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

2915±2926, 2000
7 2000 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PII: S0043-1354(00)00036-1 0043-1354/00/$ - see front matter

www.elsevier.com/locate/watres

USE OF WATER QUALITY INDICES TO VERIFY THE

IMPACT OF COÂRDOBA CITY (ARGENTINA) ON SUQUõÂ A
RIVER
SILVIA F. PESCEM and DANIEL A. WUNDERLIN*M
Universidad Nacional de CoÂrdoba, Facultad de Ciencias QuõÂ micas, Dto. BioquõÂ mica, PabelloÂn
Argentina, Ciudad Universitaria, 5000, CoÂrdoba, Argentina

(First received 1 January 1999; accepted in revised form 1 September 1999)

AbstractÐWe veri®ed 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
objectiveÐWQIsub and WQIobj) take into consideration 20 parameters. Another index (minimalÐ
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-e€ective 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 SuquõÂ a River in CoÂrdoba City (Argentina) and nearby locations.
The city urban activity produces a serious and negative e€ect 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 wordsÐwater quality, quality index, river monitoring, SuquõÂ a River, CoÂrdoba, Argentina

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

The SuquõÂ a River basin is located in a semi-arid
region of CoÂrdoba 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 drai-
nage area covers approximately 7700 km2, while
almost 900 km2 corresponds to the CoÂrdoba City
drainage area. The SuquõÂ a River begins at the San
Roque dam and ¯ows mainly from west to east.
The river is the main drinking water source of CoÂr-
doba 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 dis-
charge and then continues up to Mar Chiquita
Lake (150 km downstream) (Fig. 1). Though at pre-
sent 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; e-
mail: dwunder@bioclin.fcq.unc.edu.ar
2915
years the SuquõÂ a River has shown a high ¯ow
period, from December to April, with an estimated
¯ow greater than 15 m3 sÿ1; whereas in the dry sea-
son, from May to November, its estimated ¯ow is
always lower than 10 m3 sÿ1 with a minimum of
5 m3 sÿ1 in June (Dasso, 1998).
CoÂrdoba City has a population of approximately
1.2 million inhabitants, nearly 500,000 are con-
nected 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 e‚uents to the river as well. At the
time we began this work, there were no reports on
the water quality of the SuquõÂ 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 di€erent purposes is
well de®ned (e.g. aquatic life preservation, contact
recreation, drinking water use) (Chapman, 1992;
2916 Silvia F. Pesce and Daniel A. Wunderlin
WHO, 1987), the overall water quality is sometimes
dicult to evaluate from a large number of
samples, each containing concentrations for many
parameters (Chapman, 1992). Although any moni-
tored parameter could be analyzed either alone or
grouped according to a common feature (e.g. nitro-
gen load through the analysis of ammonia, nitrites,
nitrates and organic nitrogen), such analysis pro-
vides 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 vali-
dation (Chapman, 1992; Rauch et al., 1998; Shana-
han et al., 1998; SomlyoÂdy et al., 1998).
The use of water quality indices (WQI) is a
simple practice that overcomes many of the pre-
vious mentioned problems and allows the public
and decision makers to receive water quality infor-
mation. WQI also permits us to assess changes in
the water quality and to identify water trends
(Chapman, 1992). A quality index is a unitless num-
ber that ascribes a quality value to an aggregate set
of measured parameters. Water quality indices gen-
erally consist of sub-index scores assigned to each
Fig. 1. Map of CoÂrdoba Province (Argentina) with indication of the studied area.
parameter by comparing its measurement with a
parameter-speci®c 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 0±100% scale, with 100 repre-
senting the highest quality. The next step is to
apply weighting factors that re¯ect the importance
of each parameter as an indicator of the water qual-
ity (Boler, 1992; Conesa Fdez-Vitora, 1995; Estevan
Bolea, 1989; Zagatto et al., 1998). The so con-
structed WQI gives a number that can be associated
with a quality percentage, easy to understand for
everyone, and based on scienti®c criteria for water
quality.
In this paper we report a three-year monitoring
of SuquõÂ a River water in CoÂrdoba City and nearby
locations. We also assess the impact of urban activi-
ties (represented by sewage discharges, run-o€ and
non-point pollution), evaluated by using three
di€erent water quality indices. Two WQI (subjective
and objectiveÐWQIsub and WQIobj) take into con-
sideration 20 parameters. The other WQI (mini-
malÐWQImin) was developed considering only
three parameters: turbidity, dissolved oxygen and
 SuquõÂ a river water quality indices

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

2917
2918 Silvia F. Pesce and Daniel A. Wunderlin
either conductivity or dissolved solids. The
measured parameters include many of those rec-
ommended by the GEMS/Water UNEP program
(Global Environmental Monitoring SystemÐUnited
Nations Environmental Program) (WHO, 1987), as
well as the spatial and seasonal changes in the
water quality over the studied river section.
MATERIALS AND METHODS
Apparatus
. A pH/temperature meterÐHANNA HI9025 (with auto-
matic temperature compensation) calibrated immedi-
ately before use with two standard solutions at pH 7.01
and 10.01 (standard solutions are commercially avail-
able from HANNA Instrument).
. TurbidimeterÐHACH 2100 P calibrated according to
the method ASTM (1993) D-1889.
. SpectrophotometerÐSHIMADTZU, 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 Scienti-
®c 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, SaldaÂn) is located 2 km upstream of
the CoÂrdoba City west border, before the SaldaÂn Brook
mouth; this station is located approximately 5 km down-
stream from the main intake of CoÂrdoba City water pot-
abilization plants and it is representative of the raw
drinking water quality. Station two (Chateau Carreras) is
located about 7 km downstream from SaldaÂn, 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 SaldaÂn
and immediately before downtown CoÂrdoba; at this point
begins a cement channel that replaces the natural river
bed. Station four (Sarmiento Bridge) is located about
19 km downstream from SaldaÂn and 2 km downstream
from La CanÄada Brook mouth. La CanÄada Brook receives
some industrial e‚uents 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 SaldaÂn; where the cement channel ends
and the river returns to its natural bed. This is a rather
small industrial area. Station six (CircunvalacioÂn Bridge)
is located about 35 km downstream from SaldaÂn and 2 km
upstream from the CoÂrdoba City sewage discharge.
Station seven is located approximately 40 km downstream
from SaldaÂn and 3 km downstream from the CoÂrdoba
City sewage exit. Station eight is located about 56 km
downstream from SaldaÂn and 10 km downstream from the
discharge of a channel containing e‚uents from new
industries recently located close to the eastern boundary of
CoÂrdoba City.
Collection receptacles, sample stabilization, and trans-
portation 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.
During the ®rst year (April 1995±March 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 1996±March 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 1997±March 1998). Analyses for the second and
third years were run in duplicate (see Table 1).
Monitored parameters and analytical methods
Many of the GEMS/Water (WHO, 1987) recommended
parameters were measured during the ®rst two years
(1995±1997). Mainly those parameters necessary for water
quality indices calculations were evaluated in the third
year (1997±1998) (Tables 1 and 2). Analytical methods
were standard; APHA et al. (1992) method numbers and
other methods are cited in parentheses. Measured par-
ameters include: alkalinity (2320-B), ammonia (4500-NH3
C, direct), arsenic (3500-As C), 5-day biological oxygen
demand (BOD-5) (Association Ocial Analytical Chemists
(AOAC), 1995Ðmethod 973.44), calcium (3500-Ca D),
chloride (4500-Clÿ 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 Ocial Analytical Chemists (AOAC),
1995Ðmethod 973.50), nitrites (4500-NOÿ 2 B), permanga-
nate 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-SO2ÿ 4 E
over ®ltrate samples), sul®des (4500-S2ÿ E), surfactants
(anionic as methylene blue active substances (MBAS),
55408C), temperature (2550-B, ®eld measured), total coli-
forms (9221 B), and turbidity (2130 B). Organochlorine
pesticides were also monitored during the entire period
studied (APHA et al., 1992Ðmethod 6630).
Water quality indices (WQI) calculation
The subjective water quality index, WQIsub, was calcu-
lated on the basis of the WQI proposed by Rodriguez de
BascaroÂn (Conesa Fdez-Vitora V., 1995) as follows:
X
Ci xPi
WQIsub ˆ k i
X …1†
Pi
i
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 turbid-
ity (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 normali-
zation (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
 SuquõÂ a river water quality indices 2919

Table 1. Descriptive statistics from SuquõÂ a river monitored parameters

Parametera Monitoring Yearc Annual Wet seasond Dry seasond

stationb
Meane SDe Meane SDe Meane SDe

Ammonia (as NH+

4 ) 1 1±3 0.52 0.52 0.34 0.21 0.65 0.64
3 1±2 0.42 0.35 0.44 0.31 0.41 0.38
6 1±3 0.62 0.61 0.58 0.75 0.66 0.50
7 1±3 7.58 6.61 3.40 3.39 10.69 6.74
8 3 14.99 11.50 3.68 5.21 22.53 7.49
BOD-5 1 1±3 1.7 1.0 1.5 0.5 1.8 1.3
3 1±2 2.1 1.0 1.9 1.0 2.2 1.1
6 1±3 2.6 1.1 2.3 0.9 2.8 1.2
7 1±3 10.2 6.8 8.6 4.4 11.4 8.0
8 3 15.2 7.2 9.0 3.5 19.4 5.8
Calcium 1 1±3 28.3 8.9 25.7 8.3 30.2 9.0
3 1±2 43.6 18.9 40.3 21.6 46.1 16.7
6 1±3 47.1 25.5 45.5 22.3 48.2 28.0
7 1±3 53.9 25.1 46.0 18.5 59.8 27.8
8 3 51.4 20.3 43.0 12.2 50.7 19.5
Chloride 1 1±3 10.5 4.0 9.5 3.8 11.3 4.0
3 1±2 42.4 23.4 30.0 21.7 52.2 20.2
6 1±3 75.2 34.9 52.8 35.0 91.8 24.2
7 1±3 85.8 32.5 62.9 34.9 102.8 16.3
8 3 83.2 37.2 46.5 28.1 107.7 16.1
Chemical oxygen demand (COD) 1 1±3 33.2 25.7 32.8 29.5 33.5 23.2
3 1±2 39.4 32.8 45.7 40.8 35.1 26.4
6 1±3 40.7 37.0 37.0 38.3 43.5 36.6
7 1±3 65.1 63.3 50.3 49.8 75.8 70.4
8 3 106.5 87.3 104.6 57.2 107.8 108.4
Dissolved oxygen (DO) 1 1±3 8.6 1.1 7.9 0.6 9.0 1.2
3 1±2 8.7 1.9 7.6 0.6 9.6 2.1
6 1±3 9.0 2.5 7.8 0.6 9.9 2.9
7 1±3 5.8 1.9 6.1 1.2 5.7 2.3
8 3 3.6 1.4 4.9 0.9 2.8 0.9
Hardness 1 1±3 107 29 91 26 118 26
3 1±2 202 73 163 76 233 54
6 1±3 236 81 195 86 266 63
7 1±3 261 74 206 76 302 37
8 3 251 75 174 51 303 30
Magnesium 1 1±3 7.7 3.0 6.9 2.9 8.3 7.1
3 1±2 22.9 14.0 15.3 8.3 27.0 15.6
6 1±3 27.3 16.3 18.5 12.4 33.7 15.9
7 1±3 31.6 20.5 22.0 15.2 38.6 21.2
8 3 32.8 21.2 16.6 16.0 45.8 17.9
Nitrates 1 1±3 2.7 4.4 1.3 1.0 3.7 5.6
3 1±2 12.3 6.1 9.4 6.8 14.5 4.4
6 1±3 22.4 11.3 18.1 13.3 25.5 8.5
7 1±3 16.5 9.5 12.4 6.1 19.6 10.4
8 3 10.1 7.7 12.2 5.7 8.7 8.7
Nitrites 1 1±3 0.15 0.37 0.08 0.08 0.20 0.48
3 1±2 0.11 0.08 0.10 0.08 0.12 0.08
6 1±3 0.42 0.58 0.26 0.22 0.54 0.72
7 1±3 1.86 2.50 1.75 2.75 1.94 2.35
8 3 1.65 0.75 1.14 0.79 2.00 0.51
Oil and greases 1 1±3 176 276 82 89 255 349
3 1±2 245 309 125 141 355 382
6 1±3 117 109 112 111 121 110
7 1±3 156 192 128 119 179 238
8 3 141 145 126 113 84 63
pH 1 1±3 7.8 0.3 7.8 0.3 7.9 0.3
3 1±2 7.8 0.2 7.8 0.1 7.9 0.3
6 1±3 7.8 0.3 7.7 0.1 7.9 0.3
7 1±3 7.6 0.3 7.5 0.3 7.6 0.4
8 3 7.5 0.3 7.5 0.2 7.4 0.4
Phosphorus (orthophosphate phosphorous) 1 1±3 0.04 0.09 0.01 0.02 0.05 0.11
3 1±2 0.04 0.10 0.02 0.02 0.05 0.13
6 1±3 0.09 0.14 0.04 0.04 0.12 0.17
7 1±3 0.58 0.39 0.36 0.33 0.74 0.35
8 3 0.71 0.52 0.35 0.37 0.96 0.47
Solids: dissolved 1 1±3 170 89 158 84 180 93
3 1±2 405 248 323 241 467 244
6 1±3 605 290 478 296 699 254
7 1±3 597 240 463 230 695 199
8 3 604 227 396 207 742 101
Solids: total 1 1±3 250 188 207 79 281 237
3 1±2 495 222 410 237 560 195
6 1±3 712 262 576 269 813 211
7 1±3 726 204 588 204 828 133
(continued on next page)
2920 Silvia F. Pesce and Daniel A. Wunderlin
Table 1 (continued )

Parametera Monitoring Yearc Annual Wet seasond Dry seasond

stationb
Meane SDe Meane SDe Meane SDe

8 3 677 211 504 233 793 86

Sulfates 1 1±3 24.2 14.2 18.9 11.0 28.0 15.1
3 1±2 135.9 115.0 79.3 72.5 180.6 123.9
6 1±3 172.0 120.4 116.0 91.2 213.5 123.9
7 1±3 167.4 95.9 116.8 74.3 204.9 93.7
8 3 168.0 105.7 92.9 49.9 218.1 104.2
Surfactants (anionic as MBAS) 1 1±3 0.04 0.21 0.00 0.00 0.08 0.28
3 1±2 0.01 0.04 0.02 0.06 0.00 0.00
6 1±3 0.03 0.10 0.01 0.04 0.04 0.13
7 1±3 0.14 0.31 0.05 0.11 0.20 0.39
8 3 0.32 0.56 0.00 0.00 0.54 0.64
Temperature 1 1±3 18.5 5.3 22.7 2.4 15.4 4.7
3 1±2 19.1 5.5 23.2 2.3 15.9 5.2
6 1±3 19.4 4.9 22.5 2.5 17.0 4.8
7 1±3 20.1 5.0 23.0 2.6 18.0 5.4
8 3 18.8 3.6 21.5 2.9 17.0 2.9
Total coliforms 1 1±3 1.1E+04 2.4E+04 8.7E+03 1.4E+04 1.2E+04 2.9E+04
3 1±2 1.4E+05 2.3E+05 8.7E+04 6.9E+04 1.8E+05 3.0E+05
6 1±3 2.0E+05 2.7E+05 2.9E+05 3.3E+05 1.3E+05 2.0E+05
7 1±3 8.6E+05 1.6E+06 1.1E+06 2.1E+06 6.8E+05 1.1E+06
8 3 3.4E+06 4.8E+06 4.8E+05 4.2E+05 5.3E+06 5.4E+06
Turbidity 1 1±3 6 3 6 3 5 2
3 1±2 21 20 23 18 19 22
6 1±3 15 16 16 14 14 17
7 1±3 38 17 40 19 37 16
8 3 46 15 51 17 43 12

a
Only those parameters used for WQI calculation are reported. Detailed data for other monitored parameters are available on request.
b
1=SaldaÂn, 3=Santa Fe Bridge, 6=CircunvalacioÂn Bridge, 7=Bajo Grande, 8=CorazoÂn de MarõÂ a (data for stations 2, 4 and 5 are
available on request).
c
1=April 1995±March 1996, 12 monitored months (®ve wet and seven dry); 2=April 1996±March 1997, 11 monitored months (®ve wet
and six dry); 3=April 1997±March 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 lÿ1 pH in pH units. Temperatures in centigrade. Turbidity in NTU. Bacteria expressed as MPN
100 mlÿ1 (most probable
number per 100 ml). Values are averaged over all the determinations from the period as follows: years 1±2, n ˆ 34 (15 wet and 19
dry); years 1±3, n ˆ 54 (23 wet and 31 dry); year 3, n ˆ 20 (eight wet and 12 dry). SD ˆ 1 standard deviation. Detailed data for each
monitored year are available on request.

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 Fdez-
Vitora 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 calcu-
lated 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 par-
ameters, named minimal index (WQImin) was calculated
using:
CDO ‡ Ccond ‡ Cturb
WQImin ˆ …
3 Some selected results obtained for this ®rst year are
where CDO is the value due to dissolved oxygen after nor-
malization (Table 2); Ccond the value due to either conduc-
tivity or dissolved solids (TDS) after normalization
(Table 2); and Cturb the value due to turbidity after nor-
malization (Table 2).
All WQI were calculated monthly using a computer pro-
gram (BASIC language) especially developed for this pur-
pose (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 par-
ameter). 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 cal-
culations (mean, standard deviation and t-test at 95% of
con®dence) were performed using the Microsoft EXCEL
statistical package. Throughout the text signi®cant di€er-
ence means p < 0:05 for means comparison.
RESULTS AND DISCUSSION
During the ®rst year we explored the river beha-
vior 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.
2†
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
e€ect 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 contri-
bution 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-
 SuquõÂ a river water quality indices 2921

Table 2. Parameters concidered for WQI calculation

Parameter Relative Normalization factor (Ci)

weight (Pi)
100 90 80 70 60 50 40 30 20 10 0
Analytical valuea

Ammonia nitrogen 3 <0.01 <0.05 <0.10 <0.20 <0.30 <0.40 <0.50 <0.75 <1.00 R1.25 >1.25
BOD-5 3 <0.5 <2 <3 <4 <5 <6 <8 <10 <12 R15 >15
Calcium 1 <10 <50 <100 <150 <200 <300 <400 <500 <600 R1000 >1000
Chloride 1 <25 <50 <100 <150 <200 <300 <500 <700 <1000 R1500 >1500
Conductivityb <750 <1000 <1250 <1500 <2000 <2500 <3000 <5000 <8000 R12,000 >12,000
COD 3 <5 <10 <20 <30 <40 <50 <60 <80 <100 R150 >150
Dissolved oxygen 4 r7.5 >7.0 >6.5 >6.0 >5.0 >4.0 >3.5 >3.0 >2.0 r1.0 <1.0
Hardness 1 <25 <100 <200 <300 <400 <500 <600 <800 <1000 R1500 >1500
Magnesium 1 <10 <25 <50 <75 <100 <150 <200 <250 <300 R500 <500
Nitrates 2 <0.5 <2.0 <4.0 <6.0 <8.0 <10.0 <15.0 <20.0 <50.0 R100.0 >100.0
Nitrites 2 <0.005 <0.01 <0.03 <0.05 <0.10 <0.15 <0.20 <0.25 <0.50 R1.00 >1.00
Oil and grease 2 <0.005 <0.02 <0.04 <0.08 <0.15 <0.30 <0.60 <1.00 <2.00 R3.00 >3.00
pH 1 7 7±8 7±8.5 7±9 6.5±7 6±9.5 5±10 4±11 3±12 2±13 1±14
Phosphorus 1 <0.16 <1.60 <3.20 <6.40 <9.60 <16.0 <32.0 <64.0 <96.0 R160.0 >160.0
(orthophos-phate)
Solids: dissolved 2 <100 <500 <750 <1000 <1500 <2000 <3000 <5000 <10,000 R20,000 >20,000
Solids: total 4 <250 <750 <1000 <1500 <2000 <3000 <5000 <8000 <12,000 R20,000 >20,000
Sulfates 2 <25 <50 <75 <100 <150 <250 <400 <600 <1000 R1500 >1500
Surfactants as 4 <0.005 <0.06 <0.10 <0.25 <0.50 <0.75 <1.00 <1.50 <2.00 R3.00 >3.00
MBAS
Temperature 1 21/16 22/15 24/14 26/12 28/10 30/5 32/0 36/ÿ2 40/ÿ4 45/ÿ6 >45/<ÿ6
Total coliforms 3 <50 <500 <1000 <2000 <3000 <4000 <5000 <7000 <10,000 R14,000 >14,000
Turbidity 2 <5 <10 <15 <20 <25 <30 <40 <60 <80 R100 >100

a
Values in mg lÿ1 pH in pH units. Temperatures in centigrade. Turbidity in NTU. Bacteria expressed as MPN
100 mlÿ1 (most probable
number per 100 ml).
b
Conductivity (mS cmÿ1) 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 to evaluate the overall variation of the water quality
(DO) observed from station 1 to station 6 and with by analyzing separate parameters, though some par-
the drop in DO value at station 7 (Fig. 4). It could tial analysis is possible, like TIN in¯uence on water
be hypothesized that, in this case, the urban non-
point 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 turbu-
lence is not so important downstream from CoÂr-
doba City eastern border, where the low river basin
begins. Also from Fig. 3 it is remarkable that the
seasonal di€erence 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 moder-
ate increase from station 1 to station 7, while sul-
fates (annual means) rose from station 1 to station
5 with a further decay. These parameters did not
show an important variation upstream and down-
stream of the city sewage discharge as was the case Fig. 3. Spatial and temporal variation of inorganic nitro-
gen species during the ®rst monitoring year. q, ammonia
with DO (Fig. 4) and inorganic nitrogen species nitrogen; w, nitrate nitrogen; +, nitrite nitrogen; W, total
(Fig. 3). inorganic nitrogen (TIN) (annual mean); R, TIN (wet sea-
All these results indicate that it may be not easy son); 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 e€ect 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 Fdez-
Vitora V., 1995) for the evaluation of environmen-
tal impact. In our ®rst approach we constructed a
WQI named ``subjective'' (WQIsub), because it
includes a constant that considers the river appear-
ance (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 com-
pounds 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 lÿ1 COD are
equivalent to 1 mg lÿ1 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 de®ne
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 de-
terioration 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 statisti-
cally signi®cant 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 arti®cial bed (Fig. 4, stations
3±5) or to La CanÄada Brook discharge (Fig. 4,
stations 4±5). So, during the ®rst year, the river
water lost approximately 12% quality across the
city (Fig. 4, stations 1±6). However at station 7 and
with only 25% quality (Fig. 4), we saw the cata-
strophic 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 signi®-
cant di€erences with previous stations (1 and 3, re-
spectively). 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 approxi-
mately 16 km downstream from station 7. Station 8
was included in order to evaluate the incidence of a
channel containing e‚uents from some new large
industries on the river water quality (see experimen-
tal section). Conversely, station 3 was not moni-
tored 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 (SaldaÂn) the WQIsub gives an
average water quality of about 68% with no signi®-
cant 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 lit-
tle di€erence between wet and dry seasons observed
with TIN in the same station during the ®rst year
(Fig. 3). Downstream, a signi®cant quality drop is
observed from station 1 to station 3 and further
stations in good agreement with TIN variation
 SuquõÂ 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). Di€erences between TIN and
WQIsub spatial variations could be explained
because the nitrate nitrogen made the bigger contri-
bution 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 signi®cant quality di€er-
ences are observed between dry and wet season
from station 1 to station 6, but such di€erences are
observed for stations 7 and 8. Furthermore, station
8 does not show signi®cant di€erence 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 ap-
proximately 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 signi®cant di€erence with station 1
…p < 0:05); B=statistically signi®cant di€erence with pre-
ceding station …p < 0:05); C=statistically signi®cant di€er-
ence 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 recog-
nize the usefulness of such WQI. WQIsub showed
approximately the same trend observed when ana-
lyzing separate parameters (Table 1, Figs 3 and 4),
assigning the greater importance to critical par-
ameters such as DO and ammonia nitrogen, and
the smaller weight to other parameters (e.g. chlor-
ides and sulfates) that are not so critical for aquatic
life preservation (Table 2). However, WQIsub is
a€ected by a subjective constant (k, equation (1))
which could a€ect 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 simi-
lar to that predicted by WQIsub. However, some im-
portant 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 aver-
age number of parameters under 50% acceptability (Table
2). q, k (annual means); W, parameters under 50% accept-
ability (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 di€erent from station 1 to station 3 as
those observed from station 3 to station 6, even
when signi®cant quality di€erences 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, signi®cant di€erences 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 signi®cant
di€erences 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
signi®cant 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. Further-
more, 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 dis-
charge, 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 signi®cant di€erence with station 1
…p < 0:05); B=statistically signi®cant di€erence with pre-
ceding station …p < 0:05); C=statistically signi®cant di€er-
ence between wet and dry season …p < 0:05).
bined e€ect of the city sewage and the channel with
industrial e‚uents (Fig. 7). WQIobj also shows that
the non-point pollution from CoÂrdoba City contrib-
utes about 13% to the water quality deterioration.
Though WQIsub and WQIobj give similar infor-
mation 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 assess-
ments 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 vari-
ations measuring only a few simple parameters. On
this basis, we decided to use the data from monitor-
ing to calculate WQImin as de®ned in the exper-
imental section. The parameters used for WQImin
calculation were selected because they are important
indicators of other water quality parameters. Dis-
solved oxygen is a key factor for aquatic life. Either
conductivity or TDS should indicate the presence of
salts, mineral acids, or similar contaminants dis-
charged 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 signi®cant di€erence from station 3 to station 6,
Fig. 8). WQImin predicts a 46% drop in water qual-
ity 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 com-
bined e€ect of the city sewage and the channel with
industrial e‚uents (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. Fur-
thermore, WQImin could be used for periodic rou-
tine 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
 SuquõÂ a river water quality indices
Fig. 8. Three-year spatial and temporal evolution of
WQImin. R, wet season; *, dry season; Q, annual aver-
age. A=statistically signi®cant di€erence with station 1
…p < 0:05); B=statistically signi®cant di€erence with pre-
ceding station …p < 0:05); C=statistically signi®cant di€er-
ence 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 SuquõÂ a River water at any station during the
period studied. However, we detected the presence
of Lindane in river sediments at station 7 (GC-
ECD using pesticide standards as control, unpub-
lished results). Though the study of river sediments
is out of the scope of the present paper, further
work is currently under way.
CONCLUSIONS
CoÂrdoba City produces a negative impact on the
SuquõÂ a River water quality, particularly serious
after the city sewage discharge. The use of various
WQI produce similar trend results but di€erent
index values as well as some di€erent remarks.
WQIsub and WQIobj show statistical signi®cant tem-
poral changes from wet to dry seasons downstream
from the sewage discharge; WQIobj also predicts
such di€erences 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 im-
pression, 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-
2925
bined with WQIobj to corroborate the results. For
other similar studies, we recommend the monthly
evaluation of WQI (subjective, objective and mini-
mal) for at least two years; thereinafter water qual-
ity could be assured by evaluating WQImin monthly
(or even weekly) and WQIobj twice in the dry sea-
son and twice in the wet season.
AcknowledgementsÐThis work was partially supported by
grants from the SecretarõÂ a de Ciencia y TeÂcnica-Univ.
Nac. CoÂrdoba, the National Reseach Council
(CONICET), and the CoÂdoba Research Council
(CONICOR). Silvia F. Pesce had a fellowship from the
SecretarõÂ a de ExtensioÂn Universitaria, Univ. Nac.
CoÂrdoba. 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.
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