Characterization of Plant Accumulation of Pharmaceuticals from Soils with Their Concentration in Soil Pore Water

Predicting plant uptake of pharmaceuticals from soils is very challenging because many pharmaceuticals are ionizable compounds, which experience highly variable sorption/desorption and transformation processes in soils. This study aimed to elucidate how the equilibrium between sorbed and dissolved phases influences radish uptake of 15 pharmaceuticals from three soils with different properties. After 30 days of uptake, the accumulation of acetaminophen, carbamazepine, lamotrigine, carbadox, trimethoprim, and triclosan in radish ranked as Riddles > Capac > Spinks soil. In contrast, radish accumulation of caffeine, lincomycin, monensin, tylosin, sulfadiazine, and sulfamethoxazole exhibited the opposite order of Riddles < Capac < Spinks soil. Oxytetracycline and estrone demonstrated similar accumulation in radish grown in the three soils. Accumulation of pharmaceuticals in radish demonstrated no apparent relation with their concentration in soils. However, we identified strong positive correlation between pharmaceutical accumulation in radish and their corresponding concentration in soil pore water. These results reveal that pharmaceutical in soil pore water is the dominant fraction bioavailable to plant uptake. Relatively constant root concentration factors (RCFs) on the basis of pharmaceutical concentration in soil pore water, compared to the highly variable RCFs derived from soils, suggest that pore water-based RCF is superior for describing pharmaceutical accumulation in plants grown in soils. We recommend that pharmaceuticals in soil pore water should be evaluated and included in modeling their uptake by plants

Pesticides in Greenhouse Airborne Particulate Matter: Occurrence, Distribution, Transformation Products, and Potential Human Exposure Risks

Pesticides are frequently sprayed in greenhouses to ensure crop yields, where airborne particulate matter (PM) may serve as a carrier in depositing and transporting pesticides. However, little is known about the occurrence and fate of PM-borne pesticides in greenhouses. Herein, we examined the distribution, dissipation, and transformation of six commonly used pesticides (imidacloprid, acetamiprid, prochloraz, triadimefon, hexaconazole, and tebuconazole) in greenhouse PM (PM1, PM2.5, and PM10) after application as well as the associated human exposure risks via inhalation. During 35 days of experiment, the six pesticides were detected in all PM samples, and exhibited size- and time-dependent distribution characteristics, with the majority of them (>64.6%) accumulated in PM1. About 1.0–16.4% of initially measured pesticides in PM remained after 35 days, and a total of 12 major transformation products were elucidated, with six of them newly identified. The inhalation of PM could be an important route of human exposure to pesticides in the greenhouse, where the estimated average daily human inhalation dose (ADDinh) of the six individual pesticides was 2.1–1.2 × 104 pg/kg day–1 after application (1–35 days). Our findings highlight the occurrence of pesticides/transformation products in greenhouse PM, and their potential inhalation risks should be further concerned

From Water to Water: Insight into the Translocation of Pesticides from Plant Rhizosphere Solution to Leaf Guttation and the Associated Ecological Risks

Plant guttation is an important source of water/nutrients for many beneficial insects, while the presence of pesticides in guttation has been considered as a new exposure route for nontarget insects. This study aimed to elucidate how 15 diverse pesticides are translocated from growth media to guttation by maize plants through a hydroponic experiment. All pesticides were effectively translocated from the growth solution to maize guttation and reached a steady state within 5 days. The strong positive correlation (R2 = 0.43–0.84) between the concentrations of pesticides in guttation and in xylem sap demonstrated that xylem sap was a major source of pesticides in guttation. The relationship between the bioaccumulation of pesticides in guttation (BCFguttation) and the chemical Kow was split into two distinct patterns: for pesticides with log Kow > 3, we identified a good negative linear correlation between log BCFguttation and log Kow (R2 = 0.71); however, for pesticides with log Kow < 3, all data fall close to a horizontal line of BCFguttation ≅ 1, indicating that hydrophilic pesticides can easily pass through the plants from rhizosphere solution to leaf guttation and reach saturation status. Besides, after feeding with pesticide-contaminated guttation, the mortality of honeybees was significantly impacted, even at very low levels (e.g., ∑600 μg/L with a mortality of 93%). Our results provide essential information for predicting the contamination of plant guttation with pesticides and associated ecological risks

Direct Prediction of Bioaccumulation of Organic Contaminants in Plant Roots from Soils with Machine Learning Models Based on Molecular Structures

Root concentration factor (RCF) is an important characterization parameter to describe accumulation of organic contaminants in plants from soils in life cycle impact assessment (LCIA) and phytoremediation potential assessment. However, building robust predictive models remains challenging due to the complex interactions among chemical–soil–plant root systems. Here we developed end-to-end machine learning models to devolve the complex molecular structure relationship with RCF by training on a unified RCF data set with 341 data points covering 72 chemicals. We demonstrate the efficacy of the proposed gradient boosting regression tree (GBRT) model based on the extended connectivity fingerprints (ECFP) by predicting RCF values and achieved prediction performance with R-squared of 0.77 and mean absolute error (MAE) of 0.22 using 5-fold cross validation. In addition, our results reveal nonlinear relationships among properties of chemical, soil, and plant. Further in-depth analyses identify the key chemical topological substructures (e.g., −O, −Cl, aromatic rings and large conjugated π systems) related to RCF. Stemming from its simplicity and universality, the GBRT-ECFP model provides a valuable tool for LCIA and other environmental assessments to better characterize chemical risks to human health and ecosystems

Direct Prediction of Bioaccumulation of Organic Contaminants in Plant Roots from Soils with Machine Learning Models Based on Molecular Structures

Root concentration factor (RCF) is an important characterization parameter to describe accumulation of organic contaminants in plants from soils in life cycle impact assessment (LCIA) and phytoremediation potential assessment. However, building robust predictive models remains challenging due to the complex interactions among chemical–soil–plant root systems. Here we developed end-to-end machine learning models to devolve the complex molecular structure relationship with RCF by training on a unified RCF data set with 341 data points covering 72 chemicals. We demonstrate the efficacy of the proposed gradient boosting regression tree (GBRT) model based on the extended connectivity fingerprints (ECFP) by predicting RCF values and achieved prediction performance with R-squared of 0.77 and mean absolute error (MAE) of 0.22 using 5-fold cross validation. In addition, our results reveal nonlinear relationships among properties of chemical, soil, and plant. Further in-depth analyses identify the key chemical topological substructures (e.g., −O, −Cl, aromatic rings and large conjugated π systems) related to RCF. Stemming from its simplicity and universality, the GBRT-ECFP model provides a valuable tool for LCIA and other environmental assessments to better characterize chemical risks to human health and ecosystems

Phloem Redistribution of Pesticide Phenamacril in Plants Followed by Extensive Biotransformation

Here, we evaluated the uptake and biotransformation mechanism of the systemic fungicide phenamacril in hydroponic/soil–plant systems. Phenamacril was preferentially accumulated in shoots with the translocation factor up to 3.5 (or 6.9) in wheat (or rice) during 144 h of the uptake kinetic experiment. Apart from upward xylem translocation, phenamacril could also be redistributed from shoots to roots (0.4%) through phloem transport and then released into the rhizosphere surrounding solution (1.7%) through plant excretion via a split-root experiment. Then, 76.4% (or 70.4%) of phenamacril was transformed to 14 (or 12) metabolites in hydroponic-wheat (or hydroponic-rice) systems after 28 days of exposure, with nine of them first identified based on nontarget analysis. The proposed metabolic pathways included hydroxylation, hydrolysis, isomerization, dehydrogenation, deamination, dehydration, decarboxylation, reduction, and conjugation reactions, which were modulated by genes overexpression of metabolic enzymes (e.g., cytochrome P450). Notably, metabolite M-157 was predicted to be more persistent in environments and more toxic to rats and aquatic organisms than phenamacril by theoretical calculation. This study highlights that phloem transport and plant excretion may result in cycling chemical contamination, and the transformation products may possess elevated toxicities, thus should be considered in estimating the contamination of pesticides in crops and environments

Insight into the Long-Lasting Control Efficacy of Neonicotinoid Imidacloprid against Wheat Aphids during the Entire Growth Period

Understanding the mechanism of long-lasting control efficacy of pesticides is important for developing sustainable high-efficacy pesticides, decreasing pesticide-use frequency and environmental input. This study investigates the long-term control mechanism of imidacloprid against wheat aphids under seed treatment. The concentrations of imidacloprid and its metabolites were 2.2–69.6 times lower than their individual LC50 after 238 days of treatment, and the control efficacy was still higher than 94.6%. The mixed bioactivity tests demonstrated that the insecticidal activity of the mixture of imidacloprid and its bioactive metabolites was approximately 1.5–189.7 times greater than that of a single compound against wheat aphids. The concentrations of imidacloprid, 5-hydroxy imidacloprid, and imidacloprid olefin in top flag leaves were 0.022, 0.084, and 0.034 mg/kg, respectively, during the aphid flourishing period, which were higher than the LC50 of the mixture (0.011 mg/kg), therefore providing long-lasting control efficacy. The study provides a first insight into the synergistic effects between a pesticide and its bioactive metabolites in ensuring long-term control performance

Molybdenum Nanofertilizer Boosts Biological Nitrogen Fixation and Yield of Soybean through Delaying Nodule Senescence and Nutrition Enhancement

Soybean (Glycine max) is a crop of global significance and has low reliance on N fertilizers due to its biological nitrogen fixation (BNF) capacity, which harvests ambient N2 as a critical ecosystem service. BNF can be severely compromised by abiotic stresses. Enhancing BNF is increasingly important not only to alleviate global food insecurity but also to reduce the environmental impact of agriculture by decreasing chemical fertilizer inputs. However, this has proven challenging using current genetic modification or bacterial nodulation methods. Here, we demonstrate that a single application of a low dose (10 mg/kg) of molybdenum disulfide nanoparticles (MoS2 NPs) can enhance soybean BNF and grain yield by 30%, compared with conventional molybdate fertilizer. Unlike molybdate, MoS2 NPs can more sustainably release Mo, which then is effectively incorporated as a cofactor for the synthesis of nitrogenase and molybdenum-based enzymes that subsequently enhance BNF. Sulfur is also released sustainably and incorporated into biomolecule synthesis, particularly in thiol-containing antioxidants. The superior antioxidant enzyme activity of MoS2 NPs, together with the thiol compounds, protect the nodules from reactive oxygen species (ROS) damage, delay nodule aging, and maintain the BNF function for a longer term. The multifunctional nature of MoS2 NPs makes them a highly effective strategy to enhance plant tolerance to abiotic stresses. Given that the physicochemical properties of nanomaterials can be readily modulated, material performance (e.g., ROS capturing capacity) can be further enhanced by several synthesis strategies. This study thus demonstrates that nanotechnology can be an efficient and sustainable approach to enhancing BNF and crop yield under abiotic stress and combating global food insecurity

Chiral Triazole Fungicide Difenoconazole: Absolute Stereochemistry, Stereoselective Bioactivity, Aquatic Toxicity, and Environmental Behavior in Vegetables and Soil

In this study, the systemic assessments of the stereoisomers of triazole fungicide difenoconazole are reported for the first time, including absolute stereochemistry, stereoselective bioactivity toward pathogens (<i>Alternaria sonali</i>,<i> Fulvia fulva</i>,<i> Botrytis cinerea</i>, and <i>Rhizoctonia solani</i>), and toxicity toward aquatic organisms (<i>Scenedesmus obliquus</i>,<i> Daphnia magna</i>, and <i>Danio rerio).</i> Moreover, the stereoselective degradation of difenoconazole in vegetables (cucumber, <i>Cucumis sativus</i> and tomato, <i>Lycopersicon esculentum</i>) under field conditions and in soil under laboratory-controlled conditions (aerobic and anaerobic) was investigated. There were 1.33–24.2-fold and 1.04–6.78-fold differences in bioactivity and toxicity, respectively. Investigations on the stereoselective degradation of difenoconazole in vegetables showed that the highest-toxic and lowest-bioactive (2<i>S</i>,4<i>S</i>)-stereoisomer displays a different enrichment behavior in different plant species. Under aerobic or anaerobic conditions, (2<i>R</i>,4<i>R</i>)<i>-</i> and (2<i>R</i>,4<i>S</i>)<i>-</i>difenoconazole were preferentially degraded in the soil. Moreover, difenoconazole was configurationally stable in the test soil matrices. On the basis of biological activity, ecotoxicity, and environmental behavior, it is likely that the use of pure (2<i>R</i>,4<i>S</i>)-difenoconazole instead of the commercial stereoisomer mix may help to increase the bioactivity and reduce environmental pollution

Dynamic Transformation of Nano-MoS₂ in a Soil–Plant System Empowers Its Multifunctionality on Soybean Growth

Molybdenum disulfide (nano-MoS2) nanomaterials have shown great potential for biomedical and catalytic applications due to their unique enzyme-mimicking properties. However, their potential agricultural applications have been largely unexplored. A key factor prior to the application of nano-MoS2 in agriculture is understanding its behavior in a complex soil–plant system, particularly in terms of its transformation. Here, we investigate the distribution and transformation of two types of nano-MoS2 (MoS2 nanoparticles and MoS2 nanosheets) in a soil–soybean system through a combination of synchrotron radiation-based X-ray absorption near-edge spectroscopy (XANES) and single-particle inductively coupled plasma mass spectrometry (SP-ICP-MS). We found that MoS2 nanoparticles (NPs) transform dynamically in soil and plant tissues, releasing molybdenum (Mo) and sulfur (S) that can be incorporated gradually into the key enzymes involved in nitrogen metabolism and the antioxidant system, while the rest remain intact and act as nanozymes. Notably, there is 247.9 mg/kg of organic Mo in the nodule, while there is only 49.9 mg/kg of MoS2 NPs. This study demonstrates that it is the transformation that leads to the multifunctionality of MoS2, which can improve the biological nitrogen fixation (BNF) and growth. Therefore, MoS2 NPs enable a 30% increase in yield compared to the traditional molybdenum fertilizer (Na2MoO4). Excessive transformation of MoS2 nanosheets (NS) leads to the overaccumulation of Mo and sulfate in the plant, which damages the nodule function and yield. The study highlights the importance of understanding the transformation of nanomaterials for agricultural applications in future studies