LEACHING NITRATE AND ATRAZINE ON THE RECLAMATION TEST FIELD OF DIFFERENT DRAINPIPE SPACING I. SIMUNIC*, F. TOMIC, T. KRICKA University of Zagreb, Faculty of Agriculture, Svetosimunska 25, 10000 Zagreb, Croatia E-mail: simunic@agr.hr Abstract. The research was conduced on the Jelenščak reclamation test field in Croatia, on hydroameliorated Gleyic Podzoluvisol during five years. The basic aim of this research is to determine leaching of nitrate and atrazine in drainage water in four different drainpipe specing (15 m, 20 m, 25 m and 30 m). Maize was grown as the trial crop and the same agricultural practices were applied in all drainpipe specings in all trial years. Drainage discharge was measured continually by means of automatic elektronic ganges – limnimeters, which were set up in each variant, at the drainpipe autlet into the open canal. Drainage water was sampled every day during the discharg period. Nitrates were determined by the yellow colouring of phenol disulphonic acid: Atrazine extracted from the samples of drainage waters was determinated by gas chromatography. Data were statistically processed by means of analysis of variance. Quantity of nitrogen leached were different from year to year and carrespond to total nitrogen added with fertilization and amont of annual precipitation. The concentrations of the atrazine recorded in drainage waters varied in a wide range, with maximum values recorded soon after its application and at the start of higher drainage discharge. The results indicate that concentrations of nitrate and atrazine drainage waters exceeded the allowable values in the larger part of the year in all drainpipe spacing. There were no statistically significant differences between the tested drainage systems in drainage water contamination with nitrate and atrazine. Keywords: drainage water, maize, leaching, nitrate, atrazine. AIMS AND BACKGROUND In various soil-plant systems, pollutants may constitute a potential risk to the environment through their uptake by plants and subsequent input into the food chain, and the danger ensuing from their tendency to accumulate in vital organs of humans, animals and plants, or because of possible contamination of drinking water. The World Health Organization recommended that drinking water should contain less than 10 mg L-1 NO3-N and 0,100 µg L-1 atrazine1. Pollution of water by nitrates pesticides is an international problem2-5. Excessive nitrate concentration in water may lead to eutrophication of watercourses or stock watering. If such water is used for human consumption, it may cause methemoglobinemia in infants and animals6,7. Potential cancer risk from nitrate-N (and nitrite) and atrazine in water and food has been reported 8,9. Leaching of nitrates and atrazine from soil depends on the amount, frequency and intensity of precipitation, soil properties, crop and crop development stage, evaporation, soil tillage practices, nitrogen fertilization and application of herbicide10. The problem of nitrate leaching and atrazine leaching are even more expressed in agroecosystems of hydroameliorated, especially drained soils because of changed infiltration and filtration capabilities of these soils. Total hydroameliorated areas cover 600,054 ha in Croatia, including 117,865 ha of the pipe drainage system area. Different drainpipe spacing and different nitrogen fertilization and application of herbicide levels significantly influence soil productivity in the experimental area 11,12, but different drainpipe spacings with different agricultural practices and application of mineral fertilizers and herbicide may influence contamination of drainage water 13,14. 1 The main goal of this research was: to determine the quantity of nitrate leaching and atrazine leaching in drainage water in four different drainpipe spacing. EXPERIMENTAL Trials were carried out at the experimental amelioration field located in Jelenscak near Popovaca, on soil type defined as Gleyic Podzoluvisol. The trial involved four different drainpipe spacing variants (15 m, 20 m, 25 m and 30 m), set up in four replications. All variants were combined with gravel as contact material (ø 5-25 mm) in the drainage ditch above the pipe. Drainpipe characteristics were: length 95 m, diameter 65 mm, average slope 3‰ and average depth 1 m. Drainpipes discharged directly into open canals. Variants covered areas of 1425 m2, 1900 m2, 2375 m2 and 2850 m2, respectively. Plastic (PVC)-annular-ribbed and perforated pipes were used. Maize was grown as the trial crop and the same agricultural practices were applied in all drainpipe spacing variants during the five trial years (1991, 1993, 1996, 1999 and 2002). Sowing was done in May and harvest took place in October. All measurements were taken from May to April of the following year because soybean was planted as the next crop in rotation in May. Total nitrogen fertilization was: 175 kg/ha/year, 145 kg/ha/year, 145 kg/ha/year, 155 kg/ha/year and 164 kg/ha/year. Weed control involved application of herbicide Primextra 500, based on active substance-atrazine 20%+metolachlor 30%. Drainage discharge was measured continually by means of automatic electronic gauges-limnimeters, which were set up in each variant at the drainpipe outlet into the open canal. Drainage water was sampled every day during the discharge period. Nitrates were determined by the yellow colouring of phenol disulphonic acid and atrazine by gas chromatography. Total annual quantities of nitrogen and atrazine leached were estimated on the basis of the average monthly concentration and monthly quantity of drainage discharge. Data were statistically processed by means of the analysis of variance (ANOVA). RESULTS AND DISCUSSION The trial soil type is found in the Sava river valley at the altitude of 96.4 m a.s.l.. Average groundwater table depth is 1.15 m with strong fluctuations influenced by precipitation and drainage. Major soil properties are summarized in Table 1. According to the mechanical composition of the arable layer, the soil is silty clay. Soil swelling and shrinking properties were determined by the percentage and type of clay minerals in soil, along with humus content. When dry, the soil has a high proportion of large blocky aggregates, cracks are large and precipitation can easily percolate through the soil. When the soil is wet, clay particles swell and water retention is very low. Table 1. Major properties of drained Gleyic Podzoluvisol Profile Depth, cm Ap 0-35 Bt,g 35-75 Gso 75-115 Content of Porosity, Capacity, Bulk density, Permeability, pH particles, % % kg/dm3 m/day KCl % Silt Clay Water Air 47 46 48 44 4 1.35 0.011 5.3 45 48 49 45 4 0.011 5.2 55 39 46 42 4 0.011 7.1 2 Monthly precipitation values and the corresponding total values (i.e., sum of monthly precipitation values for the whole examined period) representative of the experimental station are presented in Table 2. According to analyses of total precipitation values and total drainage discharge values for different drainpipe spacings (Table 3), it may be concluded that differences are noticeable in the quantity and duration of drainage discharge, both between the tested drainpipe spacings in each growing season and between the trial years. Differences in the quantity of drainage discharge between drainpipe spacings in a particular year are small, but differences between years are evident. Correlation coefficients between precipitation and drainage discharge for different drainpipe spacings during the examined period are shown in Figure 1. It can be seen that there is strong correlation between precipitation and drainage discharge and a small difference between drainpipe spacings (r=0.79 up to 0.85). Duration of drainage discharge in each year increases with the width of drainpipe spacing. On the basis of ANOVA there are no statistically significant differences between drainage discharge and duration of drainage discharge at any drainpipe spacing in any trial year. Narrower drainpipe spacing and shorter duration of drainage discharge are more efficient15. There may be several reasons for these differences, primarily total precipitation amounts and their distribution, different efficiency of each particular drainpipe spacing and agricultural practices applied to maize grown during the trial period. Table 2. Monthly precipitation values and the corresponding total values (mm) Year 1991/92 1993/94 1996/97 1999/00 2002/03 V 156 44 71 107 183 VI 20 134 31 89 56 VII 160 30 90 86 130 VIII 52 119 83 66 99 IX 50 90 190 95 133 X 152 107 46 72 73 XI 108 165 135 92 113 XII 21 112 79 104 54 I 15 50 44 29 71 II 45 58 55 37 21 III 78 37 26 63 5 IV 59 79 45 77 30 Σ 916 1025 895 917 968 3 Table 3. Quantities of drainage discharge (mm) and total duration of drainage discharge (days) Drainpipe spacing (m) 15 20 25 30 15 20 25 30 15 20 25 30 15 20 25 30 15 20 25 30 Year Precipitation (mm) 1991/92 916 1993/94 1025 1996/97 895 1999/00 917 2002/03 968 Drainage discharge mm % of precipitation 228 24.9 219 23.9 213 23.3 229 25.0 266 26.0 271 26.4 268 26.1 277 27.0 198 22.1 198 22.1 203 22.7 199 22.2 174 19.0 175 19.1 166 18.1 171 18.6 273 28.2 270 27.9 277 28.6 285 29.4 Correlation between precipitation and drainage discharge Correlation coefficient 1 0,8 0,6 0,4 0,2 0 15 20 25 30 Drainpipe spacings (m) Fig. 1. Correlation between precipitation and drainage discharge Concentration of nitrogen Maximum nitrogen concentrations in all drainpipe spacing variants during the trial period exceeded the concentration of 10 mg/L (Table 4). Average values of nitrogen concentration in four years were in all drainpipe spacing variants above the allowable concentration, as well as in the year 1999/2000. Higher maximum (and also average) concentration was recorded in years with higher drainage discharge and higher rates of nitrogen fertilization (1991/92, 1993/04 and 2002/03). 4 Table 4. Average and maximum concentration of nitrogen (mg.dm-3) in drainage water Spacing variants (m) 15 20 25 30 1991/92 1993/94 1996/97 1999/00 2002/03 X Max X Max X Max X Max X Max 16.25 13.95 15.67 15.26 32.82 30.93 31.67 30.63 12.90 12.22 12.88 11.95 29.15 29.03 29.13 29.07 10.21 10.36 10.58 10.51 20.05 20.81 20.34 19.91 9.51 8.99 9.54 9.47 18.15 19.24 20.21 18.43 17.37 17.70 17.81 17.82 34.32 33.19 34.71 33.58 It can be seen (Figure 2) for drainpipe spacing of 15 m, that maximum nitrogen concentrations in all years were determined either in spring or in summer, soon after sowing and topdressing, which generally coincided with precipitation maxima (i.e., after higher drainage discharge). Similar results for nitrogen concentrations in drainage water were obtained 11,16,17. The foregoing points to the conclusion that drainage water exceeded the maximum allowable concentration of nitrates in one part of the year, that is, for up to seven months. Fluctuation of NO3-N concentrations in drainage water 35 NO3-N (mg dm-3) 30 25 20 15 10 MDK 1993 1997 1996 2000 2002 Years april march january february november december september july august may june april march january february november october 1999 december june september april march january february december october november april 1994 september march august january february december october november september may 1992 june april march january 1991 february november december july october 0 may 5 2003 MDK = maximum allowable concentrations Fig. 2. Fluctuation of nitrogen concentration in drainage water Leaching of nitrate According to analyses of total annual quantity of nitrogen leached through drainage water (Table 5), it may be concluded that differences are certain, both between the tested drainpipe spacings in each year and between trial years. Differences in the quantity of nitrogen leached between drainpipe spacings in a particular year are small, but there are greater differences between years. Table 5. Quantity of nitrogen leached through drainage water (kg.ha-1) and percentage of nitrogen leached relative to the total N added with fertilization Spacing variants (m) 15 20 25 30 1991/92 1993/94 1996/97 1999/00 2002/03 Kg/ha % Kg/ha % Kg/ha % Kg/ha % Kg/ha % 35.7 30.7 33.9 34.9 20.4 17.5 19.4 19.9 34.4 33.2 34.6 33.2 23.7 22.9 23.9 22.9 20.3 20.6 21.5 21.0 14.0 14.2 14.8 14.5 16.6 15.8 15.9 16.2 10.7 10.2 10.3 10.5 47.2 48.4 49.4 50.8 28.7 29.5 30.1 31.0 5 Lower nitrogen leaching was recorded in all drainpipe spacing variants in the periods 1996/97 and 1999/00, when the lowest drainage discharge and lower quantity of nitrogen added with fertilization were recorded. Higher leaching occurred in the years 1991/92, 1993/94 and 2002/03 (either a larger amount of nitrogen added with fertilization or higher drainage discharge). The quantity of nitrogen leached is in linear correlation with the quantity of drainage discharge12. Different quantities of leached nitrogen are influenced by climate conditions, namely the amount and distribution of precipitation (drainage discharge), crops grown, that is, their development stages, as well as by the agricultural practices and the time of their application. Concentration of atrazine It can be seen from Table 6 that different maximum and average values were determined for atrazine concentrations in drainage water, both in trial years and at different drainpipe spacings. This was influenced by the date of atrazine application, quantity and distribution of rainfall, that is, the quantity of drainage discharge, and efficiency of each particular pipe drainage system. Maximum atrazine concentrations in drainage water were recorded soon after its application and at the start of higher drainage discharge (May 1991, June 1993, 1999 and September 1996); they decreased in all years with later drainage discharge. Namely, atrazine is highly water-soluble and it is readily transported with water and degraded in soil. Table 6. Average and maximum concentrations of atrazine (μg.dm-3) in drainage water, per variants Spacing variants (m) 15 20 25 30 1991/92 1993/94 1996/97 1999/00 2002/03 X Max X Max X Max X Max X Max 1.75 1.79 1.84 1.73 7.23 7.46 7.58 7.15 1.55 1.71 1.89 1.57 6.87 6.20 6.31 6.16 0.94 0.86 0.84 0.93 2.88 2.32 2.95 2.99 1.15 1.31 1.29 1.34 5.05 5.70 5.84 5.80 1.91 1.89 1.85 1.87 7.30 7.15 7.22 7.28 It can be seen (Figure 3) for drainpipe spacing of 15 m, that maximum atrazine concentrations in all years were determined either in spring or in summer, soon after sowing and topdressing, which generally coincided with precipitation maxima (i.e., after higher drainage discharge). Results on the contamination of drainage water with atrazine, in dependence on different drainpipe spacing, are in agreement with the results18. These authors point to the fact that the quantity of atrazine leached in these parts is strongly influenced by the distribution of precipitation (drainage discharge), time of herbicide application, their quantities added, and the phenological stage of maize. In the case of the mentioned atrazine rate (1200 g/ha) applied to hydroameliorated soil and the recorded quantities of precipitation drainage discharge, atrazine concentrations were higher than the tolerated limit in 10 months in all years. 6 1991 1994 2000 Years 2002 april march january february november december september july august may june april march january february december october 1999 november june april 1997 september march january february october november 1996 december september april august march january february december october 1993 november september may 1992 june april march january february december july november MDK may 8 7,5 7 6,5 6 5,5 5 4,5 4 3,5 3 2,5 2 1,5 1 0,5 0 october Atrazine (μg dm-3) Fluctuation of atrazine concentrations in drainage water 2003 MDK = maximum allowable concentrations Fig. 3. Fluctuation of atrazine concentration in drainage water Leaching of atrazine Table 7. Quantity of atrazine leached through drainage water (g.ha-1) and percentage of atrazine leached relative to the total quantity added with aplication Spacing variants (m) 15 20 25 30 1991/92 -1 g.ha 3.99 3.92 3.92 3.96 % 0.33 0.33 0.33 0.33 1993/94 -1 g.ha 4.12 4.63 5.07 4.35 % 0.34 0.39 0.42 0.36 1996/97 -1 g.ha 1.86 1.98 1.71 1.85 % 0.16 0.17 0.14 0.15 1999/00 -1 g.ha 2.00 2.29 2.14 2.29 % 0.17 0.19 0.18 0.19 2002/03 g.ha-1 5.21 5.10 5.12 5.33 % 0.43 0.43 0.43 0.44 Atrazine was mostly lost during the growing season. Larger quantity of total atrazine leached was recorded in the first two years (higher total drainage discharge and higher concentrations) and vice verse. Atrazine losses ranged from 0.14% to 0.44%. Different quantities of leached atrazine with respect to soil texture (0.54% in clay, 0.66% in loam and 0.47% in silt-loam)19 and about 0.61% atrazine losses in silty loam 18 . 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