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1.
Antibiotics may enter soils with manure from treated animals. Because of their biological effects, antibiotics are regarded as potential micropollutants. The levels of oxytetracycline and tylosin over time were followed in faeces, bedding and manure, and then in the soil of a manured field and surrounding drainage courses, after oral treatment of calves. Fifty Simmental calves were treated for 5 days with 60 mg/kg/day of oxytetracycline. After 15 days the animals were treated for 5 days with 20 mg/kg/day of tylosin. Tylosin degraded rapidly, and was no longer detected in manure 45 days after cessation of treatment and no trace of the compound was detected in soil or surrounding water (detection limits 10 microg/l). The half-life of oxytetracycline in manure was 30 days and the compound was still detectable in this matrix (820 microg/kg) after 5 months maturation. In the manured soil oxytetracycline was detected at concentrations at least 10 times lower than the European Agency for the Evaluation of Medicinal Products threshold (100 microg/kg) requiring phase II environmental risk assessment. Oxytetracycline was not detected in the water courses (detection limit 1 microg/l). These results demonstrate that the processes occurring between faeces production and application of manure to the soil are very effective in reducing the load of TYL and OTC in the environment. For both drugs a toxicity test was performed using the alga Selenastrum capricornutum. The EC50 was 4.18 mg/l for oxytetracycline and 0.95 mg/l for tylosin. A worst-case hazard assessment for the aquatic environment was performed comparing the ratio between the measured concentrations (LOD) and effect data from previous work (OTC) or from this work (TYL). This showed ratio between toxicity levels (bacteria) (EC50=0.14 mg/l) and measured concentrations (LOD=1 microg/l) for OTC to be 140. The corresponding value for TYL (LOD=10 microg/l) was 95.  相似文献   

2.
Research was conducted on nitrogen (N) surface run-off losses following organic manure applications to land, utilising a purpose-built facility on a sloping site in Herefordshire under arable tillage. Different rates and timing of cattle slurry, farmyard manure and inorganic N and phosphorus (P) fertiliser were compared, over a 4-year period (1993-97). P losses from the same studies are reported in a separate paper. The application of cattle slurries to the silty clay loam soil increased the loss of solids and NH4(+)-N in surface water flow compared to control plots receiving inorganic fertiliser only, or no treatment, but had little effect on NO3(-)-N losses by this route. Results were consistent with other observations that rainfall events immediately after manure applications are particularly likely to be associated with nutrient run-off losses. Losses via subsurface flow (30 cm interflow) were consistently much lower than via surface water movement and were generally unaffected by treatment. Increasing slurry application rate and, in particular, slurry solids loading, increased solids and NH4(-)-N losses via surface run-off. The threshold, above which the risk of losses via surface run-off appeared to be greatly increased, was ca. 2.5-3.0 t/ha slurry solids, which approximates to the 50 m3/ha limit suggested for slurry within UK 'good agricultural practice'. Sealing of the soil surface by slurry solids appears to be a possible mechanism by which polluting surface run-off may occur following slurry application on susceptible soils. Total losses of NH4(+)-N and NO3(-)-N during the 4-year monitoring period were insignificant in agronomic terms, but average soluble N concentrations (NH4(+)-N + NO3(-)-N) in run-off, ranging from ca. 2.0 mg/l, up to 14.0 mg/l for the higher rate slurry treatments. Peak concentrations of NH4(+)-N > 30 mg/l, are such as to be of concern in sensitive catchments, in terms of the potential for contribution to accelerated eutrophication and adverse effects on freshwater biota.  相似文献   

3.
Kay P  Blackwell PA  Boxall AB 《Chemosphere》2005,59(7):951-959
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.  相似文献   

4.
Phosphorus (P) surface run-off losses were studied following organic manure applications to land, utilising a purpose-built facility on a sloping site in Herefordshire under arable tillage. Different rates and timing of cattle slurry, farm yard manure (FYM) and inorganic nitrogen (N) and P fertiliser were compared, over a 4-year period (1993-97). N losses from the same studies are reported in a separate paper. The application of cattle FYM and, especially slurry, to the silty clay loam soil increased both particulate and soluble P loss in surface water flow. Losses via subsurface flow (30 cm interflow) were consistently much lower than via surface water movement and were generally unaffected by treatment. Increased application of slurry solids increased all forms of P loss via surface run-off; the results suggested that a threshold for greatly increased risk of P losses via this route, as for N, occurred at ca. 2.5-3.0 t/ha solids loading. This approximates to the 50 m3/ha application rate limit suggested for slurry within UK 'good agricultural practice'. The studies also provided circumstantial evidence of the sealing of the soil surface by slurry solids as the major mechanism by which polluting surface run-off may occur following slurry application on susceptible soils. Losses of total and soluble P, recorded for each of the 4 years of experiments, reached a maximum of only up to 2 kg/ha total P (TP), even after slurry applications initiating run-off. Whilst these losses are insignificant in agronomic terms, peak concentrations of P (up to 30,000 micrograms/l TP) in surface water during a run-off event, could be of considerable concern in sensitive catchments. Losses of slurry P via surface run-off could make a significant contribution to accelerated eutrophication on entry to enclosed waters, particularly when combined with high concentrations of NO3(-)-N. Restricting slurry application rates to those consistent with good agronomic practice, and within the limits specified in existing guidelines on good agricultural practice, offers the simplest and most effective control measure against this potentially important source of diffuse pollution.  相似文献   

5.
The primary aerobic and anaerobic biodegradability at intermediate concentrations (50-5000 microg/l) of the antibiotics olaquindox (OLA), metronidazole (MET), tylosin (TYL) and oxytetracycline (OTC) was studied in a simple shake flask system simulating the conditions in surface waters. The purpose of the study was to provide rate data for primary biodegradation in the scenario where antibiotics pollute surface waters as a result of run-off from arable land. The source of antibiotics may be application of manure as fertilizer or excreta of grazing animals. Assuming first-order degradation kinetics, ranges of half-lives for aerobic degradation of the four antibiotics studied were 4-8 days (OLA), 9.5-40 days (TYL), 14-104 days (MET) and 42-46 days (OTC). OLA and OTC were degraded with no initial lag phase whereas lag phases from 2 to 34 days (MET) and 31 to 40 days (TYL) were observed for other substances. The biodegradation behaviour was influenced by neither the concentrations of antibiotics nor the time of the year and location for sampling of surface water. Addition of 1 g/l of sediment or 3 mg/l of activated sludge from wastewater treatment increased the biodegradation potential which is believed to be the result of increased bacterial concentration in the test solution. Biodegradation was significantly slower in tests conducted in absence of oxygen. Assessments of the toxic properties of antibiotics by studying the influence on the biodegradation rates of 14C-aniline at different concentrations of antibiotics showed that no tests were conducted at toxic concentrations.  相似文献   

6.
Kay P  Blackwell PA  Boxall AB 《Chemosphere》2005,60(4):497-507
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.  相似文献   

7.
Olaquindox (log Kow = -2.3) and metronidazole (log Kow = -0.1) both have low tendencies to sorp to particles in manure. This corresponds with the negative log Kow values of these antibiotics. Tylosin (log Kow = 1.63) and oxytetracycline (log Kow = -1.12) sorp relatively strongly to the manure particles and have log Kd values between 1.5 and 2.0. The tendency to bind to manure was ranked after increasing binding as follows: metronidazole < olaquindox < tylosin A and oxytetracycline. This order of ranking is consistent with results of sorption in soil. Our experiments illustrate that for some antibacterial agents estimation of the partitioning coefficients, Kd, cannot be made from Kow and f(oc) alone. Sorption of oxytetracycline to manure is much higher than expected from the negative log Kow value of the compound. It is believed that sorption of oxytetracycline to manure is influenced by ionic binding to divalent metal ions as such Mg2+ and Ca2+ as well as other charged compounds in the matrix. Binding of oxytetracycline to soil is stronger than the binding to manure. This is most likely due to the strong mineral related metal complexes formed between soil, metal ion and oxytetracycline. These complexes are not known to exist in manure. The relatively strong sorption of tylosin A to manure corresponds with data found for soil sorption of tylosin. Tylosin has a log Kow value of 2.5, thus it is not surprising that this drug binds strongly to manure.  相似文献   

8.
Little is known about the fate of antimicrobials during common agricultural waste handling procedures. To better define the potential scope of this problem, concentrations of antimicrobials throughout the waste treatment process were estimated based on known antimicrobial usage, and the resulting predictions of high antimicrobial concentrations indicated the need for further investigation. Samples from building pits, a solids settling basin, a holding pond, and soil amended with waste treatment byproducts were therefore analyzed for traditional chemical parameters and macrolide, lincosamide, and tetracycline antimicrobials. Substantial improvements in water quality were observed during the treatment process. While the macrolide tylosin was not detected, chlortetracycline, oxytetracycline, and lincomycin were found at high concentrations throughout the waste treatment process. Oxytetracycline and lincomycin were also detected in soil from a field amended with waste treatment byproducts.  相似文献   

9.
Three types of farm waste (cattle slurry, dirty water and farm yard manure (FYM)) were applied to hydrologically isolated grassland plots on a sloping poorly draining soil. Two applications were made, the first in October and the second in February. Application rates were 50 m(3) ha(-1) of slurry and dirty water and 50 t ha(-1) of FYM. Volumes of run-off following rainfall events and concentrations of N, P and K in run-off were measured. Losses of nutrients were higher following applications made with the soil at field capacity and rainfall soon after application. In terms of percentage loss of applied nutrients, losses were generally low. Concentration of N in run-off from the dirty water and FYM treated plots following the first application and the slurry treated plots following the second application exceeded 11.3 mg dm(-3) (a recommended limit for drinking water) although the maximum concentration recorded was 15 mg dm(-3) following FYM application. Concentration of P in run-off only exceeded 1 mg dm(-3) following the second application of cattle slurry. Concentration of K exceeded 10 mg dm(-3) following the first application of FYM and the second application of cattle slurry.  相似文献   

10.
The transport of oxytetracycline, chlortetracycline, and ivermectin from manure was assessed via surface runoff on irrigated pasture. Surface runoff plots in the Sierra Foothills of Northern California were used to evaluate the effects of irrigation water application rates, pharmaceutical application conditions, vegetative cover, and vegetative filter strip length on the pharmaceutical discharge in surface runoff. Experiments were designed to permit the maximum potential transport of pharmaceuticals to surface runoff water, which included pre-irrigation to saturate soil, trimming grass where manure was applied, and laying a continuous manure strip perpendicular to the flow of water. However, due to high sorption of the pharmaceuticals to manure and soil, less than 0.1% of applied pharmaceuticals were detected in runoff water. Results demonstrated an increase of pharmaceutical transport in surface runoff with increased pharmaceutical concentration in manure, the concentration of pharmaceuticals in runoff water remained constant with increased irrigation flow rate, and no appreciable decrease in pharmaceutical runoff was produced with the vegetative filter strip length increased from 30.5 to 91.5 cm. Most of the applied pharmaceuticals were retained in the manure or within the upper 5 cm of soil directly beneath the manure application sites. As this study evaluated conditions for high transport potential, the data suggest that the risk for significant chlortetracycline, oxytetracycline, and ivermectin transport to surface water from cattle manure on irrigated pasture is low.  相似文献   

11.
Effects of the antibiotics oxytetracycline and tylosin on soil fauna   总被引:11,自引:0,他引:11  
Baguer AJ  Jensen J  Krogh PH 《Chemosphere》2000,40(7):751-757
Antibiotics may enter the terrestrial environment when amending soils with manure. A Note of Guidance on ecological risk assessment of veterinary medicines was issued in January 1998. Hardly any information about ecotoxicological effects of already existing substances are available. This study has tested the effects of two widely used antibiotics, tylosin and oxytetracycline, on three species of soil fauna: Earthworms, springtails and enchytraeids. Neither of the substances had any effect at environmentally relevant concentrations. The lowest observed effect concentration was 3000 mg kg-1 and in many cases no effect was seen even at the highest test concentration of 5000 mg kg-1.  相似文献   

12.
Sewage samples from 4 hospitals, 1 nursery, 1 slaughter house, 1 wastewater treatment plant and 5 source water samples of Chongqing region of Three Gorge Reservoir were analyzed for macrolide, lincosamide, trimethoprim, fluorouinolone, sulfonamide and tetracycline antibiotics by online solid-phase extraction and liquid chromatography-tandem mass spectrometry. Results showed that the concentration of ofloxacin (OFX) in hospital was the highest among all water environments ranged from 1.660 μg/L to 4.240 μg/L and norfloxacin (NOR, 0.136-1.620 μg/L), ciproflaxacin (CIP, ranged from 0.011 μg/L to 0.136 μg/L), trimethoprim (TMP, 0.061-0.174 μg/L) were commonly detected. Removal range of antibiotics in the wastewater treatment plant was 18-100% and the removal ratio of tylosin, oxytetracycline and tetracycline were 100%. Relatively higher removal efficiencies were observed for tylosin (TYL), oxytetracycline (OXY) and tetracycline (TET)(100%), while lower removal efficiencies were observed for Trimethoprim (TMP, 1%), Epi-iso-chlorotetracycline (EICIC, 18%) and Erythromycin-H2O (ERY-H2O, 24%). Antibiotics were removed more efficiently in primary treatment compared with those in secondary treatment.  相似文献   

13.
Menon P  Gopal M 《Chemosphere》2003,53(8):1023-1031
The dissipation of 14C carbaryl in undisturbed soil cores, and of quinalphos (25EC and 20AF) after seed and soil treatments, was investigated under field use conditions, in a semi-arid groundnut field. Residues were analyzed by TLC and HPLC and additionally by LSC for 14C carbaryl. The harvested seed kernels were also tested for the presence of insecticide residues. The movement of carbaryl was limited to 15 cm depth in the loamy sand of Jaipur and was detected till 120 days (DT50 of 14.93 days) after application. Bound residues and 1-naphthol had a DT50 of 11.45 and 13.68 days, respectively. Irrespective of the three types of soil samples investigated, the principal metabolite formed on seed and soil treatments with quinalphos, was 2-hydroxyquinoxaline. With seed treatment, a thiol metabolite of quinalphos was also detected. Higher yields of groundnut were realized with quinalphos treatments in comparison to those from control. Post-harvest, no pesticide residues were found in seeds.  相似文献   

14.
The fate of glyphosate and its degradation product aminomethylphosphonic acid (AMPA) was studied in soil. Labeled glyphosate was used to be able to distinguish the measured quantities of glyphosate and AMPA from the background values since the soil was sampled in a field where glyphosate had been used formerly. After addition of labeled glyphosate, the disappearance of glyphosate and the formation and disappearance of AMPA were monitored. The resulting curves were fitted according to a new EU guideline. The best fit of the glyphosate degradation data was obtained using a first-order multi compartment (FOMC) model. DT(50) values of 9 days (glyphosate) and 32 days (AMPA) indicated relatively rapid degradation. After an aging period of 6 months, the leaching risk of each residue was determined by treating the soil with pure water or a phosphate solution (pH 6), to simulate rain over a non-fertilized or fertilized field, respectively. Significantly larger (p < 0.05) amounts of aged glyphosate and AMPA were extracted from the soil when phosphate solution was used as an extraction agent, compared with pure water. This indicates that the risk of leaching of aged glyphosate and AMPA residues from soil is greater in fertilized soil. The blank soil, to which 252 g glyphosate/ha was applied 21 months before this study, contained 0.81 ng glyphosate/g dry soil and 10.46 ng AMPA/g dry soil at the start of the study. Blank soil samples were used as controls without glyphosate addition. After incubation of the blank soil samples for 6 months, a significantly larger amount of AMPA was extracted from the soil treated with phosphate solution than from that treated with pure water. To determine the degree of uptake of aged glyphosate residues by crops growing in the soil, (14)C-labeled glyphosate was applied to soil 6.5 months prior to sowing rape and barley seeds. After 41 days, 0.006 +/- 0.002% and 0.005 +/- 0.001% of the applied radioactivity was measured in rape and barley, respectively.  相似文献   

15.
Antimony bioavailability in mine soils   总被引:5,自引:0,他引:5  
Five British former mining and smelting sites were investigated and found to have levels of total Sb of up to 700 mg kg(-1), indicating high levels of contamination which could be potentially harmful. However, this level of Sb was found to be biologically unavailable over a wide range of pH values, indicating that Sb is relatively unreactive and immobile in the surface layers of the soil, remaining where it is deposited rather than leaching into lower horizons and contaminating ground water. Sb, sparingly soluble in water, was unavailable to the bacterial biosensors tested. The bioluminescence responses were correlated to levels of co-contaminants such as arsenic and copper, rather than to Sb concentrations. This suggests that soil contamination by Sb due to mining and smelting operations is not a severe risk to the environment or human health provided that it is present as immobile species and contaminated sites are not used for purposes which increase the threat of exposure to identified receptors. Co-contaminants such as arsenic and copper are more bioavailable and may therefore be seen as a more significant risk.  相似文献   

16.
Watershed contamination from antibiotics is becoming a critical issue because of increased numbers of confined animal-feeding operations and the use of antibiotics in animal production. To understand the fate of tylosin in manure before it is land-applied, degradation in manure lagoon slurries at 22 degrees C was studied. Tylosin disappearance followed a biphasic pattern, where rapid initial loss was followed by a slow removal phase. The 90% disappearance times for tylosin, relomycin (tylosin D), and desmycosin (tylosin B) in anaerobically incubated slurries were 30 to 130 hours. Aerating the slurries reduced the 90% disappearance times to between 12 and 26 hours. Biodegradation and abiotic degradation occur, but strong sorption to slurry solids was probably the primary mechanism of tylosin disappearance. Dihydrodesmycosin and an unknown degradate with molecular mass of m/z 934.5 were detected. Residual tylosin remained in slurry after eight months of incubation, indicating that degradation in lagoons is incomplete and that residues will enter agricultural fields.  相似文献   

17.
Sorption and desorption of sulfadiazine in soil and soil-manure systems   总被引:10,自引:0,他引:10  
Sulfadiazine is a widely used veterinary medicine that has high potential to enter the environment, especially the soil compartment by the application of manure on agricultural land and grass land or by the deposition of dung pats on pasture. Once it reaches the soil environments, it may enter into surface and ground water. Therefore, sorption-desorption behavior of sulfadiazine was studied under laboratory conditions in five different soils varying in their physicochemical properties. A batch equilibration technique was used with initial aqueous solution concentration of sulfadiazine at 5, 0.5, 0.05, and 0.005 microg mL(-1). Sorption-desorption data in soils with and without manure were well fitted with Freundlich model in log form (r(2), 0.99). A sorption-desorption hysteresis effect was apparent in all soils. A significant amount of sulfadiazine was found tightly bound to the soil particles and did not desorb after the desorption process. Moreover, presence of manure enhanced hysteresis effect. Hysteresis coefficient (H) value from soils in absence of manure (0.9-1.0) increased to the soils in presence of manure (0.9-1.8). Soils in the absence of manure showed low level of K(D Sorp.) values ranging from 0.1 to 24.3, suggesting low level sorption of sulfadiazine with appreciable risk of run-off and leaching, and in turn, surface and ground water contamination. However, presence of manure increased the sorption tendency of sulfadiazine significantly (K(D Sorp.), 6.9-40.2). K(D) values pertaining to desorption cycle increased from 1.2-90.4 to 10.4-167.3 in absence and presence of manure, respectively.  相似文献   

18.
This study assessed the runoff potential of tylosin and chlortetracycline (CTC) from soils treated with manure from swine fed rations containing the highest labeled rate of each chemical. Slurry manures from the swine contained either CTC at 108 μ g/g or tylosin at 0.3 μ g/g. These manures were surface applied to clay loam, silty clay loam, and silt loam soils at a rate of 0.22 Mg/ha. In one trial, tylosin was applied directly to the soil surface to examine runoff potential of water and chemical when manure was not present. Water was applied using a sprinkler infiltrometer 24-hr after manure application with runoff collected incrementally every 5 min for about 45 min. A biofilm crust formed on all manure-treated surfaces and infiltration was impeded with > 70% of the applied water collected as runoff. The total amount of CTC collected ranged from 0.9 to 3.5% of the amount applied whereas tylosin ranged from 8.4 to 12%. These data indicate that if surface-applied manure contains antimicrobials, runoff could lead to offsite contamination.  相似文献   

19.
Gupta S  Gajbhiye VT 《Chemosphere》2002,47(9):901-906
Effect of concentration, moisture and soil type on dissipation of flufenacet from soil has been studied under laboratory condition. The treated soil samples (1 and 10 microg/g levels) were incubated at 25+/-1 degrees C. The effect of moisture was studied by maintaining the treated soil samples (10 microg/g level) at field capacity and submerged condition. In general, flufenacet persisted for 60-90 days at lower and beyond 90 days at high rate. The dissipation of flufenacet from soil followed first order kinetics with half-life (DT50) values ranging from 10 to 31 days. The dissipation of flufenacet was faster at low rate than high rate of application. The slow dissipation at high rate could be attributed to inhibition of microbial activity at high rate. There was little overall difference in rate of dissipation in Ranchi and Nagpur soil maintained at field capacity and submerged condition moisture regimes. In Delhi soil net dissipation was faster under field capacity moisture than submerged condition. Soil types greatly influenced the dissipation of flufenacet. Dissipation was fastest in Delhi soil (DT50 10.1-22.3 days) followed by Ranchi soil (DT50 10.5-24.1 days) and least in Nagpur soil (DT50 29.2-31.0 days). The difference in dissipation could be attributed to the magnitude of adsorption and desorption of flufenacet in these soils.  相似文献   

20.
This study was undertaken to evaluate the degradation and mobility of the herbicide tebuthiuron (N-[5-(1,1-dimethylethyl)-1,3,4-thiadiazol-2-yl]-N,N'-dimethylurea) in soil under field conditions, and its potential for leaching and groundwater contamination. A watershed, Espraiado, located over a recharge area in Brazil, was chosen for soil and water studies. At Espraiado, water samples were collected from seven wells at intervals of three months from March 2004 to June 2006 and analyzed for tebuthiuron. Other samples were taken from city wells located outside of the recharge area. To assess the potential movement to the aquifer, tebuthiuron was also applied to trial plots at the recommended label rate of 1.0 kg/ha a.i. in May of 2004, with and without sugarcane coverage, on sandy soil. Soil samples were collected during the years of 2004 and 2005, at depths intervals of 20 cm from soil surface down to 120 cm and analyzed for tebuthiuron at zero, 3, 30, 60, 90, 120, 150, 180, 240, and 300 days after application. There was no clear effect of sugarcane coverage on the tebuthiuron degradation in soils, but it moved faster into the soil where there was no cover. After 180 days there were no measurable residues in the soil, and tebuthiuron was not found below 40 cm depth in any time. Tebuthiuron had a half-life of 20 days under those conditions. No tebuthiuron residue was found in ground water samples at any sampling time.  相似文献   

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