Assessment of agricultural pesticide inert ingredient transport following modeling approach: Case study of two formulation agents in Sacramento River watershed.

This research provides the first assessment of the environmental fate and transport of agricultural pesticide formulation agents following a dynamic modeling approach. Two formulation agents of toxicological concern, Naphthalene and Solvent Naphtha (Petroleum), Heavy Aromatic, were simulated from their usage in commercially-applied pesticides. The Soil and Water Assessment Tool (SWAT) was applied to simulate these formulation agents during 2011-2014 in the agriculturally intensive Sacramento River watershed. The sensitivity and uncertainty of some key parameters were analyzed. The predicted transport masses of these formulation agents in surface water were strongly associated with rainfall. While predicted transport masses were quite small at the watershed scale (<0.01% of applied masses), they were 26-31 times higher in certain locales at the subbasin level. Since many formulation agents are widely used in pesticides throughout this and other agriculturally impacted watersheds, their potential risks in the environment need more thorough investigation by modeling and monitoring, especially for areas with heavy usage.

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.

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.

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.

Simulating concentration of bensulphuron-methyl in a drainage canal of a paddy block using a rice pesticide model.

A pesticide fate and transport model (PCPF-B) was developed to predict the runoff of pesticides from paddy plots to a drainage canal in a paddy block based on the plot scale model (PCPF-1). The block-scale model now comprises three modules: (1) a module for pesticide application, (2) a module for pesticide behaviour in paddy fields, and (3) a module for pesticide concentration in the drainage canal. The PCPF-B model was first evaluated using published data in a single plot and then was applied to predict the concentration of bensulphuron-methyl in one paddy block in the Sakura river basin, Ibaraki, Japan, where a detailed field survey was conducted. The PCPF-B model simulated well the concentration of bensulphuron-methyl in individual paddy plots. It also reflected the runoff pattern of bensulphuron-methyl at the block outlet, although overestimation of bensulphuron-methyl concentrations occurred due to uncertainty in water balance estimation. A sensitivity analysis showed that the soil adsorption coefficient of the herbicide had the greatest influence on the concentrations and cumulative loss of bensulphuron-methyl to the drainage canal.

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.

Behavior of simetryn and thiobencarb in the plough zone of rice fields.

The behavior of simetryn and thiobencarb in flooded rice soil was investigated in a 2-year study. The concentrations of simetryn and thiobencarb were in the hundreds of µg kg−1 in the top soil layer (0­5 cm) and became significantly lower in tens of µg kg−1 in the deeper soil layers (5­10 and 10­15 cm). The half-lives of the two herbicides were also shorter (36 and 17 days for simetryn and thiobencarb, respectively) in the top soil layer, as they were most affected by environmental conditions, compared with corresponding values of 82 and 69 days in the 5­10 cm soil layer. Simetryn concentration was stable, while thiobencarb's half-life was 165 days in the 10­15 cm layer. About 35% of the applied mass of simetryn and thiobencarb were found in the rice soil compartment.

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.

Soil erosion and transport of Imidacloprid and Clothianidin in the upland field under simulated rainfall condition.

Surface runoff has been recognized as an important medium of pesticides transport to surface water and groundwater causing critical risk to the aquatic ecosystem. Although total pesticide transport in surface runoff in most cases reported being below 1% of applied mass, much larger losses may occur in extreme cases. In this study, surface runoff potential of Imidacloprid and Clothianidin was investigated in an upland field with 5% slope under two simulated rainfall experiments of 70 mm/h intensity. Additionally, the downward movement of the pesticides was determined in soil (n = 87) taken at several depths on different time scales. The result showed that the second rainfall experiment caused more surface runoff than first rainfall experiment, and accounted 30.0 mm and 21.2 mm of applied rainfall, respectively. The cumulative surface runoff developed during first and second rainfall experiments was equal to 30% and 44% of the applied rainfall, respectively. The sediment transport in runoff was relatively higher in second rainfall than first rainfall, and was mostly stable after 30 min of rainfall. The chemical masses of Imidacloprid and Clothianidin were primarily transported in runoff sediments than runoff water and accounted for 10.8% and 7.93% of the applied mass, respectively. The transport of Imidacloprid both in runoff water and sediment was 1-2 times greater than that of Clothianidin. The concentrations of both pesticides were measured highest in the second fraction of runoff (10 min) collected during the first experiment. In soil, the transport of both pesticides prior to rainfall experiment was 1-2 times greater than post-rainfall experiments. The concentration of these pesticides decreased continuously with the time in the upper layer of soil; while a gradual increase of the pesticides mass was observed in the second soil layer. The cumulative mass transport of both pesticides was directly proportional to the cumulative runoff depth.

Improvement and application of the PCPF-1@SWAT2012 model for predicting pesticide transport: a case study of the Sakura River watershed.

BACKGROUND: The Soil and Water Assessment Tool combined with Pesticide Concentration in Paddy Field (PCPF-1@SWAT) model was previously developed to simulate the fate and transport of rice pesticides in watersheds. However, the current model is deficient in characterizing the rice paddy area and is incompatible with the ArcSWAT2012 program. In this study, we modified the original PCPF-1@SWAT model to develop a new PCPF-1@SWAT2012 model to address the deficiency in the rice paddy area and utilizing the ArcSWAT2012 program. Next, the new model was applied to the Sakura River watershed, Ibaraki, Japan in order to simulate the transport of four herbicides: mefenacet, pretilachlor, bensulfuron-methyl and imazosulfuron. RESULTS: The results showed that the water flow rate simulated by PCPF1@SWAT2012 was similar with the observed data. The calculated Nash-Sutcliffe efficiency coefficient (NSE) (0.73) and percent bias (PBIAS) (-20.38) suggested satisfactory performance of the model. In addition, the concentrations of herbicides simulated by the PCPF-1@SWAT2012 model were in good agreement with the observed data. The statistical indices NSE and root mean square error (RMSE) estimated for mefenacet (0.69 and 0.18, respectively), pretilachlor (0.86 and 0.18, respectively), bensulfuronmethyl (0.46 and 0.21, respectively) and imazosulfuron (0.64 and 0.28, respectively) indicated satisfactory predictions. CONCLUSION: The PCPF-1@SWAT2012 model is capable of simulating well the water flow rate and transport of herbicides in this watershed, comprising different land use types, including a rice paddy area. © 2018 Society of Chemical Industry.

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.

Biomass burning in Indo-China peninsula and its impacts on regional air quality and global climate change-a review.

Although, many biomass burning (BB) emissions products (particulate matter and trace gases) are believed to be trans-boundary pollutants that originates from India and China (the two most populous countries in Asia), the information about BB emission and related contents is limited for Indo-China Peninsula (ICP) region. This motivated us to review this region pertaining to BB emission. The main objective of the review is to document the current status of BB emission in ICP region. In order to highlight the impact of BB on regional air quality and global climate change, the role of BB emission in ICP region is also discussed. Based on the available literature and modeling simulations studies, it is evidenced that ICP is one of the hotspot regional source for aerosols in terms of BB emissions. In addition, regional emissions through BB have significant implications for regional air quality especially in the neighboring countries such as China, Taiwan and India. Our assessment highlight that there is still a general lack of reliable data and research studies addressing BB related issues in context of environmental and human health. There is therefore a critical need to improve the current knowledge base, which should build upon the research experience and further research into these issues is considered vital to help inform future policies/control strategies.

Simulation of mefenacet concentrations in paddy fields by an improved PCPF-1 model.

An improved simulation model (PCPF-1) has been evaluated for the prediction of the fate of mefenacet in an experimental paddy field. This model simulates the fate and transport of pesticide in paddy water and the top 1 cm of paddy soil. Observed concentrations of mefenacet in the paddy water and the surface soil exponentially decreased from their maximum concentrations of 0.70 mg litre(-1) and 11.3 mg kg(-1), respectively. Predicted mefenacet concentrations both in the water and surface soil were in excellent agreement with those measured during the first 2 weeks after herbicide application, but concentrations in paddy water were appreciably overestimated thereafter. The model simulated mefenacet losses through runoff, percolation and degradation to be respectively 41.9%, 6.4% and 57.3% of applied, and the mass balance error was about -6%. The model simulation implied that drainage and seepage control, especially shortly after application when herbicide concentrations are high, is essential for preventing pesticide losses from paddy fields. In focusing on pesticide concentrations in this early period the PCPF-1 model can be a beneficial tool for risk assessment of pesticide losses and in the evaluation of agricultural management for reducing pesticide pollution associated with paddy rice production.

Exposure risk assessment and evaluation of the best management practice for controlling pesticide runoff from paddy fields. Part 1: Paddy watershed monitoring.

Rice pesticide concentrations in surface water along with hydrological balance and water management conditions were investigated in a paddy watershed of about 100 ha at the Sakura river basin in Tsukuba, Japan, for 3 years from April 2002. Monitoring on different hydrological scales ranging from a paddy plot up to a watershed determined the importance of water management associated with rainfall events and the cyclic irrigation for reducing pesticide discharge into aquatic environments. Surface drainage significantly increased as a response to rainfall events greater than about 1.5 cm day(-1). A total of 16 herbicides were detected in the stream water and their peak concentrations mostly occurred from early to mid-May following the pesticide application period. Two water management factors influencing the pesticide runoff from paddy fields were defined: excess water storage capacity (EWSC) and water holding period (WHP). Uncertainty analyses of pesticide discharge from a paddy plot for dymron (daimuron) and imazosulfuron (IMS) were performed using Monte Carlo simulation (MCS) with prescribed probability of rainfall and water management practice from observations over a period of 3 years. Application of an intermittent irrigation scheme with shallow water depth practice and high drainage gate to maintain the EWSC > 2 cm and increasing WHP from the current Japanese Agricultural Chemicals Regulation law of 3-4 days to at least 10 days were recommended for reducing the pesticide runoff from paddy fields in a monsoon region such as in Japan. The combination of good water management in field plots and small-scale water cycling is the best management practice for controlling pesticide discharge from paddy watersheds.

Pesticide exposure assessment in rice paddies in Europe: a comparative study of existing mathematical models.

A comparative test was undertaken in order to identify the potential of existing mathematical models, including the rice water quality (RICEWQ) 1.6.4v model, the pesticide concentration in paddy field (PCPF-1) model and the surface water and groundwater (SWAGW) model, for calculating pesticide dissipation and exposure in rice paddies in Europe. Previous versions of RICEWQ and PCPF-1 models had been validated under European and Japanese conditions respectively, unlike the SWAGW model which was only recently developed as a tier-2 modelling tool. Two datasets, derived from field dissipation studies undertaken in northern Italy with the herbicides cinosulfuron and pretilachlor, were used for the modelling exercise. All models were parameterized according to field experimentations, as far as possible, considering their individual deficiencies. Models were not calibrated against field data in order to remove bias in the comparison of the results. RICEWQ 1.6.4v provided the highest agreement between measured and predicted pesticide concentrations in both paddy water and paddy soil, with modelling efficiency (EF) values ranging from 0.78 to 0.93. PCPF-1 simulated well the dissipation of herbicides in paddy water, but significantly underestimated the concentrations of pretilachlor, a chemical with high affinity for soil sorption, in paddy soil. SWAGW simulated relatively well the dissipation of both herbicides in paddy water, and especially pretilachlor, but failed to predict closely the pesticide dissipation in paddy soil. Both RICEWQ and SWAGW provided low groundwater (GW) predicted environmental concentrations (PECs), suggesting a low risk of GW contamination for the two herbicides. Overall, this modelling exercise suggested that RICEWQ 1.6.4v is currently the most reliable model for higher-tier exposure assessment in rice paddies in Europe. PCPF-1 and SWAGW showed promising results, but further adjustments are required before these models can be considered as strong candidates for inclusion in the higher-tier pesticide regulatory scheme.

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.

Export of radioactive cesium from agricultural fields under simulated rainfall in Fukushima.

In this study, we investigated the impact of rainfall on runoff, soil erosion and consequently on the discharge of radioactive cesium in agricultural fields in Fukushima prefecture using a rainfall simulator. Simulated heavy rainfalls (50 mm h(-1)) generated significant runoff and soil erosion. The average concentration of radioactive cesium (the sum of (134)Cs and (137)Cs) in the runoff sediments was ∼3500 Bq kg(-1) dry soil, more than double the concentrations measured in the field soils which should be considered in studies using the (137)Cs loss to estimate long-term soil erosion. However, the estimated mass of cesium discharged through one runoff event was less than 2% of the cesium inventory in the field. This suggested that cesium discharge via soil erosion is not a significant factor in reducing the radioactivity of contaminated soils in Fukushima prefecture. However, the eroded sediment carrying radioactive cesium will deposit into the river systems and potentially pose a radioactivity risk for aquatic living organisms.

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.