PeLM: modeling of pesticide-losses through runoff and sediment transport

A GIS-aided pesticide loss model (PeLM) was developed to simulate pesticide losses through surface runoff and sediment transport in watershed systems. The PeLM could tackle the movement of eroded soil along with surface runoff as well as the pesticide losses in adsorbed and dissolved phases. The contributions of different soil types in the sediment were also examined. The model was applied to the Kintore Creek Watershed of southern Ontario, Canada. The simulation results were verified through observed data, indicating a correlation level of 0.89-0.98. The results also showed that clay particles usually held the largest share of contributions to pesticide losses through soil erosion. This study is significant in the efforts for modeling nonpoint source pollution in watershed systems. It provides useful information and support for the related decisions of watershed management.     

Foliar washoff of pesticides (FWOP) model: Development and evaluation

Abstract

The Foliar Washoff of Pesticides (FWOP) Model was developed to provide an empirical simulation of pesticide washoff from plant leaf surfaces as influenced by rainfall amount. To evaluate the technique, simulations by the FWOP Model were compared to those by the foliar washoff algorithm of the Chemical, Runoff and Erosion from Agricultural Management Systems (CREAMS) Model. The two algorithms were linked individually to the Pesticide Runoff Simulator (PRS) for the comparison. Five years of test data from a Mississippi watershed were used to evaluate six insecticides (carbaryl, profenofos, methyl parathion, permethrin, phorate, and toxaphene).

Initially, the FWOP model was used to evaluate the relative impact of chemical distribution (foliage versus soil) on the subsequent foliar washoff and soil surface contributions to runoff losses. Results indicated that runoff losses were low If all of the insecticide was applied to the foliage whereas high losses occurred if applied only to the soil. When an assumed application was distributed between the plant and soil (i.e., 90% to foliage and 10% to soil), predicted runoff losses compared well with observed field data (<3% of the application rate).

Except for toxaphene, the FWOP model generally predicted less washoff and subsequent runoff losses than the CREAMS approach. Simulated toxaphene washoff losses were in good agreement with observed field data. Statistical comparisons of the two modeling approaches using the Kolmogorov‐Smirnov test showed differences in the two cumulative frequency distributions for washoff but smaller differences for runoff. Average 5‐year runoff losses, however, were greater using the CREAMS approach—by factors of 2, 3, and 3 for profenofos, methyl parathion and phorate, respectively.

Results from this study will be useful for upgrading current exposure assessment models to more accurately address foliar washoff losses of pesticides as well as for assessing the impact of foliar‐applied chemicals on environmental quality.     

Dynamic modeling of organophosphate pesticide load in surface water in the northern San Joaquin Valley watershed of California

The hydrology, sediment, and pesticide transport components of the Soil and Water Assessment Tool (SWAT) were evaluated on the northern San Joaquin Valley watershed of California. The Nash-Sutcliffe coefficients for monthly stream flow and sediment load ranged from 0.49 to 0.99 over the watershed during the study period of 1992-2005. The calibrated SWAT model was applied to simulate fate and transport processes of two organophosphate pesticides of diazinon and chlorpyrifos at watershed scale. The model generated satisfactory predictions of dissolved pesticide loads relative to the monitoring data. The model also showed great success in capturing spatial patterns of dissolved diazinon and chlorpyrifos loads according to the soil properties and landscape morphology over the large agricultural watershed. This study indicated that curve number was the major factor influencing the hydrology while pesticide fate and transport were mainly affected by surface runoff and pesticide application and in the study area.     

Management-oriented sensitivity analysis for pesticide transport in watershed-scale water quality modeling using SWAT

The Soil and Water Assessment Tool (SWAT) was calibrated for hydrology conditions in an agricultural watershed of Orestimba Creek, California, and applied to simulate fate and transport of two organophosphate pesticides chlorpyrifos and diazinon. The model showed capability in evaluating pesticide fate and transport processes in agricultural fields and instream network. Management-oriented sensitivity analysis was conducted by applied stochastic SWAT simulations for pesticide distribution. Results of sensitivity analysis identified the governing processes in pesticide outputs as surface runoff, soil erosion, and sedimentation in the study area. By incorporating sensitive parameters in pesticide transport simulation, effects of structural best management practices (BMPs) in improving surface water quality were demonstrated by SWAT modeling. This study also recommends conservation practices designed to reduce field yield and in-stream transport capacity of sediment, such as filter strip, grassed waterway, crop residue management, and tailwater pond to be implemented in the Orestimba Creek watershed.     

Persistence and runoff losses of 3 herbicides and chlorpyrifos from a corn field in the Lake Balaton watershed of Hungary

Corn is intensively cultivated in western Hungary in the basin of Lake Balaton, one of the most important water resources in eastern Europe. Pesticide runoff was measured in 1996 and 1997 from a typical corn field near Zalaegerszeg, Hungary, which drains into the Zala River, an important water source of Lake Balaton. Three herbicides, namely atrazine, acetochlor, and propizochlor, and the insecticide chlorpyrifos were applied to bare soil in a field with 5% slope and soil and runoff water pesticide concentrations were monitored. In 1997, a rainfall-runoff simulation experiment was conducted on a small sub-plot in order to measure pesticide runoff under reasonable worst-case conditions. Under natural rainfall almost all losses occurred in a large runoff event in 1996 one month after application in which 3% of atrazine and 1% of acetochlor was transported off the field. Propizochlor and chlorpyrifos losses in the same event were much lower: 0.2% and <0.01%, respectively, because of these chemicals' shorter persistence times in near-surface soil. The rainfall simulation produced only trace amounts of losses even though 4.1 cm was applied in 2 hours; the soil was extremely dry and only 0.2 cm runoff occurred containing less than 0.01% of all chemicals applied. The results suggest that intensive use of corn herbicides, which have been found to result in widespread contamination of water resources elsewhere, may be expected to have the same impact in the Balaton watershed depending on the amounts and intensities used in the basin.     

Sensitivity of agricultural runoff loads to rising levels of CO2 and climate change in the San Joaquin Valley watershed of California

The Soil and Water Assessment Tool (SWAT) was used to assess the impact of climate change on sediment, nitrate, phosphorus and pesticide (diazinon and chlorpyrifos) runoff in the San Joaquin watershed in California. This study used modeling techniques that include variations of CO₂, temperature, and precipitation to quantify these responses. Precipitation had a greater impact on agricultural runoff compared to changes in either CO₂ concentration or temperature. Increase of precipitation by ±10% and ±20% generally changed agricultural runoff proportionally. Solely increasing CO₂ concentration resulted in an increase in nitrate, phosphorus, and chlorpyrifos yield by 4.2, 7.8, and 6.4%, respectively, and a decrease in sediment and diazinon yield by 6.3 and 5.3%, respectively, in comparison to the present-day reference scenario. Only increasing temperature reduced yields of all agricultural runoff components. The results suggest that agricultural runoff in the San Joaquin watershed is sensitive to precipitation, temperature, and CO₂ concentration changes.     

晋江西溪流域茶园降雨径流产污特征

在野外模拟降雨条件下,开展了晋江西溪流域茶园和裸地的径流产沙及氮磷养分流失过程对比实验,研究结果表明,在相同降雨强度下,3种下垫面径流和产沙量顺序均为:裸地＞2年茶园＞4年茶园,径流量与产沙量之间呈显著正相关.对地表径流水相而言,2年茶园、4年茶园和裸地的TN流失量分别为:461.29、129.38和107.86 mg/m2;NO3-N流失量分别为:286.42、98.58和103.00 mg/m2,均占TN流失量的60％以上;NH4-N流失量分别为:48.67、16.19和4.42 mg/m2;Tp流失量分别为:34.71、16.47和23.88 mg/m2.对径流泥沙相而言,2年茶园、4年茶园和裸地的TN流失量分别为:379.28、44.81和747.16 mg/m2,占流失总量的比重在25.72％～87.93％之间;TP流失量分别为:27.94、4.17和58.85 mg/m2,占流失总量的比重在53.42％ ～68.36％之间.茶园的N、P主要随径流流失,而裸地以泥沙迁移为主.这说明茶叶种植具有一定的水土保持效应,且种植年限较长的茶园可显著减少随径流泥沙进入水体中的N、P元素.     

Runoff and leaching of atrazine and alachlor on a sandy soil as affected by application in sprinkler irrigation

Abstract

Rainfall simulation was used with small packed boxes of soil to compare runoff of herbicides applied by conventional spray and injection into sprinkler‐irrigation (chemigation), under severe rainfall conditions. It was hypothesized that the larger water volumes used in chemigation would leach some of the chemicals out of the soil surface rainfall interaction zone, and thus reduce the amounts of herbicides available for runoff. A 47‐mm rain falling in a 2‐hour event 24 hours after application of alachlor (2‐chloro‐N‐(2,6‐diethylphenyl)‐N‐(methoxymethyl)‐acetamide) and atrazine (6‐chloro‐N‐ethyl‐N‐(1‐methylethyl)‐1,3,5‐triazine‐2,4‐diamine) was simulated. The design of the boxes allowed a measurement of pesticide concentrations in splash water throughout the rainfall event. Initial atrazine concentrations exceeding its’ solubility were observed. When the herbicides were applied in 64000 L/ha of water (simulating chemigation in 6.4 mm irrigation water) to the surface of a Tifton loamy sand, subsequent herbicide losses in runoff water were decreased by 90% for atrazine and 91% for alachlor, as compared to losses from applications in typical carrier water volumes of 187 L/ha. However, this difference was not due to an herbicide leaching effect but to a 96% decrease in the amount of runoff from the chemigated plots. Only 0.3 mm of runoff occurred from the chemigated boxes while 7.4 mm runoff occurred from the conventionally‐treated boxes, even though antecedent moisture was higher in the former. Two possible explanations for this unexpected result are (a) increased aggregate stability in the more moist condition, leading to less surface sealing during subsequent rainfall, or (b) a hydrophobic effect in the drier boxes. In the majority of these pans herbicide loss was much less in runoff than in leachate water. Thus, in this soil, application of these herbicides by chemigation would decrease their potential for pollution only in situations where runoff is a greater potential threat than leaching.     

Pesticide concentrations in agricultural storm drainage inlets of a small Swiss catchment

Agricultural pesticides transported to surface waters pose a major risk for aquatic ecosystems. Modelling studies indicate that the inlets of agricultural storm drainage systems can considerably increase the connectivity of surface runoff and pesticides to surface waters. These model results have however not yet been validated with field measurements. In this study, we measured discharge and concentrations of 51 pesticides in four out of 158 storm drainage inlets of a small Swiss agricultural catchment (2.8 km²) and in the receiving stream. For this, we performed an event-triggered sampling during 19 rain events and collected plot-specific pesticide application data. Our results show that agricultural storm drainage inlets strongly influence surface runoff and pesticide transport in the study catchment. The concentrations of single pesticides in inlets amounted up to 62 µg/L. During some rain events, transport through single inlets caused more than 10% of the stream load of certain pesticides. An extrapolation to the entire catchment suggests that during selected events on average 30 to 70% of the load in the stream was transported through inlets. Pesticide applications on fields with surface runoff or spray drift potential to inlets led to increased concentrations in the corresponding inlets. Overall, this study corroborates the relevance of such inlets for pesticide transport by establishing a connectivity between fields and surface waters, and by their potential to deliver substantial pesticide loads to surface waters.

     

Extension of coupled multispecies metal transport and speciation (TRANSPEC) model to soil

Atmospheric deposition of metals emitted from mining operations has raised metal concentrations in the surrounding soils. This repository may be remobilized and act as a source of metals to nearby surface aquatic systems. It is important to understand metal dynamics and the impact of various chemistry and fate parameters on metal movement in the soil environment in order to evaluate risk associated with metals in terrestrial ecosystems and accurately establish critical discharge limits that are protective of aquatic biota. Here we extend our previously developed coupled multispecies metal fate-TRANsport and SPECiation/complexation (TRANSPEC) model, which was applicable to surface aquatic systems. The extended TRANSPEC, termed TRANSPEC-II, estimates the partition coefficient, K(d), between the soil-solid and -soluble phases using site-specific data and a semi-empirical regression model obtained from literature. A geochemical model calculates metal and species fractions in the dissolved and colloidal phases of the soil solution. The multispecies fugacity/aquivalence based fate-transport model then estimates inter-media transport rates such as leaching from soil, soil runoff, and water-sediment exchanges of each metal species. The model is illustratively applied to Ni in the Kelly Lake watershed (Sudbury, Ontario, Canada), where several mining operations are located. The model results suggest that the current atmospheric fallout supplies only 4% of Ni removed from soil through soil runoff and leaching. Soil runoff contributes about 20% of Ni entering into Kelly Lake with the rest coming from other sources. Leaching to groundwater, apart from runoff, is also a major loss process for Ni in the soil. A sensitivity analysis indicates that raising soil pH to above 6 may substantially reduce metal runoff and improve water quality of nearby water bodies that are impacted by runoff.     

Contribution of macroporosity to infiltration into a continuous corn no-tilled watershed: Implications for contaminant movement

Rainfall and runoff were measured for many years on small watersheds on 10–15% slopes in east-central Ohio. Surface runoff from watersheds used for corn (Zea mays L.) production was high with conventional tillage and very low with no-tillage. A 50-year storm produced 15 times more runoff from a plowed watershed than from a mulch-covered no-till watershed. Reduced runoff from the no-till surface resulted in increased percolation and enhanced the potential for transport of agricultural chemicals to the groundwater. The mulched surface of the no-till watershed also created a favorable environment for the deep burrowing earthworm, Lumbricus terrestris L., whose burrows can transmit water rapidly downward through the soil profile, thus contributing to the high infiltration rates.Open biopores and smaller structural pores were counted and measured to characterize the major flow paths of water movement in the no-till soil. Photos of horizontal surfaces at 2.5-, 7.5-, 15-, and 30 - cm depths and vertical faces of impregnated samples from the 1- and 5-cm depths were evaluated by image analysis. Number of pores was inversely proportional to pore diameter, however pores in the 0.05–1.0-mm diameter range accounted for less porosity than did those in the 1.0–5.0-mm range. The large pores were nearly vertical earthworm burrows and were continuously open from near the surface to the bedrock. Surface applications of lime increased subsoil pH in the no-till watershed but had little effect below the plow sole in the tilled watershed, suggesting that rapid movement of water in large pores can enhance chemical migration into the subsoil.     

Estimating pesticide runoff in small streams

Surface runoff is one of the most important pathways for pesticides to enter surface waters. Mathematical models are employed to characterize its spatio-temporal variability within landscapes, but they must be simple owing to the limited availability and low resolution of data at this scale. This study aimed to validate a simplified spatially-explicit model that is developed for the regional scale to calculate the runoff potential (RP). The RP is a generic indicator of the magnitude of pesticide inputs into streams via runoff. The underlying runoff model considers key environmental factors affecting runoff (precipitation, topography, land use, and soil characteristics), but predicts losses of a generic substance instead of any one pesticide. We predicted and evaluated RP for 20 small streams. RP input data were extracted from governmental databases. Pesticide measurements from a triennial study were used for validation. Measured pesticide concentrations were standardized by the applied mass per catchment and the water solubility of the relevant compounds. The maximum standardized concentration per site and year (runoff loss, R_Loss) provided a generalized measure of observed pesticide inputs into the streams. Average RP explained 75% (p < 0.001) of the variance in R_Loss. Our results imply that the generic indicator can give an adequate estimate of runoff inputs into small streams, wherever data of similar resolution are available. Therefore, we suggest RP for a first quick and cost-effective location of potential runoff hot spots at the landscape level.     

Modeling Mercury Fluxes and Concentrations in a Georgia Watershed Receiving Atmospheric Deposition Load from Direct and Indirect Sources

Abstract

This paper presents a modeling analysis of airborne mercury (Hg) deposited on the Ochlockonee River watershed located in Georgia. Atmospheric deposition monitoring and source attribution data were used along with simulation models to calculate Hg buildup in the subwatershed soils, its subsequent runoff loading and delivery through the tributaries, and its ultimate fate in the mainstem river. The terrestrial model calculated annual watershed yields for total Hg ranging from 0.7 to 1.1 μg/m². Results suggest that approximately two-thirds of the atmospherically deposited Hg to the watershed is returned to the atmosphere, 10% is delivered to the river, and the rest is retained in the watershed. A check of the aquatic model results against survey data showed a reasonable agreement. Comparing observed and simulated total and methylmercury concentrations gave root mean square error values of 0.26 and 0.10 ng/L, respectively, in the water column, and 5.9 and 1 ng/g, respectively, in the upper sediment layer. Sensitivity analysis results imply that mercury in the Ochlockonee River is dominated by watershed runoff inputs and not by direct atmospheric deposition, and that methylmercury concentrations in the river are determined mainly by net methylation rates in the watershed, presumably in wetted soils and in the wetlands feeding the river.     

Pesticide runoff model (PeRM): a case study for the Kintore Creek Watershed,Ontario, Canada

An integrated model, the Pesticide Runoff Model (PeRM), has been developed to predict pesticide losses due to runoff by considering the emission, degradation, adsorption and desorption of pesticides, as well as their movement in dissolved and adsorbed phases. The developed modeling system has been used to calculate the losses of atrazine from agricultural lands in the Kintore Creek Watershed, Ontario, Canada between 1988 and 1992. The modeling outputs have been verified against actual monitoring data, which were obtained from a water quality monitoring project carried out in the same watershed over the same period of time.     

Use of toxicity identification evaluations to determine the pesticide mitigation effectiveness of on-farm vegetated treatment systems

Evidence of ecological impacts from pesticide runoff has prompted installation of vegetated treatment systems (VTS) along the central coast of California, USA. During five surveys of two on-farm VTS ponds, 88% of inlet and outlet water samples were toxic to Ceriodaphnia dubia. Toxicity identification evaluations (TIEs) indicated water toxicity was caused by diazinon at VTS-1, and chlorpyrifos at VTS-2. Diazinon levels in VTS-1 were variable, but high pulse inflow concentrations were reduced through dilution. At VTS-2, chlorpyrifos concentrations averaged 52% lower at the VTS outlet than at the inlet. Water concentrations of most other pesticides averaged 20-90% lower at VTS outlets. All VTS sediment samples were toxic to amphipods (Hyalella azteca). Sediment TIEs indicated toxicity was caused by cypermethrin and lambda-cyhalothrin at VTS-1, and chlorpyrifos and permethrin at VTS-2. As with water, sediment concentrations were lower at VTS outlets, indicating substantial reductions in farm runoff pesticide concentrations.     

Field calibration of surface: A model of agricultural chemicals in surface waters

Abstract

Agricultural chemicals sporadically occur at detectable levels in the surface waters of intensively farmed watersheds. HSPF, a previously released model of agricultural chemicals in surface water, had been used to predict concentrations which were much higher (10 X) than those actually observed during monitoring studies. A new model, SURFACE, is described here which is much simpler than HSPF and gives better predictions of surface water concentrations. SURFACE uses PRZM, an EPA model, to calculate edge‐of‐field runoff losses and simple hydraulic routing algorithms to determine concentrations at the bottom of large river basins. In water systems sampled during 1985 and 1986, SURFACE predictions of annualized mean concentrations for alachlor, atrazine, cyanazine and metolachlor were within 0.09 ppb half of the time.     

Pesticides in the surface waters of the Camanducaia River watershed,Brazil

Abstract

Camanducaia River is part of the Piracicaba watershed responsible for pumping water into the Cantareira System, which is one of the main water sources for the metropolis of São Paulo and Campinas, Brazil. Intensive use of pesticides and hilly topography represents a situation of high risk for river water contamination. Therefore, water samples from 12 locations were collected along the Camanducaia River and its tributaries, over a period of 4?mo during the rainy season, and analyzed by GC-MS/MS or UPLC- MS/MS for the presence of 46 pesticides. Seven pesticides (fipronil, methyl parathion, metolachlor, atrazine, carbofuran, diuron, and simazine) were positively detected. Only atrazine (the most frequently detected) and diuron were present at concentrations above the limit of quantification of the analytical method (0.32 and 0.57?μg L^?1 for atrazine and diuron, respectively). Pesticides detection frequency was higher than expected for a river system where only 11.8% of the land area is under agriculture. The vulnerability of the Camanducaia basin to pesticide contamination is attributed to the high annual precipitation (> 1.5?m y^?1 in the headwaters), associated with topographical features (steep terrain) and soil types that favor surface runoff, which has been exacerbated by poor soil management practices.     

Arsenic and mercury concentrations in major landscape components of an intensively cultivated watershed

To provide an understanding of arsenic (As) and mercury (Hg) concentrations in soil, sediment, water, and fish tissues, samples were collected from a Mississippi River alluvial floodplain located in northwest Mississippi. As concentrations increased approximately an order of magnitude from water (5.12 micrograms/l) to fish tissues (36.99 micrograms/kg) and an additional two orders of magnitude in soils, lake sediments, and wetland sediments (5728, 5614, and 6746 micrograms/kg), respectively. Average Hg concentrations in water, soils, lake sediments, and fish were 2.16 micrograms/l, 55.1, 14.5 and 125 micrograms/kg, respectively. As and Hg concentrations were within published ranges for uncontaminated soil, water, and sediments. As concentrations represented a low risk. Hg concentrations were also low but showed a greater tendency to concentrate in fish tissue. The dominant mode of entry of these materials into aquatic systems is through storm-generated runoff. Since both metals accompany sediments, agricultural conservation practices such as reduced tillage, buffer riparian strips, and bordering sediment ponds or drainage wetlands will minimize watershed input to aquatic systems.     

A pesticide emission model (PEM) Part I: model development

The application of pesticides to cultivated soil and crops is a major source of pesticides that are found in the atmosphere and which are transported and deposited to land and water surfaces over distances that range from local to global scales. In this first part of a two-part paper, a pesticide emission model (PEM) is proposed for estimating the exchange with the atmosphere of pesticides applied to soils and crops. The basis of PEM is a one-dimensional numerical solution of the dynamic equations describing the advection and diffusion of heat, moisture and pesticide within the soil column and exchange with the atmosphere through heat transfer, evapotranspiration and volatilization. The soil model is coupled with an atmospheric surface layer and a simple canopy model that includes: the interception of sprayed pesticide by the crop foliage; the partitioning of pesticide within a wet or dry canopy; and, the volatilization of pesticide to the atmosphere or the wash-off to the soil by precipitation. The finite-element technique used for solving the model equations is mass conservative and multi-year periods of simulation are possible while maintaining a proper mass balance of pesticide in the soil. The model is solved using 1200 s time-steps and 49 variably spaced levels in the soil to a depth of 2 m, with the highest vertical resolution (0.002 m spacing) near the soil surface. Similarity theory is used to parameterize the fluxes of heat, moisture and pesticide through the atmospheric surface layer with hourly meteorology being provided by either climate station observations or a meteorological model. In the second part to this paper, the results of an evaluation of PEM are reported.     

Surface runoff and nitrogen (N) loss in a bamboo (Phyllostachys pubescens) forest under different fertilization regimes

Nitrogen (N) losses from agricultural fields have been extensively studied. In contrast, surface runoff and N losses have rarely been considered for bamboo forests that are widespread in regions such as southern China. The thriving of bamboo industries has led to increasing fertilizer use in bamboo forests. In this study, we evaluated surface runoff and N losses in runoff following different fertilization treatments under field conditions in a bamboo (Phyllostachys pubescens) forest in the catchment of Lake Taihu in Jiangsu, China. Under three different fertilization regimes, i.e., control, site-specific nutrient management (SSNM), and farmer's fertilization practice (FFP), the water runoff rate amounted to 356, 361, and 342 m³?ha^?1 and accounted for 1.91, 1.98, and 1.85 % of the water input, respectively, from June 2009 to May 2010. The total N losses via surface runoff ranged from 1.2 to 1.8 kg?ha^?1. Compared with FFP, the SSNM treatment reduced total nitrogen (TN) and dissolved nitrogen (DN) losses by 31 and 34 %, respectively. The results also showed that variations in N losses depended mainly on runoff fluxes, not N concentrations. Runoff samples collected from all treatments throughout the year showed TN concentrations greater than 0.35 mg?L^?1, with the mean TN concentration in the runoff from the FFP treatment reaching 8.97 mg?L^?1. The loss of NO₃ ^?–N was greater than the loss of NH₄ ⁺–N. The total loss of dissolved organic nitrogen (DON) reached 23–41 % of the corresponding DN. Therefore, DON is likely the main N species in runoff from bamboo forests and should be emphasized in the assessment and management of N losses in bamboo forest.