Pesticide contamination pattern of surface water in an urban-agricultural mediterranean watershed (Wadi Guenniche, Bizerte Lagoon, Northern Tunisia).

Two years of monthly sampling and hydrological monitoring were performed at the outlet of a Mediterranean watershed in northern Tunisia to determine the contents of 469 pesticide active ingredients and metabolites in water and evaluate their behavior. Wadi Guenniche is a tributary of the Bizerte coastal lagoon, with a watershed area of 86 km2, which exhibits pluvial cereal, legume, and orchid cultivation and irrigated market gardening. Twenty-nine pesticide active ingredients and 2 metabolites were detected in water. Twenty-four pesticide active ingredients were authorized for use in Tunisia. Among them, 14 had never been mentioned in previous farmer surveys. Five herbicides and their metabolites were the most frequently detected: aminomethylphosphonic acid (AMPA) (100%), glyphosate (94%), simazine (94%), 2,4-D (70%), and deisopropylatrazine (DIA) (47%). The detection frequency and concentration range suggested that the phytosanitary pressure and resulting water contamination are close to those on the northern Mediterranean shore. These results, in addition to characterizing the pollution state, emphasized the need for additional studies on the use and fate of pesticides on the southern shore of the Mediterranean Sea, particularly in Tunisia.

Bioinformatics analysis of the potential mechanisms of Alzheimer's disease induced by exposure to combined triazine herbicides.

BACKGROUND: The development of Alzheimer's disease (AD) is promoted by a combination of genetic and environmental factors. Notably, combined exposure to triazine herbicides atrazine (ATR), simazine (SIM), and propazine (PRO) may promote the development of AD, but the mechanism is unknown. AIM: To study the molecular mechanism of AD induced by triazine herbicides. METHODS: Differentially expressed genes (DEGs) of AD patients and controls were identified. The intersectional targets of ATR, SIM, and PRO for possible associations with AD were screened through network pharmacology and used for gene ontology (GO) and Kyoto Encyclopaedia of Genes and Genomes (KEGG) enrichment analysis. The binding potentials between the core targets and herbicides were validated by molecular docking and molecular dynamics. RESULTS: A total of 1,062 DEGs were screened between the AD patients and controls, which identified 148 intersectional targets of herbicides causing AD that were screened by network pharmacology analysis. GO and KEGG enrichment analysis revealed that cell cycling and cellular senescence were important signalling pathways. Finally, the core targets EGFR, FN1, and TYMS were screened and validated by molecular docking and molecular dynamics. CONCLUSION: Our results suggest that combined exposure to triazine herbicides might promote the development of AD, thereby providing new insights for the prevention of AD.

The feasibility of using micro concentrated multiple reflection ATR FTIR accessory in pesticide analysis.

Micro-Multiple Reflection ATR (CMRATR) spectroscopy is a technique, using specialized equipment, which allows the enhanced sensitivity of multiple reflection ATR analysis of small amounts of liquids in a confined area hitherto reserved for single reflection equipment. This technique has demonstrated a high level of sensitivity, especially when used in conjunction with an evaporative technique. In this work, the technique will be used with a miniature CMRATR accessory, which has the added advantage of compatibility with the smallest current FTIR spectrometers, to analyze pesticides. The results presented here indicate that the CMRATR/evaporative technique can serve as both qualitative and quantitative support to the existing standard methodology.

Simazine perturbs the maturational competency of mouse oocyte through inducing oxidative stress and DNA damage.

Simazine is a triazine pesticides that typically detected in ground water and soil, and can reportedly affect reproductive health in humans and animals. However, the effect of simazine on female germ cell development remains unclear. In the present study, we observed that simazine exposure decreased oocyte maturation competence and embryonic developmental capacity. Importantly, simazine exposure disrupted microtubule stability and actin polymerization, resulting in failure of spindle assembly and migration. In addition, simazine exposure impaired mitochondrial function and cytosolic Ca2+ homeostasis in both oocyte and 2-cell embryos, thus increasing the levels of reactive oxygen species (ROS). Moreover, simazine exposure induced DNA damage and early apoptosis during oocyte maturation. Collectively, our results demonstrate that simazine exposure-induced mitochondrial dysfunction and apoptosis are major causes of poor oocytes quality.

Autonomic behavioral impairment induced by simazine exposure during early life of male mouse is mediated by Lmx1a/Wnt1 pathway.

Simazine is a widely used herbicide and known as an environmental estrogen. Multiple studies have proved simazine can induced the degeneration of dopaminergic neuron resulting in a degenerative disease-like syndrome. Herein, we explored the neurotoxicity of simazine on the dopaminergic nervous system of embryos and weaned offspring during the maternal gestation period or the maternal gestation and lactation periods. We found that simazine disturbed the crucial components expression involved in Lmx1a/Wnt1 pathway of dopaminergic neuron in embryonic and weaned offspring. Furthermore, morphological and behavioral tests performed on weaned male offspring treated by simazine suggested that the grip strength, autonomic exploring, and the space sense ability were weakened, as well as the pathological damage of dopaminergic neuron was clearly observed. But, the same neurotoxicity of simazine is less significantly observed in female offspring. Our findings will provide reliable reference for the determination of environmental limits and new insight into the pathogenesis of nonfamilial neurodegenerative diseases related to environmental risk factors.

On-site preconcentration of pesticide residues in a drop of seawater by using electrokinetic trapping, and their determination by surface-enhanced Raman scattering.

The authors have developed a method for simultaneous quantification of several charged pesticides (as shown for amitrole, simazine, trichlorfon and bisultap). It is based on the use of a reduced graphene oxide-modified screen-printed electrode (RGO-SPE) and combines electrokinetic trapping (EKT) and surface-enhanced Raman scattering (SERS). When a 50 µL droplet containing negatively charged RGO and positively charged gold nanorods is placed on the SPE, the RGO and gold nanorods are selectively attracted on the surface of the SPE during EKT. This leads to the formation of sandwich-type hybrid substrates. The resulting substrates also contain Raman "hot spots" among the high-density gold nanorods. This, along with the excellent adsorption performance of RGO, makes it an excellent SERS substrate for on-site detection of the charged pesticides. The method is highly reproducible and long-term stable. The spot-to-spot variation of the intensity of the SERS is <15%, and the performance of SERS activity is maintained over a period of 6 weeks. The method works over a wide range of concentrations (0.5 nM to 4 µM) for charged pesticides under optimal conditions, with a sub-nanomolar detection limit (at a signal to noise ratio of 3). The EKT-SERS method requires only microliter volumes and takes only minutes for completion. Therefore, the method provides high sensitivity for detection while preserving the selectivity and stability required for reliable quantitative analysis. Graphical abstract A method combining electrokinetic trapping and SERS can be used for simultaneous detection of charged pesticides in a drop of seawater.

Dopaminergic Dysfunction in Mammalian Dopamine Neurons Induced by Simazine Neurotoxicity.

Many studies have shown that the pollutant simazine (6-chloro-N,N'-diethyl-1,3,5-triazine-2,4-diamine), which has been overused, inhibits the proliferation of mammalian dopaminergic cells, and affects the developmental differentiation of mammalian dopaminergic neurons. However, few studies have shown the effects of simazine on dopaminergic metabolism in these cells. Therefore, we aim to examine the metabolic effects of simazine exposure in mouse dopaminergic progenitor neurons (MN9D) at different exposure times. The cells were treated with simazine at 0, 150, 300 and 600 µM for 12, 24 and 48 h, respectively. The content of dopamine in these cells was then examined using the enzyme-linked immunosorbent assay (ELISA) kit. Real-time quantitative polymerase chain reaction (PCR) and western blotting were performed to analyze the mRNA and protein expression of aromatic amino acid decarboxylase (AADC), tyrosine hydroxylase (DYT5b), dopamine transporter (DAT), monoamine vesicular transporter 2 (VMAT2), monoamine oxidase (MAO) and catechol-O-methyl transferase (COMT). The results showed that simazine influenced the metabolism of dopamine and led to a decrease in dopamine level in these cells which may eventually lead to neurological disorders of the dopaminergic system.

Triazine herbicides inhibit relaxin signaling and disrupt nitric oxide homeostasis.

Triazines are herbicides that are widely used worldwide, and we previously observed that the maternal exposure of mice to simazine (50 or 500µg/kg) resulted in smaller ovaries and uteri of their female offspring. Here, we investigated the underlying mechanism that may account for the reproductive dysfunction induced by simazine. We found that following maternal exposure, simazine is transmitted to the offspring, as evidenced by its presence in the offspring ovaries. Analyses of the simazine-exposed offspring revealed that the expression of the relaxin hormone receptor, relaxin-family peptide receptor 1 (RXFP1), prominently decreased in their ovaries and uteri. In addition, downstream target genes of the relaxin pathway including nitric oxide (NO) synthase 2 (Nos2), Nos3, matrix metallopeptidase 9 (Mmp9), and vascular endothelial growth factor (Vegf) were downregulated in their ovaries. Moreover, AKT and extracellular signal-regulated kinases (ERK) levels and their phosphorylated active forms decreased in simazine-exposed ovaries. In vitro exposure of the human ovarian granulosa cells (KGN) and uterine endometrium cells (Hec-1A) to very low concentrations (0.001 to 1nM) of triazines including atrazine, terbuthylazine, and propazine repressed NO production with a concurrent reduction in RXFP1, NOS2, and NOS3. The inhibitory action of triazines on NO release was dependent on RXFP1, phosphoinositol 3-kinase (PI3K)/AKT, and ERK. Radioligand-binding assay also confirmed that triazines competitively inhibited the binding of relaxin to its receptor. Therefore, the present study suggests that triazine herbicides act as endocrine disrupters by interfering with relaxin hormone signaling. Thus, further evaluation of their impact on human health is imperative.

Synthesis of Isotopically Labeled (13)C3-Simazine and Development of a Simultaneous UPLC-MS/MS Method for the Analysis of Simazine in Soil.

The isotope dilution mass spectrometry (IDMS) is a highly efficient method for tackling the ion suppression in complex matrix by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), but a lack of commercial internal standards is a limiting factor for these analyses. Herein, an economical and efficient strategy for the synthesis of (13)C3-simazine via a three-step procedure was developed. The isotope-labeled internal standard was used for determination of simazine residue in soil samples. The quantitation method has a limit of detection of 0.015 µg/kg and quantitation of 0.08 µg/kg. The inter-day and intra-day precision of the method were below 4.6%. Recovery values were ranged between 92.9% and 99.2%. All the samples obtained from six provinces in China contained from 1 to 62 µg/kg of simazine.

Influence of Three Citrus Herbicides on Potential Production of Sorghum bicolor 'Topper 76-6' as a Bioenergy Crop.

Planting bioenergy crops on land previously used for citrus production may offer an alternative source of revenue for growers looking for alternative-to-citrus crops. However, residual herbicides used in citrus production may adversely affect alternative crops. This study evaluated effects of three herbicides (bromacil, norflurazon, and simazine) commonly used in citrus production on the bioenergy crop Sorghum bicolor 'Topper 76-6'. Plants were exposed to herbicides in soil for 1-5 weeks and observations of effects on photosynthetic quantum yield, leaf greenness, height, and biomass were made. Results indicate that concentrations of bromacil and norflurazon greater than 0.09 and 0.07 mg/kg and simazine >0.46 mg/kg will impair growth and development in similar soils. Concentrations below these may also be toxic.

Adsorption of simazine on zeolite H-Y and sol-gel technique manufactured porous silica: A comparative study in model and natural waters.

In this work, we studied the removal of simazine from both a model and well water by adsorption on two different adsorbents: zeolite H-Y and a porous silica made in the laboratory by using the sol-gel technique. The pH dependence of the adsorption process and the isotherms and pseudo-isotherms of adsorption were studied. Moreover, an iterative process of simazine removal from both the model and well water, which allowed us to bring the residual simazine concentration below the maximum concentration (0.05 mg L(-1)) of agrochemicals in wastewater to be released in surface waters or in sink allowed by Italian laws, was proposed. The results obtained were very interesting and the conclusions drawn from them partly differed from what could reasonably be expected.

Toxicity endpoint selections for a simazine risk assessment.

BACKGROUND: California uses simazine at one of the highest levels for states in the United States (approximately 2.5 million lbs 2006-2010). Simazine causes neuroendocrine disruption and mammary cancer in test animals. A risk assessment was prioritized by the California Department of Pesticide Regulation because of the nondietary concern for simazine exposure to occupational/nonoccupational simazine users, resident nonusers, and bystanders (especially children and children exhibiting pica) at greatest risk. METHODS: No observed effect levels (NOELs) from animal studies as well as human exposure data were used to determine nondietary values for the above populations. Registrant-submitted and open literature studies focusing on oral (major human route) effects for simazine and the major metabolites desisopropyl-s-atrazine and diaminochlorotriazine were reviewed as part of the hazard identification process. RESULTS: Developmental, reproduction, and chronic studies provided the lowest NOELs for the acute (5 mg/kg/day), subchronic (0.56 mg/kg/day), and chronic (0.52 mg/kg/day) exposure durations, respectively. A benchmark dose (95th percentile) was calculated for mammary tumorigenesis, assuming a threshold mechanism in rats (benchmark dose lower limit [95th percentile; BMDL05 ]: 2.9 mg/kg/day). Margins of exposure and uncertainty factors (100-300×, depending on exposure scenario) were used to characterize risk for designated population subgroups. CONCLUSIONS: Fetal developmental delays, endocrine disruption, and mammary tumors resulted from simazine treatment. Systemic and maternal/fetal effects determined the critical NOELs used in risk assessment. Margins of exposures for most scenarios were below acceptable levels, especially for children who may be bystanders where simazine is applied and children who exhibit pica. This risk characterization raises a concern for long-term effects in humans.

Modelling the biphasic sorption of simazine, imidacloprid, and boscalid in water/soil systems.

The sorption kinetics of simazine (6-chloro-N,N'-diethyl-1,3,5-triazine-2,4-diamine), imidacloprid (1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine), and boscalid (2-chloro-N-(4'-chlorobiphenyl-2-yl)nicotinamide), three pesticides of wide use in agriculture, was determined in five different water/soil systems over a time interval from the initial few seconds to about 1 month. In all the experiments, sorption kinetics showed a biphasic pattern characterized by an initial, relatively short phase with a high sorption rate and a later phase with much a lower sorption rate. Initial sorption capacity increased with soil organic carbon content and with sorbate hydrophobicity. We postulate that the first phase of the process involves a fast second-order sorption reaction on superficial sites of soil particles, whereas the second phase depends on diffusion-controlled migration to internal binding sites. A kinetic equation based on this hybrid model accurately fitted all data sets. Less satisfactory results were obtained employing the pseudo-first order, pseudo-second order, Elovich, two site non-equilibrium, or Weber-Morris equation. The superior performance of the hybrid model for describing boscalid sorption probably reflects the high hydrophobic character and consequent low diffusion rates of this compound. The accuracy of modelling was in any case strongly dependent on the time interval considered.

Responses to herbicides of Arctic and temperate microalgae grown under different light intensities.

In aquatic ecosystems, microalgae are exposed to light fluctuations at different frequencies due to daily and seasonal changes. Although concentrations of herbicides are lower in Arctic than in temperate regions, atrazine and simazine, are increasingly found in northern aquatic systems because of long-distance aerial dispersal of widespread applications in the south and antifouling biocides used on ships. The toxic effects of atrazine on temperate microalgae are well documented, but very little is known about their effects on Arctic marine microalgae in relation to their temperate counterparts after light adaptation to variable light intensities. We therefore investigated the impacts of atrazine and simazine on photosynthetic activity, PSII energy fluxes, pigment content, photoprotective ability (NPQ), and reactive oxygen species (ROS) content under three light intensities. The goal was to better understand differences in physiological responses to light fluctuations between Arctic and temperate microalgae and to determine how these different characteristics affect their responses to herbicides. The Arctic diatom Chaetoceros showed stronger light adaptation capacity than the Arctic green algae Micromonas. Atrazine and simazine inhibited the growth and photosynthetic electron transport, affected the pigment content, and disturbed the energy balance between light absorption and utilization. As a result, during high light adaptation and in the presence of herbicides, photoprotective pigments were synthesized and NPQ was highly activated. Nevertheless, these protective responses were insufficient to prevent oxidative damage caused by herbicides in both species from both regions, but at different extent depending on the species. Our study demonstrates that light is important in regulating herbicide toxicity in both Arctic and temperate microalgal strains. Moreover, eco-physiological differences in light responses are likely to support changes in the algal community, especially as the Arctic ocean becomes more polluted and bright with continued human impacts.

Use of computational toxicology models to predict toxicological points of departure: A case study with triazine herbicides.

BACKGROUND: Atrazine simazine and propazine, widely used triazine herbicides on food crops and in residential areas, disrupt the neuroendocrine system raising human health concerns. USEPA developed a PBPK model based on triazine common Mode of Action (MOA)-suppression of luteinizing hormone surge in female rats-to generate human regulatory points of departure (POD: mg/kg/day). We compared triazine Human Administered Equivalent Dose (AEDHuman mg/kg/day) predictions from open access computational tools to the PBPK PODs to assess concordance. METHODS: Computational tools were the following: ToxCast/Tox21 in vitro assays; Toxicogenomic databases to assess concordance with ToxCast/Tox21 targets; integrated chemical environment (ICE) models with ToxCast/Tox21 inputs to predict AEDHuman PODs and population-based age-refined high throughput toxicokinetics (HTTK-Pop) to compare to age-related PBPK PODs. RESULTS: ToxCast/Tox21 assays identified critical targets in the triazine common MOA and gene databases; ICE AEDHuman predictions were mainly concordant with the USEPA PBPK PODs quantitatively. Low fold-differences between PBPK POD and ICE AEDHuman predictions indicated that the ICE models are health-protective. HTTK-Pop age-refinements were within 10-fold of the USEPA PBPK PODs. CONCLUSIONS: CompTox tools were used to identify assay targets in the MOA and identify potential molecular initiating targets in the adverse outcome pathway for potential use in risk assessment.

Iron-Modified Biochar Strengthens Simazine Adsorption and Decreases Simazine Decomposition in the Soil.

Currently, modified biochar has been successfully used in the remediation of soil polluted with heavy metals. However, the effects of the modified biochar on pesticides (such as simazine) are still unclear. Herein, the environmental fate of simazine, such as decomposition, leaching, and adsorption in unamended soil, in the soil amended with unmodified and modified biochar (biochar + FeCl3, biochar + FeOS, biochar + Fe) were evaluated. In addition, an incubation experiment was also performed to observe the influence of modified biochar on the microbial community and diversity in the soil. The results showed that modified biochar significantly decreased the decomposition of simazine in the soil compared to its counterpart. Modified biochar also reduced the concentration of simazine in the leachate. Compared with the control, soil microbial biomass in the soil amended with unmodified biochar, biochar + FeCl3, biochar + Fe, and biochar + FeOS was decreased by 5.3%, 18.8%, 8.7%, and 18.1%, respectively. Furthermore, modified biochar changed the structure of the microbial community. This shows that modified biochar could increase the soil adsorption capacity for simazine and change the amount and microbial community that regulates the fate of simazine in the soil. This study concludes that iron-modified biochar has positive and negative effects on the soil. Therefore, its advantages and side effects should be considered before applying it to the soil.

Simazine Enhances Dark Fermentative H2 Production by Unicellular Halotolerant Cyanobacterium Aphanothece halophytica.

The halotolerant cyanobacterium Aphanothece halophytica is a potential H2 producer that induces H2 evolution under nitrogen deprivation. H2 is mainly produced via the catabolism of stored glycogen under dark anaerobic condition. H2 evolution is catalyzed by O2-sensitive bidirectional hydrogenase. The aim of this study was to improve H2 production by A. halophytica using various kinds of inhibitors. Among all types of inhibitors, simazine efficiently promoted the highest H2 production under dark conditions. High simazine concentration and long-term incubation resulted in a decrease in cell and chlorophyll concentrations. The optimal simazine concentration for H2 production by A. halophytica was 25 µM. Simazine inhibited photosynthetic O2 evolution but promoted dark respiration, resulting in a decrease in O2 level. Hence, the bidirectional hydrogenase activity and H2 production was increased. A. halophytica showed the highest H2 production rate at 58.88 ± 0.22 µmol H2 g-1 dry weight h-1 and H2 accumulation at 356.21 ± 6.04 µmol H2 g-1 dry weight after treatment with 25 µM simazine under dark anaerobic condition for 2 and 24 h, respectively. This study demonstrates the potential of simazine for the enhancement of dark fermentative H2 production by A. halophytica.

Household herbicide use as a source of simazine contamination in urban surface waters.

Contamination of urban surface waters by herbicides is an increasing concern; however, sources of contamination are poorly understood, hindering the development of mitigation and regulatory strategies. Impervious surfaces, such as concrete in driveways and paths are considered an important facilitator for herbicide runoff to urban surface waters following applications by residential homeowners. This study assessed the transferability of a herbicide from concrete pavers treated with an off-the-shelf product, containing simazine as the active herbicide, marketed for residential homeowner application to impervious surfaces. Commercially available pavers were treated according to label directions and the effects of exposure time prior to irrigation, repeated irrigations, and dry time between irrigations on transferability of simazine to runoff were assessed. Simazine transferability was greatest when receiving an initial irrigation 1 h after application, with concentrations in runoff reduced by half when exposure times prior to the first irrigation were >2 days. Concentrations remained stable for repeated irrigations up to 320 days and exposures to outdoor conditions of 180 days prior to a first irrigation. Dry time between irrigations significantly influenced simazine transfer to runoff. Dry periods of 140 days resulted in approximately a 4-times increase in simazine transferability to runoff. These results suggest that herbicides used by homeowners, or any other users, on impervious surfaces are available to contaminate runoff for prolonged time periods following application at concentrations that may pose risks to aquatic life and for reuse of harvested runoff on parks and gardens. Regulators should consider the potential of hard surfaces to act as reservoirs for herbicides when developing policies and labelling products.

Highly selective molecularly imprinted-electrochemiluminescence sensor based on perovskite/Ru(bpy)32+ for simazine detection in aquatic products.

A novel molecularly imprinted electrochemiluminescence (MIECL) sensor based on the luminescence of molecularly imprinted polymer-perovskite (MIP-CsPbBr3) layer and Ru(bpy)32+ was fabricated for simazine detection. MIP-CsPbBr3 layers were immobilized onto the surface of glassy carbon electrode as the capture and signal amplification probe, and Ru(bpy)32+ and co-reactant tripropylamine exhibited stronger electrochemiluminescence (ECL) emission. Under optimal conditions, the ECL signal of the MIECL sensor was linearly quenched, with the logarithm of simazine concentration ranging from 0.1 µg/L to 500.0 µg/L, correlation coefficient of 0.9947, and limit of detection of 0.06 µg/L. The practicality of the developed MIECL sensor method for simazine determination in aquatic samples was validated. Excellent recoveries of 86.5 %-103.9 % with relative standard deviation below 1.6 % were obtained for fish and shrimp samples at three different spiked concentrations. The MIECL sensor exhibited excellent selectivity, sensitivity, reproducibility, accuracy, and precision for simazine determination in actual aquatic samples.

Portable stirring device for the on-site extraction of environmental waters using magnetic hydrophilic-lipophilic balance tape.

The spatial heterogeneity of environmental systems makes sampling at multiple locations crucial to provide complete and representative information. The on-site application of an extraction technique simplifies the sampling logistics, increasing sample integrity during transportation and storage. This article presents a portable, simple, and low-cost device capable of performing the simultaneous on-site extraction of several environmental water samples. The device consists of a small electric motor integrated into the plastic cap of a conventional glass bottle and operated with a portable battery. The electric motor provides stirring to a novel magnetic sorptive phase based on the deposition of hydrophilic-lipophilic balance (HLB) particles over a magnetic tape. The use of open technology makes the device globally affordable. In this first approach, the isolation and preconcentration of atrazine and simazine have been selected as proof of concept. Using an internal standard made unnecessary the adjustment of the ionic strength before the extraction, thus simplifying the analytical procedure. Under the optimum conditions and using direct infusion mass spectrometry as the instrumental technique, detection limits as low as 15 ng/L were obtained. The precision calculated at three different levels was better than 8.3%. The accuracy, calculated with spiked samples, indicates the applicability of the approach for environmental water analysis.