PII: S0043-1354(00)00036-1

Wat. Res. Vol. 34, No. 11, pp. 29152926, 2000

7 2000 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
0043-1354/00/$ - see front matter

www.elsevier.com/locate/watres

USE OF WATER QUALITY INDICES TO VERIFY THE

IMPACT OF CORDOBA CITY (ARGENTINA) ON SUQU A
RIVER
SILVIA F. PESCEM and DANIEL A. WUNDERLIN*M
Universidad Nacional de Cordoba, Facultad de Ciencias Qu micas, Dto. Bioqu mica, Pabellon
Argentina, Ciudad Universitaria, 5000, Cordoba, Argentina
(First received 1 January 1999; accepted in revised form 1 September 1999)
AbstractWe veried the usefulness of water quality indices (WQI) to assess the water quality from
multiple measured parameters, and to evaluate spatial and temporal changes. Measured parameters
include many of those recommended by the GEMS/Water UNEP program. Two WQI (subjective and
objectiveWQIsub and WQIobj) take into consideration 20 parameters. Another index (minimal
WQImin) was developed considering only three parameters: turbidity, dissolved oxygen, and either
conductivity or dissolved solids. WQIsub tends to overestimate the pollution due to the use of a
subjective constant, which is not necessarily correlated with the measured parameters. WQImin shows a
similar trend to WQIsub and WQIobj at a lower analytical cost; however, it should be combined with
WQIobj to corroborate the results. The use of WQI could be of particular interest for developing
countries, because they provide cost-eective water quality assessment as well as the possibility of
evaluating trends. As a case study, we report on the use of WQI to evaluate spatial and seasonal
changes in the water quality from the Suqu a River in Cordoba City (Argentina) and nearby locations.
The city urban activity produces a serious and negative eect on the water quality; this is particularly
severe in locations following the city sewage discharge. The dry season shows the worst water quality.
7 2000 Elsevier Science Ltd. All rights reserved
Key wordswater quality, quality index, river monitoring, Suqu a River, Cordoba, Argentina

INTRODUCTION

The Suqu a River basin is located in a semi-arid

region of Cordoba province (Argentina) (Fig. 1)
with a mean annual rainfall in the range of 700
900 mm. The wet season goes from December to
April but most of the rainfall occurs during the
months of January and February. The river drainage area covers approximately 7700 km2, while
almost 900 km2 corresponds to the Cordoba City
drainage area. The Suqu a River begins at the San
Roque dam and ows mainly from west to east.
The river is the main drinking water source of Cordoba City located 35 km downstream from the
dam, and it also serves for recreation and some
sport shing. The river ows for about 40 km
across the city; downstream, near the eastern edge
of the city, the river receives the city sewage discharge and then continues up to Mar Chiquita
Lake (150 km downstream) (Fig. 1). Though at present there is not a hydrographic study, the river
ow can be estimated from the water released by
*Author to whom all correspondence should be addressed.
Tel.: +54-351-433-4187; fax: +54-351-433-4187; email: dwunder@bioclin.fcq.unc.edu.ar

the San Roque Dam (Dasso, 1998). In the last 10

years the Suqu a River has shown a high ow
period, from December to April, with an estimated
ow greater than 15 m3 s1; whereas in the dry season, from May to November, its estimated ow is
always lower than 10 m3 s1 with a minimum of
5 m3 s1 in June (Dasso, 1998).
Cordoba City has a population of approximately
1.2 million inhabitants, nearly 500,000 are connected to the city sewage; the rest of the sewage
goes into the groundwater after home treatment. In
the last 20 years the city has almost doubled its
population and many new industries have increased
the risk of toxic euents to the river as well. At the
time we began this work, there were no reports on
the water quality of the Suqu a River. Recently,
Gaiero et al. (1997) have reported the spatial and
temporal variability of heavy metals in the stream
sediments.
The evaluation of water quality in developing
countries has become a critical issue in recent years
(Ongley, 1998), especially due to the concern that
fresh water will be a scarce resource in the future.
Whereas water monitoring for dierent purposes is
well dened (e.g. aquatic life preservation, contact
recreation, drinking water use) (Chapman, 1992;

2915

2916

Silvia F. Pesce and Daniel A. Wunderlin

WHO, 1987), the overall water quality is sometimes

dicult to evaluate from a large number of
samples, each containing concentrations for many
parameters (Chapman, 1992). Although any monitored parameter could be analyzed either alone or
grouped according to a common feature (e.g. nitrogen load through the analysis of ammonia, nitrites,
nitrates and organic nitrogen), such analysis provides partial information on the overall quality.
Mathematical-computational modelling of river
water quality is possible but requires a previous
knowledge of hydraulics and hydrodynamics.
Besides, mathematical models require extensive validation (Chapman, 1992; Rauch et al., 1998; Shanahan et al., 1998; Somlyody et al., 1998).
The use of water quality indices (WQI) is a
simple practice that overcomes many of the previous mentioned problems and allows the public
and decision makers to receive water quality information. WQI also permits us to assess changes in
the water quality and to identify water trends
(Chapman, 1992). A quality index is a unitless number that ascribes a quality value to an aggregate set
of measured parameters. Water quality indices generally consist of sub-index scores assigned to each

parameter by comparing its measurement with a

parameter-specic rating curve, optionally weighted,
and combined into the nal index (Yagow and
Shanholtz, 1996). The construction of WQI requires
rst a normalization step, where each parameter is
transformed into a 0100% scale, with 100 representing the highest quality. The next step is to
apply weighting factors that reect the importance
of each parameter as an indicator of the water quality (Boler, 1992; Conesa Fdez-Vitora, 1995; Estevan
Bolea, 1989; Zagatto et al., 1998). The so constructed WQI gives a number that can be associated
with a quality percentage, easy to understand for
everyone, and based on scientic criteria for water
quality.
In this paper we report a three-year monitoring
of Suqu a River water in Cordoba City and nearby
locations. We also assess the impact of urban activities (represented by sewage discharges, run-o and
non-point pollution), evaluated by using three
dierent water quality indices. Two WQI (subjective
and objectiveWQIsub and WQIobj) take into consideration 20 parameters. The other WQI (minimalWQImin) was developed considering only
three parameters: turbidity, dissolved oxygen and

Fig. 1. Map of Cordoba Province (Argentina) with indication of the studied area.

Fig. 2. Schematic plan of Cordoba City with indication of monitoring stations.

Suqu a river water quality indices

2917

2918

Silvia F. Pesce and Daniel A. Wunderlin

either conductivity or dissolved solids. The

measured parameters include many of those recommended by the GEMS/Water UNEP program
(Global Environmental Monitoring SystemUnited
Nations Environmental Program) (WHO, 1987), as
well as the spatial and seasonal changes in the
water quality over the studied river section.

During the rst year (April 1995March 1996) water

samples were taken monthly for analysis from station 1 to
station 7. No duplicates were collected during the rst
year. During the second year (April 1996March 1997)
water samples were taken monthly for analysis from
station number 1, 3, 6 and 7 (see Discussion). Stations 1,
6, 7 and 8 were monitored monthly during the third year
(April 1997March 1998). Analyses for the second and
third years were run in duplicate (see Table 1).
Monitored parameters and analytical methods

MATERIALS AND METHODS

Apparatus
. A pH/temperature meterHANNA HI9025 (with automatic temperature compensation) calibrated immediately before use with two standard solutions at pH 7.01
and 10.01 (standard solutions are commercially available from HANNA Instrument).
. TurbidimeterHACH 2100 P calibrated according to
the method ASTM (1993) D-1889.
. SpectrophotometerSHIMADTZU, UV 1601 PC
equipped with PC-interface and analytical software.
. Chromatograph: KONIK KNK-3000 HRGC equipped
with electron capture (EC) detector and KONIK data
jet integrator. GC capillary column from J & W Scientic DB-5 (P/N 123-5032), 30 m length, 0.32 mm ID and
0.25 mm lm.
Monitoring sites and frequency
Eight monitoring stations were selected (Fig. 2). The
rst one (station 1, Saldan) is located 2 km upstream of
the Cordoba City west border, before the Saldan Brook
mouth; this station is located approximately 5 km downstream from the main intake of Cordoba City water potabilization plants and it is representative of the raw
drinking water quality. Station two (Chateau Carreras) is
located about 7 km downstream from Saldan, this river
section ows through a city district where sand extraction
and sand washing occur as well as sewage discharge from
some residential villages. Station three is located at Santa
Fe Bridge, approximately 14 km downstream from Saldan
and immediately before downtown Cordoba; at this point
begins a cement channel that replaces the natural river
bed. Station four (Sarmiento Bridge) is located about
19 km downstream from Saldan and 2 km downstream
from La Canada Brook mouth. La Canada Brook receives
some industrial euents as well as much of the run-o
from the downtown commercial area. Station ve is
located at Sargento Cabral Bridge, approximately 26 km
downstream from Saldan; where the cement channel ends
and the river returns to its natural bed. This is a rather
small industrial area. Station six (Circunvalacion Bridge)
is located about 35 km downstream from Saldan and 2 km
upstream from the Cordoba City sewage discharge.
Station seven is located approximately 40 km downstream
from Saldan and 3 km downstream from the Cordoba
City sewage exit. Station eight is located about 56 km
downstream from Saldan and 10 km downstream from the
discharge of a channel containing euents from new
industries recently located close to the eastern boundary of
Cordoba City.
Collection receptacles, sample stabilization, and transportation to the laboratory as well as sample storage were
done considering the GEMS/Water Operational Guide
(WHO, 1987). Samples were taken at least 40 cm under
the water surface and whenever it was possible, at the
middle of the stream. Samples were never taken while
raining but at least 72 h after the rain had stopped, so
that the river returned to its regular ow condition.

Many of the GEMS/Water (WHO, 1987) recommended

parameters were measured during the rst two years
(19951997). Mainly those parameters necessary for water
quality indices calculations were evaluated in the third
year (19971998) (Tables 1 and 2). Analytical methods
were standard; APHA et al. (1992) method numbers and
other methods are cited in parentheses. Measured parameters include: alkalinity (2320-B), ammonia (4500-NH3
C, direct), arsenic (3500-As C), 5-day biological oxygen
demand (BOD-5) (Association Ocial Analytical Chemists
(AOAC), 1995method 973.44), calcium (3500-Ca D),
chloride (4500-Cl B), chemical oxygen demand (COD)
(5220 A), dissolved oxygen (DO) (4500-O C), oil and
grease (O&G) (5520 B), fecal coliforms (9221 E), hardness
(2340-C), iron (3500-Fe D), magnesium (3500-Mg E),
nitrates (Association Ocial Analytical Chemists (AOAC),
1995method 973.50), nitrites (4500-NO
2 B), permanganate oxidizable compounds (POC) (Rodier, 1981), pH
(4500-H+ B, eld measured), phenolic compounds (5530
D), orthophosphate phosphorus (4500-P E over ltrate
samples), solids: dissolved (2540-C), dissolved volatile
(2540-C+E), suspended (2540-D), suspended volatile
(2540-D+E) and total (2540-B), sulfates (4500-SO2
E
4
over ltrate samples), suldes (4500-S2 E), surfactants
(anionic as methylene blue active substances (MBAS),
55408C), temperature (2550-B, eld measured), total coliforms (9221 B), and turbidity (2130 B). Organochlorine
pesticides were also monitored during the entire period
studied (APHA et al., 1992method 6630).
Water quality indices (WQI) calculation
The subjective water quality index, WQIsub, was calculated on the basis of the WQI proposed by Rodriguez de
Bascaron (Conesa Fdez-Vitora V., 1995) as follows:
X
WQIsub k

Ci xPi

Pi

where k is a subjective constant. It represents the visual

impression of river contamination (as could be evaluated
by a person without training in environmental issues). It
takes one of the following values according to the river
condition:
. 1.00=water without apparent contamination (clear or
with natural suspended solids).
. 0.75=light contaminated water (apparently), indicated
by light non-natural color, foam, light turbidity due to
no natural reasons.
. 0.50=contaminated water (apparently), indicated by
non-natural color, light to moderate odor, high turbidity (no natural), suspended organic solids, etc.
. 0.25=highly contaminated water (apparently), indicated
by blackish color, hard odor, visible fermentation, etc.
Ci is the value assigned to each parameter after normalization (Table 2).
Pi is the relative weight assigned to each parameter
(Table 2). Pi value range from 1 to 4, with 4 representing
a parameter that has the most importance for aquatic life

Suqu a river water quality indices

2919

Table 1. Descriptive statistics from Suqu a river monitored parameters

Parametera

Ammonia (as NH+

4 )

BOD-5

Calcium

Chloride

Chemical oxygen demand (COD)

Dissolved oxygen (DO)

Hardness

Magnesium

Nitrates

Nitrites

Oil and greases

pH

Phosphorus (orthophosphate phosphorous)

Solids: dissolved

Solids: total

Monitoring
stationb

1
3
6
7
8
1
3
6
7
8
1
3
6
7
8
1
3
6
7
8
1
3
6
7
8
1
3
6
7
8
1
3
6
7
8
1
3
6
7
8
1
3
6
7
8
1
3
6
7
8
1
3
6
7
8
1
3
6
7
8
1
3
6
7
8
1
3
6
7
8
1
3
6
7

Yearc

13
12
13
13
3
13
12
13
13
3
13
12
13
13
3
13
12
13
13
3
13
12
13
13
3
13
12
13
13
3
13
12
13
13
3
13
12
13
13
3
13
12
13
13
3
13
12
13
13
3
13
12
13
13
3
13
12
13
13
3
13
12
13
13
3
13
12
13
13
3
13
12
13
13

Wet seasond

Annual
Meane

SDe

Meane

SDe

0.52
0.42
0.62
7.58
14.99
1.7
2.1
2.6
10.2
15.2
28.3
43.6
47.1
53.9
51.4
10.5
42.4
75.2
85.8
83.2
33.2
39.4
40.7
65.1
106.5
8.6
8.7
9.0
5.8
3.6
107
202
236
261
251
7.7
22.9
27.3
31.6
32.8
2.7
12.3
22.4
16.5
10.1
0.15
0.11
0.42
1.86
1.65
176
245
117
156
141
7.8
7.8
7.8
7.6
7.5
0.04
0.04
0.09
0.58
0.71
170
405
605
597
604
250
495
712
726

0.52
0.35
0.61
6.61
11.50
1.0
1.0
1.1
6.8
7.2
8.9
18.9
25.5
25.1
20.3
4.0
23.4
34.9
32.5
37.2
25.7
32.8
37.0
63.3
87.3
1.1
1.9
2.5
1.9
1.4
29
73
81
74
75
3.0
14.0
16.3
20.5
21.2
4.4
6.1
11.3
9.5
7.7
0.37
0.08
0.58
2.50
0.75
276
309
109
192
145
0.3
0.2
0.3
0.3
0.3
0.09
0.10
0.14
0.39
0.52
89
248
290
240
227
188
222
262
204

0.34
0.44
0.58
3.40
3.68
1.5
1.9
2.3
8.6
9.0
25.7
40.3
45.5
46.0
43.0
9.5
30.0
52.8
62.9
46.5
32.8
45.7
37.0
50.3
104.6
7.9
7.6
7.8
6.1
4.9
91
163
195
206
174
6.9
15.3
18.5
22.0
16.6
1.3
9.4
18.1
12.4
12.2
0.08
0.10
0.26
1.75
1.14
82
125
112
128
126
7.8
7.8
7.7
7.5
7.5
0.01
0.02
0.04
0.36
0.35
158
323
478
463
396
207
410
576
588

0.21
0.31
0.75
3.39
5.21
0.5
1.0
0.9
4.4
3.5
8.3
21.6
22.3
18.5
12.2
3.8
21.7
35.0
34.9
28.1
29.5
40.8
38.3
49.8
57.2
0.6
0.6
0.6
1.2
0.9
26
76
86
76
51
2.9
8.3
12.4
15.2
16.0
1.0
6.8
13.3
6.1
5.7
0.08
0.08
0.22
2.75
0.79
89
141
111
119
113
0.3
0.1
0.1
0.3
0.2
0.02
0.02
0.04
0.33
0.37
84
241
296
230
207
79
237
269
204

Dry seasond
Meane

SDe

0.65
0.64
0.41
0.38
0.66
0.50
10.69
6.74
22.53
7.49
1.8
1.3
2.2
1.1
2.8
1.2
11.4
8.0
19.4
5.8
30.2
9.0
46.1
16.7
48.2
28.0
59.8
27.8
50.7
19.5
11.3
4.0
52.2
20.2
91.8
24.2
102.8
16.3
107.7
16.1
33.5
23.2
35.1
26.4
43.5
36.6
75.8
70.4
107.8
108.4
9.0
1.2
9.6
2.1
9.9
2.9
5.7
2.3
2.8
0.9
118
26
233
54
266
63
302
37
303
30
8.3
7.1
27.0
15.6
33.7
15.9
38.6
21.2
45.8
17.9
3.7
5.6
14.5
4.4
25.5
8.5
19.6
10.4
8.7
8.7
0.20
0.48
0.12
0.08
0.54
0.72
1.94
2.35
2.00
0.51
255
349
355
382
121
110
179
238
84
63
7.9
0.3
7.9
0.3
7.9
0.3
7.6
0.4
7.4
0.4
0.05
0.11
0.05
0.13
0.12
0.17
0.74
0.35
0.96
0.47
180
93
467
244
699
254
695
199
742
101
281
237
560
195
813
211
828
133
(continued on next page)

2920

Silvia F. Pesce and Daniel A. Wunderlin

Table 1 (continued )

Parametera

Monitoring
stationb

Sulfates

Surfactants (anionic as MBAS)

Temperature

Total coliforms

Turbidity

8
1
3
6
7
8
1
3
6
7
8
1
3
6
7
8
1
3
6
7
8
1
3
6
7
8

Yearc

3
13
12
13
13
3
13
12
13
13
3
13
12
13
13
3
13
12
13
13
3
13
12
13
13
3

Wet seasond

Annual

Dry seasond

Meane

SDe

Meane

SDe

Meane

SDe

677
24.2
135.9
172.0
167.4
168.0
0.04
0.01
0.03
0.14
0.32
18.5
19.1
19.4
20.1
18.8
1.1E+04
1.4E+05
2.0E+05
8.6E+05
3.4E+06
6
21
15
38
46

211
14.2
115.0
120.4
95.9
105.7
0.21
0.04
0.10
0.31
0.56
5.3
5.5
4.9
5.0
3.6
2.4E+04
2.3E+05
2.7E+05
1.6E+06
4.8E+06
3
20
16
17
15

504
18.9
79.3
116.0
116.8
92.9
0.00
0.02
0.01
0.05
0.00
22.7
23.2
22.5
23.0
21.5
8.7E+03
8.7E+04
2.9E+05
1.1E+06
4.8E+05
6
23
16
40
51

233
11.0
72.5
91.2
74.3
49.9
0.00
0.06
0.04
0.11
0.00
2.4
2.3
2.5
2.6
2.9
1.4E+04
6.9E+04
3.3E+05
2.1E+06
4.2E+05
3
18
14
19
17

793
28.0
180.6
213.5
204.9
218.1
0.08
0.00
0.04
0.20
0.54
15.4
15.9
17.0
18.0
17.0
1.2E+04
1.8E+05
1.3E+05
6.8E+05
5.3E+06
5
19
14
37
43

86
15.1
123.9
123.9
93.7
104.2
0.28
0.00
0.13
0.39
0.64
4.7
5.2
4.8
5.4
2.9
2.9E+04
3.0E+05
2.0E+05
1.1E+06
5.4E+06
2
22
17
16
12

Only those parameters used for WQI calculation are reported. Detailed data for other monitored parameters are available on request.
1=Saldan, 3=Santa Fe Bridge, 6=Circunvalacion Bridge, 7=Bajo Grande, 8=Corazon de Mar a (data for stations 2, 4 and 5 are
available on request).
c
1=April 1995March 1996, 12 monitored months (ve wet and seven dry); 2=April 1996March 1997, 11 monitored months (ve wet
and six dry); 3=April 1997March 1998, 10 monitored months (four wet and six dry).
d
Wet season=December, January, February, March, April. Dry season=May, June, July, August, September, October, November.
e
Values in mg l1 pH in pH units. Temperatures in centigrade. Turbidity in NTU. Bacteria expressed as MPN
100 ml1 (most probable
number per 100 ml). Values are averaged over all the determinations from the period as follows: years 12, n 34 (15 wet and 19
dry); years 13, n 54 (23 wet and 31 dry); year 3, n 20 (eight wet and 12 dry). SD 1 standard deviation. Detailed data for each
monitored year are available on request.
b

preservation (e.g. dissolved oxygen), while a value of 1

means that such parameter has a smaller impact (e.g.
chloride).
Only those parameters shown in Tables 1 and 2
were considered for WQIsub calculation (Conesa FdezVitora V., 1995). The subjective constant was evaluated
from notes on the river appearance that were taken while
sampling.
The objective water quality index (WQIobj) was calculated using equation (1) but with k = 1 in all the cases to
account only for variations due to measured parameters.
Finally, a water quality index with only three parameters, named minimal index (WQImin) was calculated
using:
WQImin

CDO Ccond Cturb

3

where CDO is the value due to dissolved oxygen after normalization (Table 2); Ccond the value due to either conductivity or dissolved solids (TDS) after normalization
(Table 2); and Cturb the value due to turbidity after normalization (Table 2).
All WQI were calculated monthly using a computer program (BASIC language) especially developed for this purpose (free copy available on request). In addition to WQI
calculation, the program also gives information on those
parameters which show a normalization factor lower than
50 (this means less than 50% acceptability for such a parameter). The program also makes the conversion from
ammonia values (Table 1) to ammonia nitrogen (Table 2)
as suggested in the literature (Conesa Fdez-Vitora V.,
1995). All WQI were averaged over the entire study period

as well as divided into wet and dry seasons. Statistical calculations (mean, standard deviation and t-test at 95% of
condence) were performed using the Microsoft EXCEL
statistical package. Throughout the text signicant dierence means p < 0:05 for means comparison.

RESULTS AND DISCUSSION

During the rst year we explored the river behavior by measuring 31 parameters recommended by
the GEMS/Water operational guide (WHO, 1987).
All these parameters were measured from station 1
to station 7 as described in the experimental section.
Some selected results obtained for this rst year are
shown in Figs 3 and 4. As it can be observed from
Fig. 3, the total inorganic nitrogen concentration
(TIN) rose from station 1 to station 7, showing the
deterioration in water quality due to the additive
eect of ammonia, nitrite, and nitrate nitrogen.
Such deterioration was particularly important from
station 2 to station 5 and from station 6 to station
7 (Fig. 3), that is, within the most populated area
and after the city sewage discharge. It is remarkable
that from station 1 to station 6 the main contribution to TIN was due to the nitrate nitrogen,
while at station 7 the main contribution was due to
the ammonia nitrogen (Fig. 3). These facts are con-

Suqu a river water quality indices

2921

Table 2. Parameters concidered for WQI calculation

Parameter

Ammonia nitrogen
BOD-5
Calcium
Chloride
Conductivityb
COD
Dissolved oxygen
Hardness
Magnesium
Nitrates
Nitrites
Oil and grease
pH
Phosphorus
(orthophos-phate)
Solids: dissolved
Solids: total
Sulfates
Surfactants as
MBAS
Temperature
Total coliforms
Turbidity

Normalization factor (Ci)

Relative
weight (Pi)
100

90

80

70

60

3
4
1
1
2
2
2
1
1

<0.01
<0.5
<10
<25
<750
<5
r7.5
<25
<10
<0.5
<0.005
<0.005
7
<0.16

<0.05
<2
<50
<50
<1000
<10
>7.0
<100
<25
<2.0
<0.01
<0.02
78
<1.60

<0.10
<3
<100
<100
<1250
<20
>6.5
<200
<50
<4.0
<0.03
<0.04
78.5
<3.20

<0.20
<4
<150
<150
<1500
<30
>6.0
<300
<75
<6.0
<0.05
<0.08
79
<6.40

<0.30
<5
<200
<200
<2000
<40
>5.0
<400
<100
<8.0
<0.10
<0.15
6.57
<9.60

<0.40
<6
<300
<300
<2500
<50
>4.0
<500
<150
<10.0
<0.15
<0.30
69.5
<16.0

<0.50
<8
<400
<500
<3000
<60
>3.5
<600
<200
<15.0
<0.20
<0.60
510
<32.0

<0.75
<10
<500
<700
<5000
<80
>3.0
<800
<250
<20.0
<0.25
<1.00
411
<64.0

<1.00
<12
<600
<1000
<8000
<100
>2.0
<1000
<300
<50.0
<0.50
<2.00
312
<96.0

R1.25
R15
R1000
R1500
R12,000
R150
r1.0
R1500
R500
R100.0
R1.00
R3.00
213
R160.0

>1.25
>15
>1000
>1500
>12,000
>150
<1.0
>1500
<500
>100.0
>1.00
>3.00
114
>160.0

2
4
2
4

<100
<250
<25
<0.005

<500
<750
<50
<0.06

<750
<1000
<75
<0.10

<1000
<1500
<100
<0.25

<1500
<2000
<150
<0.50

<2000
<3000
<250
<0.75

<3000
<5000
<400
<1.00

<5000
<8000
<600
<1.50

<10,000
<12,000
<1000
<2.00

R20,000
R20,000
R1500
R3.00

>20,000
>20,000
>1500
>3.00

1
3
2

21/16
<50
<5

22/15
<500
<10

24/14
26/12
28/10
30/5
32/0
36/2 40/4
45/6
>45/<6
<1000 <2000 <3000 <4000 <5000 <7000 <10,000 R14,000 >14,000
<15
<20
<25
<30
<40
<60
<80
R100
>100

3
3
1
1

50
40
Analytical valuea

30

20

10

Values in mg l1 pH in pH units. Temperatures in centigrade. Turbidity in NTU. Bacteria expressed as MPN
100 ml1 (most probable
number per 100 ml).
b
Conductivity (mS cm1) was not measured in this work; normalization factors from literature (Conesa Fdez-Vitora V., 1995) are included
for WQImin calculation when soluble solids are not available.

sistent with the higher level of dissolved oxygen

(DO) observed from station 1 to station 6 and with
the drop in DO value at station 7 (Fig. 4). It could
be hypothesized that, in this case, the urban nonpoint pollution contributes to the rise in TIN
mainly with nitrates, while the city sewage discharge
causes a dilution in nitrate nitrogen but a rise in
ammonia nitrogen that should lead to further DO
consumption downstream. These facts are in good
agreement with the behavior of inorganic nitrogen
and DO reported in the literature (Chapman, 1992).
In the present study, the higher DO level from
station 1 to station 6 could be attributed to the
water turbulence in this river section; such turbulence is not so important downstream from Cordoba City eastern border, where the low river basin
begins. Also from Fig. 3 it is remarkable that the
seasonal dierence observed with TIN shows the
higher concentration in the dry season, so a worse
water quality can be expected in such seasons.
The spatial variation of other parameters
measured during the rst monitoring year is shown
in Fig. 4. It is observed that alkalinity and chlorides
(annual means) show an almost continuous moderate increase from station 1 to station 7, while sulfates (annual means) rose from station 1 to station
5 with a further decay. These parameters did not
show an important variation upstream and downstream of the city sewage discharge as was the case
with DO (Fig. 4) and inorganic nitrogen species
(Fig. 3).
All these results indicate that it may be not easy

to evaluate the overall variation of the water quality

by analyzing separate parameters, though some partial analysis is possible, like TIN inuence on water

Fig. 3. Spatial and temporal variation of inorganic nitrogen species during the rst monitoring year. q, ammonia
nitrogen; w, nitrate nitrogen; +, nitrite nitrogen; W, total
inorganic nitrogen (TIN) (annual mean); R, TIN (wet season); T, TIN (dry season).

2922

Silvia F. Pesce and Daniel A. Wunderlin

quality. The lack of hydraulic and hydrodynamic

parameters from the river also precluded the use of
computational modelling. Looking for a way to
evaluate the changes in water quality due to the
combined eect of many parameters (Table 1), we
decided to calculate water quality indices (WQI)
(Chapman, 1992). The rst WQI we used was based
on that proposed in the literature (Conesa FdezVitora V., 1995) for the evaluation of environmental impact. In our rst approach we constructed a
WQI named ``subjective'' (WQIsub), because it
includes a constant that considers the river appearance (equation (1)). WQIsub accounts for 20 of the
31 measured parameters, normalized and weighted
according to values proposed in the literature for
aquatic life preservation (Conesa Fdez-Vitora V.,
1995) (Tables 1 and 2). Because COD is widely
used, we chose COD for WQIsub calculation instead
of the proposed permanganate oxidizable compounds value (POC). As we also measured POC,
we were able to establish the relationship between
COD and POC; this relationship was found to be a
10:1 ratio (COD: POC), that is 10 mg l1 COD are
equivalent to 1 mg l1 POC. This ratio was deduced
from the experimental ratios observed during the
rst monitoring year over all the stations. As the
measured COD:POC ratio ranged from 0.6:1 to
22.7:1, the used 10:1 ratio included 94% of the
measured values. In this way we were able to dene
normalization factors for COD based on values
given for POC in the literature (Conesa Fdez-Vitora
V., 1995) (Table 2).
The use of WQIsub during the rst monitoring
year rendered a trend plot that is shown in Fig. 4.

Fig. 4. Spatial variation of some selected parameters and

WQIsub during the rst monitoring year. q, alkalinity; w,
sulfates; +, chlorides; *, WQIsub; R, dissolved oxygen
(DO).

The analysis of this plot showed a water quality of

60% (annual average) in station 1. During the rst
year we also observed a slow but progressive deterioration of the river water quality downstream
from station 1 and across the city. It should be
noted that in station 3 (Santa Fe Bridge) the river
showed about 10% quality deterioration compared
with station 1. This water quality drop was statistically signicant from station 1 to station 3 but not
from station 1 to station 2 (Fig. 4, statistics not
shown). On the contrary, no important changes in
the water quality were observed during the rst
year due to the river articial bed (Fig. 4, stations
35) or to La Canada Brook discharge (Fig. 4,
stations 45). So, during the rst year, the river
water lost approximately 12% quality across the
city (Fig. 4, stations 16). However at station 7 and
with only 25% quality (Fig. 4), we saw the catastrophic impact of the city sewage discharge on the
river water quality.
Taking into consideration the results from the
rst year, we decided to improve the reliability of
the analytical results in year two, so we carried out
either duplicates or triplicates for each parameter.
Also based on the results observed during the rst
year, we decided to keep only four monitoring
stations. Stations 2, 4 and 5 were not monitored in
the second year because they did not show signicant dierences with previous stations (1 and 3, respectively). Analytical results and calculated
WQIsub from the second monitoring year showed a
tendency similar to that observed during the rst
year (data not shown).
During the third monitoring year we included a
new monitoring station (station 8), located approximately 16 km downstream from station 7. Station 8
was included in order to evaluate the incidence of a
channel containing euents from some new large
industries on the river water quality (see experimental section). Conversely, station 3 was not monitored during the third year. This decision was based
on the assumption that the river water should have
analytical values similar to those observed during
the rst and second monitoring years in this
station.
Three-year average WQIsub values as well as
some statistical treatments are shown in Fig. 5
where several facts can be analyzed. The rst one is
that the river behavior is similar to those described
for the rst monitored year using the same index
(Fig. 4). In station 1 (Saldan) the WQIsub gives an
average water quality of about 68% with no signicant variation from wet to dry season, showing that
the river has an almost constant water quality
upstream from the city. This fact agrees with the little dierence between wet and dry seasons observed
with TIN in the same station during the rst year
(Fig. 3). Downstream, a signicant quality drop is
observed from station 1 to station 3 and further
stations in good agreement with TIN variation

Suqu a river water quality indices

during the rst year (Fig. 3). However, the quality

drop measured by WQIsub, is more important from
station 1 to station 3 than from stations 3 to 6
(Fig. 5), while TIN variations are more important
from station 2 to station 5 and between stations
6 and 7 (Fig. 3). Dierences between TIN and
WQIsub spatial variations could be explained
because the nitrate nitrogen made the bigger contribution to TIN but it has only a moderate weight
within WQIsub (Table 2). WQIsub also predicts an
important quality drop from station 6 to station 7
associated with the city sewage discharge (Fig. 5).
This drop is in good agreement with the drop in
DO (Fig. 4) and the rise in ammonia nitrogen
observed during the rst year (Fig. 3). From Fig. 5
it can also be seen that no signicant quality dierences are observed between dry and wet season
from station 1 to station 6, but such dierences are
observed for stations 7 and 8. Furthermore, station
8 does not show signicant dierence with station 7
(even when the average WQIsub shows quality
improvement for annual and wet season periods).
Over the three years included in this study,
WQIsub shows an overall water quality drop of approximately 37% (annual average) for the studied
river section. More than half of this quality drop
(about 20 points less in WQIsub) can be attributed
to the city sewage discharge (Fig. 5). WQIsub also
gives satisfactory correlation with the river quality
appearance from station 1 to station 8, expressed
by the drop in the average k value (equation (1)

Fig. 5. Three-year spatial and temporal evolution of

WQIsub. R, wet season; *, dry season; Q, annual average.
A=statistically signicant dierence with station 1
p < 0:05); B=statistically signicant dierence with preceding station p < 0:05); C=statistically signicant dierence between wet and dry season p < 0:05).

2923

and Fig. 6) as well as with the deterioration in the

water quality, expressed by the increased average
number of parameters showing less than 50%
acceptability (Table 2 and Fig. 6). The evaluation
of water quality using WQIsub allowed us to recognize the usefulness of such WQI. WQIsub showed
approximately the same trend observed when analyzing separate parameters (Table 1, Figs 3 and 4),
assigning the greater importance to critical parameters such as DO and ammonia nitrogen, and
the smaller weight to other parameters (e.g. chlorides and sulfates) that are not so critical for aquatic
life preservation (Table 2). However, WQIsub is
aected by a subjective constant (k, equation (1))
which could aect the resulting objectivity; for
example, the average k value from station 8 predicts
some improvement on water quality in this station
(Fig. 6), which could not be observed through the
objective evaluation of measured parameters. On
this basis we decided to evaluate WQIobj for all the
period studied.
WQIobj gives the water quality due exclusively to
the 20 involved parameters, normalized and
weighted according to Table 2. Three-year average
WQIobj values as well as some statistical treatments
are shown in Fig. 7. From Fig. 7 we can see that,
using WQIobj, the river water quality trend is similar to that predicted by WQIsub. However, some important remarks that show the impact of k
(equation (1)) over WQIsub can be observed from
Fig. 7. The rst observation is that WQIobj shows a
starting quality of about 80% (Fig. 7, station 1);
quality values for all other stations downstream are
of course higher than those predicted by WQIsub

Fig. 6. Three-year variation of k (equation (1)) and average number of parameters under 50% acceptability (Table
2). q, k (annual means); W, parameters under 50% acceptability (annual means).

2924

Silvia F. Pesce and Daniel A. Wunderlin

because of the drop in k values used in such index

(equation (1), Fig. 6). The second observation from
Fig. 7 is that the quality drop observed with WQIobj
is not so dierent from station 1 to station 3 as
those observed from station 3 to station 6, even
when signicant quality dierences from station 1
to station 3 and 6 remain. This last fact also
suggests that k (equation (1)) tends to overestimate
the pollution on the basis of visual impression.
Comparing Figs 5 and 7 we note that, using
WQIobj, signicant dierences between dry and wet
seasons are observed just from station 6 and remain
up to station 8. As station 6 accounts for much of
the urban non-point pollution, such signicant
dierences mean that the urban non-point pollution
produces a more negative impact on water quality
during the dry season, when the river has the lower
ow. The third observation is that station 8 shows
signicant quality deterioration compared with
station 7; this evidences that the river water quality
is not improved along this section by material
settling, biodegradation, oxidation, etc. Furthermore, this last result shows that there is not a
necessary correlation between ``visual pollution'', as
measured by k (equation (1), Fig. 6), and ``objective
pollution'', as measured by WQIobj (Fig. 7).
WQIobj shows an overall water quality drop of
about 33% (annual average) for the studied river
section. A quality drop of about 15 points in
WQIobj can be attributed to the city sewage discharge, while an additional drop of approximately 5
points in WQIobj should be attributed to the com-

Fig. 7. Three-year spatial and temporal evolution of

WQIobj. R, wet season; *, dry season; Q, annual average.
A=statistically signicant dierence with station 1
p < 0:05); B=statistically signicant dierence with preceding station p < 0:05); C=statistically signicant dierence between wet and dry season p < 0:05).

bined eect of the city sewage and the channel with

industrial euents (Fig. 7). WQIobj also shows that
the non-point pollution from Cordoba City contributes about 13% to the water quality deterioration.
Though WQIsub and WQIobj give similar information on the river water quality drop (37 and
33% average annual drop respectively, Figs 5 and
7), the evaluation of such indices requires that 20
physical, chemical, and bacteriological parameters
be measured (Table 1). The analytical cost involved
could be a limiting factor for water quality assessments in developing countries with scarce budgets
for environmental studies (Ongley, 1998). In such
countries it should be useful to use a WQI which
allows the evaluation of spatial and temporal variations measuring only a few simple parameters. On
this basis, we decided to use the data from monitoring to calculate WQImin as dened in the experimental section. The parameters used for WQImin
calculation were selected because they are important
indicators of other water quality parameters. Dissolved oxygen is a key factor for aquatic life. Either
conductivity or TDS should indicate the presence of
salts, mineral acids, or similar contaminants discharged to the river. Turbidity is associated with
suspended material and also with bacteriological
contamination. Furthermore, these three parameters
can be easily evaluated (even on-line monitoring is
possible). Three-year average WQImin values as well
as some statistical treatments are shown in Fig. 8.
From Fig. 8 we can see that, using WQImin, the
river water quality trend is similar to that predicted
by WQIsub and WQIobj. The use of WQImin gives
less ``resolution'' to the trend analysis (e.g. there is
no signicant dierence from station 3 to station 6,
Fig. 8). WQImin predicts a 46% drop in water quality from station 1 to station 8, this value is not so
far from those predicted by WQIsub and WQIobj.
The use of WQImin predicts a drop of 35% in the
water quality that can be attributed to the combined eect of the city sewage and the channel with
industrial euents (Fig. 8); WQImin also predicts an
11% quality deterioration due to the city non-point
pollution. Both values are in good agreement with
those from WQIsub and WQIobj. So far, we can
state that the use of WQImin gives reasonable results
for trend analysis at a lower analytical cost. Furthermore, WQImin could be used for periodic routine monitoring, or even for on-line water quality
control. However, to give reliable trend results
using WQImin, their values should be correlated
with other indices containing more parameters,
such as WQIobj or WQIsub. In this case, it would
not be necessary to evaluate monthly WQIobj or
WQIsub in all the monitoring stations but twice in a
season (just to keep the certainty of the results with
previous monitoring).
In addition to trends evaluation, WQI calculation
uses (and provides us with) analytical information

Suqu a river water quality indices

2925

bined with WQIobj to corroborate the results. For

other similar studies, we recommend the monthly
evaluation of WQI (subjective, objective and minimal) for at least two years; thereinafter water quality could be assured by evaluating WQImin monthly
(or even weekly) and WQIobj twice in the dry season and twice in the wet season.
AcknowledgementsThis work was partially supported by
grants from the Secretar a de Ciencia y Tecnica-Univ.
Nac. Cordoba, the National Reseach Council
(CONICET), and the Codoba Research Council
(CONICOR). Silvia F. Pesce had a fellowship from the
Secretar a de Extension Universitaria, Univ. Nac.
Cordoba. D. A. Wunderlin is a member of the research
career from CONICET. The authors would like to thank
Ms N. A. Wunderlin de Vivas and unknown Water
Research reviewers for helpful discussions; they also thank
Biochemist E. B. Marcucci for her collaboration in water
analyses.

Fig. 8. Three-year spatial and temporal evolution of

WQImin. R, wet season; *, dry season; Q, annual average. A=statistically signicant dierence with station 1
p < 0:05); B=statistically signicant dierence with preceding station p < 0:05); C=statistically signicant dierence between wet and dry season p < 0:05).

that could be valuable for future computational

modelling, modelling validation, etc.
Finally, we would like to point out the fact that
we were not able to nd chlorinated pesticides in
the Suqu a River water at any station during the
period studied. However, we detected the presence
of Lindane in river sediments at station 7 (GCECD using pesticide standards as control, unpublished results). Though the study of river sediments
is out of the scope of the present paper, further
work is currently under way.
CONCLUSIONS

Cordoba City produces a negative impact on the

Suqu a River water quality, particularly serious
after the city sewage discharge. The use of various
WQI produce similar trend results but dierent
index values as well as some dierent remarks.
WQIsub and WQIobj show statistical signicant temporal changes from wet to dry seasons downstream
from the sewage discharge; WQIobj also predicts
such dierences at station 6 (immediately upstream
from the sewage discharge). The use of a subjective
constant (k ) in the WQIsub calculation tends to
overestimate the pollution due to a visual impression, which has not necessarily a correlation
with the objective measured pollution (WQIobj).
The dry season shows the worse water quality, in
good agreement with the lower river ow. WQImin
shows a similar trend to WQIsub and WQIobj at a
lower analytical cost; however it should be com-

REFERENCES

Association Ocial Analytical Chemists (AOAC) (1995)

AOAC Ocial Methods of Analysis, 16th ed. AOAC International, Gaithersburg, Maryland, (March 1998 revision).
APHA, AWWA and WEF. (1992) Standard Methods for
the Examination of Water and Wastewater, 18th Edition,
eds A. H. Greenberg, L. S. Clesceri and A. D. Eaton,
American Public Health Association, Washington, DC.
ASTM (1993) Annual Book of ASTM Standards; Section
11, Water and Environmental Technology, eds P. C.
Fazio, E. L. Gutman, S. L. Kauman, J. G. Kramer, C.
M. Leinweber, V. A. Mayer and P. A. McGee. American Society for Testing and Materials, Philadelphia, PA.
Boler R. (1992). Surface Water Quality, Hillsborough
County, Florida, 19901991. Tampa, Fla.: Hillsborough
County Environmental Protection Commission (September), p. A-2 (accessible in electronic format through
Internet at http://www.epa.gov/OWOW/OCPD).
Chapman D. (1992) Water Quality Assessment, ed. D.
Chapman, p. 585. Chapman & Hall, London (on behalf
of UNESCO, WHO and UNEP).
Conesa Fdez-Vitora V. (1995). In: Methodological Guide
for Environmental Impact Evaluation (Gua Metodologica
para la Evaluacion del Impacto Ambiental ), 2nd ed., p.
390. Mundi-Prensa, Madrid.
Dasso C. (1998). CIRSA (Centro de la Region SemiaridaSemiarid Region Center)INA (Instituto Nacional del Agua y del AmbienteNational Water and
Environment Institute), unpublished results.
Estevan Bolea M. T. (1989). In: Environmental Impact
Evaluation (Evaluacion del Impacto Ambiental ), 2nd ed.,
p. 608. Fundacion MAPFRE, Madrid.
Gaiero D. M., Roman Ross G., Depetris P. J. and Kempe
S. (1997) Spatial and temporal variability of total nonresidual heavy metals content in stream sediments from
the Suqu a River System, Cordoba, Argentina. Wat. Air
Soil Poll. 93, 303319.
Ongley E. (1998). Modernization of water quality programs in developing countries: issues of relevancy and
cost eciency. Water Quality International Sep/Oct, 37
42.
Rauch W., Henze M., Koncsos L., Reichert P., Shanahan
P., Somlyody L. and Vanrolleghem P. (1998) River
water quality modellingI. State of the art. Wat. Sci.
Tech. 38, 237244.
Rodier J. (1981). In: Water Analysis (Analisis de las
Aguas ), p. 1059. Omega, Barcelona.

2926

Silvia F. Pesce and Daniel A. Wunderlin

Shanahan P., Henze M., Koncsos L., Rauch W., Reichert

P. and Somlyody L,Vanrolleghem P. (1998) River water
quality modellingII. Problems of the art. Wat. Sci.
Tech. 38, 245252.
Somlyody L., Henze M., Koncsos L., Rauch W., Reichert
P., Shanaham P. and Vanrolleghem P. (1998) River
water quality modellingIII. Future of the art. Wat.
Sci. Tech. 38, 253260.
WHO (1987) GEMS/WATER Operational Guide. World
Health Organization, Geneva.

Yagow G. and Shanholtz V. (1996) Procedures for indexing monthly NPS pollution loads from agricultural and
urban fringe watersheds. In Proceedings of Watershed
'96 Conference, (accessible in electronic format through
Internet at http://www.epa.gov/search97cgi).
Zagatto P. A., Lorenzetti M. L., Perez L. S. N., Menegon
Jr N. and Buratini S. V. (1998) Proposal for a new
water quality index. Verh.Int. Ver. Theor. Angew.
Limnol. 26, 24492451.