Predicting rice pesticide fate and transport following foliage application by an updated PCPF-1 model.

The Pesticide Concentration in Paddy Field (PCPF-1) model has been successfully used to predict the fate and transport of granular pesticides applied to the paddy fields. However, it is not applicable for pesticides in foliar formulation while previous studies have reported that foliar application may increase the risks of rice pesticide contamination to the aquatic environment due to pesticide wash-off from rice foliage. In this study, we developed and added a foliar application module into the PCPF-1 model to improve its versatility regarding pesticide application methods. In addition, some processes of the original model such as photodegradation were simplified. The updated model was then validated with data from previous studies. Critical parameters of the model were calibrated using the Sequential Uncertainty Fitting version 2 (SUFI-2) algorithm. The calibrated model simulated pesticide dissipation trend and concentrations with moderate accuracy in the two paddy compartments including rice foliage and paddy water. The accuracy of the predicted soil concentrations could not be evaluated since no observed data were available. Although the p-factor and r-factor obtained using the SUFI2 algorithm indicated that the uncertainty encompassed in the predicted concentrations was rather high, the daily predicted pesticide concentrations in rice foliage and paddy water were satisfactory based on the NSE values (0.36-0.89). The updated PCPF-1 model is a flexible tool for the environmental risk assessment of pesticide losses and the evaluation of agricultural management practices for mitigating pesticide pollution associated with rice production.

Modeling of runoff water and runoff pesticide concentrations in upland bare soil using improved SPEC model.

The SPEC model (Predicted Environmental Concentrations in agricultural Soils) was developed and improved for the simulation of pesticide runoff. The model was applied to the Sakaecho upland bare soil field (Tokyo, Japan) to predict runoff water, sediment concentration in runoff water, pesticide concentrations in runoff water, and runoff sediment (clothianidin and imidacloprid) under artificial rainfall conditions. The results showed that the simulated time to first runoff agreed very well with the observed data. The simulated cumulative runoff, sediment yield, and imidacloprid concentration in sediment agreed well with the observed data (Nash-Sutcliffe Efficiency (NSE)>0.75). The simulated runoff rate agreed reasonably well with the observed data (NSE >0.5). The predicted clothianidin concentrations in sediment and in runoff water had acceptable agreement with the observed data (NSE >0). The results implied the model's potential to predict runoff water, sediment yield, and pesticide runoff.

Effect of chronic toxicity of the crystalline forms of TiO2 nanoparticles on the physiological parameters of Daphnia magna with a focus on index correlation analysis.

The widespread use of titanium dioxide nanoparticles (NPs) and their inevitable release into aquatic environments have caused great concerns about their ecotoxicity. However, the chronic toxicity to TiO2 NPs of aquatic organisms has not been fully understood. In particular, research is lacking on the influence of the crystalline forms of TiO2 NPs on their mechanisms of toxicity. This study investigated the chronic toxicity (i.e., 21-day toxicity tests) of 5 types of TiO2 NPs with various percentages of crystalline forms on Daphnia magna. Results revealed that the crystalline form composed of 80% anatase and 20% rutile (i.e., the M1 form) had the highest energy band gap (i.e., Eg, the energy interval between the valence band edge and the conduction band edge) and caused maximal D. magna mortality compared with other crystalline forms. The crystalline form comprising 100% rutile (i.e., the R-S form) had the lowest Eg and exhibited a minimal effect on the physiological parameters of D. magna. Moreover, in a suitable environment without TiO2 NPs, D. magna progenies could recover to a normal physiological level (e.g., the mortalities of D. magna progenies were lower than those of parental D. magna that were exposed to TiO2 NPs at a concentration of 0.5 mg/L). Correlation analysis revealed that the body length, time of first brood, and number of neonates in the first brood of D. magna were negatively correlated with titanium accumulation in vivo. Furthermore, the indices of Ti accumulation and the product of Eg and Ti accumulation (i.e., Eg × Ti accumulation) were positively correlated (p < 0.05) with D. magna mortality, thus indicating that crystalline forms with a high Eg may cause severe toxicity to aquatic organisms at the same TiO2 bioaccumulation level.

Effects of hydrophobicity of titanium dioxide nanoparticles and exposure scenarios on copper uptake and toxicity in Daphnia magna.

Titanium dioxide (TiO2) nanoparticles (NPs) encounter heavy metals in the environment under different scenarios. However, the mechanism of their joint toxicity effects on Daphnia magna remains vague. This study assessed the effects of hydrophobicity of TiO2 NPs (TDONPs) and exposure scenarios on copper uptake and toxicity in Daphnia magna. In the individual exposure scenario, hydrophilic and hydrophobic TDONPs both showed no acute toxicity to Daphnia magna, whereas individual Cu2+ exposure resulted in a 30% mortality rate. Co-exposure and sequential exposure to the two types of TDONP and Cu2+ resulted in mortality rates of 40%-50%. The mechanisms of the increased Cu2+ toxicity caused by hydrophilic and hydrophobic TDONP were different. In the presence of hydrophobic TDONPs, the Cu toxicity could be attributed to the increased bioaccumulation of Cu and Ti, leading to high oxidative stress injury. The Cu toxicity due to hydrophilic TDONPs could be induced by intensified intestinal membrane damage. The obtained data suggest that the hydrophobicity of the TDONPs plays a critical role in regulating the toxicity of Cu2+.

Antioxidant Activity of Hydrogen Nanobubbles in Water with Different Reactive Oxygen Species both in Vivo and in Vitro.

Hydrogen water as a new therapeutic antioxidant has been widely used in living organisms under stress. In this study, we applied nanobubble (NB) technology to hydrogen water. The antioxidant capacity of hydrogen NB water was studied with respect to different reactive oxygen species (ROS) both in vitro and in vivo. Using a relatively weak reduced dye, APF, we showed that hydrogen NB water can effectively remove three cytotoxic ROS, •OH, ClO-, and ONOO-, from water. Hydrogen NB water could also remove O2•-, which is a physiologically important ROS, from water. However, hydrogen water could not reduce other physiologically important ROS such as H2O2 and NO. At similar dissolved hydrogen concentrations, hydrogen NB water displayed higher antioxidant activity than hydrogen water without NB. Barley seed germination tests were used to study the antioxidant effect of hydrogen NB water on ROS generation in vivo. Our results showed that this decreased the physiological activity of barley seeds in their normal homeostatic state. Hydrogen NB water eliminated endogenous O2•- in seeds and inhibited germination. The usage of hydrogen NB water should be individually considered according to the types of cells involved. Our results offer basic data concerning the application of hydrogen NB water in different fields.

Hyperspectral Imaging in Tandem with R Statistics and Image Processing for Detection and Visualization of pH in Japanese Big Sausages Under Different Storage Conditions.

The potential of hyperspectral imaging with wavelengths of 380 to 1000 nm was used to determine the pH of cooked sausages after different storage conditions (4 °C for 1 d, 35 °C for 1, 3, and 5 d). The mean spectra of the sausages were extracted from the hyperspectral images and partial least squares regression (PLSR) model was developed to relate spectral profiles with the pH of the cooked sausages. Eleven important wavelengths were selected based on the regression coefficient values. The PLSR model established using the optimal wavelengths showed good precision being the prediction coefficient of determination (Rp2 ) 0.909 and the root mean square error of prediction 0.035. The prediction map for illustrating pH indices in sausages was for the first time developed by R statistics. The overall results suggested that hyperspectral imaging combined with PLSR and R statistics are capable to quantify and visualize the sausages pH evolution under different storage conditions. PRACTICAL APPLICATION: In this paper, hyperspectral imaging is for the first time used to detect pH in cooked sausages using R statistics, which provides another useful information for the researchers who do not have the access to Matlab. Eleven optimal wavelengths were successfully selected, which were used for simplifying the PLSR model established based on the full wavelengths. This simplified model achieved a high Rp2 (0.909) and a low root mean square error of prediction (0.035), which can be useful for the design of multispectral imaging systems.

Nanobubble Water's Promotion Effect of Barley (Hordeum vulgare L.) Sprouts Supported by RNA-Seq Analysis.

The physiological promotion effect of nanobubble (NB) water on living organisms is still a poorly understood phenomenon which was discovered 1 decade ago. Here, we analyzed the barley (Hordeum vulgare L.) embryo transcriptome following the exposure to NB water and low-concentration hydrogen peroxide (H2O2) using RNA-Seq. We found that 349 genes were differentially expressed after 24 h exposure to NB water and 97 genes were differentially expressed after exposure to H2O2 solution. Gene ontology enrichment and cluster analyses revealed that NB water induced expression of genes related to cell division and cell wall loosening. RNA-Seq, quantitative real-time polymerase chain reaction, and enzyme activity measurements all pointed to gene-encoding peroxidases as a major factor responsible for the effects of physiological enhancement due to NB water. The exogenous hydroxyl radical (•OH) produced by NB water significantly increased the expression of genes related to peroxidase and NADPH, thus leading to an increased endogenous superoxide anion (O2•-) inside the barley seed. Appropriately, low concentrations of exogenously added reactive oxygen species (ROS) and endogenous ROS played important roles in plant growth and development. When ROS levels were low, the endogenous ROS was eliminated by ascorbate peroxidase and other peroxidases instead of activating the catalase and superoxidase dismutase. This data set will serve as the foundation for a system biology approach to understand physiological promotion effects of NB water on living organisms.

PCPF-M model for simulating the fate and transport of pesticides and their metabolites in rice paddy field.

BACKGROUND: The PCPF-1 model was improved for forecasting the fate and transport of metabolites in addition to parent compounds in rice paddies. In the new PCPF-M model, metabolites are generated from the dissipation of pesticide applied in rice paddies through hydrolysis, photolysis and biological degradations. The methodology to parameterize the model was illustrated using two scenarios for which uncertainty and sensitivity analyses were also conducted. RESULTS: In a batch degradation experiment, the hourly forecasted concentrations of fipronil and its metabolites in paddy water were very accurate. In a field-scale experiment, the hourly forecasted concentrations of fipronil in paddy water and paddy soil were accurate while the corresponding daily forecasted concentrations of metabolites were adequate. The major contributors to the variation of the forecasted metabolite concentrations in paddy water and paddy soil were the formation fractions of the metabolites. The influence of uncertainty included in input parameters on the forecasted metabolite concentration was high during the peak concentration of metabolite in paddy water. In contrast, in paddy soil, the metabolite concentrations forecasted several days after the initial pesticide application were sensitive to the uncertainty incorporated in the input parameters. CONCLUSION: The PCPF-M model simultaneously forecasts the concentrations of a parent pesticide and up to three metabolites. The model was validated using fipronil and two of its metabolites in paddy water and paddy soil. The model can be used in the early stage of the pesticide registration process and in risk assessment analysis for the evaluation of pesticide exposure. © 2017 Society of Chemical Industry.

Simulating the fate and transport of nursery-box-applied pesticide in rice paddy fields.

BACKGROUND: The Pesticide Concentration in a Paddy Field model (PCPF-1) was modified by adding a root zone compartment to simulate nursery-box-applied (NB-applied) pesticide. The PCPF-NB model was validated for predicting the concentrations of NB-applied fipronil and imidacloprid in rice paddy fields using two treatment methods: before transplanting (BT) and at sowing (AS). Uncertainty and sensitivity analyses were used to evaluate the robustness of the concentrations predicted by the model. RESULTS: The hourly predicted concentrations of imidacloprid and fipronil were accurate in both paddy water and 1 cm deep paddy soil. The coefficient of determination and Nash-Sutcliffe model efficiency were greater than 0.87 and 0.60 respectively. The 95th percentiles of the predicted concentrations of fipronil and imidacloprid indicated that the influence of input uncertainty was minor in paddy water but important in paddy soil. The pesticide deposition rate and the desorption rate from the root zone were identified to be the major contributors to the variation in the predicted concentrations in paddy water and soil. CONCLUSION: The PCPF-NB model was validated for predicting the fate and transport of NB-applied fipronil and imidacloprid using the BT and AS treatment methods. © 2015 Society of Chemical Industry.

Development and validation of the SPEC model for simulating the fate and transport of pesticide applied to Japanese upland agricultural soil.

A pesticide fate and transport model, SPEC, was developed for assessing Soil-PEC (Predicted Environmental Concentrations in agricultural soils) for pesticide residues in upland field environments. The SPEC model was validated for predicting the water content and concentrations of atrazine and metolachlor in 5-cm deep soil. Uncertainty and sensitivity analyses were used to evaluate the robustness of the model's predictions. The predicted daily soil water contents were accurate regarding the number of observation points (n=269). The coefficient of determination (R 2) and Nash-Sutcliffe efficiency (NSE ) were equal to 0.38 and 0.22, respectively. The predicted daily concentrations of atrazine and metolachlor were also satisfactory since the R 2 and NSE statistics were greater than 0.91 and 0.76, respectively. The field capacity, the saturated water content of the soil and the Q 10 parameter were identified as major contributors to variation in predicted soil water content or/and herbicide concentrations.

Potential impacts of seasonal variation on atrazine and metolachlor persistence in andisol soil.

To estimate the potential effect of seasonal variation on the fate of herbicides in andisol soil, atrazine and metolachlor residues were investigated through the summer and winter seasons during 2013 and 2014 under field condition. The computed half-lives of atrazine and metolachlor in soil changed significantly through the two seasons of the trial. The half-lives were shorter in summer season with 16.0 and 23.5 days for atrazine and metolachlor, respectively. In contrast, the half-lives were longer during the winter season with 32.7 and 51.8 days for atrazine and metolachlor, respectively. The analysis of soil water balance suggested that more pesticide was lost in deeper soil layers through infiltration in summer than in winter. In addition, during the summer season, metolachlor was more likely to leach into deeper soil layer than atrazine possibly due to high water solubility of metolachlor.

Effect of rice husk gasification residue application on herbicide behavior in micro paddy lysimeter.

Effects of rice husk gasification residues (RHGR) application on the fate of herbicides, butachlor and pyrazosulfuron-ethyl, in paddy water were investigated using micro paddy lysimeters (MPLs). The dissipation of both herbicides in paddy water was faster in the RHGR treated MPL than in the control MPL. The average concentrations of butachlor and pyrazosulfuron-ethyl in paddy water in the lysimeter treated with RHGR during 21 days were significantly reduced by 51% and 48%, respectively, as compared to those in the lysimeter without RHGR application. The half-lives (DT50) of butachlor in paddy water for control and treatment were 3.1 and 2.3 days respectively, and these values of pyrazosulfuron-ethyl were 3.0 and 2.2 days, respectively. Based on this study, RHGR application in rice paddy environment is an alternative method to reduce the concentration of herbicide in paddy field water and consequently to reduce potential pollution to aquatic environment.

Insecticide washoff from concrete surfaces: characterization and prediction.

Pesticide runoff from impervious surfaces is a significant cause of aquatic contamination and ecologic toxicity in urban waterways. Effective mitigation requires better understanding and prediction of off-site transport processes. Presented here is a comprehensive study on pesticide washoff from concrete surfaces, including washoff tests, experimental data analysis, model development, and application. Controlled rainfall experiments were conducted to characterize washoff loads of commercially formulated insecticides with eight different active ingredients. On the basis of the analysis of experimental results, a semimechanistic model was developed to predict pesticide buildup and washoff processes on concrete surfaces. Three pesticide product specific parameters and their time dependences were introduced with empirical functions to simulate the persistence, transferability, and exponential characteristics of the pesticide washoff mechanism. The parameters were incorporated using first-order kinetics and Fick's second law to describe pesticide buildup and washoff processes, respectively. The model was applied to data from 21 data sets collected during 38 rainfall events, with parameters calibrated to pesticide products and environmental conditions. The model satisfactorily captured pesticide mass loads and their temporal variations for pesticides with a wide range of chemical properties (log KOW = 0.6-6.9) under both single and repeated (1-7 times) rainfall events after varying set times (1.5 h∼238 days after application). Results of this study suggested that, in addition to commonly reported physicochemical properties for the active ingredient of a pesticide product, additional parameters determined from washoff experiments are required for risk assessments of pesticide applications on urban impervious surfaces.

Behavior of butachlor and pyrazosulfuron-ethyl in paddy water using micro paddy lysimeters under different temperature conditions in spring and summer.

The behavior of butachlor and pyrazosulfuron-ethyl in paddy water was investigated using micro paddy lysimeters with prescribed hydrological conditions under ambient temperature in spring and summer for simulating two rice crop seasons. Although they were not significantly different, the dissipation of both herbicides in paddy water in the summer experiment was faster than in the spring experiment. The half-lives (DT(50)) in paddy water for spring and summer experiments were 3.2 and 2.5 days for butachlor, and 3.1 and 1.6 days for pyrazosulfuron-ethyl, respectively.

Wash off of imidacloprid and fipronil from turf and concrete surfaces using simulated rainfall.

The surface runoff of imidacloprid granular product (GR) from turf surfaces, and imidacloprid emulsifiable concentrate (EC), fipronil suspension concentrate (SC) products and fipronil byproducts from concrete surfaces was investigated during 1h rainfall simulations at 50 mm/h or 25 mm/h with product incubation times of 1.5 h, 1 d, 7 d, and 14 d. About 57.3% of the applied mass of imidacloprid, corresponding to an event mean concentration of 392.0 µg/L, was washed off from the concrete surfaces after 1.5h of incubation. After 1 d, 7 d, and 14 d of incubation on either turf or concrete surfaces, up to 5.9% of the applied mass of pesticide was removed in each of the run-off events. The maximum concentrations of pesticides were observed in the initial fraction of the runoff collected in the first rainfall event. They were 157.8, 3267.8 and 143.3 µg/L for imidacloprid GR, imidacloprid EC and fipronil SC, respectively. Imidacloprid was not persistent on concrete surfaces, with run-off concentrations below detection limits in 7d incubation experiments. The cumulative mass losses of imidacloprid from turf and fipronil from concrete had a linear relation with cumulative surface run-off depth, while cumulative mass losses of imidacloprid from concrete surfaces were better fit by a power function of the cumulative surface run-off depth. The concentrations of fipronil in the runoff from the third rainfall event at 14 d incubation time were still relatively high and ranged from 12.0 to 31.0 µg/L. A toxicity unit approach was also employed to evaluate the potential acute toxicity of fipronil and its byproducts to aquatic organisms.

Photodegradation of imidacloprid and fipronil in rice-paddy water.

Photodegradation of insecticides, imidacloprid and fipronil, in rice-paddy water under the ambient temperature was investigated. The initial concentrations were set at 58.8 and 3.1 µg/L for imidacloprid and fipronil, respectively, according to their reported initial concentrations in the rice-paddy field. The half-lives (DT(50)) of imidacloprid and fipronil were 24.2 and 36.7 h, respectively. Fipronil desulfinyl was detected as a major metabolite and fipronil sulfone was found to be a minor metabolite of fipronil in the photodegradation process. Detected mass of fipronil, fipronil desulfinyl, and fipronil sulfone at 79 h were 12.9%, 45.8%, and 5.2% of initial fipronil mass, respectively.

Simulating the dissipation of two herbicides using micro paddy lysimeters.

A set of packed micro paddy lysimeters, placed in a greenhouse, was used to simulate the dissipation of two herbicides, simetryn and thiobencarb, in a controlled environment. Data from a field monitoring study in 2003, including the soil condition and water balances, were used in the simulation. The herbicides were applied and monitored over a period of 21 d. The water balances under two water management scenarios, intermittent irrigation management (AI) and continuous irrigation management (CI), were simulated. In the AI scenario, the pattern of herbicide dissipation in the surface water of the field were simulated, following the first-order kinetics. In the CI scenario, similarity was observed in most lysimeter and field concentrations, but there were differences in some data points. Dissipation curves of both herbicides in the surface water of the two simulated scenarios were not significantly different (P>0.05) from the field data except for intercept of the thiobencarb curve in the CI scenario. The distribution of simetryn and thiobencarb in the soil profile after simulation were also similar to the field data. The highest concentrations of both herbicides were found on the topsoil layer at 0-2.5 cm depth. Only a small amount of herbicides moved down to the deeper soil layers. Micro paddy lysimeters are thus a good alternative for the dissipation study of pesticides in the paddy environment.