Effects of agricultural conditions on the leaching behaviour of veterinary antibiotics in soils.

Antibiotics may be released to soils during the application of manure as fertiliser to land. The compounds may subsequently be transported to and contaminate groundwater and surface waters. This paper describes a series of lysimeter-based studies to explore the leaching behaviour of three veterinary antibiotics (sulfachloropyridazine, oxytetracycline and tylosin) under different conditions that could occur in the agricultural environment. The specific objectives were to: (1) explore the influence of slurry amendment and incorporation on leaching; (2) assess the effects of climate on leaching behaviour; and (3) evaluate the predictive capability of a leaching model used in the regulatory assessment of veterinary medicines. Sulfachloropyridazine was detected sporadically in leachate at concentrations up to 0.66 microg L(-1) under typical irrigation conditions and more frequently at concentrations up to 8.5 microg L(-1) under extreme irrigation conditions. Incorporation and timing of rainfall had no effect on leaching behaviour. Oxytetracycline and tylosin were not detected in any leachate samples. These differences in behaviour were explained by the sorption and persistence characteristics of the compounds. Comparison of the experimental measurements with simulations from the leaching model indicated that the model greatly underestimates the transport of antibiotics to groundwater which raises questions over the application of these models in the regulatory risk assessment process.

The dissipation and transport of veterinary antibiotics in a sandy loam soil.

The environmental fate of the antibiotics sulfachloropyridazine and oxytetracycline was investigated in a sandy loam soil. Liquid pig manure was fortified with the compounds and then applied to soil plots to investigate leaching, dissipation and surface run-off under field conditions. Additionally, as the macrolide antibiotic tylosin had been administered to the pigs from which the slurry had been sourced, this was also analysed for in the samples collected. Sulfachloropyridazine dissipated rapidly with DT(50) and DT(90) values of 3.5 and 18.9 days but oxytetracycline was more persistent with DT(50) and DT(90) values of 21.7 and 98.3 days. Both sulfachloropyridazine and oxytetracyline were detected in surface run-off samples at maximum concentrations of 25.9 and 0.9microg/l respectively but only sulfachloropyridazine was detected in soil water samples at a maximum concentration of 0.78microg/l at 40cm depth 20 days after treatment. Tylosin was not detected in any soil or water samples. The results indicated that tylosin, when applied in slurry, posed very little risk of accumulating in soil or contaminating ground or surface water. However, tylosin may pose a risk if used to treat animals on pasture and risks arising from transformation products of tylosin, formed during slurry storage, cannot be ruled out. Oxytetracycline posed a very low risk of ground or surface water contamination but had the potential to persist in soils and sulfachloropyridazine posed a moderate risk of contaminating ground or surface water but had low potential to accumulate in soils. These findings were consistent with the sorption and persistence characteristics of the compounds and support a number of broad-scale monitoring studies that have measured these antibiotic classes in the environment.

Column studies to investigate the fate of veterinary antibiotics in clay soils following slurry application to agricultural land.

The environment may be exposed to veterinary medicines administered to livestock due to the application of organic fertilisers to land. For other groups of substances that are applied to agricultural land (e.g. pesticides), preferential flow in underdrained clay soils has been identified as an extremely important pathway by which pollution of surface waters can occur. Three soil column leaching experiments have therefore been carried out using a clay soil to investigate the fate of a range of antibiotics from the sulphonamide, tetracycline and macrolide groups. These column studies complemented a range of other experiments at the field and semi-field scales, as well as modelling studies which are being reported in separate papers. Each column study had a different objective. The first examined the effect of pig slurry on the mobility of antibiotics in clay loam soil. The second experiment investigated changes in soil water pH due to the application of slurry. The final experiment quantified the extent to which soil tillage prior to slurry application can reduce the leaching of antibiotic residues found in slurry. It was found that slurry had no impact on the leaching of oxytetracycline although soil water pH was affected significantly by slurry application. It was also shown that pre-tillage can substantially reduce the leaching of antibiotic residues through macroporous clay soils.

Transport of veterinary antibiotics in overland flow following the application of slurry to arable land.

The environment may be exposed to veterinary medicines administered to livestock due to the application of organic fertilisers to land. Slurry is often spread on to fields following the harvest of the previous crop. Despite recommendations to do so, the slurry may not be ploughed into the soil for some time. If precipitation occurs before incorporation then it is likely that the slurry and any antibiotic residues in the slurry will be transported towards surface waters in overland flow. This phenomenon has been investigated in a plot study and transport via 'tramlines' has been compared to that through crop stubble. Three veterinary antibiotics, from the tetracycline, sulphonamide and macrolide groups, were applied to the plots in pig slurry. Twenty four hours after the application the plots were irrigated. Following this the plots received natural rainfall. Sulphachloropyridazine was detected in runoff from the tramline plot at a peak concentration of 703.2 microgl(-1) and oxytetracycline at 71.7 microgl(-1). Peak concentrations from the plot that did not contain a tramline were lower at 415.5 and 32 microgl(-1), respectively. In contrast, tylosin was not detected at all. Mass losses of the compounds were also greater from the tramline plot due to greater runoff generation. These did not exceed 0.42% for sulphachloropyridazine and 0.07% for oxytetracycline however.

Evaluation of a lower tier exposure assessment model for veterinary medicines.

Veterinary antibiotics are used in large quantities in the European Union, and one of the key environmental exposure routes is via the application of manure containing excreted antibiotics to arable land as fertilizer. It is a legal requirement to assess the environmental risk of veterinary medicines, and this is done in two stages. A key decision parameter in phase I of these assessments is the predicted environmental concentration (PEC) in soil, and if a trigger value of 100 microg/kg is exceeded, then further phase II studies on the fate, behavior, and effects are carried out. A widely used model to calculate manure and soil PECs is the Uniform Approach. This study evaluated the Uniform Approach in two ways: first, by reviewing existing data, addressing data gaps by performing degradation studies, and then calculating soil and manure PECs for the veterinary antibiotics sulfachloropyridazine, oxytetracycline, and tylosin applied to arable land via liquid pig manure and comparing these data with the results from two field-scale fate studies; second, by collating monitoring data and making a comparison with modeled data. The data comparisons indicated that the Uniform Approach model performed conservatively, with initial PECs being up to 2 orders of magnitude greater than measured environmental concentrations, providing confidence in the use of the model in the risk assessment process, although the assumption of first-order degradation kinetics in the model may underestimate the environmental persistence of veterinary antibiotics.

A lysimeter experiment to investigate the leaching of veterinary antibiotics through a clay soil and comparison with field data.

Pharmaceuticals used in livestock production may be present in manure and slurry as the parent compound and/or metabolites. The environment may therefore be exposed to these substances due to the application of organic fertilisers to agricultural land or deposition by grazing livestock. For other groups of substances that are applied to land (e.g. pesticides), preferential flow in clay soils has been identified as an extremely important mechanism by which surface water pollution can occur. This lysimeter study was therefore performed to investigate the fate of three antibiotics from the sulphonamide, tetracycline and macrolide groups in a clay soil. Only sulphachloropyridazine was detected in leachate and soil analysis at the end of the experiment showed that almost no antibiotic residues remained. These data were analysed alongside field data for the same compounds to show that soil tillage which breaks the connectivity of macropores formed over the summer months, prior to slurry application, significantly reduces chemical mobility.

Fast and robust simultaneous determination of three veterinary antibiotics in groundwater and surface water using a tandem solid-phase extraction with high-performance liquid chromatography-UV detection.

A simple and robust analytical method is presented in which the three veterinary antibiotics oxytetracycline (OTC), sulfachloropyridazine (SCP) and tylosin (TYL) were simultaneously determined in surface water and groundwater. The three compounds were simultaneously extracted from the water samples using a mixture of methanol, EDTA and McIlvaine buffer (citric acid and sodium orthophosphate) and then cleaned-up and pre-concentrated by solid-phase extraction using sacrificial Isolute strong anion-exchange cartridges, to remove interfering organic material, and Waters Oasis hydrophilic-liphophilic balance polymer cartridges, to retain the compounds, in tandem. Analysis was performed using liquid chromatography with ultraviolet detection. Recoveries for river water samples spiked at 10 and 1 microgl(-1) were respectively 99.6+/-4.6 and 99.4+/-8.4% for OTC; 99.9+/-2.2 and 105.0+/-5.7% for SCP; and 94.9+/-2.4 and 71.6+/-8.2% for TYL. Overall limits of detection based on pre-concentrating 400 ml of sample were 0.35 microgl(-1) for OTC and TYL and 0.25 microgl(-1) for SCP.

Fate of veterinary antibiotics in a macroporous tile drained clay soil.

The environment may be exposed to veterinary medicines administered to livestock through the application of organic fertilizers to land. For other groups of substances that are applied to agricultural land (e.g., pesticides), preferential flow in underdrained clay soils has been identified as an extremely important mechanism by which pollution of surface waters can occur. This study, therefore, was performed to investigate the fate of three antibiotics from the sulfonamide, tetracycline, and macrolide groups. Pig slurry was applied to a field in arable production in two consecutive years and the fate of the compounds was monitored in the soil and drainage water. Both sulfachloropyridazine and oxytetracycline were detected in soil at concentrations up to 365 and 1691 microg/kg, respectively. Subsequently, peak concentrations of the two substances in drainflow were 613.2 and 36.1 microg/L, although mass losses to the receiving water were less than 0.5%. In contrast, tylosin was not detected at all. These findings could be explained by the persistence and sorption characteristics of the antibiotics, while preferential flow via desiccation cracks and worm channels to the tile drains was found to be the most important route for translocation of the chemicals. Thus, when the soil was disced prior to slurry application, losses were reduced significantly. It is evident that processes governing pesticide fate also apply to veterinary antibiotics.

Ultrasonic extraction of veterinary antibiotics from soils and pig slurry with SPE clean-up and LC-UV and fluorescence detection.

A simple and rapid analytical method is presented in which the three veterinary antibiotics oxytetracycline (OTC), sulfachloropyridazine (SCP) and tylosin (TYL) are simultaneously extracted and determined in four different soils. Extractions were carried out by a combination of ultrasonic agitation and vortex mixing using a mixture of methanol, EDTA and McIlvaine buffer at pH 7 as the extractant solution. The extracts were then cleaned-up by a tandem solid phase extraction (SPE) method using an Isolute SAX anion exchange cartridge to remove natural organic matter and an Oasis HLB polymeric cartridge to retain the study compounds. Analysis was by HPLC-UV with additional fluorescence detection for SCP. Recoveries were in the range 68-85% for SCP in all soil types, 58-75% for OTC in sandy soils, 27-51% for OTC in clay containing soils, 74-105% for TYL and 47-61% in a clay soil. OTC and SCP were also extracted from liquid pig manure using a mixture of EDTA and McIlvaine buffer at pH 7 with ultrasonic agitation and vortex mixing with SPE clean-up and HPLC-UV analysis. Recoveries were greater than 77% and 58% for OTC and SCP, respectively. Limits of detection were 18mugkg(-1) for OTC and SCP and 40mugkg(-1) for TYL in soils and 70mugL(-1) for OTC and 140mugL(-1) for SCP in pig slurry.