bennett, G.D., 1967.
Ground-water hydrology of Punjab, West Pakistan with
emphasis on problems caused by canal irrigation. U.S.
Geol. Surv. Water Supp. Pap., p. 1608-H.
Gulens, J., Champ, D.R., Jackson, R.E., 1979. Inuence of
redox environments on the mobility of arsenic in groundwater. In: Jenne, E.A. (Ed.), Chemical Modelling in
Aqueous Systems; Speciation, Sorption, Solubility, and
Kinetics, Am. Chem. Soc. Symp. Ser. 93, pp. 8195.
67
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