Results and discussion Directory UMM :Data Elmu:jurnal:A:Agriculture, Ecosystems and Environment:Vol81.Issue1.Oct2000:

196 A. Huber et al. Agriculture, Ecosystems and Environment 80 2000 191–204 would only be dependent upon application rates. How- ever, the probability of occurrence of watercourses at field edge is the decisive factor with regard to the re- gional importance of spray drift as a pathway for pes- ticide input into surface water. In general frequency of surface waters per unit area can be described by drainage density in km km − 2 Horton, 1932. In this study drainage density was first computed on the ba- sis of the digital surface water net 1:200.000; HAD, 1997 using GIS techniques. Due to cartographic gen- eralization the digital surface water net is represented incompletely, therefore real values were extrapolated by regression analysis taking measured drainage den- sities in 147 different agroecological zones Huber, 1998. 2.5. Other non-point sources of surface water contamination with pesticides Some non-point sources were not modeled because they are not considered to be relevant on a national scale such as atmospheric deposition or wind erosion. For the following two reasons sediment-bound pesti- cide loss was also neglected: 1. The spatial databases required for erosion calcula- tion are not available for Germany, so modeling of pesticide input is limited to the dissolved phase. 2. With Germany’s prevailing weather, soil and land use conditions, surface runoff occurs frequently causing no or hardly any soil erosion, e.g. 5 to 15 times per year according to model calculations. Heavy rainstorms including higher erosion only oc- cur once or twice per year, mainly effecting row crops. In this respect the situation differs signifi- cantly from the ones in other countries, especially in North America. Thus pesticide transport in so- lute phase is assumed to be the dominant runoff component. Burgoa and Wauchope 1995 also stated that sed- iment constitutes such a small fraction of runoff fol- lowing even highly erosive storms, that it is likely that the bulk of active ingredient will be lost in the water phase. Some authors reported a notable pesticide flux from groundwater to surface water Squillace and Thurman, 1992. However, concentrations in groundwater are generally very low Leistra and Boesten, 1989. In this study it was therefore not assumed that pesticide concentrations in surface water, which are usually higher than those in groundwater, are caused to a considerable extent by groundwater discharge.

3. Results and discussion

Model results for pesticide loss via surface runoff, tile drains and spray drift are shown in Table 2 and Fig. 3a–c. To account for parameter uncertainty inher- ent to all regional scale models, computed loads were given with ranges of variation both in Table 2 and in generated maps Fig. 4a–d. Magnitude of variation Fig. 3. Mean solid line and variation bars of modeled pesticide loss to surface waters for transport with a surface runoff, b through tile drains and c spray drift no. of active ingredients refer to Table 2. A. Huber et al. Agriculture, Ecosystems and Environment 80 2000 191–204 197 Table 2 Active ingredients considered in the study, their chemical properties and their predicted annual losses into surface waters via different pathways in Germany cumulated over all treatments, reference year 1994 e No. Active ingredient common name K oc a l kg − 1 Dt 50 day a Treated crops Runoff kg Tile drains kg Spray drift kg Total kg Mean Range b Mean Range c Mean Range d Mean Range 1. Metamitron H 156 21 Sugar beet 2423 629 –4571 11 2–15 2433 441–5138 2. Isoproturon H 100 12 Grain 1278 361–2540 947 1–6680 20 4–33 2245 5–9565 3. Ethofumesate H 131 51 Sugar beet 1030 475–2193 78 0–1658 1 0.2–2 1109 178–3853 4. Terbuthylazine H 301 88 Corn, potatoes 881 585–1662 14 0–4255 3 0.5–6 898 171–6123 5. Dichlorprop-P H 80 14 Grain 631 223–1129 0–36 8 1–13 639 224–1482 6. Metolachlor H 200 39 Corn, legumes 10 284–1029 0–47 1 0.2–2 511 96–1123 7. Chloridazon H 205 43 Sugar beet 408 238–919 0–109 0.3 0–0.6 408 76–1029 8. Dichlofluanid F 10 18 Grapevine 385 215–532 25 2–28 410 217–560 Orchards 42 21–67 105 26–405 388 48–756 535 95–1228 9. Bentazone H 28 18 Grain, potatoes 298 94–382 103 0.8–894 0.7 0.3–1 402 95–1276 10. Chlortoluron H 235 27 Grain 284 155–666 0–339 2 0.5–5 286 155–1005 11. Simazine H 201 57 Grain, corn 130 57–318 33 0–504 163 57–822 12. Mecoprop-P H 139 9 Grain 118 37–283 7 1–13 125 37–283 13. Metabenzthia- zuron H 200 20 Grain, legumes 101 32–198 0–25 0.6 0.3–1 102 32–223 14. Propineb F 3 8 Grapevine 96 31–187 11 107 31–187 Orchards 2 33–158 119 19–593 1221 155–2363 1342 174–2956 15. MCPA H 62 15 Grain, potatoes 87 0–263 0.4 0.1–0.8 87 33–421 16. Phenmedipham H 870 34 Sugar beet 85 48–132 0.2 0.04–0.4 85 48–132 17. Metazachlor H 80 6 Rape 69 9–239 1 0.2–2 70 9–239 18. Prometryn H 400 60 Grain, legumes 40 17–86 40 17–86 19. 2,4-D H 38 10 Grain, corn 25 5–68 25 5–68 Grapevine 2 2 20. Triallate H 2400 66 Sugar beet, corn, legumes 24 7–44 0.08 24 7–44 21. Mancozeb F 886 15 Orchards 3.5 4–53 754 90–1462 758 90–1462 Grapevine 21 21 2–24 42 6–77 Potatoes 0.02 0.5 1 22. Methamidophos I 5 9 All field crops 18 92 11–293 0.3 110 11–293 23. Dithianon F 2490 24 Orchards 1 536 66–1040 537 66–1040 Grapevine 9 14 23 24. Metiram F 50000 3 Grapevine 0.01 40 3–45 40 3–45 Orchards 19 22–376 19 22–376 Potatoes 0.01 0.5 1 25. Oxydemeton- methyl I 10 2 Orchards 28 4–54 28 4–54 All field crops 0.01 0.2 1 26. Maneb F 1000 42 Potatoes 1 9 2–14 10 2–16 27. Pendimethalin H 16000 126 Grain, corn, legumes 12 2 0.5–5 14 3–32 28. Bromoxynil H 184 4 Grain, corn 11 0.2 0.03–0.3 11 2–25 29. Parathion- methyl I 451 22 Orchards 0.01 10 1–25 10 2–33 Grapevine 4 1 5 Corn, rape, legumes 30. Tebuconazole F 1008 60 Grapevine 5 3 1–11 8 2–26 Grain, rape 2 4 6 31. Triadimenol F 1000 110 Orchards 0.2 8 0.1–18 8 0–19 Grapevine 0.3 0.4 1 Grain 1 1 32. Diuron H 900 68 Orchards 7 7 4–14 33. Parathion I 1316 18 Orchards 0.01 7 0.8–14 7 1–14 Grapevine 0.1 0.4 1 All field crops 0.04 1 34. Anilazine F 349 22 Grain 0.2 6 3–11 6 3–11 35. Fenpropimorph F 4178 31 Grain 0.1 4 0.8–8 4 1–8 198 A. Huber et al. Agriculture, Ecosystems and Environment 80 2000 191–204 Table 2 Continued No. Active ingredient common name K oc a l kg − 1 Dt 50 day a Treated crops Runoff kg Tile drains kg Spray drift kg Total kg Mean Range b Mean Range c Mean Range d Mean Range 36. Prochloraz F 1000 60 Grain, rape 1 2 0.4–4 3 1–6 37. Bifenox H 6450 7 Grain 0.01 1 0.2–2 1 0.2–2 38. Glyphosate H 12800 27 Grapevine 1 1 0.01–4 2 0.3–8 All field crops 0.8 0.6 1 Orchards 0.02 0.3 1 39. Trifluralin H 8500 155 Rape 0.9 1 0–2 40. Dimethoate I 20 7 All field crops 0.01 0.04 0–1 1 0–1 41. Endosulfan I 12400 50 Potatoes, rape, legumes 0.01 1 42. Linuron H 400 60 Grain 0.01 1 0–0.2 Sum 9060 1500–19,300 1490 50–16,000 3350 400–6300 13,900 2000–42,000 a Values extracted from the chemical properties data base at the German Federal Environmental Agency unpublished. b Confidence ranges in parenthesis of pesticide losses resulting with different values for sorption coefficient K OC , +100−50, disappearance time Dt 50 , +100−50 and curve number CN-value+25−25. c Confidence ranges in parenthesis with different values for K OC , Dt 50 and tile drain density +100−50. d Confidence ranges in parenthesis with various distances from surface water field crops: 2, 5, 10 m; orchards, vineyards: 5, 10, 20 m. e H=herbicide, F=fungicide, I=insecticide. for pesticide loss is different for every single pathway and was based on the sensitivity analysis performed for each model Huber, 1998; Huber et al., 1998. 3.1. Surface runoff According to model results with a total amount of ca. 9000 kg a.i. surface runoff is the dominant non-point source pathway for pesticide input into sur- face waters. It becomes clear that chemical transport with surface runoff is a more frequent phenomenon than losses via tile drains or spray drift, particularly in regions with a high spraying intensity like in the loess areas of Central Germany, along the Lower Rhine and the Danube river Fig. 4a. Sugar beets Beta vulgaris L. form an important part of crop rotation in those areas. Like other row crops sugar beets require thorough herbicide treatments in late spring to ensure crop development; in the same time the probability of significant rainfalls grows with increasing tempera- ture. That means a considerable amount of herbicides are available in a period of frequent rainstorms and low crop cover. The same applies for spring barley Hordeum vulgare L. which is sown in April and does not develop sufficient crop canopy before early summer Fig. 1. The highest annual dissipation rate 5 g ha − 1 was modeled for vineyards in the Mosel region and along the upper and middle Rhine. In contrast vineyards where also fungicides are subject to runoff transport, pesticide runoff in field crops consists nearly exclu- sively of herbicides. Cumulated losses after all calcu- lated treatments vary between 0.42 of application rate for ethofumesate to less than 0.01 for stronger bound or rapidly degradable active ingredients. In the case of isoproturon, the most frequently used her- bicide in German agriculture, calculated runoff loss was about 0.06 of the application rate. It is important to note that the approach which was developed for calculating runoff loss differs signifi- cantly from erosion modeling as neither relief infor- mation nor precipitation volume are crucial model parameters. Runoff volume is only dependent upon infiltration capacity of soil, which is a function of porosity, water content, susceptibility to crusting or crop cover. In this way it becomes clear that higher runoff losses were calculated for steep and therefore shallow soils in vineyards, while deeper soils in flat areas do not show the same runoff susceptibility un- less there exists a nonpermeable layer in the upper part of the profile. Precipitation volume is a crucial parameter in the model only with regard to its prob- ability of occurrence. The more frequent significant rainstorms occur the shorter the time is for pesticide degradation. Therefore small rainfall events, which are enough to produce runoff, outweigh extreme rain- storms in relative importance for total pesticide losses because they are by far more frequent. A. Huber et al. Agriculture, Ecosystems and Environment 80 2000 191–204 199 Fig. 4. Spatial distribution of pesticide loss to surface waters on different pathways in Germany. 3.2. Leaching and transport through tile drains For most parts of the country only neglectable amounts of pesticides are leached to 0.8 m accord- ing to model results. However, when discussing predicted pesticide leaching it has to be emphasized that PELMO shows a high sensitivity to chemi- cal properties and soil organic carbon content. The 200 A. Huber et al. Agriculture, Ecosystems and Environment 80 2000 191–204 estimated mean loss of ca. 1500 kg a.i. into sur- face waters via tile drainage for the entire area of Germany exhibits therefore a high variation for some active ingredients Fig. 3b, especially when sensitive parameter values like half-life Dt 50 or sorption coef- ficient K OC are changed. In some cases no loss was predicted using standard parameter values as given in Table 2; however, a certain loss resulted when considering parameter variation Fig. 3b. Predicted pesticide leaching rates are shown in Fig. 4d, discharge from tile drains in Fig. 4c. PELMO calculations gave high leaching rates in Northern Lowland areas where sandy soils prevail and Autumn applications to winter grain, particularly treatments with isoproturon, are more common than in other parts of the country. But only in a few regions a con- siderable leaching potential intersects with a high tile drain density. Thus, in most regions the surface water pollution is much lower than the pesticide leaching potential. A considerable limitation of accuracy of predicted leaching loss must be attributed to spatial variability of organic carbon content of arable land which could not be considered adequately on the regional scale. To reduce the number of factor combinations to a man- ageable amount, PELMO-runs were conducted with five different soil scenarios ranging from a coarse sand to a silt loam, and mean organic carbon contents in the upper soil layer from 7 to 24 g kg − 1 . Soil sce- narios were selected according to representativity for cultivated soils, nevertheless it may be possible that the model predicted erroneous pesticide leaching rates due to a too coarse classification of soils in one of the defined soil scenarios. However, even without regroup- ing soil types, the modeler has to be aware of the fact that soil classified under the same taxonomic hierar- chy offers a great variation of soil properties Loague et al., 1996. Another limitation of the model is that PELMO does not account for preferential flow. This may constitute a considerable drawback when the model is applied to heavier soils Klein, 1994; Thorsen et al., 1998. It is evident, that highly permeable and thus leaching susceptible soils are drained to a lower extent than heavier soils. However, it is possible that frequently drained soils in loess areas, which do not exhibit a high leaching poten- tial after PELMO runs Fig. 4d would be classi- fied differently when considering solute transport in macropores. 3.3. Spray drift Frede et al. 1998 stated in Europe that no field studies exist determining exclusively spraydrift in- put into surface water bodies under natural condi- tions. All monitoring studies on a catchment scale analysed a mixture of pesticide inputs from at least two or more diffuse sources, often superimposed by accidental inputs and spills. Experimental data on the fraction of total pesticide pollution of surface wa- ter originating from spray drift is restricted to worst case assessments undertaken for registration purposes Ganzelmeier et al., 1995. Applying the median val- ues of basic spray drift losses Table 1, real crop acreage, application rates and drainage density mod- eling results demonstrate that for applications in field crops, spray drift contribution to total surface water pollution is negligible at a total amount of 90 kg a.i. for Germany as a whole. Thus spray drift may con- tribute locally or temporarily to the contamination of aquatic systems but its contribution to the total annual pesticide river load is small on river basin or national scale. This conclusion does not apply to orchards where air blast application leads to a substantially higher fraction of pesticide transported to the field edge than following boom sprayer application to field crops. Furthermore, the main apple tree growing area in Ger- many is located on marshland west of Hamburg where drainage densities reach up to 100–200 km km − 2 . Natural conditions and agricultural practices interact in a way that spray drift input amounts to ca. 3000 kg a.i. according to model estimate. This input pathway outweighs by far other non-point sources of pesticide pollution in this area. Moreover, this is the only path- way where fungicides contribute to a higher extent to water pollution than herbicides in Germany Fig. 3c, Table 2. 3.4. Comparison of modeled loss to measured pesticide loads in different catchments 3.4.1. Problem of model validation In general it is difficult to compare modeled pesti- cide losses on a single pathway with experimental data A. Huber et al. Agriculture, Ecosystems and Environment 80 2000 191–204 201 Table 3 Catchment studies used for the comparison of measured pesticide river loads with predicted pesticide losses for geographic location of catchments see Fig. 5 No. Catchment no. of analysed pesticides Size km 2 Sampling period Sampling frequency Isoproturon Source a of experi- mental data Measured load kg Modeled input kg 1. Stever 5 585 1994 entire year 7 days 60.8 40.85 Gelsenwasser AG 1997 2. Nidda 5 1619 4181994–5251994 3 days 14.0 0.70 Seel et al. 1996 3. Schwarzach 6 170 4171996–421997 30 days 3.286 0.48 Wasserwirtsch.amt Würzburg 1997 4. Selz 14 363 4111995–9201995 10 days 1.413 0.308 Pflanzenschutzd. Rheinl.-Pfalz 1997 5. Frischofsbach 10 32 12281993–131995 7 days 1.173 2.935 Umweltamt Münster 1997 6. Lumda 11 129 4241993–691993 24 h 0.55 0.08 Bach and Frede 1996 7. Thierbach 6 152 4151996–1171996 30 days 0.333 0.332 Wasserwirtsch.amt Würzburg 1997 8. Wieseck 11 80 4241993–691993 24 h 0.068 0.119 Bach and Frede 1996 9. Hess. Bach 5 6 4161994–5181994 24 h 0.024 b 0.118 Fischer 1996 10. Gerrenbach 4 6 1994 entire year 24 h 0.01 0.037 Skark and Zullei-Seibert 1997 11. Lettebach 4 5 1994 entire year 24 h 0.005 0.023 Skark and Zullei-Seibert 1997 12. Blument. Aue 9 34 4201995–7161995 48 h City of Bremen 1997 13. Körsch 6 127 1241996–11271996 30 days No data No data Honnen et al. 1997 a Sources cf. Huber 1998. b Only pesticide load which originated from surface runoff, tile drains and spray drift. because plots and even small catchments studied in a short period may not be representative for an entire region. In this way only long term catchment studies should be used to prove reliability of predicted losses. Additionally, experimental data should cover the main application periods and the most frequently applied active ingredients. At present, only data sets from 13 German catchments Table 3, Fig. 5 fulfill these requirements. A major limitation of regional scale modeling is that results can never be validated in a strict sense since measured loads also include a certain amount of pesticide which did not enter the surface water system via modeled pathways. Additional inputs could occur via point sources from accidents or spills from sprayer handling on farmyards. Spills were found to be an important source of surface water pollution Frank et al., 1982. In some parts of Germany where a large number of farms is connected to public sewage plants, farmyard runoff outweighs even non-point source discharge Bach, 1996; Fischer, 1996; Frede et al., 1998. Finally, the model developed in this study estimated pesticide loss to surface waters while ex- perimental data is load at catchment outlet. Between point of entry and sampling station transformation and sorption processes may occur, hence it is possible Fig. 5. Location of catchments used for comparison of modeled pesticide losses and measured loads in surface water. 202 A. Huber et al. Agriculture, Ecosystems and Environment 80 2000 191–204 Fig. 6. Comparison between modeled non-point source inputs and measured loads of isoproturon for catchment characteristics see Table 3. that measured loads do not truly reflect total pesticide input. 3.4.2. Modeled loss versus measured load Comparison of loads of isoproturon is probably most reliable as it was measured in all catchments Fig. 7. Comparison between modeled non-point source inputs and measured loads of five frequently analysed active ingredients in 13 German catchments Table 3. except one, for that reason respective loads are shown separately in Fig. 6. Values for other herbicides which were considered in at least five catchment studies are shown in Fig. 7. Considering the limitations of the performed comparison Figs. 6 and 7 nevertheless permit several conclusions: 1. In most cases model results seem to match the magnitude of pesticide pollution in surface waters; however, it is not possible to validate prediction ac- curacy for a single pathway because no study, ex- cept Fischer 1996, listed loads for each pathway separately. 2. Fig. 7 shows that the model underestimated loads in those catchments where measured pesticide pollution exceeded about 100 g a − 1 . A possible explanation is that the existence of point sources is more probable in larger catchments, while in small catchments point sources are often excluded by selection of monitoring sites. 3. Especially in small catchments it is likely that errors due to generalization of spatial input data distort model results. For example, spatial res- olution of soil data used in this study is prob- ably too coarse to estimate pesticide runoff or leaching in catchments with an area of less than 50–100 km 2 . A. Huber et al. Agriculture, Ecosystems and Environment 80 2000 191–204 203

4. Conclusions