Chlortetracycline and tylosin runoff from soils treated with antimicrobial containing manure

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.     

Factors impacting on pharmaceutical leaching following sewage application to land

Sewage effluent application to land is a treatment technology that requires appropriate consideration of various design factors. Soil type, level of sewage pre-treatment and irrigation rate were assessed for their influence on the success of soil treatment in removing pharmaceuticals remaining after conventional sewage treatment. A large scale experimental site was built to assess treatment performance in a realistic environment. Of the factors investigated, soil type had the biggest impact on treatment performance. In particular, carbamazepine was very efficiently removed (>99%) when irrigated onto a volcanic sandy loam soil. This was in contrast to irrigation onto a sandy soil where no carbamazepine removal occurred after irrigation. Differences were likely caused by the presence of allophane in the volcanic soil which is able to accumulate a high level of organic matter. Carbamazepine apparent adsorption distribution coefficients (K(d)) for both soils when irrigated with treated sewage effluent were determined as 25 L kg(-1) for the volcanic soil and 0.08 L kg(-1) for the sandy soil. Overall, a volcanic soil was reasonably efficient in removing carbamazepine while soil type was not a major factor for caffeine removal. Removal of caffeine, however, was more efficient when a partially treated rather than fully treated effluent was applied. Based on the investigated pharmaceuticals and given an appropriate design, effluent irrigation onto land, in conjunction with conventional sewage treatment may be considered a beneficial treatment for pharmaceutical removal.     

Effect of vegetative filter strips on herbicide runoff under various types of rainfall

Narrow vegetative filter strips proved to effectively reduce herbicide runoff from cultivated fields mainly due to the ability of vegetation to delay surface runoff, promote infiltration and adsorb herbicides. A field trial was conducted from 2007 to 2009 in north-east Italy in order to evaluate the effectiveness of various types of vegetative filter strips to reduce spring-summer runoff of the herbicides mesotrione, metolachlor and terbuthylazine, widely used in maize, and to evaluate the effect of the rainfall characteristics on the runoff volume and concentration. Results show that without vegetative filter strip the herbicide load that reaches the surface water is about 5-6 g ha⁻¹ year⁻¹ for metolachlor and terbuthylazine (i.e. 0.5-0.9% of the applied rate), confirming that runoff from flat fields as in the Po Valley can have a minor effect on the water quality, and that most of the risk is posed by a few, or even just one extreme rainfall event with a return period of about 25-27 years, causing runoff with a maximum concentration of 64-77 μg L⁻¹. Mesotrione instead showed rapid soil disappearance and was observed at a concentration of 1.0-3.8 μg L⁻¹ only after one extreme (artificial) rainfall. Vegetative filter strips of any type are generally effective and can reduce herbicide runoff by 80-88%. Their effectiveness is steady even under severe rainfall conditions, and this supports their implementation in an environmental regulatory scheme at a catchment or regional scale.     

Distribution of sulfamethazine, chlortetracycline and tylosin in manure and soil of Canadian feedlots after subtherapeutic use in cattle

Feedlots are potential point sources for the flow of antibiotics into the environment due to common use of antibiotics such as sulfamethazine, chlortetracycline and tylosin. Hence soils and manures originating from a grassland control, an experimental and a commercial feedlot were analyzed and mass balances were calculated for these antibiotics. Up to 9990 μg kg⁻¹ sulfamethazine and 401 μg kg⁻¹ chlortetracycline on a dry matter basis were determined in feedlot manure. Soil concentrations were two orders of magnitude smaller. This corresponds to 7-40% of the calculated residual amount. In the commercial feedlot chlortetracycline was found down to soil depths of −40 cm; sulfamethazine was still detectable 1 year after medication. Sulfamethazine and chlortetracycline were additionally determined in manure of a control treatment in the experimental feedlot where cattle never received antibiotics. This was attributed to runoff from upslope pens. Consequently, antibiotics partially persist within feedlots and may be dislocated into the surrounding environment by vertical transport and runoff.     

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.     

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.     

Management-oriented sensitivity analysis for pesticide transport in watershed-scale water quality modeling using SWAT

The Soil and Water Assessment Tool (SWAT) was calibrated for hydrology conditions in an agricultural watershed of Orestimba Creek, California, and applied to simulate fate and transport of two organophosphate pesticides chlorpyrifos and diazinon. The model showed capability in evaluating pesticide fate and transport processes in agricultural fields and instream network. Management-oriented sensitivity analysis was conducted by applied stochastic SWAT simulations for pesticide distribution. Results of sensitivity analysis identified the governing processes in pesticide outputs as surface runoff, soil erosion, and sedimentation in the study area. By incorporating sensitive parameters in pesticide transport simulation, effects of structural best management practices (BMPs) in improving surface water quality were demonstrated by SWAT modeling. This study also recommends conservation practices designed to reduce field yield and in-stream transport capacity of sediment, such as filter strip, grassed waterway, crop residue management, and tailwater pond to be implemented in the Orestimba Creek watershed.     

Pressurized liquid extraction of six tetracyclines from agricultural soils

Veterinary antibiotics used in agriculture can be introduced into the environment through land application of animal manure, accumulating in soils and groundwaters and posing a significant risk to human health and animal well-being. As the analysis of tetracyclines in soil is challenging due to their strong interaction with soil minerals and organic carbon, the objective of this study was to develop a reliable and reproducible method for quantitative analysis of chlortetracycline and oxytetracycline, and their respective metabolites in soils. A method based on pressurized liquid extraction (PLE) with in-cell clean-up was developed for the extraction of chlortetracycline and oxytetracycline and four likely metabolites from a set of four soils. Optimized conditions included a cell size of 22?mL, soil loading of 5?g, pH of 8.0, methanol:water ratio of 3:1, 50?°C, and two cycles. Soil extracts were analysed by high-performance liquid chromatography (HPLC) coupled with ion trap mass spectrometry (MS). Recoveries of seven tetracyclines from soil ranged from 41% to 110%. The limits of detection for tetracyclines were 0.08–0.3 µg g^?1 soil, and intra- and inter-day variation ranged from 0.12–0.34%. The proposed PLE method is suitable for quantification of tetracyclines in agricultural soils at typical concentrations expected in contaminated environments.     

Assessment of manure-application effects upon the runoff water quality by algal assays and chemical analyses

The effects of manure-application mode, rate to soil, and rainfall characteristics on the quality of agricultural runoff water have been assessed by means of the algal-growth-potential test (AGPT) and chemical analyses. This study used two modes of manure application (i.e. surface mode and incorporation mode), three manure-application rates (0, 150, 300 kg N ha(-1)), and two rainfall intensities and times (i.e. 11 mm h(-1) for 142 min and 22 mm h(-1) for 71 min). The effects of the dilution of runoff water on algal growth were also examined. The algal yields obtained with runoff from soil with the incorporated manure mode are similar to those from soil without manure application and are lower than those with the surface mode of manure application. A higher manure-application rate increases the load of nutrients in the runoff and subsequently the algal yield. The dilution of runoff water can stimulate or limit the algal growth, depending on the concentration of toxicants, N (nitrogen) and P (phosphorus) from runoff and in the aquatic diluting medium. A lower rainfall intensity plus a longer rainfall time increases algal productivity. This study showed that N is the limiting factor to algal growth at low dilution but that, at high dilution or with the incorporation mode of manure application, P becomes the limiting factor to algal growth.     

The input-output balance of cadmium in a paddy field of Tokyo

Field monitoring was practiced from 2001 to 2003 to evaluate the input (irrigation, atmospheric deposition, and fertilizer application) and the output (uptake and accumulation into the above-ground biomass of rice plants and leaching) of cadmium (Cd) in a contaminated paddy field in Tokyo. The cadmium concentrations of irrigated water, open-bulk precipitation, soil solution (leaching water), rice plants collected at the harvesting stage and the chemical fertilizer and the cow manure compost applied were determined. The Cd flux of each factor was calculated by multiplying the Cd concentration by the volume or mass of the media. The annual input-output balance of Cd in the paddy field in 2001 and 2002 was estimated to be -5.44 [corrected] g ha(-1) and -2.01 [corrected] g ha(-1), respectively, indicating the loss of Cd from the paddy field, although the losses accounted for only 0.24% [corrected] and 0.089% [corrected] of the total amount of Cd in the ploughed layer soil in 2001 and 2002, respectively. Among the factors involved, the input from fertilizers (including manure compost) and the output due to the uptake by rice plants played a major role in the balance. The former largely depended on the types and amounts of fertilizers applied, and the latter on the water management practices in the paddy field, such as flooding and drainage of the surface water.     

A review of plant–pharmaceutical interactions: from uptake and effects in crop plants to phytoremediation in constructed wetlands

Pharmaceuticals are commonly found both in the aquatic and the agricultural environments as a consequence of the human activities and associated discharge of wastewater effluents to the environment. The utilization of treated effluent for crop irrigation, along with land application of manure and biosolids, accelerates the introduction of these compounds into arable lands and crops. Despite the low concentrations of pharmaceuticals usually found, the continuous introduction into the environment from different pathways makes them ‘pseudo-persistent’. Several reviews have been published regarding the potential impact of veterinary and human pharmaceuticals on arable land. However, plant uptake as well as phytotoxicity data are scarcely studied. Simultaneously, phytoremediation as a tool for pharmaceutical removal from soils, sediments and water is starting to be researched, with promising results. This review gives an in-depth overview of the phytotoxicity of pharmaceuticals, their uptake and their removal by plants. The aim of the current work was to map the present knowledge concerning pharmaceutical interactions with plants in terms of uptake and the use of plant-based systems for phytoremediation purposes.     

Effect of landfill leachate irrigation on red maple (Acer rubrum L.) and sugar maple (Acer saccharum Marsh.) seedling growth and on foliar nutrient concentrations

Greenhouse experiments were conducted to investigate the nature and severity of stresses imposed on northern hardwood tree species (red maple (Acer rubrum L.) and sugar maple (Acer saccharum Marsh.)) by the application of municipal landfill leachate. Red maple seedlings received applications of untreated and pretreated (lime, activated carbon) leachate, to both leaves and soil, at irrigation rates consistent with evapotranspirational demands. Plant height measurements indicated no significant growth effects arising from leachate application over a 7-week period. Stem diameter, however, was positively affected by applications of both untreated and lime-treated leachate diluted to 75% with deionized water. Iron foliar concentrations were significantly higher in seedlings irrigated with untreated leachate applied to leaves and soil, but not in seedlings where leachate was applied to soil only. Nitrogen foliar concentrations were substantially higher in seedlings receiving undiluted and untreated leachate applied to the soil only. The Cu concentration of the red maple foliage decreased appreciably in plants receiving moderate applications of leachate. Foliar Ca concentrations decreased notably in seedlings irrigated with untreated leachate applied to the soil and with diluted, carbon-treated leachate. The Cu concentration of the red maple foliage decreased appreciably in plants receiving applications of undiluted and 50% water-diluted lime-treated leachate while Mn levels were consistently high across all treatments. Leachate application did not cause any discernable changes in foliar concentrations of P, K, Mg, B or Zn. In an ancillary experiment, sugar maple seedlings were subjected to saturation/ drainage treatment cycles with undiluted and untreated leachate. Severe visible symptoms of vegetative stress were apparent within 24 h and 100% seedling mortality occurred after five such waterlogging cycles. Fe assimilation was apparent in both leachate treatments relative to the 24 h water treatment. Despite the short-term nature of the experiments, the results indicate how quickly forest vegetation may respond to altered chemical environments. This underscores the need for correct installation and control of leachate irrigation systems.     

Runoff and leaching of atrazine and alachlor on a sandy soil as affected by application in sprinkler irrigation

Abstract

Rainfall simulation was used with small packed boxes of soil to compare runoff of herbicides applied by conventional spray and injection into sprinkler‐irrigation (chemigation), under severe rainfall conditions. It was hypothesized that the larger water volumes used in chemigation would leach some of the chemicals out of the soil surface rainfall interaction zone, and thus reduce the amounts of herbicides available for runoff. A 47‐mm rain falling in a 2‐hour event 24 hours after application of alachlor (2‐chloro‐N‐(2,6‐diethylphenyl)‐N‐(methoxymethyl)‐acetamide) and atrazine (6‐chloro‐N‐ethyl‐N‐(1‐methylethyl)‐1,3,5‐triazine‐2,4‐diamine) was simulated. The design of the boxes allowed a measurement of pesticide concentrations in splash water throughout the rainfall event. Initial atrazine concentrations exceeding its’ solubility were observed. When the herbicides were applied in 64000 L/ha of water (simulating chemigation in 6.4 mm irrigation water) to the surface of a Tifton loamy sand, subsequent herbicide losses in runoff water were decreased by 90% for atrazine and 91% for alachlor, as compared to losses from applications in typical carrier water volumes of 187 L/ha. However, this difference was not due to an herbicide leaching effect but to a 96% decrease in the amount of runoff from the chemigated plots. Only 0.3 mm of runoff occurred from the chemigated boxes while 7.4 mm runoff occurred from the conventionally‐treated boxes, even though antecedent moisture was higher in the former. Two possible explanations for this unexpected result are (a) increased aggregate stability in the more moist condition, leading to less surface sealing during subsequent rainfall, or (b) a hydrophobic effect in the drier boxes. In the majority of these pans herbicide loss was much less in runoff than in leachate water. Thus, in this soil, application of these herbicides by chemigation would decrease their potential for pollution only in situations where runoff is a greater potential threat than leaching.     

Runoff and leaching of atrazine and alachlor on a sandy soil as affected by application in sprinkler irrigation

Rainfall simulation was used with small packed boxes of soil to compare runoff of herbicides applied by conventional spray and injection into sprinkler-irrigation (chemigation), under severe rainfall conditions. It was hypothesized that the larger water volumes used in chemigation would leach some of the chemicals out of the soil surface rainfall interaction zone, and thus reduce the amounts of herbicides available for runoff. A 47-mm rain falling in a 2-hour event 24 hours after application of alachlor (2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)-acetamide) and atrazine (6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2, 4-diamine) was simulated. The design of the boxes allowed a measurement of pesticide concentrations in splash water throughout the rainfall event. Initial atrazine concentrations exceeding its' solubility were observed. When the herbicides were applied in 64,000 L/ha of water (simulating chemigation in 6.4 mm irrigation water) to the surface of a Tifton loamy sand, subsequent herbicide losses in runoff water were decreased by 90% for atrazine and 91% for alachlor, as compared to losses from applications in typical carrier water volumes of 187 L/ha. However, this difference was not due to an herbicide leaching effect but to a 96% decrease in the amount of runoff from the chemigated plots. Only 0.3 mm of runoff occurred from the chemigated boxes while 7.4 mm runoff occurred from the conventionally-treated boxes, even though antecedent moisture was higher in the former. Two possible explanations for this unexpected result are (a) increased aggregate stability in the more moist condition, leading to less surface sealing during subsequent rainfall, or (b) a hydrophobic effect in the drier boxes. In the majority of these pans herbicide loss was much less in runoff than in leachate water. Thus, in this soil, application of these herbicides by chemigation would decrease their potential for pollution only in situations where runoff is a greater potential threat than leaching.     

Determination of the distribution coefficient (log Kd) of oxytetracycline,tylosin A,olaquindox and metronidazole in manure

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.     

Occurrence of pharmaceuticals in a municipal wastewater treatment plant: mass balance and removal processes

Occurrence and removal efficiencies of fifteen pharmaceuticals were investigated in a conventional municipal wastewater treatment plant in Michigan. Concentrations of these pharmaceuticals were determined in both wastewater and sludge phases by a high-performance liquid chromatograph coupled to a tandem mass spectrometer. Detailed mass balance analysis was conducted during the whole treatment process to evaluate the contributing processes for pharmaceutical removal. Among the pharmaceuticals studied, demeclocycline, sulfamerazine, erythromycin and tylosin were not detected in the wastewater treatment plant influent. Other target pharmaceuticals detected in wastewater were also found in the corresponding sludge phase. The removal efficiencies of chlortetracycline, tetracycline, sulfamerazine, acetaminophen and caffeine were >99%, while doxycycline, oxytetracycline, sulfadiazine and lincomycin exhibited relatively lower removal efficiencies (e.g., <50%). For sulfamethoxazole, the removal efficiency was approximately 90%. Carbamazepine manifested a net increase of mass, i.e. 41% more than the input from the influent. Based on the mass balance analysis, biotransformation is believed to be the predominant process responsible for the removal of pharmaceuticals (22% to 99%), whereas contribution of sorption to sludge was relatively insignificant (7%) for the investigated pharmaceuticals.     

Use of oxytetracycline and tylosin in intensive calf farming: evaluation of transfer to manure and soil

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.     

Erratum

The influence of soil macro-porosity and manure on atrazine (6-chloro-N-ethyl-N′-(1-methylethyl)-1,3,5-triazine-2,4-diamine) transport was investigated under laboratory conditions using disturbed and undisturbed soil columns. The macro-porosity in the soil column was obtained with CT scanning technique. Liquid manure was applied at the surface of soil column, 19 cm long and 8 cm in diameter, at a rate of 60 m³/ha. Experimental results revealed that atrazine moves faster through the soils in the presence of manure compared to soil without application of manure. The average time for elusion and the relative peak concentration in the disturbed soil column without manure was 14.5 h and 3.1%, respectively compared to 11.0 h and 6.9% in the presence of manure, respectively. Similar behavior was observed in the case of disturbed soil columns. Soil macro-porosity has shown large impact on atrazine transport, especially in the presence of manure.     

Macroporosity and manure influence on atrazine transport through soil

The influence of soil macro-porosity and manure on atrazine (6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine) transport was investigated under laboratory conditions using disturbed and undisturbed soil columns. The macro-porosity in the soil column was obtained with CT scanning technique. Liquid manure was applied at the surface of soil column, 19 cm long and 8 cm in diameter, at a rate of 60 m3/ha. Experimental results revealed that atrazine moves faster through the soils in the presence of manure compared to soil without application of manure. The average time for elusion and the relative peak concentration in the disturbed soil column without manure was 14.5 h and 3.1%, respectively compared to 11.0 h and 6.9% in the presence of manure, respectively. Similar behavior was observed in the case of disturbed soil columns. Soil macro-porosity has shown large impact on atrazine transport, especially in the presence of manure.