Surface Water Quality

An Assessment of Stream Water Quality of the Rio San Juan, Nuevo Leon, Mexico, 19951996
Jose Santos Flores Laureano and Jose Navar* ABSTRACT
Good water quality of the Rio San Juan is critical for economic development of northeastern Mexico. However, water quality of the river has rapidly degraded during the last few decades. Societal concerns include indications of contamination problems and increased water diversions for agriculture, residential, and industrial water supplies. Eight sampling sites were selected along the river where water samples were collected monthly for 10 mo (October 1995July 1996). The concentration of heavy metals and chemical constituents and measurements of bacteriological and physical parameters were determined on water samples. In addition, river discharge was recorded. Constituent concentrations in 18.7% of all samples exceeded at least one water quality standard. In particular, concentrations of fecal and total coliform bacteria, sulfate, detergent, dissolved solids, Al, Ba, Cr, Fe, and Cd, exceeded several water quality standards. Pollution showed spatial and temporal variations and trends. These variations were statistically explained by spatial and temporal changes of constituent inputs and discharge. Samples collected from the site upstream of El Cuchillo reservoir had large constituent concentrations when discharge was small; this reservoir supplies domestic and industrial water to the city of Monterrey.

he Rio San Juan watershed is located within a semiarid region between the physiographic provinces of the Great Plains of North America, the Chihuahuan Desert, and the Northern Plains of the Gulf of Mexico. Availability of water resources within the area is highly variable due to low, periodic precipitation, recurrent drought episodes, and high evapotranspira tion rates (Navar et al., 1994; Navar, 1999a). In order to meet agricultural, industrial, and residential water demands, several reservoirs (Marte R. Gomez, El Cuchillo, and La Boca) have been built along the headwaters of the major stem of the Rio San Juan. The Rio San Juan is the major tributary of the lower Rio BravoRio Grande, which runs along the border between Mexico and the USA, from Ciudad Juarez (Chihuahua) and El Paso (Texas) to its outlet into the Gulf of Mexico near Matamoros (Tamaulipas) and Brownsville (Texas). Availability of water resources has been impaired by contamination from industrial and residential sources of the Rio San Juan. In 1988, the Ministry of Urban Development and Ecology (SEDUE) classified the Rio

J.S. Flores, Faculty of Forestry, University of Toronto, 33 Wilcocks St., Toronto, ON, Canada M5S 3B3. J. Navar, Facultad de Ciencias Forestales, UANL, Carr Nacional, Km 145, Linares, Nuevo Leon, Mexico, CP 67700. Received 11 June 2001. *Corresponding author (jnavar@ccr.dsi.uanl.mx). Published in J. Environ. Qual. 31:12561265 (2002).

San Juan watershed as the third most polluted in the country. The European Union (Commission of the European Community, unpublished data, 1991) proposed a management plan for all reservoirs of the Rio San Juan watershed due to eutrophication problems from high inputs of organic matter in the main stem of the Rio San Juan. In response, the government of Nuevo Leon initiated a sanitation program in 1994 entitled Plan Monterrey IV, which included the construction of three large wastewater treatment plants and the discharge of municipal effluents and treated water to other Rio San Juan tributaries. However, even after the aforementioned tasks were completed, the public perception was that pollution problems persisted within the Rio San Juan. Heavy metal pollution in the Rio San Juan is a major concern in the Rio Bravo as well (Schmandt et al., 2000; United StatesMexico International Boundary and Water Commission, 1994), the Rio Blanco in Veracruz, Mexico (Albert and Badillo, 1986), the Rio Tijuana in Baja California, Mexico (Gersberg and Trindale, 1989), and the Rio Coatzacoalcos in Veracruz, Mexico (Toledo et al., 1989). Few water quality studies have been conducted within the Rio San Juan watershed. The National Water Commission, the official federal government agency responsible for assessing water quality in Mexico, routinely monitors some physical, chemical, and bacteriological parameters, but the monitoring program does not include the evaluation of heavy metals, pesticides, and other organic compounds. Kramar et al. (1992) evaluated the concentration of several heavy metals in sediments of the Rio Santa Catarina, an important tributary of the Rio San Juan, and described contamination by Fe, Cu, Zn, Cd, and Sr. Vogel et al. (1995) assessed the pollution of the Rio Pesqueria, another important tributary of the Rio San Juan, and reported that Be, Ni, Pb, Cd, and Sb exceeded the Mexican water quality standards for drinking water. The objectives of this current (19951996) study were to (i) assess the water quality of the Rio San Juan and (ii) analyze the temporal and spatial variations of 22 heavy metals and 23 physical, chemical, and bacteriological water quality parameters of the Rio San Juan and the tributary Rio Santa Catarina. Emphasis was placed
Abbreviations: ANOVA, analysis of variance; BOD, biological oxygen demand; COD, chemical oxygen demand; PCA, principal component analysis.

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Fig. 1. The location of the Rio San Juan watershed and the water quality monitoring stations along the Santa Catarina and San Juan rivers.

on heavy metal pollution given the lack of information in this respect. MATERIALS AND METHODS Study Area
The Rio San Juan watershed covers an area of 33 000 km2 within the Mexican states of Cohauila, Nuevo Leon, and Tamaulipas in the northeastern portion of the country. Most of the watershed area (57%) is located in Nuevo Leon. The Rio San Juan originates in the Sierra Madre Oriental mountain range approximately 30 km to the southeast of the city of Monterrey, and flows in a northeasterly direction through the Great Plains of North America and the Northern Plains of the Gulf of Mexico (Fig. 1). The river drains into the Rio Bravo near Camargo in the state of Tamaulipas. The climate of the Rio San Juan watershed area ranges from semiarid to arid. Monthly rainfall has a bimodal type of distribution, with the first peak occurring in MayJune and the second peak, the most important in terms of total depth, occurring during SeptemberOctober. Long-term mean annual precipitation (19351996) ranges from 250 to 1300 mm yr 1 (Navar, 1999a). The eastern slopes of the Sierra Madre Oriental mountain range receive up to 1600 mm yr 1, whereas the western portion of the watershed, located in the Chihuahuan Desert, receives as little as 200 mm yr 1. The Rio San Juan watershed houses a total population of approximately 5 million inhabitants (Navar, 1999b), including the metropolitan areas of Saltillo and Monterrey (Fig. 1). The study focused only on the tributary Rio Santa Catarina from

the eastern suburbs of the city of Monterrey to its junction with the Rio San Juan; and the Rio San Juan from below La Boca reservoir to El Cuchillo reservoir in the municipality of China, Nuevo Leon, 102 km to the east of Monterrey.

Methodology
A total of eight river sampling sites were selected for stream water collection and analysis: three sites were selected along the Rio Santa Catarina and five additional sites were located along the Rio San Juan, between La Boca and El Cuchillo reservoirs (Fig. 1). Twenty-two heavy metals were evaluated: Ag, Al, As, B, Ba, Be, Cd, Co, Cr, Cu, Fe, Hg, Li, Mn, Mo, Ni, Pb, Sb, Se, Si, Sn, and Zn, and two major ions, Ca and Mg. In addition, 23 physical, chemical, and bacteriological water quality parameters were assessed: color, electrical conductivity, dissolved solids, suspended solids, total solids, turbidity, alkalinity, chloride, biological oxygen demand (BOD), chemical oxygen demand (COD), detergents, oil content, total P, total hardness, nitrate as N, nitrite as N, ammonia as N, dissolved oxygen, pH, sulfate, fecal coliform bacteria, total coliform bacteria, and temperature. Heavy metal analysis consisted of three different methods of atomic absorption and emission. A PerkinElmer (Wellesley, MA) Zeeman 5100 spectrophotometer equipped with a graphite furnace was used to determine Pb. A Beckman (Fullerton, CA) Model 1272 spectrophotometer with hydride generation was used to measure the concentration of As, Hg, and Se. The remaining heavy metals were determined by the method of atomic emission by argon plasma using a Thermo Jarrell Ash

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(Franklin, MA) PolyScan 61 spectrophotometer. For chemical constituents and physical and bacteriological parameters the laboratory methods used were those of the National Water Commission (Ministry of Urban Development and Ecology, 1990) denominated the NMX-AA-XX (method number)-YY (year) protocols for water analysis; for example, the method used for alkalinity determination is NMX-AA-36-1980. Monthly water samples were collected at each of the eight sites for a 10-mo period from October 1995 to July 1996. A total of 80 stream water samples were analyzed for each parameter. However, due to several problems, the number of samples collected for fecal coliform bacteria, total coliform bacteria, detergents, and nitrate was 56, 72, 72, and 64, respectively. Water samples were collected at midstream width by way of wading and submerging plastic containers with a volume of 4 L to a depth of 20 to 30 cm. Samples analyzed for dissolved oxygen were collected and stored in 300-mL Winkler bottles, and preserved with 2 mL of manganous sulfate and 2 mL of an alkali iodide azide of sodium solution to fix the oxygen. Water samples for bacteriological analyses were collected in 125-mL sterile glass bottles. Water samples for oil content analysis were collected in 1-L glass bottles previously washed with hexane, and later preserved with 2 mL of hydrochloric acid. Water samples for heavy metal analysis were collected in 1-L acid-rinsed polyethylene containers and preserved with 3 mL of nitric acid. Discharge (Q ) was estimated by measuring stream velocity (V ) and cross-sectional area (A ) of the river channel during each sampling event. Velocity was measured using a cup-type current meter by counting the rotors number of revolutions during a measured time interval. Velocity was then estimated by using a rating table, which relates the number of revolutions and time of measurements. The cross-sectional area of the river was divided in smaller, discrete areas, where velocity was recorded. Cross-sectional areas were calculated by multiplying width, usually 2 m, and average water depth, measured at the two extreme sides of each segment. Total river discharge (Q VA ) was calculated by adding the partial discharges of each segment and is referred to as monthly instantaneous discharge.

sampling sites for all dates sampled. The probability of exceedance for heavy metals was calculated by using the cumulative distribution, according to Eq. [1] (Haan, 1986):

P (x

X)

exp

[1]

where p(x ) probability of the random variable x, less than or equal to x. Parameters , , and are shape, scale, and location parameters, respectively, which were estimated by the conventional procedure of moments. Haan (1986) reported that the skew coefficient ( ) is related to the shape parameter ( ) by Eq. [2]:

(1 (1 [ (1

3/ ) 1/ ) 2/ )

3 (1 2 3 (1 2 (1

2/ ) 1/ ) 1/ )]3/2

[2]

and with this he mathematically defined and [4]:

2

and by Eq. [3]

1/2

(1

2/ ) (1

(1 1/ )

1/ )

[3] [4]

Statistical Analysis
Constituent concentrations were compared with European Community standards (Tebutt, 1994), World Health Organization standards (Tebutt, 1994), and official Mexican standards (Secretaria de Salubridad y Asistencia, 1996) for domestic water supply, and the Mexican Water Commission standards (Ministry of Urban Development and Ecology, 1990) for ecological criteria. A total of 11 696 comparisons, which were estimated by multiplying the number of laboratory analyses for each parameter by the number of standards available for each parameter, were used for data analysis. These comparisons allowed the estimation of the number of exceedances for each sampling event, which in turn were used to establish spatial and temporal trends among sites and sampling events. In addition, the relationship between discharge and concentration of exceeding parameters or constituents was analyzed. Continuous dispersion of constituents was assessed by fitting the Weibull distribution to the concentration of heavy metals and chemical constituents, which exceeded the water quality standards. The Weibull distribution has also been used to evaluate dispersion mechanisms of odor pollution (Pringer and Schauberger, 1999) as well as other processes such as the lifetime of Escherichia coli (Hutchinson, 2000) and the dispersion of fluvial gravels (Kondolf and Adhikari, 2000). The distribution was fitted to the data generated at all eight

where and are the average and standard deviation of the random variable, respectively. The shape parameter is iteratively fitted by estimating first the skew coefficient in Eq. [3] to later solve for and . Mass flux (mg s 1 ) for each site and sampling event was calculated by multiplying the monthly concentration of each heavy metal (mg L 1 ) times discharge (L s 1 ). These calculations were used to compare spatial and temporal behavior of each heavy metal among sampling sites. The mass flux of all heavy metals was added together to obtain a single value for each site and date of sampling (total mass flux). Mass flux was used to compare heavy metal concentrations among sites and sampling events and to establish other plausible explanations of pollution dynamics in the river system. Principal component analysis (PCA) is a multivariate ordination technique used to extract information on patterns and clusters of data (Ter and Smilauer, 1998). Principal component analysis has been successfully tested to provide reasonable representation of water chemistry variables in the Cache la Poudre River in Colorado (Shieh et al., 1999). The water chemistry data of total mass flux of heavy metals was employed to detect whether sites and sampling events showed tendencies or clustering patterns. The PCA program was fed with matrix data composed of 22 heavy metals and 80 samplings: 8 sites and 10 events. In addition, the total mass flux of heavy metals was statistically analyzed using analysis of variance (ANOVA) with sampling sites and events as the major sources of variation. Multiple comparisons were conducted using Tukey statistical tests. The ANOVA and Tukey analysis provided results for each constituent (45) by sampling site and event. Therefore, the discussion centers the attention on the conclusions of this analysis rather than on reporting statistical results for each constituent. Finally, plots of total mass and standardized concentrations of heavy metals against instantaneous monthly discharge were observed to describe changes in heavy metal concentrations with changes in monthly instantaneous discharge.

RESULTS AND DISCUSSION Concentration Analysis

Of all evaluated parameters only 40 could be compared with water quality standards. There are no stan-

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Table 1. Mean heavy metal and chemical constituent concentrations and measurements of physical and bacteriological parameters that exceeded standards in water samples collected in the Rio San Juan and the Rio Santa Catarina during 1995 and 1996.
Parameter or constituent Al Sb As Ba Cd Cu Cr Fe Mn Ni Ag Pb Zn Color Electrical conductivity Dissolved solids Suspended solids Total solids Turbidity BOD COD## Detergents Oil content Total phosphorus Total hardness Nitrate as N Nitrite as N Ammonia as N Dissolved oxygen pH Sulfate Fecal coliform bacteria Total coliform bacteria NOM 57.0 NA 6.3 0.0 37.5 0.0 1.3 38.8 5.0 NA NA 1.3 0.0 76.3 NA 7.5 NA NA 60.0 NA NA 0.0 NA NA 7.5 1.6 2.5 10.0 NA 1.3 6.3 100.0 97.2 WHO 57.5 NA 6.3 NA 37.5 0.0 1.3 38.8 17.5 0.0 NA 1.3 0.0 83.8 NA 7.5 NA NA 60.0 NA NA NA NA NA 7.5 1.6 0.0 NA NA 1.3 NA 100.0 100.0 EC NA NA 7.5 7.5 87.5 3.8 1.3 87.5 31.3 NA NA 1.3 2.5 90.0 NA NA 17.5 NA NA 35.0 11.3 4.2 NA 1.3 NA 0.0 NA 45.0 NA 1.3 76.3 69.6 81.9 WR % 100.0 7.5 6.3 0.0 1.3 0.0 1.3 38.7 17.5 77.5 2.5 1.3 0.0 21.3 20.0 92.5 0.0 11.3 NA NA NA 0.0 82.5 41.3 NA 12.5 2.5 NA 0.0 0.0 6.3 26.8 NA AGR# 0.0 7.5 6.3 NA 1.3 0.0 0.0 0.0 NA 0.0 NA 0.0 0.0 NA NA 92.5 10.0 NA NA NA NA NA NA NA NA NA NA NA NA 0.0 85.0 26.8 NA LC 0.0 NA 6.3 NA 0.0 0.0 0.0 NA NA 0.0 NA 0.0 0.0 NA NA 7.5 NA NA NA NA NA NA NA NA NA 0.0 0.0 NA NA NA NA NA NA PAB 98.8 7.5 6.3 98.8 NA NA 93.8 3.8 NA NA NA NA NA NA NA NA NA NA NA NA NA 28.7 NA NA NA NA NA 25.0 3.8 NA 100.0 50.0 NA

Official Mexican standard for drinking water. World Health Organization standard for drinking water. European Community standard for drinking water. Ecological criteria of the National Water Commission for water reservoirs. # Ecological criteria of the National Water Commission for agriculture. Ecological criteria of the National Water Commission for livestock consumption. Ecological criteria of the National Water Commission for protection of aquatic biota. Not available. Biological oxygen demand. ## Chemical oxygen demand.

dards for Ca, Co, Li, Mo, Si, Sn, and Mg. In addition, only 14 heavy metals could be statistically analyzed, since Be, Hg, and Se recorded concentrations were below limits of detection. Therefore, only 11 696 comparisons could be made, of which 2190 (18.7%) exceeded the standards. Table 1 shows the mean values of the constituents and parameters that exceeded most of the water quality standards. Concentrations of Al, Ba, Cd, Cr, Fe, Mn, and Ni exceeded the standards in more samples than Ag, As, Cu, Sb, Pb, and Zn. Dissolved solids and color exceeded standards in more samples than electrical conductivity, suspended solids, and turbidity. Sulfate concentrations exceeded standards in more samples than nitrate and nitrite concentrations, and pH (Table 1). Constituents exceeding at least one standard for drinking water were Al, As, Ba, Cd, Cu, Cr, Fe, Mn, Pb, Zn, color, dissolved solids, suspended solids, turbidity, BOD, COD, detergents, total P, total hardness, nitrate as N, nitrite as N, ammonia as N, pH, sulfate, fecal coliform bacteria, and total coliform bacteria. For the ecological criteria, parameters exceeding the standards were Al, Sb, As, Ba, Cd, Cr, Fe, Mn, Ni, Ag, Pb, color, electric conductivity, dissolved solids, sulfate, total sol-

ids, detergents, oil content, total P, nitrate as N, nitrite as N, ammonia as N, dissolved oxygen, sulfate, fecal coliform bacteria, and total coliform bacteria. For the ecological criteria, a few constituents exceeded at least one standard for agriculture (Sb, As, Cd, dissolved solids, suspended solids, sulfate, fecal coliform bacteria, and total coliform bacteria) and for livestock consumption (As and dissolved solids exceeded the standards in less of 10% of the samples). Aluminum, Sb, As, Cd, Cr, Fe, Mn, Ni, Ag, color, electrical conductivity, dissolved solids, total solids, oil content, total P, nitrate as N, nitrite as N, sulfate, and fecal coliform bacteria exceeded the National Water Commission standards for water in reservoirs. The standards for protection of the aquatic biota were exceeded by the concentration of Al, Sb, As, Ba, Cr, Fe, detergents, ammonia as N, dissolved oxygen, sulfate, and fecal coliform bacteria. Table 2 shows several statistics of the constituents and parameters that exceeded most of the water quality standards. The Commission of the European Community (unpublished data, 1991) recorded, for three samples collected between 1985 and 1990 near Site 3 of this study, a P concentration of 1.5, 4.5, and 7.9 mg L 1 and

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Table 2. Concentration statistics for selected constituents and parameters that exceeded water quality standards in water samples collected in the Rio San Juan and Rio Santa Catarina in 1995 and 1996. Standards between brackets are in units in mg L 1, unless a different unit is specified.
Constituent or parameter Al (0.2, 5.0#, 0.05) Ba (0.7, 0.1, 1.0, 0.01) Cd (0.005, 0.001, 0.01#, 0.02) Cr (0.05, 1.0#,0.01) Fe (0.3, 0.1, 5.0#) Mn (0.15, 0.1, 0.05) Ni (0.1, 0.01, 0.2#, 1.0) Color (color units; 20.0, 15.0, 10.0, 75.0) Electrical conductivity (S m 1; 1000.0) Biological oxygen demand ( 3.0) Chemical oxygen demand (30.0) Total phosphorus (0.4, 0.1) Oil content (absent) Nitrate as N (10.0, 25.0, 5.0, 90.0) Ammonia as N (0.5, 0.05, 0.06) Dissolved solids (1000.0, 500.0#) Suspended solids (25.0, 500.0, 50.0#) Total Solids (1000.0) Sulfate (400.0, 150.0, 500.0, 130.0#, 0.005) Turbidity (itu; 5.0) Fecal coliform bacteria (coliform per 100 mL; 0, 20, 1000, 100#, 200) Total coliform bacteria (coliform per 100 mL; 2, 0, 50) Mean 0.517 0.067 0.005 0.021 0.362 0.067 0.015 59.6 8825 3.4 12.5 0.105 2.5 1.6 0.152 712.4 20.2 732.6 211.3 12.9 111 546.0 332 679.7 Standard deviation 0.735 0.025 0.002 0.008 0.389 0.125 0.006 68.3 2335 2.3 12.4 0.078 2.6 2.3 0.201 192.0 27.9 192.5 116.1 19.5 674 282.0 1 971 163.2 Skew coefficient 2.87 1.34 0.12 1.31 3.76 5.13 0.44 3.30 1.18 2.14 2.61 1.45 1.34 2.17 2.32 0.80 3.07 0.77 2.12 4.02 7.20 7.47

Official Mexican standard for drinking water. World Health Organization standard for drinking water. European Community standard for drinking water. Ecological criteria of the National Water Commission for water reservoirs. # Ecological criteria of the National Water Commission for agriculture. Ecological criteria of the National Water Commission for livestock consumption. Ecological criteria of the National Water Commission for protection of aquatic biota.

biological oxygen demand of 107.9, 19.3, and 5.0 mg L 1. The 1991 research determined a mean P concentration of 0.105 and a biological oxygen demand of 3.4 mg L 1, which indicated that the Plan Monterrey IV improved but did not totally eradicate contamination problems in the Rio San Juan watershed. The number of constituent analyses and parameter measurements that exceeded water quality standards varied among sites (Fig. 2). The increasing frequency in the number of exceeded constituent analyses and parameter measurements from Site 1 to 4 appears to be related to increasing residential and industrial land use between the Rio Santa Catarina and the Rio San Juan. Site 5, located downstream of the confluence of the Rio San Juan and the Rio Ramos, implies a dilution effect. The Rio Ramos originates in the Sierra Madre Oriental mountain range and flows through several small villages, where dominant land use is agriculture and industrial activity is low, resulting in the dilution of pollutant concentrations at Sites 5 and 6. The frequency of constituent analysis and parameter measurements surpassing water quality standards increased downstream from Site 6 to 8. Site 8 was located immediately downstream from the confluence of the Rio Pilon and Rio San Juan. The Rio Pilon, like the Rio Ramos, drains through landscapes dominated by agriculture with sparse industrial activity in the basin. Land use activities associated with urban centers and industry along the major stem of the Rio San Juan are contributing to increased pollution at Sites 7 and 8. The Commission of the European Community (unpublished data, 1991) found that a few kilometers downstream of Site 8, streamflow samples met several water quality

standards, but suggested that construction of El Cuchillo reservoir (closed in 1993) could deteriorate streamwater quality, which appears to be confirmed by this analysis. Because the Rio Ramos and Rio Pilon tributaries dilute some of the contamination of the main stem of the Rio San Juan and land use affects water quality upstream from the confluence of major tributaries, it is likely that backwater is having a deleterious effect on stream water quality at Site 8 and possibly Site 7. The number of constituent analyses exceeding water quality standards generally increased from 77 in October 1995 to 144 in July 1996 (Fig. 3). However, monthly

Fig. 2. The number of water quality exceedances at sampling sites along the Rio San Juan and the Rio Santa Catarina in Nuevo Leon, Mexico in 1995 and 1996.

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variations in exceedances are evident. For example, samples collected in November 1995 and January 1996 recorded 114 and 75 element concentrations exceeding water quality standards, respectively. Considering the seasonality of streamflow and assuming a steady, constant reduction of discharge of wastewater effluent into the river, other point and nonpoint sources of contamination may be affecting the river at specific time intervals at specific locations. In total, 15 heavy metal constituents (Al, Sb, Ba, B, Cd, Cu, Cr, Sn, Fe, Li, Mg, Mn, Ni, Ag, and Zn) and 14 chemical constituents and physical parameters (alkalinity, chloride, sulfate, total hardness, phosphate, nitrite, dissolved oxygen, pH, dissolved solids, suspended solids, total solids, color, electrical conductivity, and turbidity) fit the Weibull distribution (p 0.05). This tendency partially explains the diffusion process of these constituents and parameters among sites and sampling events along the main stem of the Rio San Juan and the tributary Rio Santa Catarina. Using the Weibull distribution, the probability of exceedance for Al was 0.53 and 0.88 (official Mexican standards and the ecological criteria of the National Water Commission for protection of aquatic biota, respectively), Ba was 0.99 (ecological criteria of the National Water Commission for protection of aquatic biota), Cd was 0.56 (Mexican standards), Cr was 0.93 (ecological criteria of the National Water Commission for protection of aquatic biota), Mn was 0.73 and 0.84 (Mexican standards and the ecological criteria of the National Water Commission for livestock consumption, respectively), and Ni was 0.92 (ecological criteria of the National Water Commission for livestock consumption). Point-source pollution probably played an important role in contaminating the headwaters of the Rio San Juan at several locations and at several times throughout the sampling period, and because of the diffusion process, pollution was present downstream. Inputs of the remaining constituents and parameters that did not fit the Weibull distribution may be

more important at several locations along the river or at different times during the sampling period. The relation between concentration of constituents (Al, Ba, Cd, Cr, Fe, Mn, and Ni) and instantaneous monthly discharge did not show clear trends. Due to the severe drought that occurred during the period of study (only isolated, convective storms occurred at several locations in the watershed), instantaneous monthly discharge showed a consistent, logarithmic reduction in volume. Assuming a steady input of heavy metals and constituents into the river and given the reduction of discharge, we could expect an increase in constituent concentrations over time. However, some parameters (Al, Fe, Mn, turbidity, color, suspended solids, electrical conductivity, BOD, COD, ammonia, and sulfate) showed an increase in concentration as instantaneous monthly discharge diminished through time, while many others such as Ba, Cr, Cd, Ni, dissolved solids, total solids, phosphate, and oil showed an erratic behavior, with alternating peaks and valleys through the study period. This observation demonstrates the randomness of the point-source pollution phenomenon in this watershed. Iron and Mn showed consistent patterns of decay with increasing instantaneous monthly discharge, indicating the dilution effect of discharge and the steady input of these constituents into the river.

Mass Analysis
The results of the principal component analysis, PCA, conducted on the heavy metal mass fluxes indicated that the first two eigenvalues explained 93% of the total variation. A plot of the first two eigenvectors showed two different groups, characterized by the relative metal mass flux. Cluster 1 was characterized by Sites 2 and 3, and Cluster 2 by Sites 1, 4, 5, 6, 7, and 8 (Fig. 4). The first component appeared to distinguish sampling sites associated with the nature of local point-source pollution. The second component explained a small amount

Fig. 3. The number of water quality exceedances at monthly sampling sites along the Rio San Juan and the Rio Santa Catarina in Nuevo Leon, Mexico in 1995 and 1996.

Fig. 4. The results of the principal component analysis conducted on the heavy metal mass fluxes for eight sampling sites located in the Rio San Juan of Nuevo Leon, Mexico.

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Table 3. Results of a randomized block analysis of variance (ANOVA) design for constituent analysis between sampling sites (8) and sampling events (10) for the mass flux of 21 heavy metals in the Rio San Juan of Nuevo Leon, Mexico during 19951996.
Results of a randomized block ANOVA design Heavy metal Al Sb As Ba B Cd Ca Co Cu Cr Sn Fe Li Mg Mn Mo Ni Ag Pb Si Zn CV 161.25 110.77 783.85 91.69 75.09 90.85 95.94 118.68 130.76 87.31 91.53 224.43 89.51 109.03 160.40 96.12 96.52 151.58 257.13 121.92 315.94 Mean mg s 1 226.08 29.24 11.65 38.51 103.82 2.89 90 403.14 1.72 5.72 13.62 28.96 183.00 11.26 10 765.28 16.53 5.42 8.25 6.36 1.69 4 780.94 26.74 F 4.51 6.07 1.15 7.42 9.45 7.71 6.60 5.16 6.46 7.99 7.95 2.88 7.00 5.51 3.37 6.35 6.63 7.69 1.45 5.90 1.47 Model P F 0.0001 0.0001 0.3286 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0014 0.0001 0.0001 0.0003 0.0001 0.0001 0.0001 0.1466 0.0001 0.1417 Sampling sites (P F ) 0.1001 0.0055 0.4325 0.0023 0.0001 0.0010 0.0487 0.0079 0.1250 0.0027 0.0004 0.1924 0.0001 0.0024 0.1382 0.0038 0.0056 0.0309 0.2436 0.0264 0.4120 Sampling events (P F ) 0.0001 0.0001 0.2731 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0005 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.1546 0.0001 0.0865

of variation and could be related to nonpoint-source pollution. Clusters formed by the PCA analysis were partially confirmed by the ANOVA and Tukey tests, where Sites 1, 7, and 8, recorded the largest mean mass flux and Sites 2, 3, and 4 recorded the smallest mean mass flux (p 0.05). The Tukey test ranked Site 8 with the highest mean mass flux values for 14 out of 21 heavy metals. This site recorded the highest mean monthly discharge and the second-highest constituent concentration. However, Sites 5 and 6 had the smallest frequency of exceedances but they had one of the largest estimates of instantaneous monthly discharge in the study area. This information confirms the original dilution effect theory of the tributaries Rio Ramos and Rio Pilon. The ANOVA test indicated that only seven heavy metals (Al, As, Cu, Fe, Mn, Pb, and Zn) did not show statistical differences between sampling sites (p 0.05). Aluminum, Fe, and Mn frequently exceeded set standards indicating the widespread presence of these constituents along the Rio San Juan (Table 3). The 14 heavy metals that showed statistical differences between sampling sites rarely exceeded set standards, with the exception of Cd. The PCA for the temporal analysis of heavy metal mass flux also indicated that the first two eigenvalues explained most of the total variation (86%). Therefore, a graph of the first two eigenvectors showed a weak clustering but a strong tendency with October 1995 (T1) first and July 1996 (T10) last (Fig. 5). The first PCA divides sampling events into two different seasons in heavy metal mass flux. The wet season includes Sampling Events 1 to 5 and the dry season includes Sampling Events 6 to 10. Therefore, this component can be named the seasonal input of constituents. The second PCA appears to comprise the variation explained by changes in instantaneous monthly discharge associated with the within-season variations of constituents into the river.

The statistical test confirms that the total mass of heavy metals decreased from October 1995 to July 1996. The ANOVA and Tukey tests also showed that the highest constituent means of total mass fluxes corresponded to Dates 1, 2, 3, and 4 and the lowest to Dates 8, 9, and 10 for most heavy metals (p 0.05). The reduction was partially explained by the reduction of instantaneous average monthly discharge reported from October 1995 (2472.0 L s 1 ) to July 1996 (60.0 L s 1 ). The analysis of variance showed statistical differences among sampling events for Ag, B, Ba, Ca, Cd, Co, Cr, Li, Mg, Mo, Ni, Sb, Si, and Sn, confirming the pointsource pollution theory, where the seasonality of effluent discharge exceeded set standards. On the other hand, Al, Cu, Fe, and Mn only showed statistical differences among sampling events, emphasizing that only the

Fig. 5. The results of the principal component analysis conducted on the heavy metal mass fluxes for 10 sampling events observed in the Rio San Juan of Nuevo Leon, Mexico in 19951996.

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temporal discharge of effluents exceeded set standards. Finally, As, Pb, and Zn did not show statistical differences either among sites or sampling events (Table 3). A positive nonlinear relationship between total mass flux of heavy metals and average instantaneous monthly discharge was found for all monitoring sites (Fig. 6). The increase of average instantaneous monthly discharge immediately during or after the rainy season, combined with the increase in discharge from sewage effluent, wastewater, and other industrial sources into the Rio San Juan appears to be responsible for the increase in total mass of heavy metals transported by the river. Total mass of heavy metals increases steeply with small changes in the rivers average instantaneous monthly discharge. However, the relationship attained a steady state condition when average instantaneous monthly discharge was approximately 1000 L s 1. The total mass of heavy metals became limited when the average instantaneous monthly discharge of the river was larger than 1000 L s 1 (Fig. 6). The water quality in the Rio San Juan and the Rio Santa Catarina was assessed in this study by using two contrasting approaches: the analysis of concentrations and the analysis of total masses of pollutants. The concentration approach showed that during the dry season some constituents and parameters had large concentrations that exceeded standards, and consequently jeopardized the health of the rivers aquatic ecosystem. Using the total mass analysis approach the concentration of some constituents and parameters typically decreased considerably during the rainy season. However, the total mass of material transported is significantly greater during this period due to (i) the washing effect that rainfall has over the entire watershed, especially in densely populated areas and (ii) the increased input of sewage effluents, wastewater, and other industrial discharges. For example, the Al concentration reached its highest concentration mean value in July 1996 (2.356 mg L 1 ) and the mean mass flux was 96.5 mg s 1, whereas the mean

Fig. 6. Linear and nonlinear models for the total mass of 21 heavy metals for the sites and sampling events in the Rio San Juan of Nuevo Leon, Mexico in 1995 and 1996. TM, total mass; Sx, standard error.

concentration in October 1995 was 0.584 mg L 1 but the mean mass flux reached its maximum value of 1004.6 mg s 1. Consequently, an increased pollutant load was delivered to the El Cuchillo reservoir during the rainy season. Averaging the mass flux of all 80 samples for each heavy metal and using this value to calculate the total masses, it is possible to estimate the load of metals transported by the river in Mg yr 1. Estimated metal loads in the Rio San Juan were approximately 7.1 for Al, 1.2 for Ba, 0.09 for Cd, 0.4 for Cr, 5.8 for Fe, 0.5 for Mn, and 0.3 Mg yr 1 for Ni. Thus, a water quality concern persists throughout the year with high concentrations of some constituents during the dry season and high load input into El Cuchillo reservoir during the rainy season. The Rio San Juan watershed is located in an area prone to recurrent drought episodes of different magni tudes and time scales. Navar (1999a,b) observed that the 1950s, the early 1980s, and the 1990s were characterized by below-average monthly rainfall and discharge at several gauging and climatic stations along the Rio San Juan. Schmandt et al. (1998, 2000) concluded that the drought during the 1990s has not ended in the lower Rio Bravo watershed. In droughts, such as the present one, water supplies needed for irrigation of agriculture of the Rio San Juan watershed (170 000 ha) demanded 1680 Mm3 yr 1, in contrast to 1200 Mm3 yr 1 during normal years (Navar and Rodrguez, 2002). Future drought episodes will probably worsen the concentration of several constituents and parameters, deteriorating water quality and further impairing water availability in the Rio San Juan watershed. The population of the Monterrey metropolitan area (MMA) in 1995 was 3.8 million inhabitants (Navar, 1999a), who have used 201 Mm3 yr 1 of domestic water supply. Population in the MMA is expected to increase to 6.3 million by the year 2020 (Consejo Nacional de Poblacion, 1996), with demands for domestic water estimated at 374 Mm3 yr 1 by 2020 and 545 Mm3 yr 1 by 2045 (Navar, 1999a). De la Garza (1995) observed that 89% of discharges to the Rio San Juan by the 10 000 industries in the Rio San Juan watershed exceeded the standards. Therefore, degradation of water quality in the Rio San Juan watershed may involve two factors: (i) increasing water withdrawal demands to meet domestic and industrial water supplies and (ii) increasing loads of pollutants into the river. The aquatic communities of fish, insects, and other organisms are already under stress. It was observed, in this study, that many parameters exceeded the ecological criteria of the National Water Commission for protection of aquatic biota. For example, 72.5% of the samples had P levels that exceeded the ecological criteria of the National Water Commission for protection of aquatic biota. Brooks et al. (1992) pointed out that, if P is present in water, a concentration of 0.30 mg L 1 of nitrate is enough to cause an increase in algae growth; 64% of the samples exceeded this threshold value during 19951996. Therefore, the process of eutrophication can be expected to accelerate depleting dissolved oxygen concentrations in the river and promote changes in the

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aquatic biota. The biochemical oxygen demand exceeded the European Community standard for drinking water in 35% of the samples. The susceptibility of fish to damage by toxic substances (e.g., heavy metals) increases when the level of dissolved oxygen depletes (Brooks et al., 1992). Water temperature is another important factor controlling the oxygen solubility (McDonald et al., 1991). Temperatures as high as 35 C recorded in most sites in July 1996 during times of low discharge may reduce the availability of dissolved oxygen and impair stream suitability for native fish species. The alkalinity of the stream waters combined with sedimentation of heavy metals on the river bed or the bottom of the reservoirs under anaerobic conditions may cause these constituents to become soluble and reenter the water column. This effect can be enhanced with the presence of large runoff events that normally occur during the rainy season (August, September, and October) and release large amounts of heavy metals to the El Cuchillo reservoir. The long-term effect could be an increase in heavy metal mass and concentrations in the El Cuchillo reservoir. Villarreal (1983) pointed out that four fish species (Notropis stramineus, Notropis amabilis, Dionda episcopa, and Campostoma anomalum) had become extinct due to dramatic increases in the salinity and alkalinity of the river. Villarreal et al. (1986) and Obregon (1987) also reported the bioaccumulation of Zn and Fe in two fish species (Poecilia formosa and Cichalosoma cyanoguttatum) in the Rio Santa Catarina, and bioaccumulation of Pb, Fe, and Cu in four fish species (Astyanax mexicanus, Notropis braytoni, Notropis jemezanus, and Cichlasoma cianoguttatum). Guerra (2000) found evidence that the diversityabundance of the fish community is sensitive to pollution of the Rio San Juan of Nuevo Leon, Mexico. Therefore, the sustainable management of the water resources of the Rio San Juan watershed must further address the pollution issues as a primary approach to maintain healthy aquatic ecosystems for the well being of present and future societies.

ACKNOWLEDGMENTS We are deeply grateful to the Direccion General de Educacion Tecnologica Agropecuaria (DGETA) and the Consejo Nacional de Ciencia y Tecnologia (CONACYT) in Mexico City for the valuable support to develop this research. SIREYES and PAICYT partially funded this research through Grant Agreements no. 6033 and CN 323-00. The analyses of the physical, chemical, and bacteriological parameters were conducted within the water quality laboratory of the National Water Commission in Monterrey. The Department of Pharmacology of the Faculty of Medicine, University of Nuevo Leon, conducted the analyses of heavy metals. We thank Dr. Alfredo Pineiro Lopez for his financial help for conducting this study. We express our gratitude to many of the anonymous referees who greatly helped to improve the final text.

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CONCLUSIONS
This research illustrates the persistence of pollution problems within the Rio San Juan watershed, although the magnitude of these problems has been considerably diminished with the implementation of the sanitation program Plan Monterrey IV. At times of low discharge, the concentration of several heavy metals and chemical, bacteriological, and physical parameters exceeded set standards. At times of large discharges, the concentration of several constituents and parameters diminished, but total load input into the El Cuchilllo reservoir was magnified. Efforts must continue to diminish the pollution of the Rio San Juan, to protect aquatic ecosystems, to foster continued economic development, and to prepare for the recurrence of drought episodes. Integrated, multisectorial approaches are required to deal with the contamination problem and sustainable management of the stream waters of the Rio San Juan and its tributaries.

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