Dynamic modeling of chemical fate and transport in multimedia environments at watershed scale-I: theoretical considerations and model implementation

A geo-referenced environmental fate model was developed for analyzing unsteady-state dispersion and distribution of chemicals in multimedia environmental systems. Chemical transport processes were formulated in seven environmental compartments of air, canopy, surface soil, root-zone soil, vadose-zone soil, surface water, and sediment. The model assumed that the compartments were completely mixed and chemical equilibrium was established instantaneously between the sub-compartments within each compartment. A fugacity approach was utilized to formulate the mechanisms of diffusion, advection, physical interfacial transport, and transformation reactions. The governing equations of chemical mass balances in the environmental compartments were solved simultaneously to reflect the interactions between the compartments. A geographic information system (GIS) database and geospatial analysis were integrated into the chemical transport simulation to provide spatially explicit estimations of model parameters at watershed scale. Temporal variations of the environmental properties and source emissions were also considered in the parameter estimations. The outputs of the model included time-dependent chemical concentrations in each compartment and its sub-compartments, and inter-media mass fluxes between adjacent compartments at daily time steps.     

GENERALIZED WATERSHED LOADING FUNCTIONS FOR STREAM FLOW NUTRIENTS1

ABSTRACT: Loading functions are proposed as a general model for estimating monthly nitrogen and phosphorus fluxes in stream flow. The functions have a simple mathematical structure, describe a wide range of rural and urban nonpoint sources, and couple surface runoff and ground water discharge. Rural runoff loads are computed from daily runoff and erosion and monthly sediment yield calculations. Urban runoff loads are based on daily nutrient accumulation rates and exponential wash off functions. Ground water discharge is determined by lumped parameter unsaturated and saturated zone soil moisture balances. Default values for model chemical parameters were estimated from literature values. Validation studies over a three-year period for an 850 km² watershed showed that the loading functions explained at least 90 percent of the observed monthly variation in dissolved and total nitrogen and phosphorus fluxes in stream flow. Errors in model predictions of mean monthly fluxes were: dissolved phosphorus - 4 percent; total phosphorus - 2 percent; dissolved nitrogen - 18 percent; and total nitrogen - 28 percent. These results were obtained without model calibration.     

Simulating sulfadimidine transport in surface runoff and soil at the microplot and field scale

To prevent residues of veterinary medicinal products (VMPs) from contaminating surface waters and ground water, an environmental impact assessment is required before a new product is allowed on the market. Physically based simulation models are advocated for the calculation of predicted environmental concentrations at higher tiers of the assessment process. However, the validation status of potentially useful models is poor for VMP transport. The objective of this study was to evaluate the dual-permeability model MACRO for simulation of transport of sulfonamide antibiotics in surface runoff and soil. Special focus was on effects of solute application in liquid manure, which may alter the hydraulic properties at the soil surface. To this end we used data from a microplot runoff experiment and a field experiment, both conducted on the same clay loam soil prone to preferential flow. Results showed that the model could accurately simulate concentrations of sulfadimidine and the nonreactive tracer bromide in runoff and in soil from the microplot experiments. The use of posterior parameter distributions from calibrations using the microplot data resulted in poor simulations for the field data of total sulfadimidine losses. The poor results may be due to surface runoff being instantly transferred off the field in the model, whereas in reality re-infiltration may occur. The effects of the manure application were reflected in smaller total and micropore hydraulic conductivities compared with the application in aqueous solution. These effects could easily be accounted for in regulatory modeling.     

Predicting phosphorus losses with the PLEASE model on a local scale in Denmark and the Netherlands

To reduce losses from agricultural soils to surface water, mitigation options have to be implemented as a local scale. For a cost-effective implementation of these measures, an instrument to identify critical areas for P leaching is indispensable. In many countries, P-index methods are used to identify areas as risk for P losses to surface water. In flat areas, where losses by leaching are dominant, these methods have their limitations because leaching is often not described in detail, PLEASE, is a simple mechanistic model designed to stimulate P Losses by leaching at the field scale using a limited amount of local field data. In this study, PLEASE, was applied to 17 lowland sites in Denmark and 14 lowland sites in the Netherlands. Results show that the simple model simulated measured fluxes and concentrations in water from pipe drains, suction cups, and groundwater quite well. The modeling efficiency ranged from 0.92 for modeling total-P fluxes to 0.36 fr modeling concentrations in groundwater. Poor results were obtained for heavy clay soils and eutrophic peat soils, where fluxes and concentration were strongly underestimated by the model. The poot performance for the heavy clay soil can be explained by the transport of P through macropores to the drain pipes and the underestimation of overland flow on this heavy-textured soil. In the eutrophic peat soils, fluxes were underestimated due to the release of P from deep soil layers.     

Seasonal leaching and biodegradation of dicamba in turfgrass

The leaching of surface-applied herbicides, such as dicamba (2methoxy-3,6-dichlorobenzoic acid), to ground water is an environmental concern. Seasonal changes in soil temperature and water content, affecting infiltration and biodegradation, may control leaching. The objectives of this study were to (i) investigate the leaching of dicamba applied to turfgrass, (ii) measure the degradation rate of dicamba in soil and thatch in the laboratory under simulated field conditions, and (iii) test the ability of the model EXPRES (containing LEACHM) to simulate the field transport and degradation processes. Four field lysimeters, packed with sandy loam soil and topped with Kentucky bluegrass (Poa pratensis L.) sod, were monitored after receiving three applications (May, September, November) of dicamba. Concentrations of dicamba greater than 1 mg L(-1) were detected in soil water. Although drying of the soil during the summer prevented deep transport, greater leaching occurred in late autumn due to increased infiltration. From the batch experiment, the degradation rate for dicamba in thatch was 5.9 to 8.4 times greater than for soil, with a calculated half-life as low as 5.5 d. Computer modeling indicated that the soil and climatic conditions would influence the effectiveness of greater degradation in thatch for reducing dicamba leaching. In general, EXPRES predictions were similar to observed concentration profiles, though peak dicamba concentrations at the 10-cm depth tended to be higher than predicted in May and November. Differences between predictions and observations are probably a result of minor inaccuracies in the water-flow simulation and the model's inability to modify degradation rates with changing climatic conditions.     

Simulation of Daily Flow Pathways,Tile‐Drain Nitrate Concentrations,and Soil‐Nitrogen Dynamics Using SWAT

Tile drainage significantly alters flow and nutrient pathways and reliable simulation at this scale is needed for effective planning of nutrient reduction strategies. The Soil and Water Assessment Tool (SWAT) has been widely utilized for prediction of flow and nutrient loads, but few applications have evaluated the model's ability to simulate pathway‐specific flow components or nitrate‐nitrogen (NO₃‐N) concentrations in tile‐drained watersheds at the daily time step. The objectives of this study were to develop and calibrate SWAT models for small, tile‐drained watersheds, evaluate model performance for simulation of flow components and NO₃‐N concentration at daily intervals, and evaluate simulated soil‐nitrogen dynamics. Model evaluation revealed that it is possible to meet accepted performance criteria for simulation of monthly total flow, subsurface flow (SSF), and NO₃‐N loads while obtaining daily surface runoff (SURQ), SSF, and NO₃‐N concentrations that are not satisfactory. This limits model utility for simulating best management practices (BMPs) and compliance with water quality standards. Although SWAT simulates the soil N‐cycle and most predicted fluxes were within ranges reported in agronomic studies, improvements to algorithms for soil‐N processes are needed. Variability in N fluxes is extreme and better parameterization and constraint, through use of more detailed agronomic data, would also improve NO₃‐N simulation in SWAT. Editor's note : This paper is part of the featured series on SWAT Applications for Emerging Hydrologic and Water Quality Challenges. See the February 2017 issue for the introduction and background to the series.     

Simulating pesticide leaching and runoff in rice paddies with the RICEWQ-VADOFT model

There is a current need to simulate leaching and runoff of pesticide from rice (Oryza sativa L.) paddies for assessing environmental impacts on a valuable agricultural system. The objective of this study was to develop a model for determining predicted environmental concentration (PEC) in soil, runoff, and ground water through the linkage of two models, rice water quality model (RICEWQ) and vadose zone transport model (VADOFT), to simulate pesticide fate and transport within a rice paddy and underlying soil profile. Model performance was evaluated with a field data set obtained from a 2-yr field experiment in 1997 and 1998 in northern Italy. The predictions of amount of pesticide running off from the paddy field and accumulating in the paddy sediment were in agreement with measured values. Leaching into the vadose zone accounted for approximately 19% of the applied dose, but only a small amount of chemical (<0.1%) was predicted to reach ground water at a 5-m depth due to sorption and transformation in the soil. The permeability of the soil and the water management practices in the paddy field were shown to have a strong influence on pesticide fate. These factors need to be well characterized in the field if model predictions are to be successful. The combined model developed in this work is an effective tool for exposure assessments for soil, surface water, and ground water, in the particular conditions of rice cultivation.     

COMPARISON OF 1-D AND 2-D MODELING OF OVERLAND RUNOFF AND SEDIMENT TRANSPORT1

ABSTRACT: One-dimensional and two-dimensional modeling approaches were compared for their abilities in predicting overland runoff and sediment transport. Both 1-D and 2-D models were developed to test the hypothesis that the 2-D modeling approach could improve the model predictions over the 1-P approach, based on the same mathematical representations of physical processes for runoff and sediment transport. The models developed in this study were applied to overland areas with cross slopes. A hypothetical case and an experimental study reported by Storm (1991) were used. Based on the simulation results from the selected hypothetical case and experimental study, the 2-D model provided better representation of spatial distribution of flow depths and sediment concentrations than the 1-D model. However, no significant differences in predictions of total runoff volume and sediment yield at the outlet area were found between the 1-D and 2-D models.     

Dissolved organic carbon fluxes under bare soil

The flux of dissolved organic carbon (DOC) in soil facilitates transport of nutrients and contaminants in soil. There is little information on DOC fluxes and the relationship between DOC concentration and water flux in agricultural soils. The DOC fluxes and concentrations were measured during 2.5 yr using 30 automatic equilibrium tension plate lysimeters (AETPLs) at 0.4 m and 30 AETPLs at 1.20-m depth in a bare luvisol, previously used as an arable soil. Average annual DOC fluxes of the 30 AETPLS were 4.9 g C m(-2) y(-1) at 0.4 m and 2.4 g C m(-2) y(-1) at 1.2 m depth. The average leachate DOC concentrations were 17 mg C L(-1) (0.4 m) and 9 mg C L(-1) (1.2 m). The DOC concentrations were unrelated to soil moisture content or average temperature and rarely dropped below 9 mg C L(-1) (0.4 m) and 5 mg C L(-1) (1.2 m). The variability in cumulative DOC fluxes among the plates was positively related to leachate volume and not to average DOC concentrations at both depths. This suggests that water fluxes are the main determinants of spatial variability in DOC fluxes. However, the largest DOC concentrations were inversely proportional to the mean water velocity between succeeding sampling periods, suggesting that the maximal net DOC mobilization rate in the topsoil is limited. Elevated DOC concentrations, up to 90 mg C L(-1), were only observed at low water velocities, reducing the risks of DOC-facilitated transport of contaminants to groundwater. The study emphasizes that water flux and velocity are important parameters for DOC fluxes and concentrations.     

A model for phosphorus transformation and runoff loss for surface-applied manures

Agricultural P transport in runoff is an environmental concern. An important source of P runoff is surface-applied, unincorporated manures, but computer models used to assess P transport do not adequately simulate P release and transport from surface manures. We developed a model to address this limitation. The model operates on a daily basis and simulates manure application to the soil surface, letting 60% of manure P infiltrate into soil if manure slurry with less than 15% solids is applied. The model divides manure P into four pools, water-extractable inorganic and organic P, and stable inorganic and organic P. The model simulates manure dry matter decomposition, and manure stable P transformation to water-extractable P. Manure dry matter and P are assimilated into soil to simulate bioturbation. Water-extractable P is leached from manure when it rains, and a portion of leached P can be transferred to surface runoff. Eighty percent of manure P leached into soil by rain remains in the top 2 cm, while 20% leaches deeper. This 2-cm soil layer contributes P to runoff via desorption. We used data from field studies in Texas, Pennsylvania, Georgia, and Arkansas to build and validate the model. Validation results show the model accurately predicted cumulative P loads in runoff, reflecting successful simulation of the dynamics of manure dry matter, manure and soil P pools, and storm-event runoff P concentrations. Predicted runoff P concentrations were significantly related to (r2=0.57) but slightly less than measured concentrations. Our model thus represents an important modification for field or watershed scale models that assess P loss from manured soils.     

Time Series Analysis of Nebraska Daily Rainfall Data to Simulate Atrazine Runoff1

Abstract: Measured atrazine concentrations in Nebraska surface water have been shown to exceed water‐quality standards, posing risks to humans and to the ecosystem. To assess this risk, atrazine runoff was simulated at the field‐scale in Nebraska based on the pesticide component of the AGNPS model. This project’s objective was to determine the frequency that the atrazine concentration at the field outlet exceeded three different atrazine water‐quality criteria. The simulation was conducted for different farm management practices, soil moisture conditions, and five Nebraska topographic regions. If the criteria were exceeded, a risk to the drinking water consumer or freshwater aquatic life was hypothesized to exist. Three pesticide fate and transport processes were simulated with the model. Degradation was simulated using first‐order kinetics. Adsorption/desorption was modeled assuming a linear soil‐water partitioning coefficient. Advection (runoff) was based primarily on the USDA‐NRCS curve number method. Daily rainfall from the National Weather Service was used to compute the soil moisture conditions for the 1985‐2000 growing seasons. After each runoff event, the pesticide runoff concentration was compared with each of the three atrazine water‐quality criteria. The results show that environmental receptors (i.e., freshwater aquatic species) are exposed to unacceptable atrazine runoff concentrations in 20‐50% of the runoff events.     

Coupling field observations, soil modeling, and air dispersion algorithms to estimate 1,3-dichloropropene and chloropicrin flux and exposure

Soil fumigants are volatile compounds applied to agricultural land to control nematode populations, weeds, and crop diseases. Field trials used for measuring fumigant loss from soil to the atmosphere encompass only a small proportion of the near semi-infinite parameter combinations of environmental, agronomic, and meteorological conditions. One approach to supplement field observations uses a soil physics model for fumigant emission predictions. A model is first validated against existing field study observations and then used to extrapolate results to a wider range of edaphic and climatic conditions. This work compares field observations of 1,3-dichloropropene and chloropicrin emissions to predictions from the USDA soil model CHAIN_2D. Comparison between model predictions and field observations for a Florida and California study had values between 0.62 to 0.81 and 0.99 to 1.0 for discrete and cumulative emission flux, respectively. CHAIN_2D emission rates were then coupled to several USEPA air dispersion models (ISCST3, CALPUFF6) to extend emission estimates to near field air concentrations. CALPUFF6 predicted slightly higher 1-h maximum air concentrations than ISCST3 for the same source strength (26.2-36.0% for setbacks between 1 and 250 m from the field edge, respectively). A sensitivity analysis for the CHAIN_2D/ISCST3 coupled numerical system is provided, with several soil and irrigation parameters consistently the most sensitive. Changes in the depth of incorporation, tarp material, and initial soil water content illustrate the predicted impact to emission strength and resulting near-field air concentrations with reductions of cumulative emission loss from 8.1 to 71% and average 1-h maximum air concentration reductions between 6.2 and 41% depending on the mitigation strategy chosen. Additionally, a stochastic framework based on the published SOFEA system that couples variability in experiment, model sensitivity, and site specific attributes is outlined should regional air concentration estimates resulting from fumigant use be sought.     

Pulsed redistribution of a contaminant following forest fire: cesium-137 in runoff

Of the natural processes that concentrate dispersed environmental contaminants, landscape fire stands out as having potential to rapidly concentrate contaminants and accelerate their redistribution. This study used rainfall simulation methods to quantify changes in concentration of a widely dispersed environmental contaminant (global fallout 137Cs) in soils and surface water runoff following a major forest fire at Los Alamos, New Mexico, USA. The 137Cs concentrations at the ground surface increased up to 40 times higher in ash deposits and three times higher for the topmost 50 mm of soil compared with pre-fire soils. Average redistribution rates were about one order of magnitude greater for burned plots, 5.96 KBq ha(-1) mm(-1) rainfall, compared with unburned plots, 0.55 KBq ha(-1) mm(-1) rainfall. The greatest surface water transport of 137Cs, 11.6 KBq ha(-1) mm(-1), occurred at the plot with the greatest amount of ground cover removal (80% bare soil) following fire. Concentration increases of 137Cs occurred during surface water erosion, resulting in enrichment of 137Cs levels in sediments by factors of 1.4 to 2.9 compared with parent soils. The elevated concentrations in runoff declined rapidly with time and cumulative precipitation occurrence and approached pre-fire levels after approximately 240 mm of rainfall. Our results provide evidence of order-of-magnitude concentration increases of a fallout radionuclide as a result of forest fire and rapid transport of radionuclides following fire that may have important implications for a wide range of geophysical, ecosystem, fire management, and risk-based issues.     

Transport and reaction processes affecting the attenuation of landfill gas in cover soils

Methane and trace organic gases produced in landfill waste are partly oxidized in the top 40 cm of landfill cover soils under aerobic conditions. The balance between the oxidation of landfill gases and the ingress of atmospheric oxygen into the soil cover determines the attenuation of emissions of methane, chlorofluorocarbons, and hydrochlorofluorocarbons to the atmosphere. This study was conducted to investigate the effect of oxidation reactions on the overall gas transport regime and to evaluate the contributions of various gas transport processes on methane attenuation in landfill cover soils. For this purpose, a reactive transport model that includes advection and the Dusty Gas Model for simulation of multicomponent gas diffusion was used. The simulations are constrained by data from a series of counter-gradient laboratory experiments. Diffusion typically accounts for over 99% of methane emission to the atmosphere. Oxygen supply into the soil column is driven exclusively by diffusion, whereas advection outward offsets part of the diffusive contribution. In the reaction zone, methane consumption reduces the pressure gradient, further decreasing the significance of advection near the top of the column. Simulations suggest that production of water or accumulation of exopolymeric substances due to microbially mediated methane oxidation can significantly reduce diffusive fluxes. Assuming a constant rate of methane production within a landfill, reduction of the diffusive transport properties, primarily due to exopolymeric substance production, may result in reduced methane attenuation due to limited O(2) -ingress.     

REGIONAL HYDROLOGIC RESPONSE OF LOBLOLLY PINE TO AIR TEMPERATURE AND PRECIPITATION CHANGES1

ABSTRACT: Large deviations in average annual air temperatures and total annual precipitation were observed across the southern United States during the last 50 years, and these fluctuations could become even larger during the next century. We used PnET-IIS, a monthly time-step forest process model that uses soil, vegetation, and climate inputs to assess the influence of changing climate on southern U.S. pine forest water use. After model predictions of historic drainage were validated, the potential influences of climate change on loblolly pine forest water use was assessed across the region using historic (1951 to 1984) monthly precipitation and air temperature which were modified by two general circulation models (GCMs). The GCMs predicted a 3.2°C to 7.2°C increase in average monthly air temperature, a -24 percent to + 31 percent change in monthly precipitation and a -1 percent to + 3 percent change in annual precipitation. As a comparison to the GCMs, a minimum climate change scenario using a constant 2°C increase in monthly air temperature and a 20 percent increase in monthly precipitation was run in conjunction with historic climate data. Predicted changes in forest water drainage were highly dependent on the GCM used. PnET-IIS predicted that along the northern range of loblolly pine, water yield would decrease with increasing leaf area, total evapotranspiration and soil water stress. However, across most of the southern U.S., PnET-IIS predicted decreased leaf area, total evapotranspiration, and soil water stress with an associated increase in water yield. Depending on the GCM and geographic location, predicted leaf area decreased to a point which would no longer sustain loblolly pine forests, and thus indicated a decrease in the southern most range of the species within the region. These results should be evaluated in relation to other changing environmental factors (i.e., CO₂ and O₃) which are not present in the current model.     

A polymer-ceramic composite membrane for recovering volatile organic compounds from wastewaters by pervaporation

A composite membrane was constructed on a porous ceramic support from a block copolymer of styrene and butadiene (SBS). It was tested in a laboratory pervaporation apparatus for recovering volatile organic compounds (VOCs) such as 1,1,1-trichloroethane (TCA) and trichloroethylene (TCE) from dilute aqueous solutions. This polymer-ceramic composite membrane yielded significantly higher VOC selectivity than an SBS membrane without the ceramic support, for comparable fluxes. At VOC concentrations near 100 ppm, fluxes and selectivities of VOCs were essentially independent of the number of VOCs in solution. The liquid-side boundary layer resistance dominated mass transport. The experimental data fitted the resistance-in-series model and yielded reliable membrane permeability values. This method using this high-performing membrane offers potentially cleaner and cost-effective means of recovering VOCs from contaminated streams.     

Modeling the fate of benzo[a]pyrene in the wastewater-irrigated areas of Tianjin with a fugacity model

A Level III fugacity model was applied to characterize the transfer processes and environmental fate of benzo[a]pyrene in wastewater-irrigated areas of Tianjin, China. The physical-chemical properties and transfer parameters of benzo[a]pyrene were used in the model and the concentration distribution of benzo[a]pyrene in sediment, soil, water, air, fish, and crop compartments, as well as transfer fluxes across the compartments, were then derived under steady-state assumptions. The calculated results were compared with monitoring data for air, soil, water, and sediment collected from the literature. The results indicate that there was generally good agreement and the differences were within an order of magnitude for air, soil, and sediment. The concentration of benzo[a]pyrene in the ambient air in the area was very low with a majority present sorbed to aerosol. In the water compartment, approximately 70% of benzo[a]pyrene dissolved in water phase. Relatively high concentrations of the compound were found in the soil and sediment, with the soil serving as the dominant sink in the area. Benzo[a]pyrene, with a slow metabolic rate, was found to accumulate in fish in the area.     

DRAINMOD-FOREST: Integrated Modeling of Hydrology, Soil Carbon and Nitrogen Dynamics, and Plant Growth for Drained Forests

We present a hybrid and stand-level forest ecosystem model, DRAINMOD-FOREST, for simulating the hydrology, carbon (C) and nitrogen (N) dynamics, and tree growth for drained forest lands under common silvicultural practices. The model was developed by linking DRAINMOD, the hydrological model, and DRAINMOD-N II, the soil C and N dynamics model, to a forest growth model, which was adapted mainly from the 3-PG model. The forest growth model estimates net primary production, C allocation, and litterfall using physiology-based methods regulated by air temperature, water deficit, stand age, and soil N conditions. The performance of the newly developed DRAINMOD-FOREST model was evaluated using a long-term (21-yr) data set collected from an artificially drained loblolly pine ( L.) plantation in eastern North Carolina, USA. Results indicated that the DRAINMOD-FOREST accurately predicted annual, monthly, and daily drainage, as indicated by Nash-Sutcliffe coefficients of 0.93, 0.87, and 0.75, respectively. The model also predicted annual net primary productivity and dynamics of leaf area index reasonably well. Predicted temporal changes in the organic matter pool on the forest floor and in forest soil were reasonable compared to published literature. Both predicted annual and monthly nitrate export were in good agreement with field measurements, as indicated by Nash-Sutcliffe coefficients above 0.89 and 0.79 for annual and monthly predictions, respectively. This application of DRAINMOD-FOREST demonstrated its capability for predicting hydrology and C and N dynamics in drained forests under limited silvicultural practices.     

流域污染物通量测算方法研究

流域水系内污染物通量不仅能够用于评价各类污染源的水污染物入河负荷,也是对流域污染特征,水污染物在河流水体中复杂迁移、转化过程的最直观反应。准确测算流域水系内污染物跨界通量及其时空分布是进行流域水环境风险预警和风险管理的重要前提之一。针对目前多种污染物通量测算方法在进行污染物年通量估算时,结果不确定性大这一突出问题,以流域水质监测站年内逐日流量、悬浮颗粒物监测数据作为悬浮颗粒物年通量参考值,基于以月、半月、周为周期的监测策略,将逐日流量、悬浮颗粒物监测数据重新筛选抽样构造,由此,系统分析了不同流域集水面积、污染通量监测频次和目前常用通量估算方法对污染物年通量估算不确定性的影响。所得方法和结论可为进一步制定流域污染物通量的测算规范提供方法指引和技术支持。     

Phosphorus transport pathways to streams in tile-drained agricultural watersheds

Agriculture is a major nonpoint source of phosphorus (P) in the Midwest, but how surface runoff and tile drainage interact to affect temporal concentrations and fluxes of both dissolved and particulate P remains unclear. Our objective was to determine the dominant form of P in streams (dissolved or particulate) and identify the mode of transport of this P from fields to streams in tile-drained agricultural watersheds. We measured dissolved reactive P (DRP) and total P (TP) concentrations and loads in stream and tile water in the upper reaches of three watersheds in east-central Illinois (Embarras River, Lake Fork of the Kaskaskia River, and Big Ditch of the Sangamon River). For all 16 water year by watershed combinations examined, annual flow-weighted mean TP concentrations were >0.1 mg L(-1), and seven water year by watershed combinations exceeded 0.2 mg L(-1). Concentrations of DRP and particulate P (PP) increased with stream discharge; however, particulate P was the dominant form during overland runoff events, which greatly affected annual TP loads. Concentrations of DRP and PP in tiles increased with discharge, indicating tiles were a source of P to streams. Across watersheds, the greatest DRP concentrations (as high as 1.25 mg L(-1)) were associated with a precipitation event that followed widespread application of P fertilizer on frozen soils. Although eliminating this practice would reduce the potential for overland runoff of P, soil erosion and tile drainage would continue to be important transport pathways of P to streams in east-central Illinois.