Spatial chemical variability of surface water in the Nhecolândia, Pantanal (MS), Brazil. Elisângela Rosemeri Curti Martins1, Sônia Maria Furian Dias2, Laurent Barbiero3, Tatiana Mascari Parizzoto4, Ary Tavares Rezende Filho5. Doutoranda do Depto. Geografia Física/FFLCH/USP, Bolsista CNPq, elismartiss@yahoo.com.br 2 Profª Drª Depto Geografia Física/FFLCH/USP, furian@usp.br 3 Prof. Dr. IRD-França/CENA/USP (Lab. de Ecologia Ambiental e Geoprocessamento), barbiero@lmtg.obs-mip.fr 4 Mestranda do Depto. Geografia Física/FFLCH/USP – Bolsista Fapesp - tatiparizotto@hotmail.com 5 Prof. MSc. Depto de Geografia UFMS – CPNA/Campus Nova Andradina/MS, ary.rezende@gmail.com This research was supported by FAPESP N° 2008/09086-7 and 2009/53524-1 Summary The upper Paraguay River basin belongs to the second biggest hydrographic system of South America, i.e. the Platino System. It shows a huge alluvial plain, called “Pantanal of Mato-Grosso”, which is considered the largest tropical wetland of the planet. The Nhecolândia, a sub region of the Pantanal located south of the Taquari River, presents an extremely complex sub-surface draining system. Its landscape consists of thousands of saline or freshwater lakes and ponds, co-existing in close proximity, and is crossed by draining fields active during the floods of the wet season. The saline lakes are usually isolated from the draining fields system by forested sandy banks, locally called ‘cordilheiras’, and therefore without apparent connection with the flooding waters. Most authors considered the presence of salt in these lakes as a heritage of a former accumulation process during the arid phases of the Pleistocene. However, recent hydrological studies carried out on these lakes suggest that the salinity results from present day evaporation process of the regional waters. Very few works were dedicated to the spatial distribution of salinity, whose organization, at regional scale, could help to understand the origins of salinity and the processes that control it as well. The objective of this paper is twofold: first it aims at analyzing, at a regional scales, the spatial distribution of surface waters salinity through the study of two variables the electrical conductivity (EC) and the pH. Second, at a local scale, it aims to describe the organization of the soil cover through non destructive electromagnetic inductions methods (Apparent Electrical Conductivity, ECa) in order to better understand the dynamic of the water. The regional study of EC and pH of surface waters revealed four fundamental points: 1. the existence of very wide conductivity and pH range; 2. a correlation between pH and EC of water; 3. a low range (<200m) for the spatial distribution of these variables; 4. a bimodal distribution of the variables pH and EC along their range. To this information provided by the study at a regional scale, we must add a standard distribution of ECa values around the lakes reflecting a standard and singular morphology in the soil cover and showing that the lakes are surrounded by sub-surface rises of soil horizons with low permeability, working as a threshold and governing the flow of water. At the beginning of the wet season, accumulation of rainfall in the Pantanal causes a rise in the water level. When it exceeds the morphological threshold, it flows down toward the depressions of the lakes (Fig. X). The average quantity of water Q flowing annually towards the lakes depends on the relative level of the threshold with respect to the regional fresh watertable. Q is decreasing with increasing high of the threshold. Two cases may occur: if Q+P<ETP, then the lake salinity increases every year. Otherwise, if Q+P>ETP, then the lake is flushed every year and the salinity is maintained at a low level. The above-described hydrological regime explains how lakes subjected to the same amount of evaporation and rainfall can have different dissolved ion concentrations. Because it is a cumulative process, it explains the large range of salinity observed in the region. It also explains the bimodal distribution of the electrical conductivity observed on a large number of about 80 lakes. Because a single type of water, evolving in an alkaline pathway, is subjected to concentration and dilution, it explains the good relationship observed between pH and EC. The very local control of the salinity is in agreement with the low spatial range for pH and EC (<200m) observed with the geostatistical treatement. The complementary data acquired at different scales, with appropriate statistical and geostatistical treatments, allow to generalize an hydrochemical functioning described on only one lake in the region, to the entire Nhecolândia. Keywords: drains, lakes, space distribution, salinity, electrical conductivity, pH. Introduction The common feature of wetlands is the presence of physical, chemical, geochemical and biological characteristics reflecting the type of flooding or moisture that they are submitted, including the presence of redoxymorphic soils and hydrophilic vegetation. These landscapes fall into the category of ‘interface systems’ or ‘intermediate’ as they are distinct from both the terrestrial and aquatic ecosystems (Fustec & Lefeuvre 2000; Barbiero et al. 2002; 2007; 2008; Reddy & Delaune 2008). The management of water resources in these areas is complex and requires studies to support geotechnical appropriate procedures. Therefore, wetlands have attracted a great international scientific interest. Given these specificities of wetlands, and the number of factors that affect the water chemistry, it is difficult to assess which factor is predominant in the variability of these environments. Studies conducted in the Pantanal, in particular in the sub-region of the Nhecolândia showed that the main axis of variability is the water salinity. The salinity of the many ponds and lakes has always been attributed to former salt accumulations inherited from dry periods during the Pleistocene (Ab'Saber, 1988; Klammer, 1982; Tricart, 1982), but recent studies have shown that it is the result of current processes of water concentration by evaporation (Barbiero et al., 2002). Both the saline and freshwater lakes have different water regimes, since they are largely controlled by the surrounding soil organization at different stages in a fast dynamic of formation and destruction (Rezende Filho, 2006 , Barbiero et al., 2008). The objective of this study is to analyze both the spatial distribution of salinity of surface waters at a regional scale and the organization of soil system at a local scale, in order to determine whether they present a regular distribution patterns in the landscape of the Nhecolândia. Material and methods The study area is located in the Upper Paraguay Basin, western-central Brazil. From a morphological point of view, the basin consists of three macro-physiographic features: plateaus, depressions, and the plain of the pantanal, with temporary or permanently flooded area (Alvarenga et al., 1984; ANA, 2004; Ab'Saber, 2006). The Nhecolândia, one of the largest sub-region of the Pantanal, corresponds to the southern part of the Taquari alluvial fan (Figure 1). It is delimited in the north by the river Taquari, in the south by the river Negro, in the west by a portion of the Paraguay River, and in the east by the escarpment of Maracaju plateau. A peculiarity of the Nhecolândia is the presence of about 12000 lakes and ponds. Saline and non-saline waterbodies coexist in the landscape sometimes at a short distance from each other (200 m). They are usually separated by forested ridges called ‘cordilheiras’. The lanscapes is crossed by ‘vazantes’ acting as draining fields during the floods. These ponds and lakes can be permanent or temporary, depending on the frequency and intensity of the floods. Figure 1. Location of the Nhecolândia region in the Pantanal wetland. The grey circle denotes the studied area, north of the Negro River. Two variables, the electrical conductivity (EC) and pH were analyzed in a set of 80 lakes and ponds, to understand the spatial distribution of salinity at a regional scale. Measurements were performed directly in the field using of a conductivity meter (HI 9838), and a pH meter (HI 95143). The points of measurement were georeferenced in UTM coordinates (Universal Transverse Mercator). The organization of the soil cover has been studied around 4 lakes selected to cover a wide range of electrical conductivity of the waters. Direct observations (auger holes and excavated pits) were associated with geophysical surveys by low frequency electromagnetic induction. Two devices were used EM38-MK2 and EM31-MK2 (Geonics Ltd., Ontario, Canada). Both devices have a different spacing between the transmitter and receiver coils (1m for the EM38 and 3.66m for the EM31) and a different induction frequency (14.6kHz for the EM38 and 9.8kHz for the EM31). This gives to each device a different depth of investigation that is about 2 m for the EM38 and 6 m for the EM31, when used in vertical position. A maximum spacing of 10 m was maintained between two successive measurement points. Statistical and geostatistical treatments were performed on the raw data (EC, pH and ECa) including, an analysis of the distribution of the variables and of the experimental variogram, and an adjustment of a theoretical model by the least squares method, then kriging and mapping. Results The EC values range from 42 to 24350 µS/cm and pH from 5.9 to 9.95. These large ranges of pH and EC reflect highly contrasted environments. The distributions of the EC and pH are shown in the histograms in Figure 2b and 2c. Figure 2. Histograms showing the distribution of: a – EC; b - Log10(EC) and c - pH. The histogram of the variable EC (Figure 2a) shows a distribution shifted towards the lowest class of conductivity (0-2500 µS/cm), which included about 70% of the samples. This kind of distribution is far from a normal distribution and cannot be used directly to study the spatial distribution. A logarithmic transformation (Figure 2b) allows to better apportion the data along the EC range. Therefore, the variable log10(EC) will be studied in the following. This variable log10(EC) shows a bimodal distribution, with a first mode focused on the value 2.6 (~ EC 400 µS/cm) and a second lower mode on the value 4 (EC ~ 10000 µS/cm). There is therefore a deficit of surface water with EC values close to 1250 µS/cm. The pH values are relatively well distributed along the range. Therefore, the raw pH data were directly used in spatial analysis. This histogram has also bimodal feature, with the first mode from 6 to 8, involving 26 measurement points, and the second one from 8 to 10, obtained on 24 waterbodies. Descriptive statistics performed from the data set, Log10(EC) and pH are presented in Table 1. The coefficient of variation of these logarithmic variables, reflecting the great heterogeneity. Table 1. Descriptve statistics obtained from Log10(CE) e pH values. The experimental semivariograms for log10(EC) and pH values are presented on Figure 3. Both are characterized by a very short range, less than 200m, indicating that the maximum of variability is reached for small distances in the landscape. pH Electrical Condutivity (EC) 30000000 1.8 1.6 25000000 1.4 1.2 Variogram Variogram 20000000 15000000 10000000 1 0.8 0.6 0.4 5000000 0.2 0 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 Distance 0 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 Distance Figure 3. Semivariograms of Log10(EC) and pH showing the low spatial range below 200 m. Indeed, in the field we observed that the lakes and ponds have very contrasting salinity, although they are located very close to each other. The results emphasizes that there is no dependence between the waterbodies for the studied variables in the Nhecolândia. Figure 4 shows an example of distribution of ECa values obtained with the EM38 around the ‘Salina Verde’ lake. The ECa values range from 50 to 220 mS/s. The distribution is unimodal, centered in a mode of about 120 mS/m. This kind of distribution approximates a normal distribution, and can be directly used to study the spatial distribution. Figure 4. Frequency histogram of ECa values obtained around ‘Salina Verde’ lake. The experimental variogram has a range of about 60 m without nugget effect (Figure 5). The sill is approximately 1000. This variogram shows that the minimal distance of 10 meters between successive measurement points is sufficient to evaluate the spatial variability of the variable ECa. The experimental variogram was better fitted with an exponential model. Experimental Variogram 1000 900 800 Variogram 700 600 500 400 300 200 100 0 0 20 40 60 80 100 120 140 160 180 200 220 240 Distance Figure 5. Experimental variograma of ECa data (EM38 in vertical position) and adjusted model for the soil cover around ‘Salina Verde’. 7847000 220 a 200 7846900 180 b d 160 140 c 7846800 120 mS/m 100 7846700 80 60 7846600 40 20 7846500 7846400 598800 598900 599000 599100 599200 599300 Figure 6. Distribution map for ECa values around ‘Salina Verde’. The maps produced by electromagnetic induction show similar structures around all the lakes, which can be illustrated on the example of ‘Salina Verde’ (Figure 6) and ‘Salina 60mil’ (Figure 7). Immediately around the lakes, there are high ECa values (140-190 mS/m) that reflect to the presence of a clay horizon at topsoil, with a maximum thickness of 0.3m (a). Further outside, there is a continuous ring-shaped structure (b) with values in the range of 100-140 mS/m. Auger surveys show that this ringshaped structure corresponds to a rise, in sub-surface, of a sandy clay green horizon, very consistent and locally cemented. Just behind, there are discontinuous areas (c) with higher ECa values (in the range of 180-220 mS/m) corresponding to the presence of highly saline water (15000 to 80000 µS/cm) at approximately 1 m deep. Further away from the saline lake, ECa values decrease (d) due to the topographic elevation associated with the thickening of the sandy surface horizon, which becomes more than 2 m thick. The ECa variations result from deep changes in the soil, which are not anymore detectable with the EM38 device. In contrast, the EM31 detects a decrease in ECa values, then a slight increase at about 60-100m from the lake shore (arrow on Figure 7), before a further decline. Direct auger observations show that the increased in ECa again corresponds to a rise in the sandy clay consistent green material, generally approaching 2 m from the soil surface. Figure 7: Oblique view of ECa distribution around ‘Salina 60 mil’ using EM31 in vertical position. Discussion The regional study of the electrical conductivity of surface waters revealed four fundamental points: 1. the existence of a very high conductivity range, while the climatic conditions (ETP-P ± 300 mm) do not favor a salinization by evaporation, neither to preserve the salinity in the landscape; 2. a correlation between pH and EC of water; 3. a low range (<200m) for the spatial distribution of log10(EC); 4. a bimodal distribution of log10(EC) and pH values. To this information provided by the study at a regional scale, we must add a standard distribution of ECa values around the lakes reflecting a standard morphology in the soil cover. These points will be discussed below. The identification of high EC and pH ranges in surface waters of the Nhecolândia have already been mentioned in previous studies, and it can be regarded as a peculiarity of this region (Barbiero et al. 2002; Fernandez, 2007, Mariot et al., 2007, Barbiero et al., 2008, Furquim et al., 2008, 2010 b). The current climate conditions, with mean annual precipitation of about 1100 mm and mean evaporation of about 1300 mm, are not favorable to the accumulation or maintenance of salinity. In this context, the high range in the surface water EC and pH may reflect two characteristics of the process responsible for this range: 1. this can be a very powerful process, such as the presence of a stock of salt accumulated during earlier arid phases, and that would still mark locally the water chemistry; 2. It can also be a system of accumulation of dissolved elements, cumulative from year to year, leading to saline waters isolated from the current transfers of fresh water across the Pantanal, and thus protected from a desalination by the circulating water. The correlation between pH and EC is also consistent with previous work (Barbiero et al., 2002, 2007, 2008) carried out at a local scale or on a reduced number of samples. In the region, the waters may result from each other by simple process of concentration and dilution. They evolve in a sodic alkaline pathway, and the concentration is then accompanied by an increase in the pH that can reach quite rapidly values close to 10. This good correlation between pH and EC indicates that the chemistry is framed in a unique chemical regional pattern that is relatively well known. The short range in the distribution of conductivity values of surface waters shows that there is no possible extrapolation of EC beyond the same lake, the value of 200 m corresponding approximately to the minimum distance between two neighbouring lakes. We can therefore conclude that the process that controls the chemical characteristics of surface waters acts in the soil cover between two neighbouring lakes. The bimodal distribution of salinity provides additional information. It shows that the process that controls the concentration of lake water either guides the water towards high salinity, or conversely towards dilute water, more in line with the waters that flow regionally in the landscape. The soil mantle as evidenced by the ECa survey shows that the lakes are surrounded by subsurface rises of soil horizons with low permeability. Such morphology of the soil cover is in every respect similar to what has been described in other parts of the Nhecolândia by Sakamoto (1997). This soil system is therefore representative of the region. The concordance between these ring-shaped structures and the presence of lakes, and the mineralogical composition of their clay fraction, emphasize a chemical sedimentation, probably induced by the concentration of the solutions. The genesis of these concentric structures was discussed by Barbiero et al. (2008). The information collected at both the regional and the local scale is in agreement with the singular limnological functioning described below. At the beginning of the wet season, accumulation of rainfall in the Pantanal causes a rise in the water level. When it exceeds the morphological threshold, it flows down toward the depressions of the lakes (Figure 8). Conversely, during the dry season, saline and fresh watertables are disconnected and the threshold acts as a barrier against the backward propagation of saline water toward the fresh sandy aquifer. Figura 8. Model of hydrochemical functioning of a saline lake during the flood (1) and during the dry season (2), modified from Barbiero et al. (2008). In summary, the salinity in the lakes depends on the average quantity of water Q flowing annually towards the lakes, which in its turn depends on the relative height of the threshold with respect to the regional fresh watertable (Figure 9). Q is decreasing with increasing height of the threshold. Two cases may occur: if Q<ETP-P, then the lake salinity increases every year leading to a saline environment. Otherwise, if the threshold is low, it is easily exceeded by the watertable and then we have Q>ETP-P. The lake is flushed every year and the salinity is maintained at a low level. Figure 9. Influence of the height of the morphological threshold on the hydrological regime of lakes in the Nhecolândia: 1: the high level of the threshold leads to Q<ETP-P; 2: the low level of the threshold leads to Q>ETP-P. The above-described limnological regime explains how lakes subjected to the same amount of evaporation and rainfall can have different dissolved ion concentrations. Because it is a cumulative process, it explains the large range of salinity observed in the region. It also explains the bimodal distribution of the electrical conductivity observed on a total number of about 80 lakes. Because a single type of water, evolving in an alkaline pathway, is subjected to concentration and dilution, it explains the good relationship observed between pH and EC. The very local control of the salinity by the presence of threshold between the lakes is in agreement with the low spatial range for EC (<200m) observed on the variogram (Figure 3). Conclusion The objective of this study was to understand the distribution of the salinity, a major aspect in the variability of surface waters in the Nhecolândia. Through an appropriate statistical and geostatistical treatment, the data collected show that there is no organization of the salinity at the regional scale. In contrast, the low spatial range measured indicates that the salinity is controlled locally by the presence of thresholds governing the hydrological regime of each lake. These thresholds were here identified by geophysical surveys using electromagnetic induction methods. 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