1 Sulphate leaching in an organic crop rotation on sandy soil in Denmark 2 3 J. Eriksen*, M. Askegaard 4 5 Department of Crop Physiology and Soil Science, Danish Institute of Agricultural 6 Sciences, PO Box 50, DK-8830 Tjele, Denmark. 7 8 9 * Corresponding author. Tel: +45 89 99 18 70; Fax: +45 89 99 17 19; E-mail: Jorgen.Eriksen@agrsci.dk 10 11 Abstract 12 13 Sulphate leaching losses may reduce the long-term possibility of maintaining the S 14 supply of crops in low input farming systems. Sulphate leaching and S balances were 15 investigated in an organic dairy/crop rotation (barley [Hordeum vulgare] grass-clover 16 [Lolium perenne/Trifolium repens] grass-clover barley/pea [Pisum arvénse] 17 winter wheat [Tritucum aestivum] fodder beet [Beta vulgaris]) from 1994 until 1998. 18 The importance of climatic conditions and use of different organic manure types at 19 different application rates for sulphate leaching were investigated and related to the 20 concurrent nitrate leaching. As an average of years, sulphate leaching from the crop 21 rotation was 20 kg S ha-1, which was equivalent to 60% of the total input to the rotation. 22 Sulphate leaching was very variable over the years (4-45 kg S ha-1 for the same crop) 23 and closely related to the annual drainage volume (r2=0.99; P<0.01). The same 24 relationship between drainage and nitrate leaching was not significant. No differences 25 were observed in sulphate leaching between the organic manure types or the application 26 rates, but significant differences were found in sulphate leaching between the different 27 crops in the rotation. In the year with the largest drainage volume, there was a 28 significant correlation between the S input in irrigation and sulphate leaching (r2=0.69; 29 P<0.05). The S balance was slightly positive when averaged over the four years, as 30 more S was imported than removed. Thus, immediate S deficiency may not occur, but 31 in the longer term a negative S balance must be expected in this crop rotation. However, 32 even with a positive overall S balance, the S input is not necessarily synchronised with 1 1 plant needs. In order to maintain a sufficient S supply in the future when further 2 reductions in the atmospheric deposition are expected, it is important to reduce leaching 3 losses of sulphate. 4 5 Keywords: Leaching; Nitrate; Organic farming; Sulphate; Sulphur balances 6 7 8 1. Introduction 9 10 During the last decade sulphur (S) deficiency has become widespread in Northern 11 Europe. This is mainly caused by the desulphurisation of industrial flue gas as a result 12 of national policies to reduce concentrations of primary air pollutants and by changes in 13 the composition of commercial fertilisers towards lower S contents. In Denmark, S 14 containing fertilisers are now commonly used in all crops to avoid S deficiency. Where 15 commercial fertilisers cannot be used (e.g., organic farming systems) there is concern 16 whether the S requirement of plants will be met in the longer term (Nguyen et al., 17 1995). 18 Plant and soil tests have been used for assessing the S requirement of crops. 19 However, it was suggested by Nguyen and Goh (1994a) that under steady state 20 conditions, mass-balance S models are more reliable than traditional soil or plant S tests 21 for assessing long-term annual requirements. If a balance approach is used for 22 estimating the S demand of a crop or an agricultural system, precise predictions must be 23 obtained for S input (atmospheric deposition and S in fertiliser and irrigation water) and 24 S output (harvested crops and leaching losses). Precise estimates are easily obtained for 25 all items in the balance except leaching losses, which is unfortunate since leaching 26 losses in temperate regions may be the major S output (McGrath and Zhao, 1995). 27 The retention of sulphate in soils is dependent on the nature of the colloidal 28 system, pH, concentration of sulphate and the concentration of other ions in the solution 29 (Harward and Reisenauer, 1966). The amount of sulphate adsorbed depends on the 30 surface area of the clay, and the surface charge (Bohn et al., 1986). The effect of pH on 31 sulphate adsorption is related to the net charge of Fe and Al oxides. If pH in the soil is 32 lower than zero point of charge (ZPC) it will lead to a positive surface because of 2 1 hydration of the metal oxides, and sulphate will be absorbed in the soil. In agricultural 2 soils, however, pH is often higher than ZPC leading to low retention of sulphate in the 3 soils. Thus, Curtin and Syers (1990) found that virtually all sulphate in soils with pH>6 4 was in solution. Even for soil with a marked capacity to retain sulphate, the strength of 5 the retention seems weak. Chao et al. (1962) found that adsorbed sulphate could be 6 removed by repeated extraction with water. Finally, sulphate adsorption is influenced by 7 the presence of other anions. The order of adsorption strength of anions in soils is: 8 hydroxyl>phosphate>sulphate>nitrate/chloride (Tisdale et al., 1984). As a consequence, 9 sulphate leaching may be subject to considerable variations caused by differences in soil 10 or climatic conditions and by the differences in agricultural management. 11 Some workers have used field lysimeters to study sulphate leaching from arable 12 land (Shepherd and Bennett, 1998; Tveitnes et al., 1996), pastures (Sakadevan et al., 13 1993a; 1993b) or forest soils (e.g., Prietzel et al., 1995; Sogn and Abrahamsen, 1998). A 14 less costly alternative to lysimeters is the suction cup technique, which has been widely 15 used for nitrate determination in soil water (e.g., Lord and Shepherd, 1993; Francis et 16 al., 1992). In structured clay soils this method has serious limitations because water 17 from macro pores by-pass the cups by preferential flow in fissures (Grossman and 18 Udluft, 1991; Hatch et al., 1997). On sandy soils, however, the suction cup technique 19 has proved useful for estimating the concentration of the anions nitrate (Djurhuus and 20 Jacobsen, 1995), chloride (Barbee and Brown, 1986) and sulphate (Alewell et al., 21 1997). 22 The objective of this work was to determine sulphate leaching from an organic 23 six-course crop rotation during a four-year period. The importance for sulphate leaching 24 of climatic conditions (precipitation) and use of different organic manure types at 25 different application rates was investigated and related to the simultaneous nitrate 26 leaching. Sulphur balances were determined in order to evaluate the long-term 27 possibility of an adequate S supply for the crops in the rotation. 28 29 30 2. Materials and methods 31 3 1 2.1. Experimental site 2 3 The dairy crop rotation is located at Research Centre Foulum, in the central part of 4 Jutland (9°34’E, 56°29’N). The soil is classified as an Orthic Alisol with 77 g clay kg-1 5 soil, 16 g C kg-1 soil and 0.21 g total S kg-1 soil. The fields were converted to organic 6 farming in 1987, where a six-year rotation (barley – grass-clover – grass-clover – 7 barley/pea/ryegrass – winter wheat – fodder beets) was introduced as replacement for a 8 conventional cereal rotation. 9 10 2.2. Field trial 11 12 All S data were collected in the rotation in an experiment designed for studying nutrient 13 flows, especially nitrogen, in organic farming systems. The experiment has been 14 described in detail by Eriksen et al. (1999). In summary, four organic fertiliser 15 treatments were established in four replicates in autumn 1993 and spring 1994. The 16 treatments represented two systems of cattle housing based on either slurry alone or a 17 combination of slurry and deep litter at two livestock densities. The livestock densities 18 were 0.9 and 1.4 livestock units (LU) per hectare. One LU is equivalent to 1 milking 19 cow of a large breed. In slurry, dry matter and total-S contents in dry matter were 6-8% 20 and 0.40-0.55%, respectively. In deep litter, dry matter and total-S contents in dry 21 matter were 27-31% and 0.30-0.97%, respectively. 22 Each of the six fields in the rotation was divided into four blocks with treatments 23 in plots of 15x18 m. Following one cut of herbage, the grass-clover fields were grazed 24 by cattle from early June. The treatments with 0.9 and 1.4 LU ha-1 were grazed by two 25 separate groups of heifers. On average the grass-clover fields were subject to 455 26 animal days ha-1 yr-1. After spring-ploughing the 2nd year grass-clover, barley was sown 27 in a mixture with pea and ryegrass, which in July was harvested green for silage 28 production. The stubble field was ploughed in late September and winter wheat was 29 sown. After harvest of winter wheat, the field was left undisturbed, except for 2-3 30 passes with a harrow for weed control, until the following spring when fodder beet was 31 sown. The beet field was harvested in October-November and left undisturbed until 32 spring when barley was sown with a mixture of white clover and ryegrass to establish 4 1 the following grass-clover field. Occasionally, irrigation was used especially to 2 maintain the grass-clover fields in summer (average 94 mm yr-1). Cereals were irrigated 3 less intensively (average 44 mm yr-1). 4 Harvest yields were obtained from an area of 36 to 108 m2 depending on the crop. 5 A plot combine was used for cereals and grass-clover, whereas fodder beets was 6 removed by hand. Dry matter content of subsamples was determined after drying at 7 80°C and total-S was determined by turbidimetry after wet-ashing with magnesium 8 nitrate and perchloric acid (Nes, 1979). 9 10 2.3. Sulphate leaching 11 12 Prior to installation the ceramic suction cups were washed in 0.1 M HCl and rinsed in 13 tap water. The ceramic cups were tested by applying vacuum to the cups while inserted 14 in a nutrient solution (20 µg SO4-S l-1). For this test 16 cups were used, eight had 15 previously been installed in the field for at least one year and eight were new. Sulphate 16 concentrations were determined in the nutrient solution and in the solution extracted by 17 the ceramic cups. 18 In each of the 96 plots three ceramic suction cups were installed before 19 experiment start at a depth of 1 m and with an internal distance of 2 m. Every two or 20 four weeks, depending on precipitation, a suction of approximately 80 kPa was applied 21 three days prior to sampling. During this period, the suction decreased as a result of 22 water sampling. The samples were either analysed separately or bulked for the three 23 replicates per plot before analysis for sulphate concentrations. Before November 1995 24 sulphate concentrations in water were determined using barium perchlorate/thorin 25 titration (Haartz et al., 1979). From this date onwards extracts were filtered through a 26 0.45 m filter and sulphate was measured using suppressed anion chromatography. The 27 HPLC was equipped with a guard column (IonPac AG4A-SC 4 mm, Dionex, CA), an 28 analytical column (AS4A-SC 4mm, Dionex, CA), an Anion Suppressor (ASRS-I 4 mm, 29 Dionex, CA) and a Pulsed Eletrochemical Detector (Dionex, CA). The mobile phase 30 consisted of 1.8 mM Na2CO3/1.7 NaHCO3 and was passed through the system at 2.0 31 ml/min. 5 1 The water balance was calculated using the model Evacrop (Olesen and 2 Heidmann, 1990) where inputs were daily measurements of meteorological data 3 (precipition, temperature and evaporation), type of crop, time of sowing, cutting and 4 irrigation and soil physical parameters. Sulphate leaching was estimated using the 5 trapezoidal rule (Lord and Shepherd, 1993), assuming that sulphate concentrations in 6 the extracted soil water represented average flux concentrations. The accumulated 7 leaching was calculated from 1 April to 31 March. In the four experimental years 8 variations in climatic conditions resulted in differences in drainage of more than 500 9 mm (Table 1). 10 11 12 3. Results 13 14 3.1. Sulphate concentrations in soil water 15 16 It has been observed that new ceramic suction cups can release sulphate to the sample 17 creating a difference between concentrations in soil water and in the sample 18 (Grossmann et al., 1987). When analysing samples extracted from a nutrient solution 19 using old and new ceramic suction cups, no differences were found between 20 concentrations in the nutrient solution and any of the samples extracted by the cups. 21 Thus, this type of ceramic probe did not release sulphate. 22 Sulphate concentrations were determined throughout the experimental period, on 23 average 13 times per year. It cannot be ruled out that peaks of high sulphate 24 concentrations occurred between two sampling dates. The sulphate concentrations in the 25 six fields in the rotation are shown in Fig. 1. Sulphate concentrations were generally 26 below 20 mg SO4-S l-1. 27 28 3.2 Sulphate leaching 29 30 The estimated annual leaching losses of sulphate are shown in Table 2. Differences in 31 sulphate leaching between years were caused by differences in drainage volume. An 32 extremely good relationship (r2=0.99; P<0.01) existed between the average annual 6 1 drainage and the average annual sulphate leaching (Fig. 2). The correlation between 2 drainage and nitrate leaching was not significant (Eriksen et al., 1999). 3 No significant differences in sulphate leaching were observed between the organic 4 fertiliser treatments or the livestock densities, but differences in sulphate leaching from 5 the different crops in the rotation were significant (Table 2). 6 7 3.3. Yield and S content of harvested materials 8 9 Generally, increased livestock density (organic fertiliser application) increased yields of 10 cereals in the rotation by 10-15% (Eriksen et al., 1999). The main cause was probably 11 the nitrogen content of the fertiliser. At least no significant differences were found 12 between treatments in the S content of plant material (Table 3). The experiment did not 13 include any conventionally treated plots so statistical comparison with conventional 14 farming was not possible. However, when comparing S concentrations with Danish 15 standard values for S content in plant material (Strudsholm et al., 1997) it seems likely 16 that the organically grown crops had lower S contents than conventionally grown crops, 17 as has been found by Nguyen et al. (1995). 18 19 3.4. S balance 20 The S balance for the crop rotation is shown in Table 4. Volatilisation from crops or soil 21 was ignored as the amount of S emitted from these sources was considered insignificant 22 (Janzen and Ellert, 1998). Inputs through irrigation water was 9.5 kg S ha-1, which was 23 44% of the total-S input. Compared with the S removal in plant material of 9.8 kg S ha-1 24 the input through irrigation was significant. When including the contribution from 25 atmospheric deposition estimated from Hovmand et al. (1994) the overall S balance 26 becomes positive. Considering that inputs through irrigation and atmospheric deposition 27 clearly exceed the S uptake by plants, it is not surprising that sulphate leaching is a 28 major S output (on average 66% of total S output). 29 30 31 4. Discussion 32 7 1 As an average of the years 1994-97 sulphate leaching from the crop rotation was 20 kg 2 S ha-1, which was equivalent to 60% of the total input to the rotation. Sulphate leaching 3 was very variable, ranging from 4 to 45 kg S ha-1 for the same crop in different years. 4 Thus, it is very important to have an estimate for sulphate leaching when using a mass 5 balance approach for determining the S status of a crop rotation or a farm, especially for 6 soils in temperate regions with high winter rainfall and with a low sulphate retaining 7 capacity. 8 Sulphate leaching was closely related to drainage volume as also found by 9 Shepherd and Bennett (1998). Differences in S uptake by plants and the application of S 10 in animal manure did not explain the differences in sulphate leaching from the different 11 crops. In 1994, when the largest drainage volume was found, there was a significant 12 correlation between the S input in irrigation and sulphate leaching (r2=0.69; P<0.05). If 13 this was caused by the precipitation being well above average (Table 1) then the 14 relationship between S input in irrigation and sulphate leaching must be expected to be 15 insignificant in most years. The S content of ground water used for irrigation was 18 mg 16 SO4-S l-1, which is typical for Danish conditions (Simmelsgaard, 1996). Considering 17 that at present 18% of Danish farm land can be irrigated (Anonymous, 1997) locally the 18 S contribution from this source is considerable. 19 Grazing animals in the grass-clover fields did not affect the pattern of sulphate 20 leaching as was the case with the simultaneously determined nitrate leaching. Every 21 year high peaks of nitrate concentrations were observed in 2nd year grass-clover in at 22 least one of the four replicates (Eriksen et al., 1999) due to urination by the grazing 23 cattle. Similar behaviour of sulphate concentrations could be expected since urinary S 24 can contribute significantly to S leaching (Nguyen and Goh, 1994b). But in our 25 experiment sulphate concentrations did not show any random variations in the grass- 26 clover fields as did nitrate. The coefficient of variation (CV) for sulphate leaching in 27 grass-clover (5-48%, average 23%) was no different from that of the arable crops in the 28 rotation (5-64%, average 26%). When investigating sheep dung and urine on pasture 29 Sakadevan et al. (1993b) found no increase in sulphate leaching in agreement with our 30 results. This was explained by S in dung primarily being in an organic form. A slightly 31 higher adsorption strength of sulphate compared with nitrate could also cause a faster 8 1 movement of nitrate to 1 m depth following urination. This is supported by Uhlen 2 (1994), who found that leaching of sulphate was delayed relative to that of nitrate. 3 The overall average S balance was slightly positive, as more S was imported than 4 removed. The question remaining is what will happen if the S input decreases either 5 because of reductions in atmospheric deposition or reductions in the use of irrigation? 6 Initially, lower inputs will reduce sulphate leaching losses (Bristow and Garwood, 7 1984), which will only partly compensate for the reductions in input. Therefore, 8 immediate S deficiency may not occur but in the longer term a negative S balance must 9 be expected in this crop rotation. However, even with a positive overall S balance, the S 10 input is not necessarily synchronised with plant needs. Monoghan et al. (1999) found 11 that 50% of grain S in wheat had been accumulated by the plant before anthesis. At this 12 time soil S needs to be available or otherwise the well-known negative effects on yield 13 and quality of the grain may occur (eg. Randall and Wrigley, 1986). In organic farming 14 systems where animal manure is the sole S source, the S supply is limited at this time as 15 the plant-availability of S in animal manure is low for crops with a short growing season 16 (Eriksen et al., 1995). 17 18 19 5. Conclusions 20 21 Considerable sulphate leaching occurred in the organic crop rotation equivalent to 60% 22 of the total input. Although immediate S deficiency may not occur a negative S balance 23 must be expected in the longer term. 24 In order to maintain a sufficient S supply in the future when further reductions in 25 the atmospheric deposition are expected, it is important to reduce leaching losses of 26 sulphate. It has been demonstrated that a catch crop succeeding the main crop can 27 absorb nitrate from the root zone during autumn and winter and thereby reduce nitrate 28 leaching (Thorup-Kristensen and Nielsen, 1998). Similar beneficial effects of catch 29 crops on sulphate leaching may be expected, and we are currently investigating this 30 possibility. 31 32 9 1 Acknowledgements 2 3 Financial support was provided by the Ministry of Food, Agriculture and Fisheries in 4 the research programme “Organic Farming 1993-97”. The technical assistance of 5 Holger Bak and the staff at Foulumgaard is gratefully acknowledged. 6 7 8 References 9 10 Anonymous, 1997. Agricultural statistics 1997. Statistics Denmark. Copenhagen. 11 Alewell, C., Bredemeier, M., Matzner, E., Blanck, K., 1997. Soil solution response to 12 experimentally reduced acid deposition in a forest ecosystem. J. Environ. Qual. 13 26, 658-665. 14 15 16 17 18 19 20 21 22 23 Barbee, G.C., Brown, K.W., 1986. 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B, 13 Soil and Plant Sci. 44, 201-207. 13 Table 1 Precipitation and drainage (mm) in the experimental years as average of all crops Year Precipitation Calculated drainage at 1 m´s depth April to Sept. Oct. to March 1 April to 31 March 1994-95 456 478 578 1995-96 281 121 64 1996-97 233 363 208 1997-98 402 406 338 Normal 334 292 not calculated 14 Table 2 Sulphate leaching. Average of fertiliser treatments (kg SO4-S ha-1). Values with the same letter are not significantly different within the column (P<0.05) 1994-95 1995-96 1996-97 1997-98 Average Barley 44a 3c 15b 37a 25a 1st year grass-clover 45a 4b 20a 29b 24a 2nd year grass-clover 41ab 4b 15b 22c 21b Barley/pea wholecrop 35b 2d 10cd 14d 15c Winter wheat 44a 3cd 7d 26bc 20b Fodder beets 22c 7a 12c 23c 16c Average 38 4 13 25 20 15 Table 3 Yield and S content in plant material from the crop rotation as average of treatments Plant fraction 1994 Av. 1995 SD Av. 1996 SD Av. 1997 SD Av. SD Yield (Mg ha-1 year-1) Barley straw 2.9 0.2 5.6 0.4 3.7 0.1 4.1 0.2 Barley grain 3.7 0.3 4.0 0.4 4.2 0.2 4.1 0.5 1st year grass-clover*) 3.5 0.1 4.1 0.1 3.3 0.1 4.2 0.2 2nd year grass-clover*) 3.2 0.4 4.7 0.4 3.6 0.4 5.6 0.3 Barley/pea wholecrop 8.8 0.7 7.8 0.6 8.7 0.4 8.7 0.6 Winter wheat straw 4.0 0.3 4.6 0.3 5.9 0.5 5.1 0.2 Winter wheat grain 4.6 0.3 4.5 0.3 6.0 0.4 5.2 0.1 Fodder beet roots 8.5 0.2 9.0 0.2 12.9 0.7 14.5 0.3 Fodder beet tops 3.0 0.2 2.7 0.1 3.7 0.2 3.7 0.2 S content (g kg-1) Barley straw 1.2 <0.1 1.0 0.1 1.5 <0.1 1.1 0.1 Barley grain 0.9 <0.1 1.0 0.1 1.2 0.1 1.2 <0.1 1st year grass-clover*) 1.3 <0.1 1.5 <0.1 1.7 <0.1 1.4 0.1 2nd year grass-clover*) 1.5 0.1 1.5 0.1 1.8 0.1 1.4 <0.1 Barley/pea wholecrop 1.6 0.1 1.2 0.1 1.5 <0.1 1.2 <0.1 Winter wheat straw 1.0 <0.1 1.1 <0.1 1.5 0.1 0.8 <0.1 Winter wheat grain 1.2 0.1 1.1 <0.1 1.3 <0.1 1.3 <0.1 Fodder beet roots 0.4 <0.1 0.5 <0.1 0.5 0.1 0.5 <0.1 Fodder beet tops 2.2 0.1 2.7 0.1 2.8 0.1 2.8 0.1 *) Results in grass-clover are from first cut, after which the plots were grazed by cattle 16 Table 4 S balance. Average of the growth seasons 1994-97 and of organic fertiliser treatments (kg S ha-1). SE in brackets Barley 1st yr. 2nd yr. Barley/ Winter Fodder grass-cl. grass-cl. pea wheat beets Average Input Atmospheric dep.*) 11.0 11.0 11.0 11.0 11.0 11.0 11.0 Animal manure 17.3 (2.8) 0.0 5.5 (1.6) 4.8 (1.6) 18.6 (1.7) 27.1 (1.9) 12.2 Irrigation 10.2 (0.9) 17.1 (1.4) 16.7 (1.4) 3.3 (1.5) 10.0 (0.7) 0.0 9.5 Plant material 9.1 (0.4) 6.2 (0.1) 6.6 (0.3) 11.8 (0.5) 10.4 (1.0) 14.7 (0.9) 9.8 Weight gain cattle 0.1 (<0.1) 0.7 (<0.1) 0.8 (<0.1) 0.0 0.0 0.0 0.3 Leaching 24.6 (4.3) 24.3 (3.9) 20.6 (3.6) 15.3 (3.2) 19.8 (4.3) 15.7 (1.8) 20.0 4.7 (4.9) -3.1 (3.7) 5.2 (3.6) -8.0 (2.7) 9.4 (3.0) 7.7 (2.3) 2.6 Output Balance *) Estimated from Hovmand et al. (1994) 17 Figure captions Fig. 1. Sulphate concentrations in drainage extracted by ceramic suction cups at 1 m depth in the six-course crop rotation. Error bars: SE Fig. 2. Correlations between annual drainage and annual leaching of sulphate and nitrate in the organic crop rotation. Average of treatments and crops 18