Atrazine Degradation Products Research Articles

Deep degradation of atrazine in water using co-immobilized laccase-1-hydroxybenzotriazole-Pd as composite biocatalyst

The efficient and green removal technology of refractory organics such as atrazine in water has been an important topic of research in water treatment. A novel membrane composite biocatalyst Lac-HBT-Pd/BC as prepared for the first time by co-immobilizing laccase, mediator 1-hydroxybenzotriazole (HBT) and metal Pd on functionalized bacterial cellulose (BC) to investigate the removal of atrazine and degradation of its intermediates under mild ambient conditions. It was found that atrazine could be completely degraded in 5 h by the catalysis of Lac-HBT-Pd/BC, and the removal rate of degradation intermediates from atrazine was about 85% after continuous catalysis, which achieved deep degradation of atrazine. The effect of electrochemical activity and radical stability of the membrane composite biocatalysts loaded with Pd was investigated. The possible degradation pathways were proposed by identifying and analyzing the deep degradation products of atrazine. The Lac-HBT-Pd/BC demonstrated deep degradation of atrazine and favorable reusability as well as considerable adaptability to various water qualities. This work provides an important reference for preparing new kinds of biocatalysts to degrade refractory organic pollutants in water.

Occurrence of contaminants of emerging concern and their risks to the Pantanal Sul-Mato-Grossense aquatic biota, Brazil

The Aquidauana River is an important ecological corridor in the Pantanal biome. However, the growth of agricultural and urban areas along its banks has contributed to the deterioration of its water quality, consequently putting the aquatic biota at risk. Our objectives were to evaluate: 1) the composition of the landscape around six sampling sites located in the Aquidauana River middle section; and 2) the quality of its water by determining limnological parameters, concentrations of contaminants of emerging concern (CECs), and the risks to native aquatic biota. Water samples were collected in November 2020. We observed the conversion of native riparian vegetation to extensive pasture areas and anthropic occupation around the sampling sites. We observed that the chlorophyll and total ammoniacal nitrogen values were above the standards established by Brazilian legislation in all samples. Studies focused on the quantification of CECs in the Pantanal waters are scarce, and to the best of our knowledge, this is the first study that investigated the presence of pharmaceuticals in the Aquidauana River. All 30 CECs analyzed were detected in at least one water sample. Eleven CECs were quantified with eight pesticides (atrazine, diuron, hexazinone, tebuthiuron, azoxystrobin, carbendazim, tebuconazole, and fipronil) and one atrazine degradation product (atrazine-2-hydroxy), caffeine, and bisphenol A. The concentrations of atrazine herbicide observed in the water samples pose risks for protecting aquatic biota (RQs >1). Therefore, the native biota of the Pantanal biome is vulnerable to several types of toxic contaminants observed in the water, which can cause the disappearance of native and endemic species in this region. Establishing a monitoring program, improving sanitation infrastructure, and intensifying good agricultural practices are essential for reducing and controlling the entry of CECs into the Aquidauana River and the Pantanal water system.

Abiotic transformation of atrazine in aqueous phase by biogenic bixbyite-type Mn2O3 produced by a soil-derived Mn(II)-oxidizing bacterium of Providencia sp.

Recently, biogenic Mn oxides (BioMnOx) are considered as the promising degradation agents for environmental organic contaminants. However, little information is available for the degradation of atrazine by BioMnOx. In this work, BioMnOx, generated by a soil-derived Mn(II)-oxidizing bacterium, Providencia sp. LLDRA6, was explored to degrade atrazine. To begin with, collective results from mineral characterization analyses demonstrated that this BioMnOx was biogenic bixbyite-type Mn2O3. After that, purified biogenic Mn2O3 was found to exhibit a much higher removal efficiency for atrazine in aqueous phase, as compared to unpurified biogenic Mn2O3 and LLDRA6 biomass. During the atrazine removal by biogenic Mn2O3, six intermediate degradation products were discovered, comprising deethylatrazine (DEA), hydroxylatrazine (HA), deethylhydroxyatrazine (DEHA), ammeline, cyanuric acid, and 5-methylhexahydro-1,3,5-triazine-2-thione (MTT). Particularly, the intermediate, MTT, was considered as a new degradation product of atrazine, which was not described previously. Meanwhile, Mn(II) ions were released from biogenic Mn2O3, and on the surface of biogenic Mn2O3, the content of hydroxyl O species increased at the expense of that of lattice and water O species, but the fundamental crystalline structure of this Mn oxide remained unchanged. Additionally, no dissociative Mn(III) was found to involve in atrazine degradation. In summary, these results demonstrated that both the non-oxidative and oxidative reactions underlay the degradation of atrazine by biogenic Mn2O3.

Influence of Cd on atrazine degradation and the formation of three primary metabolites in water under the combined pollution.

To understand the influence of Cd on atrazine (ATZ) degradation in aqueous solution, the degradation of different initial levels of ATZ (0.1, 0.5, 1.0, and 2.0mg·L-1) was investigated in the presence and absence of Cd2+ in a 20-day laboratory experiment. It was found that Cd2+ caused a significant decrease in ATZ degradation and increased its half-life from 17-34days to 30-57days (p < 0.0001). Regarding the three most common metabolites of ATZ, deethylatrazine (DEA) and deisopropylatrazine (DIA) were detected in water earlier than hydroxyatrazine (HYA). The DEA content was several times higher than the DIA and HYA contents, regardless of the presence or absence of Cd2+. In the presence of Cd2+, the DIA content was significantly lower and the HYA content was significantly higher. Furthermore, Cd2+ had a dose-dependent effect on HYA formation. Our results indicated that the coexistence of Cd2+ and ATZ resulted in greater herbicide persistence, thereby possibly increasing the risk of environmental contamination. DEA was still the predominant ATZ degradation product detected in water under the combined pollution, which was similar to the ATZ tendency.

Removal of herbicide atrazine by a novel biochar based iron composite coupling with peroxymonosulfate process from soil: Synergistic effect and mechanism

Over the past decade, herbicides contaminated soil poses a serious threat to humans and environment. In this study, a novel biochar supported zero valent iron (BC-nZVI) was used as a heterogeneous catalyst activating peroxymonosulfate (PMS) for the removal of herbicide atrazine (ATZ) from soil. The results revealed that the removal of ATZ by BC-nZVI/PMS process was superior to that of BC/PMS or nZVI/PMS process. A synergistic effect between BC/PMS and nZVI/PMS processes has been successfully achieved in BC-nZVI/PMS process, and nearly 96% of ATZ removal was obtained at optimum reaction conditions. BC-nZVI/PMS process exhibited an excellent performace on ATZ removal compared with BC-nZVI/H2O2 or BC-nZVI/persulfate (PS) process. PMS decomposition by BC-nZVI/PMS process was higher than the sum of BC/PMS and nZVI/PMS processes. A low Cu concentration accelerated ATZ removal, and Cu was also effectively immobilized. SO4− was the predominant reactive oxygen species responsible for ATZ degradation, and OH and 1O2 also took part in reaction. Four kinds of ATZ degradation products were identified, and ATZ degradation could be achieved through de-alkylation, dechlorination and hydroxylation processes. A reaction mechanism of PMS activation by BC-nZVI was proposed based on the synergistic effect of BC and nZVI. In addition to ATZ, coexisting pollutants such as 2,4-dichlorophenol (2,4-DCP), Cu and Cd were also simultaneously removed from soil.

Removal of atrazine in catalytic degradation solutions by microalgae Chlorella sp. and evaluation of toxicity of degradation products via algal growth and photosynthetic activity

Degradation solutions containing atrazine need to be further purified before they are discharged into the aquatic environment. With the objectives of evaluating removal capacity of the microalga Chlorella sp. toward atrazine in degradation solutions and toxicity of the degradation products, we investigated the removal efficiency (RE) and bioaccumulation of atrazine in the microalgae after an 8 d exposure to diluted degraded solutions containing 40 μg/L and 80 μg/L of atrazine as well as degradation products in the present study. Moreover, pure atrazine solutions with similar concentrations were simultaneously inoculated with the microalgae in order to distinguish the influence of the products. The photocatalytic degradation results showed that 31.4% of atrazine was degraded after 60 min, and three degradation products, desisopropyl-atrazine (DIA), desethyl-atrazine (DEA), and desethyl-desisopropyl-atrazine (DEIA) were detected. After an 8-d exposure, 83.0% and 64.3% of atrazine were removed from the degraded solutions containing 40 μg/L and 80 μg/L of atrazine, respectively. In comparison with the control, i.e., pure atrazine solution with equal concentration, Chlorella sp. in the degraded atrazine solution showed lower RE and growth rate. The photosynthetic parameters, especially performance index (PIABS), clearly displayed the differences between treatments. The values of PIABS of Chlorella sp. cultured in degradation atrazine for 8 days were significantly lower (P < 0.01) than that in the corresponding pure atrazine, suggesting potential inhibitory effect of degradation products on the microalgae. Atrazine and the degradation products inhibited algal photosynthesis via depressed light absorption and electron transport, and reduced utilization of light energy via energy dissipation. Our results demonstrated that microalgae Chlorella sp. had an encouraging atrazine removal potential and the degradation products of atrazine may inhibit algal growth and removal capability. This study may be useful for the application of microalgae in herbicide wastewater treatment and understanding algal removal of atrazine in natural aquatic environment.

Electrochemical degradation of aqueous alachlor and atrazine: products identification, lipophilicity, and ecotoxicity

This work studied the electrochemical degradation of alachlor and atrazine (alone and mixed with each other) using a filter-press cell, a dimensionally stable anode (DSA Ti/Ru0.3Ti0.7O2), initial pH 3.0, and temperature at 25 °C. The best operational conditions for alachlor (0.33 mmol L-1) degradation were obtained by a 32 factorial design, in which the factors/levels were: NaCl concentration (0.05, 0.1, and 0.15 mol L-1) and current density (10, 30, and 50 mA cm-2). Thus, 93.1% alachlor removal and 71.2% mineralization were achieved using 0.15 mol L-1 NaCl and 30 mA cm-2. In addition, the initial degradation products (DPs) of alachlor and atrazine were identified by liquid chromatography coupled to mass spectrometry (LC-MS). Acute and chronic ecotoxicities for three trophic levels (fishes, daphnids and green algae) and lipophilicity (log D, pH 7.4) of the DPs were also estimated using the ECOSAR 1.11 and ChemAxon Calculator software, respectively. The present study showed that the electrochemical degradation is an efficient method for removing the herbicides alachlor and atrazine from water and that the DPs formed have lower pollution potential than their original compounds.

Transfer and degradation of the common pesticide atrazine through the unsaturated zone of the Chalk aquifer (Northern France)

Groundwater in the Chalk aquifer is an important water resource whose quality has degraded due to fertilizer and pesticide use. Atrazine, classified as a priority substance, has been one of the most applied pesticides and also one of the most frequently detected pesticides in groundwater. The present study investigated the transfer and degradation of atrazine in the unsaturated zone of the Chalk aquifer in Northern France. The study was conducted in an underground quarry (Saint-Martin-le-Noeud), which provides a direct access to the water table and intercepts the unsaturated zone at different depths. The lake and the ceiling percolation of 16 sites throughout the quarry were followed. For 16 sites, the percolating flow rate and lake level were measured and the lake water was sampled for nitrate, atrazine and deethylatrazine (DEA, main degradation product of atrazine) analysis over 2.5 years. High spatial variations in hydrodynamics (percolating flow rate and lake level) and in lake water quality (atrazine between 55±11 and 202±40 ng L−1 and DEA between 269±53 and 1727±345 ng L−1) indicate that the properties of the unsaturated zone influence the transfer and the degradation of atrazine. A counterclockwise hysteresis characterizes the relationship between the lake level and atrazine concentration. Temporal variation shows that the atrazine is transferred through the matrix and fractures with a delay caused by the sorption process that differs in atrazine and DEA. The layer of clay-with-flints is shown to favor the degradation of atrazine near the surface. Preferential pathways may be created below clay-with-flints, through which the transfer of atrazine is quicker.

Biodegradation of Atrazine by the Novel Klebsiella variicola Strain FH-1.

Bacterial strain FH-1 with high efficiency of degrading Atrazine is separated by means of enrichment culture from the soil applied with Atrazine for many years. FH-1, recognized as Klebsiella variicola based on phylogenetic analysis of 16S rDNA sequences, can grow with Atrazine which is the sole nitrogen source. In fluid inorganic salt medium, the optimal degradation temperature, pH value, and initial concentration of Atrazine are 25°C, 9.0, and 50 mg L–1, respectively, and the degradation rate of Atrazine by strain FH-1 reached 81.5% in 11 d of culture. The degrading process conforms to the kinetics equation of pesticide degradation. Among the metal ions tested, Zn2+ (0.2 mM) has the most significant effect of facilitation on the degradation of Atrazine. In the fluid medium with Zn2+, the degradation rate of Atrazine is increased to 72.5%, while the Cu2+ (0.2 mM) inhibits the degradation of Atrazine. The degradation products of Atrazine by strain FH-1 were identified as HEIT (2-hydroxyl-4-ethylamino-6-isopropylamino-1,3,5-triazine), MEET (2-hydroxyl-4,6-bis(ethylamino)-1,3,5-triazine), and AEEO (4,6-bis(ethylamino)-1,3,5-triazin-2(1H)-one) by HPLC-MS/MS. Three genes (atzC, trzN, and trzD) encoding for Atrazine degrading enzymes were identified by PCR and sequencing in strain FH-1. This study provides additional theoretical support for the application of strain FH-1 in bioremediation of fields polluted by Atrazine.

Efficient atrazine degradation catalyzed by manganese porphyrins: Determination of atrazine degradation products and their toxicity evaluation by human blood cells test models.

Atrazine (ATZ) is an herbicide that has been considered an environmental pollutant worldwide. ATZ contaminates groundwaters and can persist in soils for up to a year causing several environmental and health problems. This study aimed to investigate ATZ degradation catalyzed by manganese porphyrins as biomimetic cytochrome P450 models. We used PhIO, PhI(OAc)2, H2O2, t-BuOOH, m-CPBA, or Oxone® as oxidant under mild conditions and evaluated a range of manganese porphyrins as catalyst. Concerning oxidant, iodosylbenzene provided the best result-ATZ degradation catalyzed by one of the studied manganese porphyrins in acetonitrile was as high as 47%. We studied the same catalyst/oxidant systems in natural water from a Brazilian river as solvent and obtained up to 100% ATZ degradation when iodobenzene diacetate was the oxidant, regardless of the manganese porphyrin. Besides the already known ATZ degradation products, we also identified unexpected degradation compounds (ring-opening products). Toxicity tests showed that the latter products were capable of proliferate blood cells because they did not show toxicity under the evaluated conditions.

Mechanism and Kinetic Analysis of Degradation of Atrazine by US/PMS

The degradation effect, degradation mechanism, oxidation kinetics, and degradation products of Atrazine (ATZ) by Ultrasound/Peroxymonosulfate (US/PMS) in phosphate buffer (PB) under different conditions were studied. It turned out that the degradation rate of US/PMS to ATZ was 45.85% when the temperature of the reaction system, concentration of PMS, concentration of ATZ, ultrasonic intensity, and reaction time were 20 °C, 200 μmol/L, 1.25 μmol/L, 0.88 W/mL, and 60 min, respectively. Mechanism analysis showed that PB alone had no degradation effect on ATZ while PMS alone had extremely weak degradation effect on ATZ. HO• and SO4−• coexist in the US/PMS system, and the degradation of ATZ at pH7 is dominated by free radical degradation. Inorganic anion experiments revealed that Cl−, HCO3−, and NO3− showed inhibitory effects on the degradation of ATZ by US/PMS, with Cl− contributing the strongest inhibitory effect while NO3− showed the weakest suppression effect. According to the kinetic analysis, the degradation kinetics of ATZ by US/PMS was in line with the quasi-first-order reaction kinetics. ETA with concentration of 1 mmol/L reduced the degradation rate of ATZ by US/PMS to 10.91%. Product analysis indicated that the degradation of ATZ by US/PMS was mainly achieved by dealkylation, dichlorination, and hydroxylation, but the triazine ring was not degraded. A total of 10 kinds of ATZ degradation intermediates were found in this experiment.

Effects of biochar amendment on the sorption and degradation of atrazine in different soils

ABSTRACTSugarcane top-derived biochar was added to an alluvial soil, a moist soil and a paddy soil at the rate of 0.2% and 0.5% (w/w). After the addition of 0.2% and 0.5% biochar, the sorption coefficients (Kd) of atrazine (Ce = 10 mg L−1) were increased by 26.97% and 79.58%, respectively, in the moist soil with a low level of total organic carbon (TOC), while it increased by 31.43% and 60.06%, respectively, in the paddy soil with a high TOC content. The half-time persistence values of atrazine in the alluvial soil, moist soil and paddy soil were 28.18, 23.74 and 39.84 d, respectively. In the 0.2% biochar amended soils, the corresponding half-times of atrazine for the alluvial soil, moist soil and paddy soil were extended by 10.33, 11.81 and 1.42 d, and they were prolonged by 16.83, 17.52 and 14.74 d, respectively, in the 0.5% biochar amended soils. Atrazine degradation products (deisopropylatrazine and desethylatrazine) decreased after they accumulated to 3.2 and 1 mg kg−1, respectively. Generally, increasing sorption was accompanied by decreasing degradation of atrazine which is found in biochar-amended soils.

Degradation of atrazine and structurally related s-triazine herbicides in soils by ferrous-activated persulfate: Kinetics, mechanisms and soil-types effects

The occurrence of s-triazine herbicides in soils and groundwaters has been reported globally and remediation of these contaminated sites are essentially imperative, especially at accidental spill sites. Present work investigated the feasibility of using Fe2+ catalyzed persulfate (PS) to effectively degrade s-triazine herbicides (e.g., atrazine (ATZ), terbuthylazine (TEA) and ametryn (AMT)) in soils. The degradation kinetics, mechanisms and soil-types effects were systematically investigated. For arable soil A1, extent of degradation reached 80% for 100 mg kg−1 ATZ contaminated soil after 600 min (PS/Fe2+ of 16.6 mM/16.6 mM) at 23 °C. Increasing PS and Fe2+ dosages could enhance ATZ degradation. Acidic condition was favorable for the degradation of ATZ with Fe2+/PS process and the contribution of SO4− to the overall degradation of ATZ decreased as initial pH increased. The ethyl group and chloride substituent on molecular structure of ATZ affected its degradation comparing to other two s-triazine herbicides. ATZ degradations in two arable soils and one paddy soil indicated that different soils with various physical-chemical properties, such as soil organic matter, available and total Fe contents, may influence the ATZ degradation. Moreover, a total of five degradation products of ATZ were identified in soil A1 by Fe2+/PS process. Three degradation pathways including alkyl chain oxidation, dealkylation and dechlorination-hydroxylation reactions with the underlying oxidation mechanisms were tentatively proposed.

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.

Low environmentally relevant levels of bioactive xenobiotics and associated degradation products cause cryptic perturbations of metabolism and molecular stress responses in Arabidopsis thaliana

Anthropic changes and chemical pollution confront wild plant communities with xenobiotic combinations of bioactive molecules, degradation products, and adjuvants that constitute chemical challenges potentially affecting plant growth and fitness. Such complex challenges involving residual contamination and mixtures of pollutants are difficult to assess. The model plant Arabidopsis thaliana was confronted by combinations consisting of the herbicide glyphosate, the fungicide tebuconazole, the glyphosate degradation product aminomethylphosphonic acid (AMPA), and the atrazine degradation product hydroxyatrazine, which had been detected and quantified in soils of field margins in an agriculturally intensive region. Integrative analysis of physiological, metabolic, and gene expression responses was carried out in dose-response experiments and in comparative experiments of varying pesticide combinations. Field margin contamination levels had significant effects on plant growth and metabolism despite low levels of individual components and the presence of pesticide degradation products. Biochemical and molecular analysis demonstrated that these less toxic degradation products, AMPA and hydroxyatrazine, by themselves elicited significant plant responses, thus indicating underlying mechanisms of perception and transduction into metabolic and gene expression changes. These mechanisms may explain observed interactions, whether positive or negative, between the effects of pesticide products (AMPA and hydroxyatrazine) and the effects of bioactive xenobiotics (glyphosate and tebuconazole). Finally, the metabolic and molecular perturbations induced by low levels of xenobiotics and associated degradation products were shown to affect processes (carbon balance, hormone balance, antioxidant defence, and detoxification) that are likely to determine environmental stress sensitivity.

Rapid extraction and determination of atrazine and its degradation products from microporous mineral sorbents using microwave-assisted solvent extraction followed by ultra-HPLC-MS/MS

We have evaluated three methods for the extraction of atrazine and six of its degradation products from microporous mineral sorbents. Soxhlet extraction and ultrasonic extraction, which work well on soils and sediments, recover only <15 % of the atrazine from a dealuminated Y zeolite. Closed-vessel microwave-assisted extraction, in contrast, gives much better recoveries. This is attributed to the accelerated mass transfer at elevated temperatures and the displacement by the solvent forced into the mineral micropores under elevated pressures. Under the optimized conditions, the recovery of atrazine from the hydrophilic Y zeolites (Si/Al ratios <8) is almost quantitative, and ∼77 % for the more hydrophobic ones. The extraction efficiencies for the degradation products of atrazine in the hydrophilic zeolites (74.1–100 %) are also higher than those in the hydrophobic ones (22.3–44.2 %). The extracted compounds were quantified by a combination of ultra-HPLC and tandem MS and resulted in detection limits between 0.04 and 1.41 mg kg−1 on a hydrophilic Y zeolite (Si/Al = 2.55), and of 0.09–2.35 mg kg−1 on a hydrophobic zeolite (Si/Al = 15). The method was applied to study the degradation of atrazine sorbed on dealuminated Y zeolites.

Impact of grass filter strips length on exported dissolved masses of metolachlor, atrazine and deethylatrazine: a four‐season study under natural rain conditions

AbstractHerbicides atrazine and metolachlor have been detected in water bodies across the world. The objective of this study was to assess the efficiency of 0‐m, 3‐m, 6‐m and 9‐m grass filter strips to reduce masses of dissolved metolachlor, atrazine and deethylatrazine (a degradation product of atrazine) exported in runoff. For that purpose, 16 uncultivated plots (3‐m wide × 65‐m long) with 0‐m‐, 3‐m‐, 6‐m‐ and 9‐m‐long grass filter strips were setup in a completely randomized block design. During four seasons, masses of dissolved atrazine, metolachlor and deethylatrazine were determined for the first four to five rain events, under natural rain conditions, after atrazine and metolachlor application. Generally, grass filter strips reduced exported herbicide masses by more than 90% and influenced atrazine and metolachlor dissipation kinetics in the field. The 3‐m grass filter strip (area ratio source/strip of 22:1) usually provided a reduction in exported herbicide masses similar to the 6‐ or 9‐m grass filter strips. Therefore, under the present experimental soil and climate conditions, a grass filter strip of 3 m would be a good compromise between environmental protection of surface waters against atrazine and metolachlor contamination and conservation of agricultural land use. Such an approach contributes to the acceptability by producers to implement optimized best management practices such as vegetated filter strips for the preservation of the quality of water resources.

Degradation of atrazine by Fenton and modified Fenton reactions

For 50 years, farmers around the world have relied on the herbicide atrazine—one of the triazine family of herbicides—to fight weeds in corn, grain sorghum, sugar cane, and other crops. Although prohibited in the European Union because of widespread contamination of waterways and drinking water supplies, it is still one of the most widely used herbicides in the world. Atrazine and some of its degradation products are among the most commonly found xenobiotics in groundwater and soils in the world. It is also an endocrine disruptor that causes abnormal reproductive development and immune suppression in wildlife. The purpose of this study was to identify the degradation products of atrazine. Fenton reaction treatment, a hydroxyl radical oxidation process recently developed for the degradation of aqueous pesticide waste, was applied to the degradation of atrazine. Classical and modified Fenton reactions have been used as Advanced Oxidation Process treatment methods. A HPLC method was developed and optimized for the identification of resulting degradation products. In general, very good atrazine degradation efficiencies were achieved by both of the methods used. The degradation products, such as oxalic acid, urea, formic acid, acetic acid, and acetone, were identified by HPLC with a photodiode array detector.

Impact of Grass and Grass with Poplar Buffer Strips on Atrazine and Metolachlor Losses in Surface Runoff and Subsurface Infiltration from Agricultural Plots

In many areas of intensive corn production, atrazine and metolachlor are among the most commonly found herbicides in surface and ground water. This 2-yr study compared the impact of grass and grass+tree buffer strips on the exported masses of atrazine, metolachlor, and a degradation product of atrazine, desethylatrazine (DEA). The experimental system consisted of four replicate plots in a three-way completely randomized design (no buffer zone, grass buffer zone, and grass+tree buffer strips). The field plots were 5 m wide and 30 m long and grown in corn. The grass and grass+tree buffer strips were 5 m and had the same grass vegetation except for eight young hybrid poplars. Over the 2-yr study, surface runoff and subsurface infiltration water (under the buffer strip) were collected after the initial three rainfall events after herbicide application. Dissolved atrazine, metolachlor, and DEA were analyzed by gas chromatography/mass spectrometry. The presence of buffer strips decreased the exported masses of atrazine and metolachlor in surface runoff. A three-way ANOVA with treatment (type of buffer strip), water (surface runoff or subsurface infiltration), and time between herbicide application and rainfall event as factors showed a significant reduction (40-60% in 2004 and 75-95% in 2005) in the total (surface runoff+infiltrated water) exported masses of atrazine and metolachlor in the presence of buffer strips. Rainfall events after herbicide application were different between the 2 yr and greatly affected the flow distribution (e.g., subsurface infiltration) and the leached herbicide concentrations. No significant difference in the capacity to reduce herbicide exports was observed between grass and grass+tree buffer strip treatments; the poorly developed young poplar biomass at the time of the study may partly explain this observation.

REPRODUCTIVE HEALTH OF BASS IN THE POTOMAC, USA, DRAINAGE: PART 2. SEASONAL OCCURRENCE OF PERSISTENT AND EMERGING ORGANIC CONTAMINANTS

The seasonal occurrence of organic contaminants, many of which are potential endocrine disruptors, entering the Potomac River, USA, watershed was investigated using a two-pronged approach during the fall of 2005 and spring of 2006. Passive samplers (semipermeable membrane device and polar organic chemical integrative sampler [POCIS]) were deployed in tandem at sites above and below wastewater treatment plant discharges within the watershed. Analysis of the samplers resulted in detection of 84 of 138 targeted chemicals. The agricultural pesticides atrazine and metolachlor had the greatest seasonal changes in water concentrations, with a 3.1- to 91-fold increase in the spring compared with the level in the previous fall. Coinciding with the elevated concentrations of atrazine in the spring were increasing concentrations of the atrazine degradation products desethylatrazine and desisopropylatrazine in the fall following spring and summer application of the parent compound. Other targeted chemicals (organochlorine pesticides, polycyclic aromatic hydrocarbons, and organic wastewater chemicals) did not indicate seasonal changes in occurrence or concentration; however, the overall concentrations and number of chemicals present were greater at the sites downstream of wastewater treatment plant discharges. Several fragrances and flame retardants were identified in these downstream sites, which are characteristic of wastewater effluent and human activities. The bioluminescent yeast estrogen screen in vitro assay of the POCIS extracts indicated the presence of chemicals that were capable of producing an estrogenic response at all sampling sites.