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Chapter 5

Downloaded by UNIV MASSACHUSETTS AMHERST on September 7, 2012 | http://pubs.acs.org Publication Date: March 8, 2005 | doi: 10.1021/bk-2005-0899.ch005

Long-Term Fate of the Herbicide Azimsulfuron in a Rice-Grown Lysimeter over Six Consecutive Years 1

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J. K. Lee , F. Führ , S. H. Park , E. Y. Lee , Y. J. Kim , and K. S. Kyung 3

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Department of Agricultural Chemistry, Chungbuk National University, Cheongju 361-763, South Korea Institute of Chemistry and Dynamics of the Geosphere 5, Radioagronomy, Forschungszentrum Jülich GmbH, D-52425 Jülich, Germany Pesticide Safety Division, National Institute of Agricultural Science and Technology, Suwon 441-707, South Korea 2

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The long-term fate of the sulfonylurea herbicide azimsulfuron used in rice paddies was investigated using a lysimeter (0.564 m IDx1msoil depth) which simulatesfloodedricepaddies and had been treated with [pyrazole-4- C]azimsulfuron (specific activity, 2.05 MBq/mg) 28 days after rice transplanting. The treated amount (60 g a.i./ha) was four times larger than the ordinary dosage for analytical convenience. The amount of 14CO evolvedfromthefloodedsoil surface during the rice growing period of 12 weeks and thatfromthe non-flooded soil surface for 9 weeks after harvest were 0.09 and 4.73% of the applied C-radioactivity, respectively, indicating that the degradation of azimsulfuron in soil is much faster under the aerobic conditions than under thefloodedanaerobic ones. The loss by volatilizationfromthe soil surface was negligible. The total C-radioactivities absorbed and translocated byriceplants, leachedfromthe lysimeter, and remaining in the soil throughout six years amounted to 4.01,9.98, and 47.5% of the originally applied amount, respectively. The brown rice grain contained the residue far less than the MRL of 0.1 mg/kg. It can be concluded that azimsulfuron will not reach environmentally significant concentrations in groundwater in practical use, based on the fact that the originally treated amount was four times larger than the ordinary dosage. 14

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© 2005 American Chemical Society In Environmental Fate and Safety Management of Agrochemicals; Clark, J., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2005.

51 Herbicides are an important tool in modern agriculture for the control of various weeds. In recent years, however, environmental and ecotoxicological concerns have been increased over the contamination of groundwater and the potential impact of soilapplied herbicides on non-target aquatic organisms due to leaching through soil profile and run-off on the soil surface (7). To prevent or minimize their risk, it will be helpful to elucidate the temporal and spatial fate and behavior of the pesticides in the environment using lysimeters with the aid of radiotracers. A number of lysimeter studies have been conducted for this purpose, in terms of their leaching, volatilization, mineralization, chemical and microbial degradation, and bioavailability to the target plant, typically by using C-radiolabelled compounds (2-9). Azimsulfuron (1 -(46-a^ethoxypyrimidin-2-yl)-3-[ 1 -methyl-4-(2-methyl-2Htetrazol-5-yl)pyrazol-5-ylsulfonyl]urea) is a selective post-emergence sulfonylurea herbicide used for the control of Echinochba species and most of the annual and perennial broad-leaved and sedge weeds inrice{Oryza sativa) paddies in Korea (10). The initial herbicidal symptoms of this herbicide were known to be cessation of growth and chlorosis, followed by reddish colouration, then necrosis (77). Sulfonylurea degradation in soil is mainly due to chemical hydrolysis and microbial breakdown, the latter being an important factor for field dissipation (12-16). Photodegradation and volatilization would be relatively minor dissipation processes (77). Nevertheless, the most significant degradation mechanisms for azimsulfuron in rice paddies were reported to be indirect photolysis and metabolism in soil (75). Despite their relatively great mobility in soil, sulfonylurea herbicides do not pose a potential problem in groundwater by virtue of their low application rates, low toxicities, and the relatively rapid degradation and/or disappearance characteristics in soil (73). Relatively little information has been available on the environmental fate of azimsulfuron, including leaching, metabolism in soil and plants, and bioavailability to the target crop. The purpose of this investigation is to elucidate the long-term fate of azimsulfuron which was treated to thericepaddy soil using a C-radiotracer treated once to therice-grownlysimeter simulating the rice paddy conditions for six consecutive years.


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Materials and Methods Lysimeter and Preparation of Soil Core A cylindrical lysimeter was manufactured with stainless steel of 8 mm in thickness. Its surface area was 0.254 m , the height 1.1 m, and the inner diameter 0.564 m. An undisturbed monolithic soil core of 1.0 m was obtained by pressing the lysimeter down into aricepaddy soil with the aid of a fork-crane as described elsewhere^, 4,7,9). It was carried to the lysimeter station on campus and installed on the ground to collect the leachate through the soil profile and to trap the C0 and "C-volatile organic compounds ( C-VOCs) evolvedfromthe soil surface. The lysimeter for collecting leachates and the device for trapping C0 and C-VOCs were shown previously^,). Water was added to the lysimeter to maintain 5 cm of water-depth over the soil surface and the lysimeter was equilibrated for a month. The physicochemical properties of the lysimeter soil layers are presented in Table I. 2

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In Environmental Fate and Safety Management of Agrochemicals; Clark, J., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2005.

52 Growing ofRke Plants


Prior to transplanting rice plants, the lysimeter soil was fertilized with N-P-K at a ratio of 150-90-110 kg/ha, except that in the case of the nitrogen fertilizer 80% of the total was applied at the beginning and the rest 20% at the earing stage. The rice seedlings (Oryza sativa cv Akibare, Japan) grownfor35 days were transplanted onto the lysimeter soil in June each year for six consecutive years. Nine hills were transplanted with three seedlings per hill. To simulate the rice paddy, the soil was flooded throughout the cultivation period. After rice harvest, the lysimeter was left uncovered. 14

Application of [ C]Azûnsulfuron and Cultivation 14

rPyrazole-4- C]azimsulfuron (specific activity, 2.05 MBq/mg; purity, >99%, Figure 1) was supplied by DuPont. The commercial granular formulation, Gulliver (0.05% azimsulfuron), in which azimsulfuron was replaced by [ C]azimsulfuron as a tracer, was applied onto the lysimeter soil at a rate of 60 g ai/ha 28 days after rice transplanting only once in the first year. For investigating the long-term behavior of azimsulfuron in terms of leaching, degradation in soil, and absorption and translocation byriceplants, die applied amount was four times larger than the real application rate of 15 g ai. /ha recommended in Korea. The total amount and C-radioactivity of azimsulfuron applied were 1.51 mg and 3.09 MBq, respectively. The [ C]azimsulfuron dissolved in about 10 mL of methanol and the formulation without azimsulfuron were added to about 200 g of soil. After the methanol had evaporated, the treated soil was uniformly spread on the submerged lysimeter soil planted with rice seedlings. Rice plants were grown for six consecutive years according to the same methods as described above. l4

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Table L Physicochemical properties of each soil layer of the lysimeter

Sou depth (cm) 0-10 10-20 20-30 30-40 40-50 50-60 60-70 70-80 80-90 90-100

PH (H&, 1:5) 6.4 5.9 6.3 7.2 7.4 7.4 7.2 6.9 6.9 6.5

Organic CEC matter (cmol(+)/ Texture kg soil) (%) L* 2.3 12.8 L 2.5 13.1 L 1.9 12.7 SiL 12.2 1.1 L 0.8 9.2 SiCL" 0.8 13.0 L 0.8 14.1 L 0.6 11.9 L 9.6 0.5 SiL 0.5 11.1 c

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Cation exchange capacity, *Loam, 'Silt loam, ^ilty clay loam (Reproducedfromreference9.)



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Figure 1. Structuralformula and labelled position (*) of[pyrazole-4C]azimsulfuron supplied by DuPont. Specific activity: 2.05MBq/mg, Purity :>99%. 14

Leachate

After the treatment of the lysimeter soil with azimsulfuron, the leachate percolated through the lysimeter was collected weekly in a 20-L polyethylene container for six years, and the volume and radioactivity were measured on a weekly basis. The Cradioactivity in the leachate was measured with a liquid scintillation counter (Tri-Carb 1500, Packard Instrument Co., Downers Grove, 111., U.S.A.). In addition, the Cradioactivities of the leachates were partitioned between methylene chloride and distilled water to examine the changes in their polarities with time. That is, 5 mL of the leachates which were acidified to pH 2 with hydrochloric acid was put in the screwcapped tubes and 5 mL of methylene chloride was added. The tubes are agitated vigorously for a few minutes. After phase separation, 3 mL of organic and aqueous phase, each, was taken and the C-radioactivity measured. 14

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Mineralization and Volatilization of Azimsulfuron R

Pyrex glass devices (8 cm i.d. χ 25 cm long) with an inlet and an outlet were used to trap C0 and C-VOCs evolved from the lysimeter soil treated with [ C]azimsulfuron as reported by Lee et al (3). Four of them were placed on the surface of the lysimeter soil and C0 -free air was supplied to them through the inlet at a rate of 1.2-1.5 mL min" using a vacuum pump connected with the outlet via the serial traps of C0 and C-VOCs. Each glass device covered an area of 50.24 cm , representing about 1/50 of the area of the lysimeter soil surface. C0 and C-VOCs were trapped in 1 Ν NaOH and 0.1 Ν H S0 , respectively, only for 21 weeks of the first year and the radioactivities were measured weekly or biweekly. The total amounts of C0 and C-VOCs evolved during mat period were calculated by multiplying the respective average value obtained with one of the four devices by 50. 14

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Results and Discussion Mineralization and Volatilization 14

As can be seen in Figure 2, the amount of C0 evolvedfromthe flooded soil surface of the lysimeter during 12 weeks of the rice cultivating period after application of [ C]azimsulfuron in the first year was 0.09% of the originally applied Cradioactivity. Meanwhile, the amount of C0 evolved from the non-flooded soil surface for 9 weeks after harvest increased remarkably up to 4.73% of the treated C This result strongly indicated that the microbial degradation of azimsulfuron in rice paddy soil was much faster under the aerobic conditions than under the flooded anaerobic ones. Lee et al. (Ρ) reported that the microbial degradation of the insecticide imidacloprid treated torice-growinglysimeters was predominant in soil and the larger amount of C0 was evolvedfromthe dry soil surface of the lysimeter thanfromthe flooded one. They also suggested that the abrupt increase in C0 evolution from the dry soil surface would be due to the fact that many intermediate degradation products formed photochemically and/or microbiologically during the cultivation period were able to be readily mineralized to C0 under the dry aerobic conditions. Volatilization of the chemical from the lysimeter soil surface during that period was at the background levels. Carter (18) reported that volatilization losses are most significant for pesticide residues remaining on the surface of bare soil but their losses by volatilization are low for herbicides. Especially, incorporation into the soil profile can significantly reduce losses. 2

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Soil and Plant Analysis 14

To measure the C-radioactivity distributed in the lysimeter soil profile after harvest, the soil sample of each 5-cm layer was collected down to the 40-cm depth in the first year ( 21 weeks after application), the 50-cm depth in the second year, the 70cm depth in the fourth year, and the 90-cm depth in the sixth year with a soil core sampler attached to a stainless steel core of 5.05-cm diameter and 100 cm volume. Soil samples were taken vertically from three random spots of the soil, and those corresponding to the same soil layer were combined after air-drying and ground in a mortar for analysis. The amount of C in each soil layer was determined by combusting aliquots of the mixed soils. Thericeplants were separated into straw, ear without grains, chaff, and brownricegrains, freeze-dried, and pulverized with a cutting mill to measure the radioactivity by combustion. 0.3 g of each plant or soil sample was combusted with a Biological Oxidizer (R. J. Harvey Instrument Corporation, U.S.A., OX-400)togive C0 which was absorbed in the C-cocktail (CARBO MAX PLUS LUMAC*LSC B.V., The Netherlands). The radioactivity was measured by LSC. The toluene cocktail was used for measuring the C-radioactivity in organic solvents that were evaporated before addition of the cocktail. The radioactivity of C0 trapped in 1 Ν NaOH and C-VOCs absorbed in 0.1 Ν H S0 was measured using Aquasol (Packard, U.S.A.) as a cocktail. 3

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Flooded conditions of the grafting period

rice-

Non-flooded conditions of the postharvest period

ι—«—ι—'—ι—•—ι— —ι—«—ι—•—ι— —ι— —ι—•—ι— —ι— —r 0 2 4 6 8 10 12 14 16 18 20 1

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Weeks after application

Figure 2. Mineralization and volatilization of[l ^C]azimsulfuron from the soil surface to the air during the experimental period of 21 weefa in thefirstyear. MCRadioactivity applied = 100%.

Leachates from the lysimeter

As can be seen in Table Π, the total radioactivities of leachates through the lysimeter soil profile for six consecutive years were 9.98% of the original C-radioactivity applied, corresponding to an average of 0.55 #g/L as the azimsulfuron equivalent calculated on the basis of the specific C-radioactivity of the azimsulfuron applied. Comparing the annual amounts of C percolated through the lysimeter for six consecutive years, the amount increased remarkably in the third year after application and showed a tendency to decrease gradually thereafter, indicating the slow leaching of the azimsulfuron-derived C in soil. Peak concentration appeared in the third year, reaching the level of 0.79 #g/L. Lee et al (7) reported that the amounts of C percolated through the tworice-growinglysimeters treated with the sulfonylurea herbicide cinosulfuron during four consecutive years were less than 3% of the C applied. 1

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Partition of the C-radioactivity of the leachates between aqueous phase and organic phase

Since an increase in the radioactivity of the aqueous phase with time indicates the gradual formation of polar degradation products of azimsulfuron in soil, the leachates collected during thefirstthree years were acidified to pH 2 with hydrochloric acid and the C-radioactivity therein was partitioned between aqueous phase and organic phase. As can be seen in Figure 3, more than 93% of the radioactivity in the first year was distributed in the aqueous phase and less than 7% was distributed in the organic phase. 14


56 Table Π. Amounts of "C-radioactivity leached through the lysimeter soil treated once with [ C]azimsulfuron throughout six consecutive yean. C-Radioactivhy applied =100% 14


Period (Year)

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Amount Concentration of "COriginal Volume of leached azimsulfuron leachate Radioactivity amount leached (%)applied (mg) (mg) equivalent (jUgfL) (L)

1st

12.546

0.106

1.51

0.002

0.159

lst-2nd

36.066

0.224

1.51

0.003

0.083

lst-3rd

109.766

4.161

1.51

0.063

0.574

lst-4th

158.453

6.627

1.51

0.100

0.631

lst-5th

190.583

7.980

1.51

0.120

0.630

lst-6th

275.380

9.980

1.51

0.151

0.548

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Meanwhile, in the second year, the C-radioactivity distributed in the aqueous phase decreased down to 58.3%, and that in the organic phase increased up to 41.7%. However, in the third year, the C-radioactivity of the aqueous phase increased again up to more than 76.4% and that of the organic phase was less than 41.7%. The increased C-radioactivity in the organic phase in the second year would be due to the slow and steady leaching of the unchanged azimsulfuron and/or less polar degradation products. In addition, in order to elucidate the C-radioactivity contained in the leachates, they were acidifiedtopH 2 and extracted with methylene chloride. When the concentrated extract was subjected to autoradiography, no parent azimsulfuron could be detected (the autoradiogram is not presented). This fact indicates that after 5 years or so, the parent chemical is no longer present in the leachates. 14

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Figure 3. Partition ofthe C-radioactivity of the leachatesfromthe lysimeter treated with f C]azimsulfuron between aqueous and organic phase. C-Radioactivity of aqueous phase + C-radioactivity of organic phase = 100%. 4

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57 Distribution of "C-radioactivity in rice plants 14

The C-radioactivity absorbed and translocated into each part ofriceplants for six consecutive years is presented in Table ΠΙ. C-Radioactivity was detected in all parts such as straw, ears without grains, chaff, and brown rice grains until the sixth cultivation year and the total amount of C-radioactivity distributed in rice plants except for roots was 4.01% of the original C-radioactivity applied. Larger amounts of azimsulfuron equivalents (0.10-1.50%) were distributed in the straw than in any other parts. More than 90% of the total C-radioactivity inriceplants excluding roots remained in the straw except for 80.47% in the sixth year, while 0.15-7.81% in brown rice grain. However, the amounts in the straw decreased gradually year after year. The maximum residue limit (MRL) of azimsulfuron for brownricegrain set by both Korea and Japan is 0.1 mg/kg. From the viewpoint of its safe use, each brown rice grain harvested every year contained the residue far below the MRL, irrespective of the applied amount four times larger than the recommended one in Korea. l4

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Table ID. Amounts (%) of the C-radioactivhy absorbed and translocated in each part of rice plants grown on the lysimeter soil treated with [ C]azimsulfuron. CRadioactivity applied - 100% 14

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Part of rice plants

Total 1st

2nd

3rd

4th

5th

6th

Straw

1.502 (0.122)*

0.613 (0.022)

0.612 (0.010)

0.459 (0.009)

0.429 (0.029)

0.103 (0.003)

3.718

Ears without rice grain

0.007 (0.017)

0.006 (0.020)

0.028 (0.010)

0.008 (0.015)

0.002 (

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