Comparison of atrazine losses in three small headwater catchments.

Understanding the processes causing herbicide transport to surface waters is crucial to determine mitigation options to reduce these losses. To this end, we investigated the atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) transport in three agricultural catchments (1.1-2.1 km2) in the watershed of Lake "Greifensee" (Switzerland). In 1999, atrazine application data were recorded for all three catchments. Time proportional samples were taken at a high temporal resolution at the catchment outlets. Extremely wet conditions caused large relative losses from the catchments, ranging between 0.6 and 3.5% of the amount applied. Most of the atrazine load was due to event-driven diffuse losses from the fields. Farmyard runoff contributed less but caused the highest concentrations (up to 31 microg L(-1)) in the brooks. The maximum concentrations due to diffuse losses varied between 1.2 and 8.2 microg L(-1) among the catchments. Despite different absolute concentration levels, the concentration time-series were very similar. It seems that the travel-times within the catchments were mainly controlled by the rainfall pattern with little influence of the catchment properties. These properties, however, caused the relative losses to vary by a factor of 6 between the catchments. This variability could be partly explained by differences in the connectivity of the fields to the brooks and by their hydrological soil properties. A comparison of the losses from the three catchments with those from the entire watershed of Lake Greifensee demonstrated that they were representative for the larger area. Hence, the study results provide a good data set to evaluate distributed models predicting herbicide losses.

Simultaneous assessment of sources, processes, and factors influencing herbicide losses to surface waters in a small agricultural catchment.

To take appropriate measures to minimize agricultural herbicide inputs into surface waters, detailed knowledge is required about all the factors that control the losses of a given compound from point sources (i.e., farmyards) as well as from the diffuse sources (i.e., the fields) within a given catchment. In this and in a companion paper, we present the results of a comprehensive field study, in which the temporal and spatial variability of the losses of three herbicides (atrazine, dimethenamid, and metolachlor) into the surface waters within a small catchment (2.1 km2) were investigated on different scales (i.e., field scale to whole catchment) after a controlled application of the compounds. In this paper, we discuss the loss dynamics of the three herbicides (and some of their metabolites) from the whole catchment over a period of 67 d after application. An identical mixture of the three herbicides was applied on 13 cornfields within 12 h, allowing for a comparison of their losses under identical meteorological conditions. Thanks to a high temporal sampling resolution, it was possible to distinguish between losses from a farmyard and losses from the fields. Farmyard losses contributed less than 20% to the total loads but caused the highest concentrations. The major herbicide losses from the agricultural fields occurred during the first two rain events after application that led to significant surface runoff and preferential flow into tile drains. In the soils of all fields, dimethenamid declined somewhat faster than atrazine and metolachlor, whereas atrazine was mobilized most effectively to runoff water. Relative losses of the three compounds did not vary by more than a factor of 3 (0.82, 0.27, and 0.41% of the mass applied for atrazine, dimethenamid, and metolachlor, respectively). Highest peak concentrations at the outlet of the catchment were found for atrazine (i.e., approximately 8 microg L(-1) for a short period (<2 h) due to point source losses and between 1 and 3.5 microg L(-1) during more than 24 h due to diffuse losses).

Variability of herbicide losses from 13 fields to surface water within a small catchment after a controlled herbicide application.

Diffuse losses from agricultural fields are a major input source for herbicides in surface waters. In this and in a companion paper, we present the results of a comprehensive field study aimed at assessing the overall loss dynamics of three model herbicides (i.e., atrazine, dimethenamid, and metolachlor) from a small agricultural catchment (2.1 km2) and evaluating the relative contributions of various fields having different soil and topographical characteristics. An identical mixture of the three model herbicides as well as an additional pesticide for identification of a given field were applied within 12 h on 13 cornfields (total area approximately 12 ha), thus ensuring that the herbicides were exposed to identical meteorological conditions. After the simultaneous application, the concentrations of the compounds were monitored in the soils and at the outlets of three subcatchments containing between 4 and 5 cornfields each. Particular emphasis was placed on the two rain events that led to the major losses of the herbicides. The rank orders of herbicide dissipation in the soils and of the compound-specific mobilization into runoff were the same in all three subcatchments and were independent of the field characteristics. In contrast, the field properties caused the relative losses from two subcatchments to differ by up to a factor of 56 during the most important event, whereas compound-specific differences of the three neutral herbicides caused the losses to vary only by a factor of 2 during the same event. The enormous spatial variability was mainly caused by factors influencing the fraction of rain that was lost to surface water by fast transport mechanisms. Thus, the key factors determining the spatially variable herbicide losses were the permeability of the soils, the topography, and the location of subsurface drainage systems. These results illustrate the large potential to reduce herbicide losses by avoiding application on risk areas.

Quantification of the new triketone herbicides, sulcotrione and mesotrione, and other important herbicides and metabolites, at the ng/l level in surface waters using liquid chromatography-tandem mass spectrometry.

The LC/ESI/MSMS method allows the trace quantification (ng/l) of the new triketone herbicides, i.e. sulcotrione and mesotrione, and important herbicides and metabolites, in natural waters. Solid phase extraction (SPE) for sample enrichment is performed with OASIS (recoveries 94-112% for parent herbicides). Neutral and acidic compounds were analyzed separately with ESI in positive and negative mode, respectively. Quantification limits varied between 0.5 and 10 ng/l. The acidic herbicides detection was improved by a neutralizing post-column addition solution. The influence of ion suppression on quantification is discussed in detail. It is shown that we could overcome this problem and achieve reliable quantification using isotope labeled internal standards (ILIS) for every single analyte. The methods performance is illustrated with samples from a lake depth profile.

Occurrence and fate of carbamazepine, clofibric acid, diclofenac, ibuprofen, ketoprofen, and naproxen in surface waters.

Although various single-concentration measurements of pharmaceuticals are available in the literature, detailed information on the variation over time of the concentration and the load in wastewater effluents and rivers and on the fate of these compounds in the aquatic environment are lacking. We measured the concentrations of six pharmaceuticals, carbamazepine, clofibric acid, diclofenac, ibuprofen, ketoprofen, and naproxen, in the effluents of three wastewater treatment plants (WWTPs), in two rivers and in the water column of Lake Greifensee (Switzerland) over a time period of three months. In WWTP effluents, the concentrations reached 0.95 microg/L for carbamazepine, 0.06 microg/L for clofibric acid, 0.99 microg/L for diclofenac, 1.3 microg/L for ibuprofen, 0.18 microg/L for ketoprofen, and 2.6 microg/L for naproxen. The relative importance in terms of loads was carbamazepine, followed by diclofenac, naproxen, ibuprofen, clofibric acid, and ketoprofen. An overall removal rate of all these pharmaceuticals was estimated in surface waters, under real-world conditions (in a lake), using field measurements and modeling. Carbamazepine and clofibric acid were fairly persistent. Phototransformation was identified as the main elimination process of diclofenac in the lake water during the study period. With a relatively high sorption coefficient to particles, ibuprofen might be eliminated by sedimentation. For ketoprofen and naproxen, biodegradation and phototransformation might be elimination processes. For the first time, quantitative data regarding removal rates were determined in surface waters under real-world conditions. All these findings are important data for a risk assessment of these compounds in surface waters.

Phototransfomation of ticlosan in surface waters: a relevant elimination process for this widely used biocide--laboratory studies, field measurements, and modeling.

The phototransformation of the widely used biocide triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol) was quantified for surface waters using artificial UV light and sunlight irradiation. The pH of surface waters, commonly ranging from 7 to 9, determines the speciation of triclosan (pKa = 8.1) and therefore its absorption of sunlight. Direct phototransformation of the anionic form with a quantum yield of 0.31 (laboratory conditions at 313 nm) was identified as the dominant photochemical degradation pathway of triclosan. Combining the photochemical parameters with actual meteorological data and field measurements allowed us to validate a model describing the behavior of triclosan in the water column of a Swiss lake (Lake Greifensee). From August to October 1999, direct phototransformation accounted for 80% of the observed total elimination of triclosan from the lake. The remaining major sink for triclosan was the loss in the outflow. Thus, during the summer season, direct phototransformation appears to be a major elimination pathway of triclosan in this lake. Based on absorption spectra and quantum yield data, the phototransformation half-lives of triclosan were calculated under various environmental conditions typical for surface waters. Daily averaged half-lives were found to vary from about 2 to 2000 days, depending on latitude and time of year.

Sources of pesticides in surface waters in Switzerland: pesticide load through waste water treatment plants--current situation and reduction potential.

Concentrations of pesticides in Swiss rivers and lakes frequently exceed the Swiss quality goal of 0.1 microg/l for surface waters. In this study, concentrations of various pesticides (e.g., atrazine, diuron, mecoprop) were continuously measured in the effluents of waste water treatment plants and in two rivers during a period of four months. These measurements revealed that in the catchment of Lake Greifensee, farmers who did not perfectly comply with 'good agricultural practice' caused at least 14% of the measured agricultural herbicide load into surface waters. Pesticides, used for additional purposes in urban areas (i.e. protection of materials, conservation, etc.), entered surface waters up to 75% through waste water treatment plants.

Quantification of veterinary antibiotics (sulfonamides and trimethoprim) in animal manure by liquid chromatography-mass spectrometry.

A fast and cost effective method was developed to extract and quantify residues of veterinary antimicrobial agents (antibiotics) in animal manure by liquid-liquid extraction and liquid chromatography-mass spectrometry. The compounds investigated include six sulfonamides, one metabolite, and trimethoprim. The method was performed without sample clean up. Recoveries from spiked manure slurry samples (spike level = 1 mg/kg) were as follows: sulfaguanidine (52%), sulfadiazine (47%), sulfathiazole (64%), sulfamethazine (89%), its metabolite N4-acetyl-sulfamethazine (88%), sulfamethoxazole (84%), sulfadimethoxine (51%), and trimethoprim (64%). Relative standard deviations of the recoveries were less than 5% within the same day and less than 20% between days. The limit of quantification was below 0.1 mg/kg liquid manure slurry for all compounds and calibration curves obtained from extracts of spiked samples were linear up to a level of 5 mg/kg liquid manure, except for trimethoprim (0.01-0.5 mg/kg). Analysis of six grab samples taken in Switzerland from manure pits on farms where medicinal feed had been applied revealed total sulfonamide concentrations of up to 20 mg/kg liquid manure.