Deethylatrazine Research Articles

The influence of vermicompost on atrazine microbial degradation performance and pathway in black soil, Northeast China

The atrazine (ATR) is extensively used in dryland crops like corn and sorghum in black soil region of Northeast China, posing ecological risks due to toxic metabolites. Vermicompost are known for soil organic pollution remediation but their role in pesticide degradation in black soil remains understudied. The influence of vermicompost on the microbial degradation pathway of atrazine was assessed in this study. Although vermicompost didn't significantly boost atrazine removal, they notably aided in primary metabolite degradation, hydroxyatrazine (HYA), deisopropylatrazine (DIA), and deethylatrazine (DEA), reducing their content by 38.67 %. They also altered the soil microbial community structure, favoring atrazine-degrading bacteria like Proteobacteria, Firmicutes, and Actinobacteria. Five secondary degradation products were identified in vermicompost treatments. Atrazine degradation occurred via dechlorination, dealkylation, and deamination pathways mainly by Nocardioidacea, Streptomycetaceae, Bacillaceae, Sphingomonadaceae, Comamonadaceae and Nitrososphaeraceae. pH and available nitrogen (AN) influenced microbial community structure and atrazine degradation, correlating with vermicompost application rates. Future black soil remediation should optimize application rates based on atrazine content and soil properties.

Multiple barriers as an efficient treatment for removing pesticides aiming direct potable reuse: A pilot scale study

Water reuse for potable purposes can represent a realistic source supply of drinking water in areas with water scarcity. Therefore, combining conventional wastewater treatment technologies with advanced technologies is necessary to remove contaminants and obtain high-quality and safe water. In this study, the pesticides and degradation products, atrazine (ATZ), hydroxyatrazine (ATZOH), deethylatrazine (DEA), deisopropylatrazine (DIA), simazine (SMZ), ametryn (AMT), diuron (DIU), 2,4-D, fipronil (FIP), fipronil sulfide (FIP-SF) and fipronil sulfone (FIP-SN) were evaluated in effluent after membrane bioreactor (MBR), effluent after advanced treatment by multiple barriers (MBR, reverse osmosis, UV/H2O2 and activated carbon), in tap water collected in the urban region of Campinas and in the Atibaia River (water supply source from city of Campinas). The pesticide concentrations in the Atibaia River and the post-MBR effluent ranged between 1 and 434 ng L−1 and 1 and 470 ng L−1, respectively. Therefore, the Atibaia River and the post-MBR effluent had the same magnitude pesticide concentrations. In the production of potable water reuse, after the multiple barriers processes, only fipronil (1 ng L−1) and atrazine (3 ng L−1) were quantified in some of the samples. In tap water from Campinas, atrazine, ATZOH, DEA, diuron, and 2,4-D were quantified in concentrations ranging between 3 and 425 ng L−1. Therefore, when comparing drinking water obtained from conventional treatment with potable water reuse, according to the pesticides studied, it is possible to conclude that the advanced treatment used on a pilot scale is promising for use in a potable water reuse plant. However, studies involving more microbiological and chemical parameters should be conducted to classify potable water reuse as drinking water.

Contribution of differential alteration in oxidative stress and anti-oxidation related molecular signals to toxicity difference between atrazine and its main metabolites in nematodes

As a widely used herbicide, atrazine and its two main metabolites of deethylatrazine (DEA) and deisopropylatrazine (DIA) pose an exposure risk for both human beings and animals in the environment. In this study, Caenorhabditis elegans was selected as an in vivo model to compare the toxicity between atrazine and its main metabolites. Upon exposure from the larval stage L1 to adult day 3, both DEA and DIA showed less toxicity on locomotion and reproduction compared with atrazine at concentration of 0.001, 0.01 0.1 and 1 mg/L for parental generation. In addition, exposure to DEA and DIA at concentration of 0.1 mg/L also induced less transgenerational toxicity on locomotion than exposure to atrazine for both parental generation and offspring of F1–F4. Accordingly, exposure to DEA and DIA caused less ROS production and alteration in the expression of some genes (mev-1, gas-1, and clk-1) governing oxidative stress compared to atrazine. Meanwhile, DEA and DIA lead to less increase in expression of superoxide dismutase genes (sod-2 and sod-3) and SOD-3::GFP than atrazine. Moreover, atrazine and its two main metabolites differentially activated the daf-16 encoding FOXO transcriptional factor in insulin signaling pathway during the control of downstream target of SOD-3. Overall, our results highlighted the important role of oxidative stress and anti-oxidation related molecular signals in mediating toxicity of atrazine, DEA and DIA, which provided a novel explanation for the different toxicity between atrazine and its main metabolites.

Promoted dissipation and detoxification of atrazine by graphene oxide coexisting in water.

The herbicide atrazine (ATZ) has a detrimental effect on the health of aquatic ecosystems and has become a global concern in recent years. But the understanding of its persistence and potential toxicity under combined pollution, especially in the coexistence of other emerging pollutants, remains limited. In this work, the dissipation and transformation of ATZ in combination with graphene oxide (GO) in water were investigated. Results showed that dissipation rates of ATZ dramatically increased by 15-95% with half-lives shortened by 15-40% depending on initial concentrations of ATZ, and the products were mainly toxic chloro-dealkylated intermediates (deethylatrazine (DEA) and deisopropylatrazine (DIA)), but their contents were significantly lower under the coexistence of GO compared to ATZ alone. In the presence of GO, the nontoxic dechlorinated metabolite hydroxyatrazine (HYA) was detected earlier than 2-9days, and ATZ transformation into HYA was increased by 6-18% during 21-day incubation periods. This study indicated that the coexistence of GO enhanced the dissipation and detoxification of ATZ. From a remediation standpoint, GO-induced hydrolytic dechlorination of ATZ can reduce its ecological toxicity. But the environmental risks of ATZ for aquatic ecosystem under the coexistence of GO should still be given the necessary prominence due to the potential hazard of ATZ adsorbed on GO and the predominant degradation products (DEA and DIA).

Enhanced phytoremediation of atrazine-contaminated soil by vetiver (Chrysopogon zizanioides L.) and associated bacteria.

The intensive and long-term use of atrazine (ATZ) has led to the contamination of agricultural soils and non-target organisms, posing a series of threats to human health through the transmission of the food chain. In this study, a 60-day greenhouse pot experiment was carried out to explore the phytoremediation by Chrysopogon zizanioides L. (vetiver). The uptake, accumulation, distribution, and removal of ATZ were investigated, and the degradation mechanisms were elucidated. The results showed that the growth of vetiver was inhibited in the first 10 days of the incubation; subsequently, the plant recovered rapidly with time going. Vetiver grass was capable of taking up ATZ from the soil, with root concentration factor ranging from 2.36 to 15.55, and translocating to the shoots, with shoot concentration factor ranging from 7.51 to 17.52. The dissipation of ATZ in the rhizosphere soil (97.51%) was significantly higher than that in the vetiver-unplanted soil (85.14%) at day 60. Metabolites were identified as hydroxyatrazine (HA), deethylatrazine (DEA), deisopropylatrazine (DIA), and didealkylatrazine (DDA) in the samples of the shoots and roots of vetiver as well as the soils treated with ATZ. HA, DEA, DIA, and DDA were reported first time as metabolites of ATZ in shoots and roots of vetiver grown in soil. The presence of vetiver changed the formation and distribution of the dealkylated products in the rhizosphere soil, which remarkably enhanced the occurrence of DEA, DIA, and DDA. Arthrobacter, Bradyrhizobium, Nocardioides, and Rhodococcus were the major atrazine-degrading bacterial genera, which might be responsible for ATZ degradation in the rhizosphere soil. Our findings suggested that vetiver grass can significantly promote ATZ degradation in the soil, and it could be a strategy for remediation of the atrazine-contaminated agricultural soil.

Ultimate fate and possible ecological risks associated with atrazine and its principal metabolites (DIA and DEA) in soil and water environment

Atrazine (AT) is a triazine herbicide widely used to control weeds in several crops. De-isopropylatrazine (DIA) and de-ethylatrazine (DEA) are two of the eight primary metabolites produced by AT breakdown in soil and water. The physico-chemical properties of the soil determine their final fate. So, this study aimed to assess the function of clay loam and sandy loam soils in determining their ultimate fate and the potential ecological risks to non-target species during their persistence in soil and transportation to water bodies. The soil in pots was spiked with standard solutions of AT, DEA, and DIA at 0.3 and 0.6 mg/kg for the persistence study. The leaching potential was determined by placing soils in Plexi columns and spiking them with 50 and 100 µg standard solutions. Liquid-liquid extraction was used to prepare the samples, which were then analyzed using GC-MS/MS. The dynamics of dissipation were first-order. AT, DEA and DIA disappeared rapidly in sandy loam soil, with half-lives ranging from 6.2 to 8.4 days. AT and its metabolites had a significant amount of leaching potential. In sandy loam soil, leaching was more effective, resulting in maximal residue movement up to 30–40 cm soil depth. The presence of a notable collection of residues in leachate fractions suggests the potential for surface and groundwater contamination. In particular, DEA and DIA metabolites caused springtail Folsomia candida and earthworm Eisenia fetida to have longer and greater unacceptable risks. If the residues comparable to the amount acquired in leachate fractions reach water bodies, they could cause toxicity to a variety of freshwater fish, aquatic arthropods, amphibians, and aquatic invertebrates. Future studies should take a more comprehensive approach to evaluate ecological health and dangers to non-target species.

Removal of atrazine from submerged soil using vetiver grass (Chrysopogon zizanioides L.)

The long-term widespread application of atrazine poses significant threats to the eco-environment and human health. To investigate the potential of vetiver (Chrysopogon zizanioides L.) for phytoremediation of the environmental media contaminated by atrazine, an indoor incubation experiment was conducted in submerged soil over 30 days. Results showed that the chlorophyll level of the vetiver was not significantly affected by exposure to atrazine. Vetiver could take up and accumulate atrazine from submerged soil and peaked around the 20th day with a concentration of 1.0 mg kg−1 in leaf. The metabolites Hydroxyatrazine (HA), deethylatrazine (DEA), Deisopropylatrazine (DIA), and didealkylatrazine (DDA) were detected in the leaf on the 30th day, indicating vetiver could degrade atrazine inside the leaf tissue. The atrazine removal rate in the vetiver planted and unplanted jars were 69.72 and 60.29%, respectively, indicating that 9.43% higher atrazine removal was achieved in the presence of vetiver (p < 0.05). The atrazine dissipation in the submerged soil followed first-order kinetics, the degradation constant was 0.066, and the half-life of atrazine dissipation was shortened by 6.86 days in the presence of vetiver. The present study suggests that vetiver can take up atrazine from submerged soil and accumulate in the leaf, which could then degrade in the leaf. Novelty statement: Although the fate of atrazine in agricultural soils has been extensively investigated through various experiments, little is known about the effect of vetiver grass on atrazine dissipation from submerged soil. With the identification of soil-leaf transportation and four metabolites in vetiver leaf and soils, significantly accelerated atrazine dissipation from the submerged soil was achieved in the presence of vetiver. Particularly, the formation of less toxic dealkylated products in the leaf indicated vetiver is a promising grass for atrazine removal from submerged soil.

Occurrence of Banned and Currently Used Herbicides, in Groundwater of Northern Greece: A Human Health Risk Assessment Approach.

The presence of pesticide residues in groundwater, many years after their phase out in European Union verifies that the persistence in aquifer is much higher than in other environmental compartments. Currently used and banned pesticides were monitored in Northern Greece aquifers and a human health risk assessment was conducted. The target compounds were the herbicides metolachlor (MET), terbuthylazine (TER), atrazine (ATR) and its metabolites deisopropylatrazine (DIA), deethylatrazine (DEA) and hydroxyatrazine (HA). Eleven sampling sites were selected to have representatives of different types of wells. Pesticides were extracted by solid-phase extraction and analyzed by liquid chromatography. MET was detected in 100% of water samples followed by ATR (96.4%), DEA and HA (88.6%), DIA (78.2%) and TER (67.5%). ATR, DIA, DEA, HA, MET and TER mean concentrations detected were 0.18, 0.29, 0.14, 0.09, 0.16 and 0.15 μg/L, respectively. Obtained results were compared with historical data from previous monitoring studies and temporal trends were assessed. Preferential flow was the major factor facilitating pesticide leaching within the month of herbicide application. Moreover, apparent age of groundwater and the reduced pesticide dissipation rates on aquifers resulted of long-term detection of legacy pesticides. Although atrazine had been banned more than 18 years ago, it was detected frequently and their concentrations in some cases were over the maximum permissible limit. Furthermore, human health risk assessment of pesticides was calculated for two different age groups though drinking water consumption. In all examined wells, the sum of the HQ values were lower than the unity. As a result, the analyzed drinking water wells are considered safe according to the acute risk assessment process. However, the presence of atrazine residues causes concerns related with chronic toxicity, since ATR R values were greater than the parametric one of 1 × 10−6 advised by USEPA, for both age groups.

Detection of Atrazine and its metabolites by photonic molecularly imprinted polymers in aqueous solutions

Water contamination caused by atrazine (ATZ) application in agriculture is a risk to the environment and human health. Common analytical methods are expensive and complex. A sensor for low-cost and simple detection of ATZ and its metabolites, deethylatrazine (DEA) and deisopropylatrazine (DIA), in aqueous solutions was developed by combining colloidal crystal with molecular imprinting technique. The sensor is formed by 3D interconnected macroporous structure with numerous nanocavities derived from ATZ and its metabolites imprinting in a thin polymeric film. Molecularly Imprinted Polymers (MIPs) were characterized by Fourier Transform Infrared spectroscopy (FTIR) and Scanning Electron Microscopy (SEM) and were incubated in solutions at variable concentrations. Target molecules were specifically absorbed in nanocavities and caused swelling in the polymer resulting in changes of Bragg diffraction peak wavelength. Kinetic tests showed that rebinding equilibrium was reached within 20 minutes. The sensor had a dynamic range of 0.1 to 10 ppb for quantifying target analytes in aqueous solutions with limit of detection of 0.1, 0.2, and 0.3 ppb, and limit of quantification of 0.33, 0.66, and 1 ppb for ATZ, DEA, and DIA, respectively. Cross-reactivity tests were conducted in 1 and 5 ppb solutions combining all three targets and showed absence of positive interference effects and low probability of false positives given by individual sensors. MIPs were examined in natural waters containing ATZ and its metabolites contamination, showing good agreement with real concentrations of targets. The MIP yields rapid and efficient detection of target molecules in aqueous solutions close to environmentally relevant concentrations.

New insights into atrazine degradation by the novel manganese dioxide/bisulfite system: Product formation and Mn reuse

Fenton and Fenton-like systems have been successfully applied in treatment of refractory pollutants in water and wastewater, but the formation and disposal of large amounts of ferric sludge is a matter of concern. This study demonstrated that Mn(IV)/HSO3− system could effectively degrade atrazine (ATZ) through generation of Mn(III) and SO4•− as primary reactive intermediates and meanwhile the sludge could be well controlled. Mn(IV) could be in situ regenerated from oxidation of Mn(II) (i.e., Mn(IV) final transformation product in Mn(IV)/HSO3− system) by oxygen under alkaline condition, and was reused for efficiently catalyzing HSO3− to degrade ATZ. The metal ions (e.g., Ca(II), Mg(II), Zn(II) and Al(III)) commonly used as coagulant had negligible effects on ATZ degradation by Mn(IV)/HSO3− system. The oxidation products of ATZ were identified to further clarify the role of various reactive intermediates in Mn(IV)/HSO3− system. Deethyl-atrazine (DEA) and atrazine amide (CDIT) were two primary products during ATZ transformation by Mn(IV)/HSO3− system. The molar ratio of CDIT to DEA ([CDIT]/[DEA]) was quantified to be 3.0–4.0 during ATZ transformation by Mn(IV)/HSO3− system, which was much higher than those (∼2.3 and ∼0.7) obtained in the cases of authentic SO4•− and •OH oxidation (i.e., UV/PDS and UV/H2O2 system), respectively. This result indicated that Mn(III) was a more selective reactive intermediate than SO4•−, which was also proved by tertiary butanol scavenging experiments. Based on these findings, the Mn(IV)/HSO3− system may be operated in a sequencing batch reactor (SBR) as a durable, efficient, and recyclable technology to treat recalcitrant contaminants in water and meanwhile to achieve ‘zero discharge’ of sludge.

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.

Water treatment intensification using a monophasic hybrid process coupling nanofiltration and ozone/hydrogen peroxide advanced oxidation

This study assesses the feasibility of designing a hybrid ozonation / nanofiltration membrane process that can simultaneously oxidize and reject contaminants while exhibiting reduced membrane fouling. An innovative monophasic configuration, in which a pre-ozonated water was mixed at the membrane cell inlet to the water to be treated doped with H2O2 (at equimolar concentrations of H2O2 and O3), was implemented, allowing to avoid an ozone-enriched gas flow in the membrane cell. Thus, two commercial polymer membranes, NP10 (polyethersulfone) and NF270 (polyamide), were assessed in a cross-flow configuration despite their low-ozone compatibility compared with ceramic membranes. Ozone removal yields>90% were obtained whatever the studied water matrix. Fast ozone decomposition initiation reactions with H2O2 and with some moieties of the natural organic matter were responsible for a low ozone lifetime in the liquid bulk, allowing to protect the membranes from ozone and radicals. Deethylatrazine (DEA) was used as a radical tracer, allowing to determine Rct values with orders of magnitude of 10-6 and 10-7 in drinking water and a river water sample, respectively. The concentrations of two pharmaceuticals, carbamazepine and sulfamethoxazole, in the permeate and the retentate were lower than the detection limit in drinking water when the PES membrane was tested. During treatment of the river water sample, membrane fouling dropped by a factor two while there was no alteration of both the PES and PA membranes. Finally, thanks to synergistic effects induced by contaminant oxidation and rejection, dissolved organic content and DEA were both removed at around 70% when PA membrane, exhibiting a tighter microstructure than PES, was used.

Seasonal variations in atrazine degradation in a typical semienclosed bay of the northwest Pacific ocean

Pesticides are widely used to alleviate pest pressure in agricultural systems, and atrazine is a typical diffuse pollutant and serves a sensitivity index for environmental characteristics. Based on the physicochemical properties of parent substances, degradation products of pesticides may pose a greater threat to aquatic ecosystems than pesticides. Atrazine and three primary degradation products (deethylatrazine (DEA), deisopropylatrazine (DIA) and didealkylatrazine (DDA)) were investigated in a semienclosed bay of the western Pacific Ocean. Seasonal surface water and suspended particulate sediment (SPS) samples were collected from the estuary and bay in January, April, and August 2019. The level of pesticide contamination was lower in the bay than in the estuary, and the pesticide concentration in the dissolved phase was higher than that in the adsorbed phase. The average concentrations of atrazine and the three degradation products in the three seasons ranged from 2.42 to 328.46 ng/L in water and from 0.07 to 12.75 ng/L in SPS. The proportion of atrazine among the four detected pollutants decreased from 0.7 to 0.1 in surface water and from 0.3 to 0.1 in SPS over the seasons. As the main degradation products, the concentration proportions of DDA and DEA reached as high as 0.6 in August. The ratio of DEA to atrazine (DEA/ATR) increased from January to August, which indicated the progressive degradation process in the bay. Single-factor analysis of variance and principal component analysis indicated that atrazine degradation was sensitive to temperature, dissolved oxygen, and salinity. These three factors accounted for almost 70% of the seasonal variance in atrazine without a quantification assessment of photolysis or bacteria. The spatial distributions of DEA in the three seasons demonstrated that wind and currents also played important roles in pollutant redistribution. The seasonal temporal and spatial correlations between water and SPS demonstrated the degradation patterns of atrazine in marine conditions, supporting the need for future detailed toxicity studies.

Estrogen Disrupting Pesticides in Nebraska Groundwater: Trends between Pesticide-contaminated Water and Estrogen-related Cancers in An Ecological Observational Study

Estrogen disrupting pesticides (EDP) are pesticides that modify estrogen activities in estrogen-producing vertebrates. A substantial amount of these pesticides has been detected in human tissues, and they function directly to disrupt estrogen synthesis or effector cells. This study examines EDP’s ecological distribution across Nebraska counties and its association with estrogen-related cancers (ERC). To determine the ecological distribution of selected EDP, county-level choropleth maps were created. Moreover, EDP was tested in separate linear models with different ERC to determine the association between ERC and EDP across Nebraska counties. Exposure data for this county-level study was obtained from the quality assessed agrichemical contaminant Nebraska groundwater database between 1 January 1974 and 31 December 2012. Acetochlor, atrazine, and its metabolites, deethylatrazine (DEA), and de-isopropyl atrazine (DIA) were the most frequently detected EDP in Nebraska groundwater. Moreover, Nebraska county-level potential confounder for ERC such as physically unhealthy days, % adult smoking, % obese adult, % uninsured, and % binge drinking were obtained from County Health Rankings 2010. ERC, which is the outcome variable (breast cancer, uterine cancer, and prostate cancer), were obtained from the Nebraska State profile of the National Cancer Institute. This was expressed as county-level age-standardized incidence cancer rates between 1 January 2013 and 31 December 2017. Data characteristics were determined using percentages, mean, median, 25th and 75th percentile, minimum and maximum values. The relationship between county-level cancer rates and % wells positive for pesticides after adjusting for the county level potential confounders were analyzed in a linear regression model. Water supply wells positive for atrazine and DEA were observed to cluster in the South and South East counties of Nebraska. Furthermore, breast cancer and prostate cancer incidence rates were higher in the southeast of Nebraska with more atrazine and DEA. However, breast cancer and prostate cancer were not significantly associated in a linear regression model with any of the observed EDP. In contrast, uterine cancer was statistically associated with % water supply wells positive for acetochlor (β = 4.01, p = 0.04). While consistent associations were not observed between ERC and EDP from the GIS and the linear regression model, this study’s results can drive future conversation concerning the potential estrogenic effects of acetochlor, atrazine, and its metabolites on the incidence of breast, uterine and prostate cancer in the State of Nebraska.

Aquaculture-derived distribution, partitioning, migration, and transformation of atrazine and its metabolites in seawater, sediment, and organisms from a typical semi-closed mariculture bay.

Atrazine (ATR) is one of the most commonly used herbicides that could directly impair the growth and health of organisms in mariculture areas and adversely affect human health through the food chain. This study investigated the contaminant occurrence, migration, and transformation of ATR and three of its chlorinated metabolites, namely deethylatrazine (DEA), deisopropylatrazine (DIA), and didealkylatrazine (DDA), in surface seawater, sediment, and aquatic organisms from the Xiangshan Harbor. ATR was detected in all samples, while DIA and DDA were only respectively detected in aquatic and seawater samples. The distribution of ATR and its metabolites presented different patterns depending on the geographic location and showed a higher level in the aquaculture area than that in the non-aquaculture area. The bioaccumulation of ATR in aquaculture organisms showed that benthic organisms, such as Ditrema, and Sinonovacula constricta (Sin), had increased levels. The ecological risks indicated that ATR posed medium or high risks to algae in the water phase of the study area. The microcosm experiment showed that the main fate of ATR in the simulated microenvironment was sedimentation, which followed the first-order kinetic equation. The ATR in the sediment could be enriched 3-5 times in Sin, and its major metabolites were DEA and DIA.

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.

Potential for the Biodegradation of Atrazine Using Leaf Litter Fungi from a Subtropical Protection Area.

The intense use of pesticides in agricultural activities for the last several decades has caused contamination of the ecosystems connected with crop fields. Despite the well-documented occurrence of pesticide biodegradation by microbes, natural attenuation of atrazine (ATZ), and its effects on ecological processes in subtropical forested areas, such as Iguaçu National Park located in Brazil, has been poorly investigated. Subtropical environments sustain a great degree of fungal biodiversity, and the patterns and roles of these organisms should be better understood. This work aimed to evaluate nine ligninolytic-producer fungi isolated from the INP edge to degrade and detoxify ATZ solutions. ATZ degradation and the main metabolites produced, including deisopropylatrazine and deethylatrazine (DEA), were analyzed using dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometer. Four fungi were able to degrade ATZ to DEA, and the other five showed potential to grow and facilitate ATZ biodegradation. Furthermore, two strains of Fusarium spp. showed an enhanced potential for detoxification according to the Allium cepa (onion) test. Although the isolates produced ligninolytic enzymes, no ligninolytic activity was observed in the biodegradation of ATZ, a feature with ecological significance. In conclusion, Ascomycota fungi from the INP edge can degrade and detoxify ATZ in solution. Increasing the knowledge of biodiversity in subtropical protected areas, such as ecosystem services provided by microbes, enhances ecosystem conservation.

Thirty-year monitoring of s-triazine herbicide contamination in the aquifer north of Vicenza (north-east Italy)

The aquifer north of Vicenza, Italy, is one of the main and most studied drinking water reservoirs within the Veneto region. The area is an intensive cropland, and monitoring of s-triazine herbicides and metabolites has been carried out since the late eighties. This study analysed the trends of atrazine (ATR), terbuthylazine (TBZ), deethyl-atrazine (DEA), and deethyl-terbuthylazine (DET) concentrations from 1987 to 2016 and related the variations of agricultural land use, herbicide load, and pesticide regulations to the residence time of pollutants in the aquifer. In total, 785 water samples collected from 82 selected check wells were analysed with high-resolution gas chromatography combined with mass spectrometry. Non-detects were substituted by one-half the limit of detection. Over the 30 years of monitoring, concentrations of all of the pollutants decreased at all sampling sites. Since the beginning, TBZ and DET residues have been systematically lower than ATR and DEA, respectively, with more than 70% of the data below the limit of detection and never exceeding the European Maximum Acceptable Concentration (MAC) for a single pesticide (0.1 μg/L). The highest concentrations of ATR and DEA showed a spatial shift along the flow direction, suggesting an increase in groundwater residence time from the recharge zone to the accumulation zone of the aquifer. The last residues of ATR were found 27 years after its ban.Although all of the concentrations were lower than those found elsewhere in Europe, the sum of s-triazines overcame the MAC in 20% of the samples. Considering the structural and toxicological similarities of s-triazines, these findings confirm the necessity of better characterisation of the toxicological risk posed by mixtures.

Chloro-triazine transport to streams–evaluating methods for partitioning deisopropylatrazine sources

Streams in the Salt River Basin (SRB) of northeastern Missouri, USA, have been chronically contaminated by atrazine and metabolites, with peak annual transport occurring from spring to early summer. Since 2005, increased fall-applied simazine has introduced a second chloro-triazine herbicide that degrades to deisopropylatrazine (DIA), creating the need for a method to partition DIA between its two parent sources – i.e., DIA derived from atrazine (DIAATR) and that from simazine (DIASIM). Distinguishing DIA parent sources would extend current understanding of chloro-triazine transport, leading to more accurate risk assessments and improved watershed-scale load estimates. The objectives of this study were to evaluate proposed methods for DIA partitioning, and to apply the most effective method to estimate DIAATR and DIASIM concentrations and loads. Three DIA partition methods were developed and statistically evaluated: 1) edge-of-field (EOF) based on DIA and deethylatrazine (DEA) concentrations in runoff from atrazine treated fields; 2) DIA:DEA concentration ratios (D2R) in runoff from atrazine treated fields; and 3) concentration ratios of simazine:atrazine (SAR) in streams. Stream samples were collected year-round at 7 SRB stream sites from 2005 to 2010 and daily, quarterly, and annual concentrations and loads of atrazine, DEA, DIA, and simazine computed. The SAR method was superior to EOF and D2R in its ability to estimate concentrations and loads of DIASIM and DIAATR that were more accurate and highly correlated to observed transport of simazine, atrazine, and DIA. The SAR method results demonstrated the differences in DIASIM and DIAATR transport timing, with peak DIASIM transport occurring from mid-Nov to Apr and peak DIAATR transport from May to Jun. Dual season triazine applications within a watershed substantially increased the period of high chloro-triazine concentrations in streams from ~3 to ~8 months/yr, potentially increasing the risk of toxicity to aquatic ecosystems.

Atrazine Transport through a Soil-Epikarst System.

Row crop and livestock production contaminate soils and groundwater of the karst aquifers within south-central Kentucky's Pennyroyal Plateau. Transport of atrazine from field application to the epikarstic drainage system beneath a field with active row-crop farming was investigated. The Crumps Cave study site is a shallow autogenic drainage system with a recharge area of ∼1 ha that contains two epikarst drains (WF-1 and WF-2) which were monitored for atrazine, deethylatrazine (DEA), and deisopropylatrazine (DIA) concentrations from January 2011 to May 2012. Atrazine concentrations in both drains did not increase above winter background levels for nearly 2 mo after application when levels suddenly spiked and reached peak concentrations for the study during an event in May 2011. Atrazine, DEA, and DIA were detected in 100% of samples, and metabolites accounted for 54 to 94% of the monthly total loads, except in May 2011. Median dealkylated metabolite/atrazine ratios (DMAR) were ∼5:1 at both sites, and seasonal DMAR patterns corresponded with changes in soil temperature. These data support the hypothesis that a combination of sorption and degradation in the soil column above the epikarst controlled the transport of atrazine and its metabolites. This resulted in delayed atrazine transport after application and prolonged transport of atrazine and its weakly sorbed metabolites to the epikarst aquifer. Management practices that reduce herbicide inputs, such as diverse crop rotations, cover crops, and use of low-rate and strong-sorbing herbicides, would improve groundwater quality in areas of the Corn Belt with intensive row cropping on karst topography.