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The coexistence of herbicide atrazine (ATZ) and the nanomaterial graphene oxide (GO) in natural water bodies will be an inevitable scenario due to their widespread application and consequent release into aquatic ecosystems. But the dissipation of ATZ with GO and the response of the microbial community to their combination are still not clear. Here, we investigated the dissipation dynamics and transformation of ATZ with and without GO in river water after 21-d incubation. In the presence of GO, ATZ residue significantly decreased by 11%-43%; the transformation of ATZ markedly increased by 11%-17% when ATZ concentrations were not above 1.0 mg∙L -1 . The direct adsorption of ATZ on GO, mainly via π-π interactions, proton transfer and hydrogen bonding, contributed 54%-68% of the total increased ATZ dissipation by GO. ATZ and ATZ+GO exerted effects of similar magnitude on microbial OTU numbers with an increase of bacterial diversity. The coexisting GO increased the relative abundance of ATZ-degradation bacteria and Chitinophagales, thus improving ATZ transformation. This work indicated that the coexistence of GO at environmentally relevant concentrations can effectively reduce ATZ residues and promote the transformation of ATZ to degradation products in river water; nevertheless, the potential risk of GO acting as an ATZ carrier should be given more prominence., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

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 2-9 days, 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)., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

To evaluate combined effects of co-existed pesticides and nanomaterials on aquatic plants, the toxicity of herbicide atrazine (ATZ) on Iris pseudacorus in the presence and absence of Graphene oxide (GO) was investigated using chlorophyll a fluorescence transients. Results showed that GO reduced ATZ accumulation in plant. ATZ or ATZ combined with GO mainly blocked electron transport beyond Q A at PSII as indicated by the sharp rise of the J-step level of fluorescence rise kinetics. The pronounced increase in Fm and the loss of I-step were observed when ATZ was at 2.0 mg·L - 1 implying the damage on the oxygen evolution complex and PSI. GO at environmentally relevant concentration did not exhibit significant photosynthetic inhibitory effects on I. pseudacorus. GO at 1.0 mg·L - 1 promoted photosynthesis of I. pseudacorus under ATZ stress at 2.0 mg·L - 1 . These result indicated that the presence of GO alleviated the photosynthesis inhibition by ATZ at high levels., (© 2022. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

The combined pollution, instead of single pollution, has become a widespread contamination phenomenon in aquatic environment. However, little information is now available about the joint effects of the combined pollution, especially co-existed pesticides and heavy metals, on aquatic plants. In the present study, using continuous excitation chlorophyll fluorescence parameters and the OJIP transient, comparisons of herbicide atrazine (ATZ) phytotoxicity on Iris pseudacorus between in the presence and absence of cadmium (Cd) were evaluated over an exposure period of three weeks under laboratory conditions. Results showed that both ATZ and Cd were toxic to I. pseudacorus. The ratio F v /F o , specific electron transport energy (ET 0 /RC), and photochemistry efficiency (PI abs and PI total ) of this emergent plant species at individual ATZ and Cd concentrations were significantly lower than those of the control. ATZ mainly inhibited electron transport beyond Q A at PSII acceptor side as indicated by the sharp rise of the J-step level of fluorescence rise kinetics. A pronounced K-step and the loss of I-step due to the damage on the OEC and PSI also occurred when ATZ was at or above 1.0 mg·L -1 . In comparison to ATZ alone, ATZ combined with Cd resulted in a lower amplitude rise in J-step with apparent J-I and I-P phases; and significantly lower F o with higher F v /F o , as well as greater ET 0 /RC with higher values of PI abs and PI total . However, the adverse influences of ATZ combined with Cd on the above indicators were still significant as compared with the control. Therefore, the coexistence of Cd alleviated the individual phytotoxicities of ATZ, whereas combined pollution of ATZ and Cd still induced the decline in photosynthetic performance of I. pseudacorus, and its potential ecological impacts on the aquatic vegetation cannot be ignored. Our findings offer a better understanding of the joint effects of the pesticide and heavy metal on non-target aquatic plants, and provided valuable insights into the interaction of these pollutants in aquatic environment., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

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 2.0 mg·L -1 ) was investigated in the presence and absence of Cd 2+ in a 20-day laboratory experiment. It was found that Cd 2+ caused a significant decrease in ATZ degradation and increased its half-life from 17-34 days to 30-57 days (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 Cd 2+ . In the presence of Cd 2+ , the DIA content was significantly lower and the HYA content was significantly higher. Furthermore, Cd 2+ had a dose-dependent effect on HYA formation. Our results indicated that the coexistence of Cd 2+ 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.

Atrazine is frequently detected in surface runoff and poses a potential threat to the environment. Grass hedges may minimize runoff loss of atrazine from crop fields. Therefore, the effectiveness of two grass hedges (Melilotus albus and Pennisetum alopecuroides) in controlling atrazine runoff was investigated using simulated rainfall on lands at different slope gradients (15 and 20%) in northern China. Results showed that a storm (40 mm in 1 h), occurring 4 h after atrazine application, caused a loss of 3% of the applied amount. Atrazine loss under 20% slope was significantly greater than that under 15% slope in control plots. Atrazine exports associated with the water fraction accounted for the majority of total loss. Pennisetum hedges were more efficient in controlling atrazine loss with runoff compared to Melilotus hedges. No significant difference in the capacity of grass hedges to reduce atrazine exports was observed between 15 and 20% slopes. These findings suggest grass hedges are effective in minimizing atrazine runoff in northern China, and Pennisetum hedges should be preferentially used on sloping croplands in similar climatic regions.

The emergent plants Acorus calamus, Lythrum salicaria, and Scirpus tabernaemontani were exposed to atrazine for 15, 30, 45, and 60 days in a hydroponic system. Effects were evaluated investigating plant growth, chlorophyll (Chl) content, peroxidase (POD) activity, and malondialdehyde (MDA) content. Results showed that selected plants survived in culture solution with atrazine ≤8 mg L(-1), but relative growth rates decreased significantly in the first 15-day exposure. Chla content decreased, but MDA increased with increasing atrazine concentration. S. tabernaemontani was the most insensitive species, followed by A. calamus and L.salicaria. The growth indicators exhibited significant changes in the early stage of atrazine exposure; subsequently, the negative impacts weakened and disappeared. Plant growth may be more representative of emergent plant fitness than physiological endpoints in toxicity assessment of herbicides to emergent plants.

The emergent hydrophyte Iris pseudacorus was constantly exposed over a 35-day period to atrazine in the laboratory. It could survive at an atrazine level up to 32 mg/L. Its relative growth rates were inhibited significantly when exposure dosage reached at or exceeded 2 mg/L (p < 0.05). No observed effect concentration and lowest observed effect concentration for growth were 1 and 2 mg/L, respectively. Chlorophyll a and b contents of the plant in all treatment groups were affected significantly, and chlorophyll a/b ratios of all atrazine treatment levels were pronouncedly higher than those of the control within 5 days of exposure (p < 0.05), but thereafter recovered to the level of the control. Differences of photosynthetic efficiency were significant between all atrazine treatments and the control; except for 1 mg/L on day 1 and 5, and 2 mg/L on day 1. I. pseudacorus did not show phytotoxicity symptoms after 35 days exposure to atrazine below 2 mg/L level, but photosynthetic efficiency had begun to decline.

A hydroponic system was used to evaluate atrazine (ATZ) removal and uptake by three emergent hydrophytes, Iris pseudacorus, Lythrum salicaria and Acorus calamus, determining their potential as phytoremediation agents for ATZ-contaminated water. After 20 days of exposure, the relative growth rate of plants in sterile conditions was less than in natural conditions. ATZ amount in a culture solution planted with emergent plants decreased significantly compared with an unplanted solution, and the removal rate of ATZ in natural conditions was greater than in sterile conditions (p < 0.05). The degradation contributions of I. pseudacorus, L. salicaria and A. calamus were 75.6, 65.5 and 61.8%, respectively. Those of the corresponding microbial population in the solution were 5.4, 11.4 and 17.4%, respectively. Emergent plants play a dominant role in reducing the ATZ level in the water body and could be used as phytoremediation agents.