Desethylterbuthylazine Research Articles

DETERMINATION OF PESTICIDES IN RIVER SURFACE WATERS OF CENTRAL CHILE USING SPE-GC-MS MULTI-RESIDUE METHOD

In areas with agricultural activity, the excessive use of pesticides can contaminate water resources. That is why a multi-residue method based on solid-phase extraction (SPE) and gas chromatography analysis coupled to mass spectrometry (GS-MS) was used to determine eleven pesticides and five degradation products in surface water of Central Chile. The parameters that can affect the efficiency of the SPE process were optimized considering the information available in bibliography. As in other studies, the best results were obtained when 500 mL of water was pre-concentrated using Oasis HLB polymer cartridges and acetone and acetonitrile were used as solvents for the elution. To ensure good quantification, matrix-matched standards were used, providing good linearity in the studied concentration range (0.10-1.5 μg L-1), with recovery percentages > 60%, precisions 87% of the pesticides analyzed in this research were detected in more than one sampled site in both seasons. The most ubiquitous compounds were desethylterbuthylazine (DET), pyrimethanil, cyprodinil and diazinon, and the compounds detected in highest concentration were simazine and degradation products derived from triazines. Las Cabras and Tahuilla irrigation canals presented the highest concentrations of pesticides. Significant differences were found in the total concentration of pesticides for sites sampled at the end of the summer and winter season.

Dissipation dynamics of terbuthylazine in soil during the maize growing season.

Ever since terbuthylazine (TBA) replaced atrazine in herbicide crop treatment, its much greater persistence has raised considerable environmental concern. The aim of our field experiment was to establish the dissipation dynamics of TBA and its degradation product desethylterbuthylazine (DET) in soil over five months of maize growth. We applied TBA as part of pre-emergent treatment in the regular and double-the-regular amounts. Soil samples were collected periodically at the following depths: 0-10 cm, 10-20 cm, 20-30 cm, and 30-50 cm. For TBA and DET soil residue analysis we used microwave-assisted extraction with methanol, followed by HPLC-UV/DAD. Regardless of the application rate, more than 80 % of the applied TBA dissipated from the first 50 cm of soil in the two months after herbicide application and 120 mm of rainfall. Three months later (at maize harvest), less than 4 % of total TBA remained in the soil, mostly in the top 20 cm rich with organic carbon on which TBA is likelier to adsorb. The loss of TBA from soil coincided with the rise in DET, especially the top soil layers, during the periods of low rainfall and highest soil temperatures. This points to biodegradation as the main route of TBA dissipation in humic soils. The applied amount had no significant effect on TBA dissipation in the top (humic) layers, but in the layers with less than 1 % of organic carbon, it was higher when the doublethe- regular dose was applied.

Seasonal variation of chloro-s-triazines in the Hartbeespoort Dam catchment, South Africa

Seasonal variation of eight chloro-s-triazine herbicides and seven major atrazine and terbuthylazine degradation products was monitored in the Hartbeespoort Dam catchment using gas chromatography–mass spectrometry (GC–MS) and liquid chromatography-mass spectrometry (LC-MS/MS). Lake, river and groundwater were sampled from the Hartbeespoort Dam catchment over four seasons and the downstream Jukskei River was monitored during the winter season. Triazine herbicide concentrations in the Hartbeespoort Dam were in the order atrazine>simazine>propazine>ametryn>prometryn throughout the four seasons sampled. Triazine herbicide concentrations in the Hartbeespoort Dam surface water were highest in summer and gradually decreased in successive seasons of autumn, winter and spring. Terbuthylazine was the only triazine herbicide detected at all sampling sites in the Jukskei River, though atrazine recorded much higher concentrations for the N14 and Kyalami sites, with concentrations of 923 and 210ngL−1 respectively, compared to 134 and 74ngL−1 for terbuthylazine. Analytical results in conjunction with river flow data indicate that the Jukskei and Crocodile Rivers contribute the greatest triazine herbicide loads into the Hartbeespoort Dam. No triazine herbicides were detected in the fish muscle tested, showing that bioaccumulation of triazine herbicides is negligible. Atrazine and terbuthylazine metabolites were detected in the fish muscle with deethylatrazine (DEA) being detected in both catfish and carp muscle at low concentrations of 0.2 and 0.3ngg−1, respectively. Desethylterbuthylazine (DET) was detected only in catfish at a concentration of 0.3ngg−1. With atrazine herbicide groundwater concentrations being >130ngL−1 for all seasons and groundwater ∑triazine herbicide concentrations ranging between 527 and 367ngL−1, triazine compounds in the Hartbeespoort Dam catchment may pose a risk to humans and wildlife in light findings of endocrine and immune disrupting atrazine effects by various researchers.

On-line solid-phase extraction method for determination of triazine herbicides and degradation products in seawater by ultra-pressure liquid chromatography–tandem mass spectrometry

A fast, simple, selective and sensitive method has been developed for the determination of nine triazine herbicides (ametryn, atrazine, cyanazine, prometryn, propazine, simazine, simetryn, terbuthylazine and terbutryn) and eight degradation products (desethyl atrazine, desethyl-desisopropyl atrazine, desethyl 2-hydroxyatrazine, desethyl terbuthylazine, desisopropyl atrazine, desisopropyl 2-hydroxyatrazine, 2-hydroxyatrazine and 2-hidroxyterbuthylazine) in seawater samples. On-line solid-phase extraction coupled with ultra-pressure liquid chromatography-tandem mass spectrometry was employed for simultaneous analysis of all compounds in 11min. Validation parameters were studied through the estimation of the limits of detection and quantification, calibration curves and precision. Limits of quantification ranged from 0.023 to 0.657μgL−1. Good linearity was obtained for all compounds with R2>0.99 in all cases. Furthermore, inter-day precision (0–2.1%) and intra-day precision (0–3.9%) were shown to be satisfactory. On-line solid-phase extraction recoveries in spiked unpolluted seawater sample were evaluated and acceptable values (80.3–99.8%) with adequate RSD (0.1–3.1%) were found.Finally, the proposed method was applied to the analysis of the target compounds in seawater samples collected from seawater nearby a zone of intensive horticulture of Matosinhos (Portugal). The concentrations of the herbicides were below the limit of detection in all cases.

Catabolism of terbuthylazine by mixed bacterial culture originating from s-triazine-contaminated soil.

The s-triazine herbicide terbuthylazine (TERB) has been used as the main substitute of atrazine in many EU countries for more than 10years. However, the ecological consequences of this substitution are still not fully understood. Since the fate of triazine herbicides is primarily dependent on microbial degradation, in this paper, we investigated the ability of a mixed bacterial culture, M3-T, originating from s-triazine-contaminated soil, to degrade TERB in liquid culture and soil microcosms. The M3-T culture grown in mineral medium with TERB as the N source and citrate as the C source degraded 50mgL(-1) of TERB within 3days of incubation. The culture was capable of degrading TERB as the sole C and N source, though at slower degradation kinetics. A thorough LC-MS analysis of the biodegradation media showed the formation of hydroxyterbuthylazine (TERB-OH) and N-t-butylammelide (TBA) as major metabolites, and desethylterbuthylazine (DET), hydroxydesethylterbuthylazine (DET-OH) and cyanuric acid (CA) as minor metabolites in the TERB degradation pathway. TBA was identified as a bottleneck in the catabolic pathway leading to its transient accumulation in culture media. The supplementation of glucose as the exogenous C source had no effect on TBA degradation, whereas citrate inhibited its disappearance. The addition of M3-T to sterile soil artificially contaminated with TERB at 3mgkg(-1) of soil resulted in an accelerated TERB degradation with t 1/2 value being about 40 times shorter than that achieved by the native microbial community. Catabolic versatility of M3-T culture makes it a promising seed culture for accelerating biotransformation processes in s-triazine-contaminated environment.

Monitoring of selected priority and emerging contaminants in the Guadalquivir River and other related surface waters in the province of Jaén, South East Spain

The province of Jaén counts with four natural parks, numerous rivers, reservoirs and wetlands; moreover, it is probably the region with higher olive oil production in the world, which makes this zone a proper target to be studied based on the European Water Framework Directive 2000/60/CE. The aim of this survey is to monitor a total number of 373 compounds belonging to different families (pesticides, PAHs, nitrosamines, drugs of abuse, pharmaceuticals and life-style compounds) in surface waters located at different points of the province of Jaén. Among these compounds some priority organic substances (regulated by the EU Directive 2008/105/EC) and pollutants of emerging concern (not regulated yet) can be found. A liquid chromatography electrospray time-of-flight mass spectrometry (LC–TOFMS) method covering 340 compounds was developed and applied, together with a gas chromatography triple–quadrupole mass spectrometry (GC–MS/MS) method which enabled the analysis of 63 organic contaminants (30 of these compounds are analyzed by LC–TOFMS as well). From April 2009 to November 2010 a total of 83 surface water samples were collected (rivers, reservoirs and wetlands). In this period numerous organic contaminants were detected, most of them at the ngL−1 level. The most frequently priority substances found were chlorpyrifos ethyl, diuron and hexachlorobenzene. Within the other groups, the most frequently detected compounds were: terbuthylazine, oxyfluorfen, desethyl terbuthylazine, diphenylamine (pesticide family); fluorene, phenanthrene, pyrene (PAHs group), codeine, paracetamol (pharmaceuticals compounds) and caffeine, nicotine (life-style compounds). As is could be expected, the total concentration of emerging contaminants is distinctly larger than that of priority pollutants, highlighting the importance of continuing with the study of their presence, fate and effects in aquatic environments. However, concentration levels (at the ng per liter level) are low in general for both kinds of contaminants which minimizes the possible harmful effect on the environment.

Skeletonema marinoi (Bacillariophyceae) sensitivity to herbicides and effects of temperature increase on cellular responses to terbuthylazine exposure

The North East area of Italy is an intensively farmed area, where the use of herbicides has increased dramatically during the last years. Some of the most detected herbicides are triazine compounds, such as: simazine (SIM), terbuthylazine (TBA), its degradation product desethyl-terbuthylazine (D-TBA) and other herbicides, such as metolachlor (MET). In this paper, the sensitivity of the diatom Skeletonema marinoi to the most detected herbicides (TBA, D-TBA, SIM and MET) was preliminarily studied. All the pollutants tested significantly inhibited the diatom growth and photosynthetic efficiency (from the concentration of 15μgL−1) with the exception of TBA which had the strongest effects on S. marinoi starting from the concentration of 5μgL−1. Consequently, cellular physiological responses to TBA exposure (1, 5, 10, 20 and 30μgL−1) were further studied at increasing temperature conditions (15, 20 and 25°C). Inhibition of growth rate and photosynthetic efficiency was observed earlier and determined by lower TBA levels than those affecting cell growth. These responses were significantly enhanced at increasing temperature conditions when growth rates were higher than those measured at 15°C. Carbon cell content increased in the cultures exposed to high concentrations of TBA (from 20μgL−1) compared to the controls, especially at high temperatures. Cell chlorophyll significantly increased from the added concentration of 10μgL−1 of TBA at all the temperatures and, as a consequence, also the Chl:C ratio significantly increased. The C:N ratio followed the pattern of nitrate uptake and was characterized, at all the temperatures, by low values during the lag phase in cultures with 20 and 30μgL−1 of TBA; in these conditions, in fact, the nutrient in the medium was exhausted later then in the controls. Only cultures exposed to 30μgL−1 of TBA at 25°C, which stopped to take up nutrients earlier and could not increase chlorophyll levels, did not display any growth capacity. This study shows that S. marinoi is affected by TBA concentrations lower than those affecting some harmful flagellate species frequently observed in the Adriatic Sea. Thus, it raises the question of the combined effects of herbicides pollution and high temperature pressures on phytoplankton composition.

Biomonitoring short- and long-term exposure to the herbicide terbuthylazine in agriculture workers and in the general population using urine and hair specimens

The aim of this work was to evaluate short-term and long-term exposure to terbuthylazine (TBA) in agriculture workers (AW), rural residents (RR), and urban residents (UR) using urine and hair specimens. Twelve AW, 13 RR, and 17 UR were included in the study. Urine spot samples were collected with two different protocols. AW urine samples were collected before the application season (February, U0), at bedtime on the day of TBA application (March–May, U1), and prior to the next shift on the day after TBA application (U2). RR and UR urine samples were collected on any day during the application season (Ue). Hair samples were collected for all subjects before the application season (February, H0) and at the end of the season (June, H1). TBA and its metabolite desethylterbuthylazine (DET) were measured by liquid chromatography coupled with triple quadrupole mass spectrometry detection. DET was exclusively found in urine, while TBA was mostly found in the hair. In the AW, the urinary levels of DET were not detected in the U0 samples, and they increased to median levels of 1.81 and 2.94μg/L in the U1 and U2 samples, respectively (p<0.001). In the RR and UR, DET was not detected in the Ue samples. In the UR, TBA was not detected in the H0 samples, and the median levels of TBA were 0.01ng/mg hair in both the AW and RR. In the H1 samples, the median TBA levels were not detected, 0.01, and 0.08ng/mg hair in the UR, RR, and AW, respectively (p<0.001). Urinary DET and hair TBA are promising candidates for biomonitoring short- and long-term exposure to TBA. The use of this herbicide in agriculture leads to exposure in rural residents.

Quantitative and qualitative differences in the metabolism of pesticides in biobed substrates and soil

Biobed substrates commonly exhibit high degradation capacity. However, degradation does not always lead to detoxification and information on the metabolic pathways of pesticides in biobeds is scarce. We studied the degradation and metabolism of three pesticides in selected biomixtures and soil. Biomixtures stimulated degradation of terbuthylazine and metribuzin, whereas chlorpyrifos degraded faster in soil. The latter was attributed to the lipophilicity of chlorpyrifos which increased adsorption and limited biodegradation in organic-rich biomixtures. Although the same metabolites were detected in all substrates, qualitative and quantitative differences in the metabolic routes of pesticides in the various substrates were observed. Chlorpyrifos was hydrolyzed to 3,5,6-tricholorpyridinol (TCP) which was further degraded only in compost-biomixture CBX1. Metabolism of terbuthylazine in compost biomixtures (BX) and soil resulted in the formation of desethyl-terbuthylazine (DES) which was fully degraded only in the compost-biomixture CBX2, whereas peat-based biomixture (OBX) promoted the hydroxylation of terbuthylazine. Desamino- (DA) (dominant) and diketo- (DK) metribuzin appear as intermediate metabolites in all substrates and were further transformed to desamino-diketo-metribuzin (DADK) which was fully degraded only in compost-biomixture GSBX. Overall, lower amounts of metabolites were accumulated in biomixtures compared to soil stressing the higher depuration efficiency of biobeds.

Occurrence of pesticides and some of their degradation products in waters in a Spanish wine region

A multi-residual analytical method based on solid phase extraction (SPE) followed by liquid chromatography–electrospray ionisation–mass spectrometry (LC–MS) was developed to monitor pesticides in natural waters. Fifty-eight compounds, including herbicides, fungicides, insecticides and some of their degradation products, were surveyed to evaluate the quality of natural waters throughout the wine-growing region of La Rioja (Rioja DOCa). Ninety-two sampling points were selected, including surface and ground waters that could be affected by agricultural activities covering the region’s three sub-areas. Different parameters that may affect the efficiency of the SPE procedure were optimised (sorbent type, elution solvent and sample volume), and matrix-matched standards were used to eliminate the variable matrix effect and ensure good quantification. The developed method allows the determination of target compounds below the level established by the European Union for waters for human use with suitable precision (relative standard deviations lower than 18%) and accuracy (with recoveries over 61%). Forty compounds included in this study (six insecticides, 12 herbicides, 16 fungicides and six degradation products) were detected in one or more samples. The herbicides terbuthylazine, its metabolite desethyl terbuthylazine, fluometuron and ethofumesate and the fungicides pyrimethanil and tebuconazole were the compounds most frequently detected in water samples (present in more than 60% of the samples). Concentrations above 0.1 μg L−1 were detected for 37 of the compounds studied, and in several cases recorded values of over 18 μg L−1. The results reveal the presence of pesticides in most of the samples investigated. In 64% of groundwaters and 62% of surface waters, the sum of compounds detected was higher than 0.5 μg L−1 (the limit established by EU legislation for the sum of all pesticides detected in waters for human use).

Spatial and temporal trend of groundwater contamination from terbuthylazine and desethyl-terbuthylazine in the Lombardy Region (Italy).

In the last few years, several monitoring programs were established as an effect of the EU Directives which included requirements for monitoring the quality of water resources (drinking water, groundwater and surface water). Plant Protection Products (PPPs) are an obvious target for monitoring activities, since they are directly released into the environment. In Italy, the National Environmental Protection Agency (ISPRA) has recently published several reports containing the results of the National Plans for Control of Environmental Effects of PPPs. These documents contain the collection of monitoring data related to the presence of PPP residues in surface and groundwater systems. In this paper, these results (monitoring campaigns from 2005 to 2009) were analysed. Particularly, the attention was focused on the concentration levels of terbuthylazine (TBZ) and its metabolite desethyl-terbuthylazine (DTZ) detected in the groundwater systems of the Lombardia Region (Northern Italy). The analysis allowed us to identify the spatial and temporal trends of contamination of both substances. Furthermore the DTZ/TBZ ratio was calculated in order to recognize point and non-point sources of contamination.

Terbuthylazine and other triazines in Italian water resources

The concern on the presence of pesticides in Italian water resources historically broke out around 1980 after severe episodes of ambient, raw water and drinking water contamination due to some herbicides, atrazine (ATR), its metabolites desethylatrazine (DEA) and deisopropylatrazine (DIA), simazine, cyanazine, bentazone, molinate, which affected mainly the maize, grain and rice producing floodplains and karst areas of the northern Regions. Due to the risks of human exposure, in the early 1990 the use of atrazine was banned in Italy and was replaced by terbuthylazine (TERB). In a few years, TERB became a chemical of concern, together with its main metabolite desethylterbuthylazine (DET), because of alerting detections in surface and groundwater resources. Up to now, the risk of contamination of water resources by TERB, DET, DEA and, in some extent ATR, is of relevance in Italy due to their present and past wide employment in agriculture, the discharges or seepages in particularly vulnerable areas, their unfavorable intrinsic properties, e.g. poor sorption and high persistence, their mobility by drift, leaching and runoff in vadose zones, aquifers and surface water. So, unsurprisingly, results from national monitoring of ambient water and raw water indicate that TERB, DET, DEA and residual ATR, despite its withdrawal, are detected at remarkable frequencies and, sometimes, at levels higher than pesticide quality standards under the Italian Decrees for the protection of surface water (specifically, raw waters doomed at the drinking water abstraction), groundwater and drinking water (tap water), that is 0.1–0.5μg/l for individual pesticides and for total pesticides, respectively, including relevant metabolites. On the other hand, in these last years, the control measures in drinking water production adopted by the waterworks Companies and the regional and central health Authorities, also in the view of the recent WHO approaches under the Water Safety Plans, ensure that levels of any pesticide residue (also involving TERB, DET, DEA, ATR) in finished tap water meet parametric values for pesticides. Therefore, in these last years, no derogation to the parametric values for drinking water has been required. The aim of this paper is to contribute to widen the knowledge on the water impact of these important water pollutants giving sound details on present usages, levels and frequencies of detection in water bodies in Italy, on their key chemiodynamic properties, e.g. soil half-lives (DT50) and soil to organic carbon partition (Koc) available in the open literature, particularly for TERB metabolites, and some details on legal provision adopted at the national level. In fact, a more effective protection of water supplies, particularly against TERB and DET, has been pursued in the late 2000s by the Italian Health Ministry through the adoption of consistent provisions aimed at mitigating emissions of TERB in routine agricultural activities, and by the Italian Ministry of the Environment through the adoption of specific Environmental Quality Standards for TERB and its metabolite DET, ATR, SIM for the protection of surface waters.

Determination of terbuthylazine and desethylterbuthylazine in human urine and hair samples by eletrospray ionization-liquid chromatography/triple quadrupole mass spectrometry

Terbuthylazine (TBA) is a widely applied herbicide and an environmental contaminant. Following its use, humans, such as agricultural workers and rural residents, may be exposed. An isotope-dilution liquid chromatography coupled to electrospray-tandem mass spectrometry method for the determination of TBA, and its metabolite desethylterbuthylazine (DET) in human urine and hair was developed and validated. Under the optimised conditions, analytes were extracted from urine using a solid phase cartridge or from hair by sonication in methanol. Analytes were separated using a C18 reversed-phase chromatographic column and quantified, after positive ionization using a heated electrospray source, by a triple quadrupole mass detector in the selected reaction monitoring mode. Validation showed linear dynamic ranges up to 100 μg/L or 5.00 ng/mg hair, inter- and intra-run precisions <7%, and accuracies within 12% of spiked concentrations. Limits of quantification were 0.25 μg/L in urine and 0.01 ng/mg hair for both TBA and DET. Matrix effect evaluation showed that the isotope dilution approach allowed for the control of bias sources. TBA and DET were determined in specimens of agriculture workers exposed to TBA using the validated method. Hair samples contained TBA levels in the low nanogram per milligram range, and urine samples contained DET levels in the low microgram per liter range. Conversely, TBA levels in urine samples and DET levels in hair samples were always below the limit of quantification.

A field study of the impact of different irrigation practices on herbicide leaching

Agricultural practices, such as subsurface drainage, irrigation and tillage, may significantly affect pesticide leaching and, consequently, the risk of groundwater contamination. The aim of the present study was to investigate the impact of different irrigation systems on herbicide leaching to shallow groundwater through direct monitoring at the field scale in northern Italy over a 3-year period. Concentrations of the herbicide terbuthylazine (TBA) and its metabolite desethylterbuthylazine (DES) were monitored on 10 farms cropped with maize and irrigated by sprinkler, basin and border systems. Considering the results grouped according to the different irrigation systems, the mean TBA and DES concentrations was lower than the arbitrary non-health based legal limit of 0.1 μg/L using sprinkler and border systems, while it was 0.19 and 0.30 μg/L respectively for TBA and DES using basin systems. However, since many factors other than the irrigation systems can contribute to pesticide leaching and in a field study it is impossible to discriminate between all the different variables, the concentrations of both compounds were simulated with and without irrigation using the model MACRO 5.1 in order to gain a deeper understanding of the role of irrigation on leaching. First, the groundwater table depth, which was measured daily in all fields, was used to calibrate the model and thus achieve a good soil hydrology calibration. To assess the performance of the model the root mean squared error (RMSE) was used. RMSE ranged from 0.2 to 0.5 m, showing that a satisfactory hydrology calibration was obtained. Afterward, the solutes were modelled and the results showed that under non-irrigated conditions, concentrations of both compounds would be very low. These findings validate the hypothesis that careful selection of agricultural practices, such as the type of irrigation, can reduce pesticide leaching.

Influence of Different Organic Amendments on the Leaching and Dissipation of Terbuthylazine in a Column and a Field Study

Terbuthylazine (TA) is a herbicide that has been introduced for weed control in corn cultivations as a direct replacement for atrazine. Because incorporation of different organic amendments (OAs) is a common practice in this crop, this study investigated the effects of different OAs, including urban sewage sludge, poultry compost, and corn straw on the dissipation and metabolism of TA. A column study and a field dissipation study were used. In the column study, no residues of TA and desethyl-terbuthylazine (DETA) were detected in the leachate of amended and non-amended columns. The addition of OAs increased the persistence of TA and DETA in the upper soil layers (0-10 cm) but did not affect the mobility of TA and DETA in either experiment. Although the presence of OAs led to a significant increase in DETA production in the upper soil layers, the presence of DETA in lower depths did not significantly differ with the non-amended soil in either experiment. A gradual accumulation of DETA was evident in the soil layers amended with corn straw, whereas a rapid formation of DETA and a gradual decline thereafter was observed in the other treatments. Overall, the addition of OAs did not appear to significantly influence the mobility of TA and DETA, which did not move below the top 30 cm, thus indicating low risk for ground water contamination. In addition, the dissipation rate of TA in the field was faster than that in the column study.

Fast determination of herbicides in waters by ultra‐performance liquid chromatography/tandem mass spectrometry

A rapid multiresidue method for the analysis of more than 40 herbicides (such as simazine, terbuthylazine and diuron) in waters has been developed and validated by ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC/MS/MS). Prior to chromatographic determination, the samples were extracted using a solid-phase extraction procedure. The analysis was performed on an Acquity UPLC BEH C(18) column using a gradient elution profile and a mobile phase consisting of methanol and an aqueous solution of formic acid (0.01%). Other chromatographic and MS/MS parameters were optimised in order to improve selectivity and sensitivity of the analytes. The analytes were detected using electrospray ionisation (ESI)-MS/MS in positive ion mode with multiple reaction monitoring (MRM), optimising parameters such as voltage cone, capillary voltage, source and desolvation temperature, and desolvation and cone gas flow. The optimised method provides a rapid separation (less than 10 min) of the selected herbicides in the assayed matrices, and it was validated by the analysis of spiked blank matrix samples. Good linearity was obtained and the repeatability of the method was less than 20% for the lowest calibration point. The limits of detection ranged from 0.002 to 0.02 microg/L, and the limits of quantification from 0.005 to 0.05 microg/L, which were below the values specified by the European Union. Finally, the method was successfully applied to real environmental samples from Andalusia (southern Spain). Terbuthylazine, simazine, atrazine desisopropyl and desethyl terbuthylazine were the herbicides most frequently found in water samples.

Leaching potential of carbamates and their metabolites and comparison with triazines

This paper reports the results of a laboratory study aimed at defining the leaching potential of the following pesticides and respective metabolites belonging to the families of N-methylcarbamates and triazines: benfuracarb (BF), carbofuran (CF), 3-keto-carbofuran (3KC) and 3-hydroxy-carbofuran (3HC), atrazine (ATR), simazine (SIM), terbuthylazine (TER), deethylatrazine (DEA), deisopropylatrazine (DIA) and desethylterbuthylazine (DET). All tested compounds, but BF, are very mobile in soil. Triazines exhibited a relatively high persistence, especially DEA, with a DT 50 of 72 days. On the contrary, all the tested carbamates resulted easily degradable in soil with a partial exception represented by CF, with a DT 50 of 12 days. The GUS indices show high leaching potentials for all the tested triazines and CF. The GUS index of 3KC lies in the typical area of transient compounds; those of BF and 3HC clearly exhibited a non-leaching behaviour. In the leachate corresponding to the BF column, the parent compound was found at low concentration while its main metabolite, CF, reached much higher values. Also, when applied as parent compound, CF was determined at high values, whereas its metabolites 3KC and 3HC were never detected in the leachates. As to triazines, in the ATR column, the parent compound was found at high levels in the leachate, where DEA exhibited values more than 4 times higher than DIA. In the SIM column DIA reached levels 8-fold higher than those in the ATR column. TER occurred at levels close to that of ATR in the respective leachate; DET was found at high levels whereas DIA was not detectable.

Studies on mobility and degradation pathways of terbuthylazine using lysimeters on a field scale.

Terbuthylazine [N2-tert-butyl-6-chloro-N4-ethyl-1,3,5-triazine-2,4-diamine] degradation pathways in agricultural soils were evaluated by following the appearance and mobility of its main transformation products: dealkylated and hydroxylated derivatives. Three experimental degradation studies in open field were performed in different hydraulic conditions: constant hydraulic head on topsoil, achieved to simulate the highest-risk situation for the aquifer, intermittent artificial precipitation to simulate a medium-risk situation; and natural precipitation to reproduce the lowest-risk condition. Concentrations of terbuthylazine transformation products derived from dealkylation and hydroxylation reactions were measured in leachates and soil samples collected during the three experiments. Desethylterbuthylazine (DET) and deethylterbuthylazine-2-hydroxide [DETH; 4-amino-6-terbutylamino-(1,3,5)-triazine-2-OH] were found to be the highest-leaching compounds and therefore can be considered as potential pollutants for aquifer contamination.