Sodium dodecyl sulphate-enhanced desorption of atrazine: effect of surfactant concentration and of organic matter content of soils

A study was made of the adsorption-desorption of atrazine in aqueous medium in five soils with organic matter (OM) contents in the range 1.4-10.3% and also of the desorption of the herbicide in aqueous solutions of the anionic surfactant sodium dodecyl sulphate (SDS) at critical micelle concentrations (cmc) of 0.75, 1.50, 5 and 10. The adsorption and desorption isotherms in water together with the desorption isotherms in SDS solutions with concentrations of 0.75 and 1.50 cmc fit the Freundlich adsorption equation. All the desorption isotherms displayed hysteresis. The increase or reduction in hysteresis of the desorption isotherms in SDS solutions with respect to those of desorption in water depend on the SDS concentration and on the OM content of the soils. Below the cmc, SDS only increases the desorption of atrazine in the soil with the highest OM content (10.3%). However, above the cmc (5 and 10 cmc) the desorption of atrazine increases in all soils, the efficiency of desorption increasing with the OM content of the soils.     

Lack of effects of atrazine on estrogen-responsive organs and circulating hormone concentrations in sexually immature female Japanese quail (Coturnix coturnix japonica)

The widely used herbicide, atrazine, has been reported to exhibit reproductive toxicity in rats and amphibians. The present studies investigate toxicity of atrazine in Japanese quail and its ability to influence reproduction in sexually immature females. Atrazine was administered in the diet at concentrations from 0.001 to 1000 ppm (approximately 109 mg kg-1 per day) or systemically via daily subcutaneous injections (1 and 10 mg kg-1) or Silastic implants. Atrazine did not cause overt toxicity in sexually immature female quail (no effects on change in body weight, feed intake, mortality or on circulating concentrations of the stress hormone, corticosterone). It was hypothesized that if atrazine were to have estrogenic activity or to enhance endogenous estrogen production, there would be marked increases in the weights of estrogen sensitive tissues including the oviduct, the liver and the ovary together with changes in gonadotropin secretion. However, atrazine had no effect on either liver or ovary weights. Atrazine in the diet increased oviduct weights at 0.1 and 1 ppm in some studies. These effects were not consistently observed and were not significant when data from studies were combined. Systemic administration of atrazine had no effect on oviduct weights. Dietary (concentrations from 0.001 to 1000 ppm) and systemically administered atrazine had no effect on circulating concentrations of luteinizing hormone (LH). The present studies provide evidence for a lack of general or reproductive toxicity of atrazine in birds.     

Influence of microbial and synthetic surfactant on the biodegradation of atrazine

The present study reports the effect of surfactants (rhamnolipids and triton X-100) on biodegradation of atrazine herbicide by strain A6, belonging to the genus Acinetobacter. The strain A6 was able to degrade nearly 80 % of the 250-ppm atrazine after 6 days of growth. The bacterium degraded atrazine by de-alkylation process. Bacterial cell surface hydrophobicity as well as atrazine solubility increased in the presence of surfactant. However, addition of surfactant to the mineral salt media reduced the rate and extent of atrazine degradation by decreasing the bioavailability of herbicide. On the contrary, addition of surfactant to atrazine-contaminated soil increased the rate and extent of biodegradation by increasing the bioavailability of herbicide. As compared to triton X-100, rhamnolipids were more efficient in enhancing microbial degradation of atrazine as a significant amount of atrazine was removed from the soil by rhamnolipids. Surfactants added for the purpose of hastening microbial degradation may have an unintended inhibitory effect on herbicide degradation depending upon contiguous condition, thus highlighting the fact that surfactant must be judiciously used in bioremediation of herbicides.     

Effects of ionic strength and temperature on adsorption of atrazine by a heat treated kerolite

The adsorption of 6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine (atrazine) on a heat treated kerolite sample at 600 degrees C (K-600) from pure water solution at 10 degrees C, 25 degrees C and 40 degrees C has been studied. The influence of the presence of 0.1 M KCl in the medium was also investigated for a better understanding of variables affecting the adsorption of this herbicide. The experimental adsorption data points were fitted to the Langmuir equation in order to calculate the adsorption capacities (Xm) of the samples; Xm values range from 2.3x10(3) mg kg-1 (pure water solution at 40 degrees C) up to 15.2x10(3) mg kg-1 (0.1 M KCl solution at 10 degrees C). The adsorption data were also fitted to the Freundlich equation in order to clarify the influence of the presence of 0.1 M KCl on atrazine adsorption. The parameter K10 obtained from this equation (adsorption capacity at an equilibrium solution concentration of atrazine equal to 10 mg l-1) shows clearly that the presence of 0.1 M KCl in the medium tends to increase the adsorption of atrazine in the range of temperature studied. The adsorption experiment also showed that the lower temperature, the more effective the adsorption of atrazine from both, pure water and 0.1 M KCl solutions. The values of the removal efficiency (R) obtained ranged from 39% at 40 degrees C (pure water solution) up to 93% at 10 degrees C (0.1 M KCl solution).     

Effect of surfactants at low concentrations on the sorption of atrazine by natural sediment.

A series of experiments were carried out to determine the effect of surfactants at low concentrations on the sorption of atrazine by natural sediments. With surfactant concentrations ranging from 0 to 20 mg/ L, anionic and cationic surfactants appreciably reduce the adsorption of atrazine, while nonionic surfactant decreases the adsorption of atrazine at concentrations equal to or less than 1 mg/L and increases adsorption at higher concentrations. Desorption of atrazine in the presence of different sodium dodecylbenzene sulfonate (SDBS) concentrations shows that a portion of the bound pesticide resists desorption in the SDBS free system. However, the addition of SDBS accelerates the desorption of atrazine. Furthermore, the nature of sediment and the contacting sequence of SDBS, at 10 mg/L, with the sediment, also influence the adsorption of atrazine. The conclusions in this study could be explained partially by the effect of the type and concentration of surfactants and the characteristics of sediments.     

Modelling of atrazine transport in the presence of surfactants

Laboratory experiments were conducted to examine the effect of detergents on transport of atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine] through loam and sandy loam soils under saturation conditions. The Convection Dispersion Equation (CDE) was used to model and quantify the effects of detergents on atrazine model parameters: the retardation factor (R), pore velocity (v) and dispersion coefficient (D). The transport parameters were estimated using moment technique and partition coefficient obtained from batch experiments and compared with best-fitted parameters, R and D, keeping pore velocity constant. Results indicated the CDE model was not successful in predicting atrazine transport in the presence of surfactants at high concentrations. In the case of anionic surfactant with Elora loam, the average predicted R and D from moment technique of 3.4 and 11.1 cm2/h, respectively were significantly different than fitted parameters (R = 39 and D = 227 cm2/h). The poor performance of CDE in the presence of surfactants results from physiochemical changes in herbicide solubility and retention to the soil matrix rather than changes in soil hydraulic properties since the predicted pore water velocities from moment technique were similar to those measured during leaching experiments. Nevertheless, BTC analysis with CDE showed that land application of anionic surfactant (sulphonic) significantly increased R and D and decrease v for both soils. Addition of sulphonic increased R of atrazine by 12 and 26 folds for loam and sandy loam soils, respectively. On the other hand non-ionic surfactants seemed to decrease R, especially in sandy loam soil, thus facilitating atrazine leaching through soil. Non-equilibrium conditions seemed to govern atrazine transport in the presence of surfactants; double peaks in breakthrough curves were observed, indicating a need for mathematical models to account for such phenomena. Atrazine dispersion and tailing seemed to be higher through Elora loam compared to Caledon sandy loam due to higher aggregation of the Elora soil.     

Determination of commonly used polar herbicides in agricultural drainage waters in Australia by HPLC

The present study describes the application of different extraction techniques for the preconcentration of ten commonly found acidic and non-acidic polar herbicides (2,4-D, atrazine, bensulfuron-methyl, clomazone, dicamba, diuron, MCPA, metolachlor, simazine and triclopyr) in the aqueous environment. Liquid-liquid extraction (LLE) with dichloromethane, solid-phase extraction (SPE) using Oasis HLB cartridges or SBD-XC Empore disks were compared for extraction efficiency of these herbicides in different matrices, especially water samples from contaminated agricultural drainage water containing high concentrations of particulate matter. Herbicides were separated and quantified by high performance liquid chromatography (HPLC) with an ultraviolet detector. SPE using SDB-XC Empore disks was applied to determine target herbicides in the Murrumbidgee Irrigation Area (NSW, Australia) during a two-week survey from October 2005 to November 2005. The daily aqueous concentrations of herbicides from 24-h composite samples detected at two sites increased after run-off from a storm event and were in the range of: 0.1-17.8 microg l(-1), < 0.1-0.9 microg l(-1) and 0.2-17.8 microg l(-1) at site 1; < 0.1-3.5 microg l(-1), < 0.1-0.2 microg l(-1) and < 0.2-3.2 microg l(-1) at site 2 for simazine, atrazine and diuron, respectively.     

Evaluation of photolysis and hydrolysis of atrazine and its first degradation products in the presence of humic acids

Relative importance of hydrolysis and photolysis of atrazine and its degradation products in aqueous solutions with dissolved humic acids (HA) has been assessed under exposure to sunlight and under UV irradiation. Quantum yield for direct photolysis of atrazine at 254 nm was 0.037 mol photon(-1), the reaction order was 0.8. Atrazine, desethylatrazine and desisopropylatrazine converted to their 2-hydroxy analogs with rate constants 0.02-0.08 min(-1) in clear solutions, while addition of HA (300 mg L(-1)) caused a 10-fold increase in rate constants. Hydroxyatrazine was not degraded. No evidence of photo-Fenton reaction was found. Under exposure to solar light, atrazine, desethylatrazine and desisopropylatrazine were converted to 2-hydroxy analogs only at pH 2 because of acid hydrolysis and possible contribution of photolysis. At lower HA concentration, only their light-shielding effect was noticed, while at higher concentrations, HA-catalysed hydrolysis prevailed. Hydroxyatrazine concentration diminished at all pH values in solutions without HA exposed to sunlight.     

Nitrogen limited biobarriers remove atrazine from contaminated water: laboratory studies

Atrazine is one of the most frequently used herbicides. This usage coupled with its mobility and recalcitrant nature in deeper soils and aquifers makes it a frequently encountered groundwater contaminant. We formed biobarriers in sand filled columns by coating the sand with soybean oil; after which, we inoculated the barriers with a consortium of atrazine-degrading microorganisms and evaluated the ability of the barriers to remove atrazine from a simulated groundwater containing 1 mg L(-1) atrazine. The soybean oil provided a carbon rich and nitrogen poor substrate to the microbial consortium. Under these nitrogen-limiting conditions it was hypothesized that bacteria capable of using atrazine as a source of nitrogen would remove atrazine from the flowing water. Our hypothesis proved correct and the biobarriers were effective at removing atrazine when the nitrogen content of the influent water was low. Levels of atrazine in the biobarrier effluents declined with time and by the 24th week of the study no detectable atrazine was present (limit of detection<0.005 mg L(-1)). Larger amounts of atrazine were also removed by the biobarriers; when biobarriers were fed 16.3 mg L(-1) atrazine 97% was degraded. When nitrate (5 mg L(-1) N), an alternate source of nitrogen, was added to the influent water the atrazine removal efficiency of the barriers was reduced by almost 60%. This result supports the hypothesis that atrazine was degraded as a source of nitrogen. Poisoning of the biobarriers with mercury chloride resulted in an immediate and large increase in the amount of atrazine in the barrier effluents confirming that biological activity and not abiotic factors were responsible for most of the atrazine degradation. The presence of hydroxyatrazine in the barrier effluents indicated that dehalogenation was one of the pathways of atrazine degradation. Permeable barriers might be formed in-situ by the injection of innocuous vegetable oil emulsions into an aquifer or sandy soil and used to remove atrazine from a contaminated groundwater or to protect groundwater from an atrazine spill.     

Suitability of dye-clay complexes for removal of non-ionic organic compounds from aqueous solutions

Aqueous sorption of phenol, atrazine and naphthalene was measured on complexes formed from Na-montmorillonite (Fischer bentonite) and the organic cationic dyes crystal violet and rhodamine-B. Sorption isotherms were found to be non-linear. This agrees well with the rigid nature of the dye-clay organic coverage, which provides a finite surface for adsorption. High values of organic carbon-normalized distribution coefficients reached 20,000-25,000 for atrazine on rhodamine-B-montmorillonite, 7000 for atrazine on crystal violet-montmorillonite, and 1500 for phenol on crystal violet-montmorillonite. As such, dye-clays may significantly extend the variety of organoclay sorbents that effectively reduce aqueous concentrations of non-ionic organic compounds.     

Triazine and metolachlor herbicide residues in farm areas of the Lower Fraser valley, British Columbia, Canada

Crop soils, ditch sediments and water flowing from several Lower Fraser River (LFR) farm areas of British Columbia, Canada, to salmon tributary streams of that river were sampled in 2004-2005 to quantify for residues of triazine [atrazine, desethylatrazine (a transformation product of atrazine), propazine, and simazine] and metolachlor (a chloroacetamide) herbicides. Average concentrations [microg kg-1 dry weight (d.w.)] of triazine (10,110) and metolachlor (8,910) herbicides detected in crop soils at the start (May 2004, 2005) of the growing season were about 17 and 6 times, respectively, higher than those found for both herbicide groups during (June-Sept, 2004, 2005) the growing season. In contrast, mean concentrations (microg L-1) of triazines (0.092) and metolachlor (0.014) in permanent ditches adjacent to farms were about 7 and 28 times, respectively, lower at the start than during the growing season. Both herbicide groups in ditch sediments were detected only during the growing season at concentrations averaging about 315 microg kg-1 d.w. The risk potential of these herbicides for non-target aquatic organisms inhabiting permanent farm ditches contiguous to tributary streams of the LFR during the growing season is evaluated and discussed.     

Wet peroxide degradation of atrazine

The high temperature (150-200 degrees C), high pressure (3.0-6.0 MPa) degradation of atrazine in aqueous solution has been studied. Under these extreme conditions atrazine steadily hydrolyses in the absence of oxidising agents. Additionally, oxygen partial pressure has been shown not to affect atrazine degradation rates. In no case mineralisation of the parent compound was observed. The addition of the free radical generator hydrogen peroxide to the reaction media significantly enhanced the depletion rate of atrazine. Moreover, partial mineralisation of the organics was observed when hydrogen peroxide was used. Again, oxygen presence did not influence the efficiency of the promoted reaction. Consecutive injections of hydrogen peroxide throughout the reaction period brought the total carbon content conversion to a maximum of 65-70% after 40 min of treatment (suggesting the total conversion of atrazine to cyanuric acid). Toxicity of the effluent measured in a luminometer decreased from 93% up to 23% of inhibition percentage. The process has been simulated by means of a semi-empirical model.     

Atrazine removal in agricultural infiltrate by bioaugmented polyvinyl alcohol immobilized and free Agrobacterium radiobacter J14a: a sand column study

Bench-scale sand column breakthrough experiments were conducted to examine atrazine removal in agricultural infiltrate by Agrobacterium radiobacter J14a (J14a) immobilized in phosphorylated-polyvinyl alcohol compared to free J14a cells. The effects of cell loading and infiltration rate on atrazine degradation and the loss of J14a were investigated. Four sets of experiments, (i) tracers, (ii) immobilized dead cells, (iii) immobilized cells, and (iv) free cells, were performed. The atrazine biodegradation at the cell loadings of 300, 600, and 900 mg dry cells L(-1) and the infiltration rates of 1, 3, and 6 cm d(-1) were tested for 5 column pore volumes (PV). The atrazine breakthrough results indicated that the immobilized dead cells significantly retarded atrazine transport. The atrazine removal efficiencies at the infiltration rates of 1, 3, and 6 cm d(-1) were 100%, 80-97%, and 50-70%, respectively. Atrazine degradation capacity for the immobilized cells was not significantly different from the free cells. Both infiltration rate and cell loading significantly affected atrazine removal for both cell systems. The bacterial loss from the immobilized cell system was 10-100 times less than that from the free cell system. For long-term tests at 50 PV, the immobilized cell system provided consistent atrazine removal efficiency while the atrazine removal by the free cells declined gradually because of the cell loss.     

Biological and chemical transformation of atrazine in coastal aquatic sediments

The degradation and distribution potential of atrazine, a persistent triazine herbicide, into three chemical fractions were measured in coastal aquatic sediments in the laboratory over time. Sediments with varying organic carbon contents were extracted with an organic solvent followed by an alkali hydrolysis reaction, and atrazine, deethylatrazine (DEA) and deisopropylatrazine (DIA) were quantified in the aqueous, solvent, and basic fractions using gas chromatography-mass spectrometry. The total amount of atrazine and its metabolites recovered after 95 days varied by site and ranged from 5% to 30% in which 95% was atrazine found primarily in the solvent fraction. Sediment organic carbon was positively correlated with the distribution of atrazine into the basic fraction and the decline in the total amount recovered. No DIA was detected in laboratory spiked sediments and transformation to DEA was limited in all sediments and made up less than 1% of the mass balance. The production and persistence of DEA were inversely correlated to organic carbon; sediments with less carbon and limited binding sites had increased formation and persistence of DEA. A secondary metabolite, methylated atrazine (M-ATR) not previously documented to be derived from atrazine, was chemically produced, detected in all sediments and time points, and concentrations were an order of magnitude higher than DEA. Based on results from spiked estuarine sediments, atrazine and M-ATR may have the potential to persist in the environment while DEA and DIA may not be an ecological threat due to their limited formation.     

Experimental in situ chemical peroxidation of atrazine in contaminated soil

Lab-scale experiments of in situ chemical oxidation (ISCO), were performed on soil contaminated with 100 mg kg(-1) of atrazine (CIET). The oxidant used was hydrogen peroxide catalysed by naturally occurring minerals or by soluble Fe(II) sulphate, added in aqueous solution. The oxidation conditions were: CIET:H2O2=1:1100, 2 PV or 3 PV reaction volume, Fe(II):H2O2=0, 1:22, 1:11. Stabilized (with KH2PO4 at a concentration of 16 g l(-1)) or non-stabilized hydrogen peroxide was used. The pH of the reagents was adjusted to pH=1 with sulphuric acid, or was not altered. Results showed that the addition of soluble Fe(II) increased the temperature of the soil slurry and the use of stabilized hydrogen peroxide resulted in a lower heat generation. The treatment reduced the COD of the soil of about 40%, pH was lowered and natural organic matter became less hydrophobic. The highest atrazine conversion (89%) was obtained in the conditions: 3 PV, Fe(II):H2O2=1:11 with stabilized hydrogen peroxide added in two steps. The stabilizer only increased H2O2 life-time significantly when soluble Fe(II) was added. Results indicate as preferential degradation pathway of atrazine in soil dechlorination instead of dealkylation.     

Concentrations and specific loads of glyphosate, diuron, atrazine, nonylphenol and metabolites thereof in French urban sewage sludge

Indirect soil pollution by heavy metals and organics may occur when sewage sludge is used as fertilizer. It is essential to define the nature and amounts of pollutants contained in sewage sludge in order to assess environmental risk. Here, we present results from a one-year monitoring of herbicides (glyphosate, diuron and atrazine) and their major degradates in sewage sludge sampled from three wastewater treatment plants and one composting unit in the vicinity of Versailles, France. The concentrations of these compounds were determined, as well as these of the surfactant nonylphenol. We demonstrated the presence of glyphosate and aminomethylphosphonic acid at the mg kg(-1) (dry matter) level in all samples. Diuron was detected at the microg kg(-1) (d.m.) level, whereas its degradate and triazine compounds were below the limits of quantification. Nonylphenol amounts were higher than the future European limit value of 50 mg kg(-1) (d.m.).     

Influence of humic substances on the photolysis of aqueous pesticide residues

The present work investigated the direct and indirect photolysis of pesticide residues (atrazine, imazaquin, iprodione), in aqueous solutions and under UV-visible radiation (280-480nm). Different kinds of humic substances (HS) were added to samples in order to evaluate their behaviour as possible photocatalysts and their effect on the photolysis of pesticides. The fulvic acids were purchased from the International Humic Substances Society, and they were added to samples in concentrations ranging from 1 to 150 mgl(-1). Titanium dioxide was used as the photocatalyst, in concentration ranging from 10 to 150 mgl(-1). Pesticides photolysis were measured by UV-visible absorption spectroscopy and differential pulse polarography with all used pesticides, reaching total degradation after 2h of irradiation, thus indicating a fast direct photolysis. Photocatalysis by TiO(2) could increase the pesticides photolysis rate up to 40%. This effect, however, was not observed for imazaquin photolysis. Again, except for imazaquin, HS presence showed a positive effect in increasing pesticide degradation, but only within specific concentration ranges (below 10mg l(-1) for iprodione and about 30mgl(-1) for atrazine). Above these ranges HS induce a decrease in the pesticides photolysis rate. Spin-trapping measurements by electronic paramagnetic resonance spectroscopy, using the spin-trap DMPO, showed that HS are able to photogenerate hydroxyl radicals, increasing the pesticides molecule degradation. However, the HS also react with the photogenerated hydroxyl radical, influencing the pesticide photolysis, leading to a decrease in the photolysis rate and causing it to be strongly dependent on the nature and concentration of residues in the water to be treated.     

Release behavior of triazine residues in stabilised contaminated soils

This paper reports the release behavior of two triazines (atrazine and simazine) in stabilised soils from a pesticide-contaminated site in South Australia. The soils were contaminated with a range of pesticides, especially with triazine herbicides. With multiple extractions of each soil sample with deionised water (eight in total), 15% of atrazine and 4% of simazine residues were recovered, resulting in very high concentrations of the two herbicides in leachate. The presence of small fractions of surfactants was found to further enhance the release of the residues. Methanol content up to 10% did not substantially influence the concentration of simazine and atrazine released. The study demonstrated that while the stabilisation of contaminated soil with particulate activated carbon (5%) and cement mix (15%) was effective in locking the residues of some pesticides, it failed to immobilise triazine herbicides residues completely. Given the higher water solubility of these herbicides than other compounds more effective strategies to immobilise their residues is needed.     

Pesticide storage and release in unsaturated soil in Illinois, USA.

The chemical fate and movement of pesticides may be subject to transient storage in unsaturated soils during periods of light rainfall, and subsequent release into shallow groundwater by increased rainfall. The objective of this study was to conduct field-scale experiments to determine the relative importance of transient storage and subsequent release of agrichemicals from the vadose zone into potential aquifers. Two field-scale experiments were conducted under a rain exclusion shelter. In the 1x experiment, atrazine and chlorpyrifos were applied at application-rate equivalents (1.6 kg ha(-1) and 1.3 kg ha(-1), respectively). In the 4x experiment, atrazine was applied in an amount that was four times greater than that usually applied to fields (6.7 kg ha(-1)). Water was either applied to simulate rain or withheld to simulate dry periods. In the 1x experiment, atrazine was detected in the water samples whereas chlorpyrifos was not detected in the majority of the samples. The dry period imposed on the treatment plot did not appear to result in storage of the chemicals, whereas the wet period resulted in greater leaching of atrazine, although the concentrations remained less than the Maximum Contaminant Level of 3 microg L(-1). Both chemicals were detected in soil samples collected from a 20- to 30-cm depth, but it appeared that both chemicals dissipated before the field experiment was concluded. It appeared that the one-time application of atrazine and chlorpyrifos at the label rates did not result in a sufficient mass to be stored and flushed in significant concentrations to the saturated zone. When atrazine was applied at 4x and a longer drought period was imposed on the treatment plot, the resulting concentrations of dissolved atrazine were still less than 3 microg L(-1) . Atrazine was detected in only the near-surface (0 to 15 cm) soil samples and the herbicide dissipated before the onset of the dry period in the treatment plot. The results of this field study demonstrated that atrazine and chlorpyrifos were not sufficiently persistent to be stored and then released in significantly large concentrations to the saturated zone. The dissipation half-life of atrazine in the 4x application was about 44 days. This study, in addition to others, suggested that atrazine may be less persistent in surface soil than has been generally reported.     

Interactions of sodium azide with triazine herbicides: effect on sorption to soils

Sodium azide (NaN(3)) is one of the biocides commonly used to inhibit microbial growth during sorption experiments. However, a few reports have suggested that NaN(3) can react with the analyte of interest. In this study, the interactions of NaN(3) with triazine herbicides were investigated and the effect of atrazine transformation on its sorption to soil was evaluated. The concentration of atrazine in the presence of NaN(3) decreased significantly over period of time. After 14 days, only 38% of the initial atrazine concentration (10 mg l(-1)) was detected in a solution containing 1,000 mg l(-1) NaN(3) at pH 5.5. The magnitude and the rate of atrazine transformation increased with increase in NaN(3) load and with decrease in pH. In contrast to atrazine behavior, the concentrations of prometon and ametryn did not change during the experiment. GC/MS analysis indicated that the chlorine atom of atrazine is replaced by the azide group yielding 2-azido-4-(ethylamino)-6-(isopropylamino)-s-triazine. Atrazine transformation by NaN(3) significantly affected sorption of herbicide to soil. The presence of NaN(3) affects indirectly the sorption of atrazine due to competitive effect of its derivative. Our results demonstrated that the application of NaN(3) as a biocide in sorption-desorption experiments must be carefully evaluated. This issue is vital for sorption experiments conducted over long periods of time or/and with concentration of NaN(3) higher than 100 mg l(-1).