J. Agric. Food Chem. 2004, 52, 6217−6227
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Leaching of Pesticides from Biobeds: Effect of Biobed Depth and Water Loading PAUL FOGG
AND
ALISTAIR B. A. BOXALL
Cranfield Centre for EcoChemistry, Shardlow Hall, Shardlow, Derby DE72 2GN, United Kingdom
ALLAN WALKER
AND
ANDREW JUKES
Horticulture Research International, Wellesbourne, Warwickshire CV35 9EF, United Kingdom
Pesticides may be released to farmyard surfaces as a result of spillages, leakages, and the decontamination of tractors and sprayers. Biobeds can be used to intercept and treat contaminated runoff, thus minimizing losses to the environment. Previous studies using lined and unlined biobeds showed that water management was the limiting factor for both systems. While lined biobeds effectively retained pesticides, the system rapidly became water logged and degradation was slow. Studies using unlined biobeds showed that >99% of the applied pesticides were removed by the system, with a significant proportion degraded within 9 months. However, peak concentrations of certain pesticides (Koc < 125) were unacceptable to the regulatory authorities. These experiments were designed to optimize the design and management of unlined biobeds. Experiments performed to investigate the relationship between biobed depth and water loading showed that biobeds need to have a minimum depth of 1-1.5 m. The surface area dimension of the biobed depends on the water loading, which is controlled by the nature and frequency of pesticide handling activities on the farm. Leaching losses of all but the most mobile (Koc < 15) pesticides were 94% for all compounds. The limit of quantification was 0.23 µg L-1 for isoproturon, 0.12 µg L-1 for pendimethalin, 0.11 µg L-1 for chlorpyrifos, 0.22 µg L-1 for chlorothalonil, 0.10 µg L-1 for epoxiconazole, and 0.08 µg L-1 for dimethoate. HPLC Analysis. Concentrations of isoproturon, mecoprop, and metsulfuron-methyl in extracts from the water loading and depth studies were determined by HPLC using a Spectra Physics SP8810 pump linked to a Kontron 430 UV detector. Samples (20 µL) were injected using a Spectra Physics SP8775 autosampler. Separation was achieved using a Genesis C8 column (250 mm × 4.6 mm) (Jones Chromatography, Hengoed, United Kingdom). The mobile phase used was acetonitrile: methanol:0.05 M acetic acid (27:28:45) with a flow rate of 1.7 mL min-1, which gave retention times of 3.4, 5.0, and 7.5 min for metsulfuron-methyl, isoproturon, and mecoprop-P, respectively. The detection wavelength was 230 nm for all three substances. The limit of quantification was 0.05 µg L-1 for metsulfuron-methyl and mecoprop and 0.03 µg L-1 for isoproturon. LC/MS Analysis. Concentrations of metsulfuron-methyl in water were determined by LC/MS, operated in positive electrospray reaction monitoring mode (ES +MRM). Separation was achieved using a Spherisorb C8 3 µm ODS2 column (150 mm × 1.0 mm) (Jones Chromatography). The mobile phase used was methanol:10 mN ammonium formate:acetonitrile (47.5:47.5:5) with a flow rate of 50 µL min-1 and an injection volume of 2.5 µL. Quantification was achieved by comparison between the two transitions (m/z 382/167) quantification and (m/z 382/199) confirmation. Metsulfuron-methyl was reported if both transitions were present at around the correct ratio (10:1). The estimated limit of detection was 0.6 µg L-1. Bromide. Concentrations of potassium bromide were determined using two methods of ion chromatography. For the water loading experiment, water samples (0.5 mL) were filtered (0.2 µm) and analyzed using a Dionex DX-100 (Dionex UK Ltd., Maccelsfield, Cheshire). Samples (25 µL) were injected neat with a typical retention time of 2.3 min. The system was calibrated using a series of standards with known concentrations of bromide with a limit of detection set at 1.1 mg L-1. For the depth and water loading experiments, a Metrohm (Herisau, Switzerland) 790 Personal ion chromatograph and 813 compact autosampler were used. Analytical columns used were Metrohms’, Metrosep RP guard, Metrosep A Supp 4/5 guard, and Metrosep A Supp 4 (250 mm × 4.0 mm). A 20 µL injection loop and isocratic eluent of composition 1.8 mM sodium carbonate/1.7 mM sodium hydrogen carbonate were used giving a typical retention time of 8.5 min. All samples were filtered at 0.45 µm (Whatman 13 mm polysulfone syringe) prior to loading into the proprietary autosampler cartridges. The limit of quantification was 0.5 mg L-1, with a limit of detection at 0.1 mg L-1. RESULTS
Water Loading. The rainfall for the study period (January to September 2000) was 11% above average and totaled 486.3 mm. The leachate samples were collected on 28 occasions over the 244 day monitoring period. Cumulative leachate volumes from lysimeters receiving only direct inputs of rainfall ranged from 3.4 to 5.1 L. From lysimeters connected to the 0.135 m2 concrete slabs, leachate volumes ranged from 45.2 to 56.4 L and from those connected to the 0.54 m2 concrete slabs the volume recorded ranged from 103.7 to 177.6 L. A rapid breakthrough of bromide was observed 7 DAT for the lysimeters connected to the 0.54 and 0.135 m2 concrete slabs as compared to 57 DAT for the lysimeters receiving only direct inputs of rainfall (Figure 1). The maximum concentrations of bromide were measured 7 DAT from lysimeters connected to the 0.54 m2 slabs, 29 DAT from those connected to the 0.135 m2 slabs, and 221 DAT from those receiving only direct inputs of rainfall. With the exception of chlorpyrifos in lysimeters connected to 0.135 m2 slabs, the highest concentrations of
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J. Agric. Food Chem., Vol. 52, No. 20, 2004
Fogg et al. Table 2. Mass Balance for 0.5 m Long Biobed Columns Subjected to a Hydraulic Loading of 9747 L m-2 (Connected to 0.54 m2 Concrete Slabs)
Figure 1. Cumulative amounts of bromide measured in leachate collected
from lysimeters filled with 50 cm of biomix and subjected to three different hydraulic loadings.
pesticide were measured in leachate collected from lysimeters connected to 0.54 m2 slabs (Figure 2). For lysimeters receiving the highest hydraulic loading, concentrations of pesticide ranged from 1.21 µg L-1 for epoxiconazole to 1167 µg L-1 for isoproturon. For lysimeters receiving the water loading from 0.135 m2 slabs, the highest concentrations of pesticide ranged from to 0.35 µg L-1 for epoxiconazole to 258 µg L-1 for isoproturon, and for lysimeters receiving only direct inputs of rainfall, the highest concentrations of pesticide ranged from 0.57 µg L-1 for epoxiconazole to 1.65 µg L-1 for chlorpyrifos. The cumulative losses of isoproturon and dimethoate from lysimeters connected to 0.54 m2 slabs were 6.37 and 6.08% of the amount applied, respectively, with losses of each of the remaining pesticides being 99.5% (chlorpyrifos) was dissipated. The total amount of pesticide either retained or degraded by the system was >93%. For lysimeters with a medium hydraulic loading between 0.002 (epoxiconazole) and 0.61% (dimethoate) leached, 0.02 (dimethoate) and 34% (epoxiconazole) were associated with the biomix matrix and 85% (pendimethalin) to
Figure 2. Average concentrations of (a) isoproturon, (b) pendimethalin, (c) chlorpyrifos, (d) chlorothalonil, (e) epoxiconazole, and (f) dimethoate measured in leachate collected from 0.5 m long biobeds subjected to a high (0) and medium (O) water loadings and those receiving only direct inputs of rainfall.
J. Agric. Food Chem., Vol. 52, No. 20, 2004
Leaching of Pesticides from Biobeds
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Table 4. Mass Balance for 0.5 m Long Biobed Columns Subjected to a Hydraulic Loading of 486 L m-2 (Direct Inputs of Rainfall Only)
pesticide
% leached
% degraded
% retained
maximum concn (µg L-1)a
average concn (µg L-1)
isoproturon pendimethalin chlorpyrifos chlorothalonil epoxiconazole dimethoate
0.000 0.002 0.002 0.001 0.001 0.004
98.81 82.80 96.51 90.55 67.15 99.88
1.19 17.20 3.49 9.45 32.85 0.11
0.59 1.00 0.55 0.65 0.24 0.22
0.09 0.31 0.11 0.18 0.03 0.11
a
This is the highest concentration averaged across the three treated replicates.
>99.7% (isoproturon) was degraded. The total amount of pesticide either retained or degraded by the system was >99.3%. For lysimeters with no additional hydraulic loading,
