Influence of irrigation methods and an adjuvant on the persistence of carbaryl on pakchoi

Influence of irrigation methods and use of an adjuvant on the persistence of the carbaryl (1-naphthyl N-methylcarbamate) on pakchoi [Brassica rapa L. subsp. chinensis (Rupr.) Olsson] was studied using a commercial enzyme linked immunosorbent assay kit. After applying carbaryl at a.i. 10.6 g L(-1) with or without an adjuvant (Latron B-1956) to leaves, plants were provided water daily by either overhead or basal application. Pesticide residue on leaf tissues was examined immediately after pesticide application and on 2, 4, 6, and 8 d after pesticide application. Use of the adjuvant did not affect the initial deposit of the pesticide, however pesticide persistence was improved with the adjuvant regardless of irrigation. Overhead irrigation contributed to rapid loss of the pesticide by washing carbaryl from the leaf surface. The longest half-life of carbaryl (6.5 d) was detected on plants receiving basal irrigation plus the adjuvant while the shortest half-life (2 d) was observed when plants were treated with overhead irrigation and no adjuvant.     

A model for linking the effects of parathion in soil to its degradation and bioavailability kinetics

Parathion is an insecticide of a group of highly toxic organophosphorus compounds. To investigate the dissipation and toxicological impact of parathion [O,O-diethyl O-(4-nitrophenyl) phosphorothioate] and its highly toxic metabolite, paraoxon, soil laboratory experiments were conducted in columns during a 19-d experiment under variably saturated conditions. Water and pesticide transport, sorption, and biodegradation of parathion were measured in three soil pools (soluble phase, weakly and strongly sorbed phases) using C-labeled pesticide. The effects of parathion and its metabolite on the mobility of soil nematodes were observed and then modeled with an effective variable, which combined pesticide concentration and time of application. Results showed that parathion was highly sorbed and slowly degraded to a mixture of metabolites. The parent compound and its metabolites remained located in the top 0.06-m soil layer. A kinetic model describing the sorption, biodegradation, and allocation into different soil pools of parathion and its metabolites was coupled with heat and water transport equations to predict the fate of parathion in soil. Simulated results were in agreement with experimental data, showing that the products remained in the upper soil layers even in the case of long-term (11-mo) simulation. The strongly sorbed fraction may be regarded as a pesticide reservoir that regularly provides pesticide to the weakly sorbed phase, and then, liquid phase, respectively. From both modeling and observations, no major toxicological damage of parathion and paraoxon to soil nematodes was found, although some effects on nematodes were possible, but at the soil surface only (0.01- and 0.02-m depth).     

Impact of data quality and model complexity on prediction of pesticide leaching

Accurate input data for leaching models are expensive and difficult to obtain which may lead to the use of "general" non-site-specific input data. This study investigated the effect of using different quality data on model outputs. Three models of varying complexity, GLEAMS, LEACHM, and HYDRUS-2D, were used to simulate pesticide leaching at a field trial near Hamilton, New Zealand, on an allophanic silt loam using input data of varying quality. Each model was run for four different pesticides (hexazinone, procymidone, picloram and triclopyr); three different sets of pesticide sorption and degradation parameters (i.e., site optimized, laboratory derived, and sourced from the USDA Pesticide Properties Database); and three different sets of soil physical data of varying quality (i.e., site specific, regional database, and particle size distribution data). We found that the selection of site-optimized pesticide sorption (Koc) and degradation parameters (half-life), compared to the use of more general database derived values, had significantly more impact than the quality of the soil input data used, but interestingly also more impact than the choice of the models. Models run with pesticide sorption and degradation parameters derived from observed solute concentrations data provided simulation outputs with goodness-of-fit values closest to optimum, followed by laboratory-derived parameters, with the USDA parameters providing the least accurate simulations. In general, when using pesticide sorption and degradation parameters optimized from site solute concentrations, the more complex models (LEACHM and HYDRUS-2D) were more accurate. However, when using USDA database derived parameters, all models performed about equally.     

Comparison of Two Parametric Methods to Estimate Pesticide Mass Loads in California’s Central Valley1

Saleh, Dina K., David L. Lorenz, and Joseph L. Domagalski, 2010. Comparison of Two Parametric Methods to Estimate Pesticide Mass Loads in California’s Central Valley. Journal of the American Water Resources Association (JAWRA) 00(0):1‐11. DOI: 10.1111/j.1752‐1688.2010.00506.x Abstract: Mass loadings were calculated for four pesticides in two watersheds with different land uses in the Central Valley, California, by using two parametric models: (1) the Seasonal Wave model (SeaWave), in which a pulse signal is used to describe the annual cycle of pesticide occurrence in a stream, and (2) the Sine Wave model, in which first‐order Fourier series sine and cosine terms are used to simulate seasonal mass loading patterns. The models were applied to data collected during water years 1997 through 2005. The pesticides modeled were carbaryl, diazinon, metolachlor, and molinate. Results from the two models show that the ability to capture seasonal variations in pesticide concentrations was affected by pesticide use patterns and the methods by which pesticides are transported to streams. Estimated seasonal loads compared well with results from previous studies for both models. Loads estimated by the two models did not differ significantly from each other, with the exceptions of carbaryl and molinate during the precipitation season, where loads were affected by application patterns and rainfall. However, in watersheds with variable and intermittent pesticide applications, the SeaWave model is more suitable for use on the basis of its robust capability of describing seasonal variation of pesticide concentrations.     

Measuring sorption of hydrophilic organic compounds in soils by an unsaturated transient flow method

Determination of sorption of hydrophilic, weakly sorbing organic compounds in soil by conventional batch methods using a slurried suspension is often prone to considerable errors because small changes in the solution concentration on equilibration must be accurately determined. This difficulty is exacerbated for compounds susceptible to degradation, which also decreases the solution concentration. The objective of this study was to determine sorption of hydrophilic pesticides by applying an unsaturated transient flow method, which enables determination of sorption at sufficiently small solution to soil ratios. The method makes use of piston-like displacement of the antecedent solution in equilibrium with sorbed phase when pesticide-free water is infiltrated into a soil column spiked with a pesticide. Pesticide sorption and the solution concentration are inferred from a plot of total pesticide content per unit mass of soil vs. water content in a region where the antecedent solution is accumulated. Thus, extraction of solution from relative dry soil is unnecessary. We tested this method for two hydrophilic pesticides, monocrotophos [dimethyl (E)-1-methyl-2-(methyl-carbamoyl) vinyl phosphate] and dichlorvos (2,2-dichlorovinyl dimethyl phosphate). The sorption coefficient, K(d), obtained for monocrotophos was slightly lower than that by batch method (K(d) = 0.10 vs. 0.19 L kg(-1)), whereas for dichlorvos, a compound highly susceptible to degradation, the unsaturated flow method yielded a much smaller K(d) (0.19 vs. 3.22 L kg(-1)). The K(d) values for both compounds were consistent with the observed retardation in the pesticide displacement in the columns. The proposed method is more representative of field conditions and particularly suitable for weakly sorbing organic compounds in soils.     

Molecular weight of dissolved organic matter-napropamide complex transported through soil columns

Soil-derived dissolved organic matter (DOM) has been shown to form stable complexes with the herbicide napropamide [2-(alpha-naphthoxy-N,N-diethylpropionamide] capable of enhancing the transport of napropamide through soil columns. Two soils, one containing sewage sludge-derived organic matter (SS) and the other having only natural organic matter (NoSS) were treated with napropamide and allowed to dry to promote complex formation. Soil columns were prepared by packing a 10-cm layer of untreated, dry, sieved soil followed by an overlying 5-cm layer of napropamide-treated soil. Columns were irrigated and the effluent collected and placed in dialysis chambers. After equilibration napropamide concentrations were determined on both sides of the membrane and complex and quantified based on the amount of napropamide unable to cross the membrane. it was found that for the SS soil 7% and for the NoSS 2.4% of the applied napropamide underwent facilitated transport. In addition, most of the complex transported through the columns had a molecular weight between 500 and 1000 Daltons (Da). The solutions from the SS soil were also found to have formed at least two distinct complexes that were resolved after passing through the untreated soil layer. The results obtained were in agreement with other published results and the techniques used offer a way to separate and concentrate DOM complexes from column effluents for further characterization.     

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.     

Numerical modeling of diazinon transport through inter-row vegetative filter strips

A numerical simulation model of pesticide runoff through vegetative filer strips (PRVFS) was developed as a tool for investigating the effects of pesticide transport mechanisms on VFS design in dormant-sprayed orchard. The PRVFS model was developed applying existing theories such as kinematic wave theory and mixing zone theory for pesticide transport in the bare soil area. For VFS area, the model performs flow routing by simple mass accounting in sequential segments and the pesticide mass balance by considering pesticide washoff and adsorption processes on the leaf, vegetative litter, root zone and soil. Model sensitivity analysis indicated that pesticide transfer from surface soil to overland flow and pesticide washoff from the VFS were important mechanisms affecting diazinon transport. The VFS cover ratio and rainfall intensity can be important design parameters for controlling diazinon runoff using inter-row VFS in orchard. The PRVFS model was validated using micro-ecosystem simulation of diazinon transport for 0, 50 and 100% VFS cover conditions. The PRVFS model is shown to be a beneficial tool for evaluating and analyzing possible best management practices for controlling offsite runoff of dormant-sprayed diazinon in orchards during the rainy season.     

Pesticide fate and transport throughout unsaturated zones in five agricultural settings, USA

Pesticide transport through the unsaturated zone is a function of chemical and soil characteristics, application, and water recharge rate. The fate and transport of 82 pesticides and degradates were investigated at five different agricultural sites. Atrazine and metolachlor, as well as several of the degradates of atrazine, metolachlor, acetochlor, and alachlor, were frequently detected in soil water during the 2004 growing season, and degradates were generally more abundant than parent compounds. Metolachlor and atrazine were applied at a Nebraska site the same year as sampling, and focused recharge coupled with the short time since application resulted in their movement in the unsaturated zone 9 m below the surface. At other sites where the herbicides were applied 1 to 2 yr before sampling, only degradates were found in soil water. Transformations of herbicides were evident with depth and during the 4-mo sampling time and reflected the faster degradation of metolachlor oxanilic acid and persistence of metolachor ethanesulfonic acid. The fraction of metolachlor ethanesulfonic acid relative to metolachlor and metolachlor oxanilic acid increased from 0.3 to >0.9 at a site in Maryland where the unsaturated zone was 5 m deep and from 0.3 to 0.5 at the shallowest depth. The flux of pesticide degradates from the deepest sites to the shallow ground water was greatest (3.0-4.9 micromol m(-2) yr(-1)) where upland recharge or focused flow moved the most water through the unsaturated zone. Flux estimates based on estimated recharge rates and measured concentrations were in agreement with fluxes estimated using an unsaturated-zone computer model (LEACHM).     

Sorption and transport of 17beta-estradiol and testosterone in undisturbed soil columns

Land-applied domestic animal wastes contain appreciable amounts of 17beta-estradiol (henceforth, estradiol) and testosterone. These sex hormones may be transported through soil to groundwater and streams, where they may adversely affect the environment. Previous column transport studies with these hormones used repacked soil and did not consider preferential flow. We, therefore, determined the sorption and transport characteristics of estradiol and testosterone in undisturbed soil columns (15-cm i.d. by 32-cm height). In the sorption experiment, isotherms for estradiol and testosterone were nonlinear with Freundlich exponents (n) less than one. Sorption of both hormones decreased with soil depth, and estradiol sorbed more strongly than testosterone. Average estradiol Freundlich sorption coefficients (K(f)) values were 36.9 microg(1 - n) mL(n) g(-1) for the 0- to 10-cm soil depth and 25.7 microg(1 - n) mL(n) g(-1) for the 20- to 30-cm soil depth. Average testosterone K(f) values were 26.7 microg(1 - n) mL(n) g(-1) for the 0- to 10-cm soil depth and 14.0 microg(1 - n) mL(n) g(-1) for the 20- to 30-cm soil depth. In the transport experiment, 27% of the estradiol and 42% of the testosterone leached through the soil columns. Approximately 50% of the remaining soil-bound hormones were sorbed in the top 10 cm of soil. In almost all instances, breakthrough concentrations of estradiol, testosterone, and a chloride tracer peaked simultaneously. Simultaneous breakthrough and HYDRUS-1D transport parameters indicated both chemical and physical nonequilibrium processes affected hormone transport. This suggests hormones placed on soil surfaces may contaminate groundwater under conditions of preferential flow.     

Assessment of herbicide leaching risk in two tropical soils of Reunion Island (France)

Application of organic chemicals to a newly irrigated sugarcane (Saccharum officinarum L.) area located in the semiarid western part of Reunion Island has prompted local regulatory agencies to determine their potential to contaminate ground water resources. For that purpose, simple indices known as the ground water ubiquity score (Gustafson index, GUS), the retardation factor (RF), the attenuation factor (AF), and the log-transformed attenuation factor (AFT) were employed to assess the potential leaching of five herbicides in two soil types. The herbicides were alachlor [2-chloro-2',6'-diethyl-N-(methoxy-methy) acetanilide], atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-1,3,5-triazine], diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea], 2,4-D [(2,4-dichlorophenoxy) acetic-acid], and triclopyr [((3,5,6-trichloro-2-pyridyl)oxy) acetic-acid]. The soil types were Vertic (BV) and Andepts (BA) Inceptisols, which are present throughout the Saint-Gilles study area on Reunion Island. To calculate the indices, herbicide sorption (K(oc)) and dissipation (half-life, DT50) properties were determined from controlled batch experiments. Water fluxes below the root zone were estimated by a capacity-based model driven by a rainfall frequency analysis performed on a 13-yr data series. The results show a lower risk of herbicide leaching than in temperate regions due to the tropical conditions of the study area. Higher temperatures and the presence of highly adsorbent soils may explain smaller DT50 and higher K(oc) values than those reported in literature concerning temperate environments. Based on the RF values, only 2,4-D and triclopyr appear mobile in the BV soil, with all the other herbicides being classified from moderately to very immobile in both soils. The AFT values indicate that the potential leaching of the five herbicides can be considered as unlikely, except during the cyclonic period (about 40 d/yr) when there is a 2.5% probability of recharge rates equal to or higher than 50 mm/d. In that case, atrazine in both soils, 2,4-D and triclopyr in the BV soil, and diuron and alachlor in the BA soil present a high risk of potential contamination of ground water resources.     

Predicting and measuring environmental concentration of pesticides in air after soil application

Pesticides can volatilize into the atmosphere, which affects the air quality. The ability to predict pesticide volatilization is an essential tool for human risk and environmental assessment. Even though there are several mathematical models to assess and predict the fate of pesticides in different compartments of the environment, there is no reliable model to predict volatilization. The objectives of this study were to evaluate pesticide volatilization under agricultural conditions using malathion [ O,O-dimethyl-S-(1,2-dicarbethoxyethyl)-dithiophosphate], ethoprophos (O-ethyl S,S-dipropylphosphorodithioate), and procymidone [N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide] as test compounds and to evaluate the ability of the Pesticide Leaching Model (PELMO) to calculate the predicted environmental concentrations of pesticides in air under field conditions. The volatilization rate of procymidone, malathion, and ethoprophos was determined in a field study during two different periods (December 1998 and September 1999) using the Theoretical Profile Shape (TPS) method. The experiments were performed on bare silty soil in the Bologna province, Italy. Residues in the air were continuously monitored for 2 to 3 wk after the pesticide applications. The amount of pesticide volatilized was 16, 5, and 11% in December 1998 and 41, 23, and 19% in September 1999 for procymidone, malathion, and ethoprophos, respectively. In both these experiments, the PELMO simulations of the concentration of ethoprophos and procymidone were in good agreement with the measured data (factor +/- 1.1 on average). The volatilization of malathion was underestimated by a factor of 30 on average. These results suggest that volatilization described by PELMO may be reliable for volatile substances, but PELMO may underpredict volatilization for less-volatile substances.     

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.     

MODEL FOR PREDICTING TRANSPORT OF PESTICIDES AND THEIR METABOLITES IN THE UNSATURATED ZONE1

ABSTRACT: A finite element model based on Galerkin's upstream weighted residual technique was developed to predict the simultaneous convective-dispersion transport and transformations of pesticides and their metabolites in the unsaturated zone. Transformations of the parent compound and its metabolites were assumed to be first-order reactions for oxidation and hydrolysis, while adsorption of the pesticide species (parent compound and metabolites) to the soil components was assumed to be represented by a linear equilibrium (Freundlich type) isotherm. Volatilization and plant root uptake of pesticides in the solution phase were neglected in the analysis. The proposed model was used to simulate the transport and transformation of aldicarb and its metabolites, aldicarb sulfoxide and aldicarb sulfone, in the soil profile. Several examples are used to demonstrate the accuracy, validity, and applicability of the proposed model. Simulated results indicate that the proposed model can potentially be used to estimate the mass flux of water, and pesticide and pesticide metabolite concentrations in the subsurface environment. However, further verification of the model against actual field data is needed to fully demonstrate the model's potential.     

Modeling macropore flow effects on pesticide leaching: inverse parameter estimation using microlysimeters

Macropore flow is a key factor determining pesticide fate, but models accounting for this process need parameters that cannot be easily measured. This study was conducted to investigate the use of inverse techniques to estimate parameters controlling macropore flow and pesticide fate in the dual-permeability model MACRO. Undisturbed columns were sampled at three landscape positions (hilltop, slope, hollow) with contrasting texture and organic carbon content. Transient leaching experiments were performed for an anionic tracer and the herbicide MCPA (4-chloro-2methylphenoxy acetic acid) during a 4-mo period, first under natural rainfall, and then under controlled irrigation in the laboratory. The tracer breakthrough for the liner-textured soil from the hilltop showed strong evidence of macropore flow, resulting in a rapid leaching of MCPA, while leaching was minimal from the organic-rich hollow soil, since macropore flow was weaker and adsorption stronger. The MACRO model was linked to the inverse modeling program SUFI (Sequential Uncertainty Fitting) to enable calibration of nine key model parameters. Based on calculated model efficiencies, MACRO-SUFI gave generally good predictions of water movement and tracer and pesticide transport, although some errors were attributed to difficulties in simulating the effects of soil moisture on degradation and the timing of water outflows. Even after calibration, significant uncertainties remained for some key parameters controlling macropore flow. Nevertheless, the parameter estimates were significantly different between landscape positions and could also be related to basic soil properties. The posterior uncertainty ranges could probably be reduced with a more exhaustive sampling of the parameter space and improved experimental designs.     

SIMULATION OF HERBICIDE CONCENTRATIONS IN STORMFLOW FROM FORESTED WATERSHEDS1

The breakpoint rainfall hydrology and pesticide options of the field scale model CREAMS (Chemicals, Runoff, and Erosion from Agricultural Management Systems) were used to predict average concentrations of hexazinone [3 cyclohexyl-6-(dimethyl-amino)-1-methyl-1,3,5-triazine-2,4(1H,3H)-dione] in stormflow from four forested watersheds in the upper Piedmont region of Georgia. Predicted concentrations were compared with measured concentrations recorded over a 13-month period. CREAMS accurately predicted hexazinone concetrations in the initial stormflow events which also contained the highest concentrations. The model underestimated the hexazinone concentrations in stormflow two months and greater following pesticide application. In a companion study, the daily rainfall option of the CREAMS model was used to evaluate the reltive risk associated with the maximum expected concentration of hexazinone, bromacil (5-bromo-3 sec-butyl-6 methyuracil), picloram (4-amino-3,5,6 trichloropicolinic acid), dicamba (3,6-dichloro-0-anisic acid), and triclopyr {[(3,5,6-trichloro-2-pyridinyl)oxy] acetic acid} in stormflow from small forested watersheds. The model predicted the following order of potential residue appearance in stormflow: bromacil>triclopyr>hexazinone>picloram>dicamba. Subsurface movement of residues via interflow and deep leaching losses are not simulated by the version of CREAMS used in these studies.     

Review of Pesticide Retention Processes Occurring in Buffer Strips Receiving Agricultural Runoff1

Arora, Kapil, Steven K. Mickelson, Matthew J. Helmers, and James L. Baker, 2010. Review of Pesticide Retention Processes Occurring in Buffer Strips Receiving Agricultural Runoff. Journal of the American Water Resources Association (JAWRA) 46(3):618-647. DOI: 10.1111/j.1752-1688.2010.00438.x Abstract: Review of the published results shows that the retention of the two pesticide carrier phases (runoff volume and sediment mass) influences pesticide mass transport through buffer strips. Data averaged across different studies showed that the buffer strips retained 45% of runoff volume (ranging between 0 and 100%) and 76% of sediment mass (ranging between 2 and 100%). Sorption (soil sorption coefficient, K_oc) is one key pesticide property affecting its transport with the two carrier phases through buffer strips. Data from different studies for pesticide mass retention for weakly (K_oc < 100), moderately (100 < K_oc < 1,000), and strongly sorbed pesticides (K_oc > 1,000) averaged (with ranges) 61 (0-100), 63 (0-100), and 76 (53-100) %, respectively. Because there are more data for runoff volume and sediment mass retention, the average retentions of both carrier phases were used to calculate that the buffer strips would retain 45% of weakly to moderately sorbed and 70% of strongly sorbed pesticides on an average basis. As pesticide mass retention presented is only an average across several studies with different experimental setups, the application of these results to actual field conditions should be carefully examined.