Atmospheric deposition of pesticides to an agricultural watershed of the Chesapeake Bay

The Choptank River watershed, located on the Delmarva Peninsula of the Chesapeake Bay, is dominated by agricultural land use, which makes it vulnerable to runoff and atmospheric deposition of pesticides. Agricultural and wildlife areas are in close proximity and off-site losses of pesticides may contribute to toxic effects on sensitive species of plants and animals. High-volume air samples (n = 31) and event-based rain samples (n = 71) were collected from a single location in the watershed representing regional background conditions. Surface water samples were collected from eight stations in the tidal portion of the river on five occasions during 2000. Chlorothalonil, metolachlor, atrazine, simazine, endosulfan, and chlorpyrifos were frequently detected in the air and rain, with maximal concentrations during the period when local or regional crops were planted. The wet deposition load to the watershed was estimated at 150 +/- 16, 61 +/- 7, and 51 +/- 6 kg yr(-1) for chlorothalonil, metolachlor, and atrazine, respectively. The high wet deposition load compared with the estimated annual usage for chlorothalonil (13%) and endosulfan (14-90%) suggests an atmospheric source from outside the watershed. Net air-water gas exchange fluxes for metolachlor varied from -44 +/- 19 to 9.3 +/- 4.1 ng m(-2) d(-1) with negative values indicating net deposition. Wet deposition accounted for 3 to 20% of the total metolachlor mass in the Choptank River and was a more important source to the river than gas exchange. Estimates of herbicide flux presented here are probably a low estimate and actual rates may be significantly higher in areas closer to pesticide application.     

Occurrence and fate of pesticides in four contrasting agricultural settings in the United States

Occurrence and fate of 45 pesticides and 40 pesticide degradates were investigated in four contrasting agricultural settings--in Maryland, Nebraska, California, and Washington. Primary crops included corn at all sites, soybeans in Maryland, orchards in California and Washington, and vineyards in Washington. Pesticides and pesticide degradates detected in water samples from all four areas were predominantly from two classes of herbicides--triazines and chloroacetanilides; insecticides and fungicides were not present in the shallow ground water. In most samples, pesticide degradates greatly exceeded the concentrations of parent pesticide. In samples from Nebraska, the parent pesticide atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine] was about the same concentration as the degradate, but in samples from Maryland and California atrazine concentrations were substantially smaller than its degradate. Simazine [6-chloro-N,N'-diethyl-1,3,5-triazine-2,4-diamine], the second most detected triazine, was detected in ground water from Maryland, California, and Washington. Metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] rarely was detected without its degradates, and when they were detected in the same sample metolachlor always had smaller concentrations. The Root-Zone Water-Quality Model was used to examine the occurrence and fate of metolachlor at the Maryland site. Simulations accurately predicted which metolachlor degradate would be predominant in the unsaturated zone. In analyses of relations among redox indicators and pesticide variance, apparent age, concentrations of dissolved oxygen, and excess nitrogen gas (from denitrification) were important indicators of the presence and concentration of pesticides in these ground water systems.     

Pesticide and Transformation Product Detections and Age‐Dating Relations from Till and Sand Deposits1

Abstract:  Pesticide and transformation product concentrations and frequencies in ground water from areas of similar crop and pesticide applications may vary substantially with differing lithologies. Pesticide analysis data for atrazine, metolachlor, alachlor, acetochlor, and cyanazine and their pesticide transformation products were collected at 69 monitoring wells in Illinois and northern Indiana to document occurrence of pesticides and their transformation products in two agricultural areas of differing lithologies, till, and sand. The till is primarily tile drained and has preferential fractured flow, whereas the sand primarily has surface water drainage and primary porosity flow. Transformation products represent most of the agricultural pesticides in ground water regardless of aquifer material – till or sand. Transformation products were detected more frequently than parent pesticides in both the till and sand, with metolachlor ethane sulfonic acid being most frequently detected. Estimated ground‐water recharge dates for the sand were based on chlorofluorocarbon analyses. These age‐dating data indicate that ground water recharged prior to 1990 is more likely to have a detection of a pesticide or pesticide transformation product. Detections were twice as frequent in ground water recharged prior to 1990 (82%) than in ground water recharged on or after 1990 (33%). The highest concentrations of atrazine, alachlor, metolachlor, and their transformation products, also were detected in samples from ground water recharged prior to 1990. These age/pesticide detection relations are opposite of what would normally be expected, and may be the result of preferential flow and/or ground‐water mixing between aquifers and aquitards as evident by the detection of acetochlor transformation products in samples with estimated ground‐water ages predating initial pesticide application.     

Fate and toxicity of endosulfan in Namoi River water and bottom sediment

Endosulfan (6,7,8,9,10,10,-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide) sorption (standardized to 1% total organic carbon and dry weight) was significantly (P < 0.05) more concentrated on the large (>63 microm) particle fraction compared with smaller size fractions (<5 microm and 5-24 microm) of bottom sediments from the Namoi River, Australia. Following completion of the particle size fractionation (6 to 12 wk) and a sediment toxicity assessment (2 wk), the sediments showed large decreases in concentrations of alpha-endosulfan that coincided with an increase in endosulfan sulfate concentrations and minimal changes in beta-endosulfan concentrations. In the Namoi River, similar patterns were observed in the composition of total endosulfan in monthly measurements of bottom sediments and in passive samplers placed in the water column following runoff from cotton (Gossypium hirsutum L.) fields. The toxicity of endosulfan sulfate in river water indicated by the nymphs of the epibenthic mayfly Jappa kutera, was more persistent than the alpha- and beta-endosulfan parent isomers due to its longer half-life. This suggests that endosulfan sulfate would contribute most to previously observed changes in population densities of aquatic biota. Measured concentrations of total endosulfan in river water of up to 4 microg L(-1) following storm runoff, exceed the range of the 96-h median lethal concentration (LC50) values in river water for both alpha-endosulfan (LC50 = 0.7 microg L(-1); 95% confidence interval [CI] = 0.5 to 1.1) and endosulfan sulfate (LC50 = 1.2 microg L(-1); 95% CI = 0.4 to 3.3). In contrast, the 10-d LC50 value for total endosulfan in the sediment toxicity test (LC50 = 162 microg kg(-1); 95% CI = 120 to 218 microg kg(-1)) was more than threefold higher than the highest measured concentration of total endosulfan in field samples of bottom sediment (48 microg kg(-1)). This suggests that pulse exposures of endosulfan in the water column following storm runoff may be more acutely toxic to riverine biota than in contaminated bottom sediment.     

Pesticide removal from container nursery runoff in constructed wetland cells

The increased use of pesticides by container nurseries demands that practices for removal of these potential contaminants from runoff water be examined. Constructed wetlands may be designed to clean runoff water from agricultural production sites, including container nurseries. This study evaluated 14 constructed wetlands cells (1.2 by 4.9 m or 2.4 by 4.9 m, and 30 or 45 cm deep) that collected pesticide runoff from a 465-m2 gravel bed containerized nursery in Baxter, TN. One-half of the cells were vegetated with bulrush, Scirpus validus. The cells were loaded at three rates or flows of 0.240, 0.120, and 0.060 m3 d(-1). Herbicides-simazine (Princep) [2-chloro-4,6-bis(ethylamino)-s-triazine] and metolachlor (Pennant) [2-chloro-N-(2-ethyl-6-methylphenyl)-N-2-methoxy-1-methylethyl-acetamide] -were applied to the gravel portion of the container nursery at rates of 4.78 and 239 kg ha(-1), respectively, 9 July 1998, and at rates of 2.39 and 1.19 kg ha(-1), respectively, 17 May 1999. Pesticides entering the wetland and wetland cell water samples were analyzed daily to determine pesticide removal. At the slower flow rate, which corresponds to lower mass loading and greater hydraulic retention times (HRTs), a greater percentage of pesticides was removed. During the 2-yr period, cells with plants removed 82.4% metolachlor and 77.1% simazine compared with cells without plants, which removed 63.2% metolachlor and 64.3% simazine. At the lowest flow rate and mass loading, wetland cells removed 90.2% metolachlor and 83% simazine. Gravel subsurface flow constructed wetlands removed most of the pesticides in runoff water with the greatest removal occurring at lower flow rates in vegetated cells.     

The impact of agricultural runoff on the quality of two streams in vegetable farm areas in Ghana

A study of two small streams at Akumadan and Tono, Ghana, was undertaken during the rain and dry season periods between February 2005 and January 2006 to investigate the impact of vegetable field runoff on their quality. In each stream we compared the concentration of current-use pesticides in one site immediately upstream of a vegetable field with a second site immediately downstream. Only trace concentrations of endosulfan and chlorpyrifos were detected at both sites in both streams in the dry season. In the wet season, rain-induced runoff transported pesticides into downstream stretches of the streams. Average peak levels in the streams themselves were 0.07 microg L(-1) endosulfan, 0.02 microg L(-1) chlorpyrifos (the Akumadan stream); 0.04 microg L(-1) endosulfan, 0.02 microg L(-1) chlorpyrifos (the Tono stream). Respective average pesticide levels associated with streambed sediment were 1.34 and 0.32 microg kg(-1) (the Akumadan stream), and 0.92 and 0.84 microg kg(-1) (the Tono stream). Further investigations are needed to establish the potential endosulfan and chlorpyrifos effects on aquatic invertebrate and fish in these streams. Meanwhile measures should be undertaken to reduce the input of these chemicals via runoff.     

Simulated fate and transport of metolachlor in the unsaturated zone, Maryland, USA

An unsaturated-zone transport model was used to examine the transport and fate of metolachlor applied to an agricultural site in Maryland, USA. The study site was instrumented to collect data on soil-water content, soil-water potential, ground water levels, major ions, pesticides, and nutrients from the unsaturated zone during 2002-2004. The data set was enhanced with site-specific information describing weather, soils, and agricultural practices. The Root Zone Water Quality Model was used to simulate physical, chemical, and biological processes occurring in the unsaturated zone. Model calibration to bromide tracer concentrations indicated flow occurred through the soil matrix. Simulated recharge rates were within the measured range of values. The pesticide transport model was calibrated to the intensive data collection period (2002-2004), and the calibrated model was then used to simulate the period 1984 through 2004 to examine the impact of sustained agricultural management practices on the concentrations of metolachlor and its degradates at the study site. Simulation results indicated that metolachlor degrades rapidly in the root zone but that the degradates are transported to depth in measurable quantities. Simulations indicated that degradate transport is strongly related to the duration of sustained use of metolachlor and the extent of biodegradation.     

Transport and fate of nitrate and pesticides: hydrogeology and riparian zone processes

There is continuing concern over potential impacts of widespread application of nutrients and pesticides on ground- and surface-water quality. Transport and fate of nitrate and pesticides were investigated in a shallow aquifer and adjacent stream, Cow Castle Creek, in Orangeburg County, South Carolina. Pesticide and pesticide degradate concentrations were detected in ground water with greatest frequency and largest concentrations directly beneath and downgradient from the corn (Zea mays L.) field where they were applied. In almost all samples in which they were detected, concentrations of pesticide degradates greatly exceeded those of parent compounds, and were still present in ground waters that were recharged during the previous 18 yr. The absence of both parent and degradate compounds in samples collected from deeper in the aquifer suggests that this persistence is limited or that the ground water had recharged before use of the pesticide. Concentrations of NO(-)(3) in ground water decreased with increasing depth and age, but denitrification was not a dominant controlling factor. Hydrologic and chemical data indicated that ground water discharges to the creek and chemical exchange takes place within the upper 0.7 m of the streambed. Ground water had its greatest influence on surface-water chemistry during low-flow periods, causing a decrease in concentrations of Cl(-), NO(-)(3), pesticides, and pesticide degradates. Conversely, shallow subsurface drainage dominates stream chemistry during high-flow periods, increasing stream concentrations of Cl(-), NO(-)(3), pesticides, and pesticide degradates. These results point out the importance of understanding the hydrogeologic setting when investigating transport and fate of contaminants in ground water and surface water.     

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).     

Residues of endosulfan and other selected organochlorine pesticides in farm areas of the Lower Fraser Valley, British Columbia, Canada

Crop soils, ditch sediments, and water flowing from several farm areas to salmon tributary streams of the Fraser River in the Lower Fraser Valley (LFV) of British Columbia, Canada, were sampled in 2002-2003 to quantify for residues of an organochlorine cyclodiene pesticide, endosulfan (END = alpha-endosulfan + beta-endosulfan + endosulfan sulfate). Residues from historical use of other selected organochlorine pesticides, namely, cyclodienes (aldrin, alpha-chlordane, gamma-chlordane, dieldrin, endrin, endrin aldehyde, heptachlor, and heptachlor epoxide), hexachlorocyclohexanes [alpha-benzene-hexachloride (alpha-BHC), beta-BHC, delta-BHC, and gamma-BHC (lindane)], and DDT-related compounds (p,p-DDT, p,p-DDD, p,p-DDE, and methoxychlor) were also determined. Reference and background levels of these pesticides in ditches leading to fish streams were obtained from pristine watershed areas. Varying amounts of END residues were detected in soils (<0.02-5.60 mg kg(-1) dry wt.) and ditch sediments (<0.02-3.33 mg kg(-1) dry wt.) in mainly three of five farm areas sampled. Likewise, residues (excluding END) of other selected organochlorine compounds such as aldrin, BHC, chlordane, endrin, p,p-DDT, methoxychlor, and their respective major transformation products (endosulfan sulfate, dieldrin, endrin aldehyde, heptachlor, heptachlor epoxide, p,p-DDD, and p,p-DDE) were found in crop soils (<0.02-16.2 mg kg(-1) dry wt.) and sediments (<0.02-9.73 mg kg(-1) dry wt.). Most of these pesticides (END: <0.01-1.86 microg L(-1); other selected organochlorine pesticides: <0.0.1-1.50 microg L(-1)) were also found in ditch water leading to salmon streams in several farms. The END levels of crop soils from the same LFV study farms in 1994 and 2003 indicated an estimated decline of 22% to 1.35 mg kg(-1) dry wt. during that period. This reduction was probably due to the increasing use of alternate pesticides (e.g., organophosphorus compounds). Some possible biological implications of these pesticide residues on nontarget organisms in the LFV are discussed.     

ATRAZINE AND METOLACHLOR OCCURRENCE IN SHALLOW GROUND WATER OF THE UNITED STATES, 1993 TO 1995: RELATIONS TO EXPLANATORY FACTORS1

ABSTRACT: Since 1991, the U.S. Geological Survey has been conducting the National Water Quality Assessment (NAWQA) Program to determine the quality of the Nation's water resources. In an effort to obtain a better understanding of why pesticides are found in shallow ground water on a national scale, a set of factors likely to affect the fate and transport of two herbicides in the subsurface were examined. Atrazine and metolachlor were selected for this discussion because they were among the most frequently detected pesticides in ground water during the first phase of the NAWQA Program (1993 to 1995), and each was the most frequently detected compound in its chemical class (triazines and acetanilides, respectively). The factors that most strongly correlated with the frequencies of atrazine detection in shallow ground‐water networks were those that provided either: (1) an indication of the potential susceptibility of ground water to atrazine contamination, or (2) an indication of relative ground‐water age. The factors most closely related to the frequencies of metolachlor detection in ground water, however, were those that estimated or indicated the intensity of the agricultural use of metolachlor. This difference is probably the result of detailed use estimates for these compounds being available only for agricultural settings. While atrazine use is relatively extensive in nonagricultural settings, in addition to its widespread agricultural use, metolachlor is used almost exclusively for agricultural purposes. As a result, estimates of agricultural applications provide a less reliable indication of total chemical use for atrazine than for metolachlor. A multivariate analysis demonstrated that the factors of interest explained about 50 percent of the variance in atrazine and metolachlor detection frequencies among the NAWQA land‐use studies examined. The inclusion of other factors related to pesticide fate and transport in ground water, or improvements in the quality and accuracy of the data employed for the factors examined, may help explain more of the remaining variance in the frequencies of atrazine and metolachlor detection.     

Herbicides in ground water beneath Nebraska's Management Systems Evaluation Area

Profiles of ground water pesticide concentrations beneath the Nebraska Management Systems Evaluation Area (MSEA) describe the effect of 20 yr of pesticide usage on ground water in the central Platte Valley of Nebraska. During the 6-yr (1991-1996) study, 14 pesticides and their transformation products were detected in 7848 ground water samples from the unconfined water table aquifer. Triazine and acetamide herbicides applied on the site and their transformation products had the highest frequencies of detection. Atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4,-diamine] concentrations decreased with depth and ground water age determined with 3H/3He dating techniques. Assuming equivalent atrazine input during the past 20 yr, the measured average changes in concentration with depth (age) suggest an estimated half-life of >10 yr. Hydrolysis of atrazine and deethylatrazine (DEA; 2-chloro-4-amino-6-isopropylamino-s-triazine) to hydroxyatrazine [6-hydroxy-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine] appeared to be the major degradation route. Aqueous hydroxyatrazine concentrations are governed by sorption on the saturated sediments. Atrazine was detected in the confined Ogallala aquifer in ultra-trace concentrations (0.003 microg L(-1)); however, the possibility of introduction during reverse circulation drilling of these deep wells cannot be eliminated. In fall 1997 sampling, metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] was detected in 57% of the 230 samples. Metolachlor oxanilic acid [(2-ethyl-6-methylphenyl)(2-methoxy-1-methylethyl) amino]oxo-acetic acid] was detected in most samples. In ground water profiles, concentrations of metolachlor ethane sulfonic acid [2-[(ethyl-6-methylphenyl)(2-methoxy-1-methylethyl)amino]-2-oxo-ethanesulfonic acid] exceeded those of deethylatrazine. Alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide] was detected in <1% of the samples; however, alachlor ethane sulfonic acid [2-[(2,6-diethylphenyl)(methoxymethyl)amino]-2-oxoethanesulfonic acid] was present in most samples (63%) and was an indicator of past alachlor use.     

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.     

Behavior of pesticide residues in agricultural soil and adjacent River Kuywa sediment and water samples from Nzoia sugarcane belt in Kenya

An inventory survey conducted to determine pesticide usage in a sub-catchment of the Nzoia sugarcane belt found a variety of pesticides used in the sub-catchment, which are reported in this paper. Analysis of soil samples from seven fallow experimental field plots left uncultivated for various periods from 3 to 96?months after cultivation with pesticide application indicated persistence of high concentrations of pesticide residues in the soil, with estimated soil half-lives (in years) ranging from 0.72 to 57.75 for organochlorines and from 1.13 to 8.25 for herbicides. The mean water concentrations (in ??g/L) of the pesticide residues in River Kuywa, which flows through the Nzoia Nucleus Estate sugarcane farms, ranged from 0.12 (lindane) to 1.36 (p,p??-DDT) for organochlorines and from 0.14 (atrazine) to 1.75 (diuron) for herbicides during the heavy rains period in August 2008 while the mean sediment concentrations (in ??g/g) ranged from 0.28 (lindane) to 1.87 (endrin) for organochlorines and 0.39 (hexazinone) to 4.61 (alachlor) for herbicides. The mean concentrations of residues in water during the light rain period in December 2008 ranged from 0.17 (p,p??-DDT) to 0.71 (aldrin) for organochlorines and 0.01 (atrazine) to 1.74 (alachlor) for herbicides while the sediment concentrations ranged from 0.38 (p,p??-DDT) to 1.145 (aldrin) for organochlorines and 0.74 (atrazine) to 1.98 (alachlor) for herbicides. Although DDT, aldrin, dieldrin, and endrin were not reported in the survey, their presence in the fallow experimental field plot soils and in River Kuywa water and sediment could indicate previous application, lack of recorded data or illegal usage since 1997 when they were banned. Notably, the concentrations of alachlor, diuron, cypermethrin, and hexazinone in the water column were substantial indicating their extensive usage and residual persistence in the sub-catchment, with subsequent wash-off and leaching into River Kuywa. The concentration levels of some of the individual pesticides exceeded the EU limit requirements for drinking water and indicated potential risk to humans and cattle if the water is used without treatment.     

Evaluation of Three Watershed‐Scale Pesticide Environmental Transport and Fate Models1

Abstract: The U.S. Environmental Protection Agency (USEPA) Office of Pesticide Programs (OPP) has completed an evaluation of three watershed‐scale simulation models for potential use in Food Quality Protection Act pesticide drinking water exposure assessments. The evaluation may also guide OPP in identifying computer simulation tools that can be used in performing aquatic ecological exposure assessments. Models selected for evaluation were the Soil Water Assessment Tool (SWAT), the Nonpoint Source Model (NPSM), a modified version of the Hydrologic Simulation Program‐Fortran (HSPF), and the Pesticide Root Zone Model‐Riverine Water Quality (PRZM‐RIVWQ) model. Simulated concentrations of the pesticides atrazine, metolachlor, and trifluralin in surface water were compared with field data monitored in the Sugar Creek watershed of Indiana’s White River basin by the National Water Quality Assessment (NAWQA) program. The evaluation not only provided USEPA with experience in using watershed models for estimating pesticide concentration in flowing water but also led to the development of improved statistical techniques for assessing model accuracy. Further, it demonstrated the difficulty of representing spatially and temporally variable soil, weather, and pesticide applications with relatively infrequent, spatially fixed, point estimates. It also demonstrated the value of using monitoring and modeling as mutually supporting tools and pointed to the need to design monitoring programs that support modeling.     

Spray deposition of two insecticides into surface waters in a South African orchard area

Drift from pesticide spray application can result in contamination of nontarget environments such as surface waters. Azinphos-methyl (AZI) and endosulfan (END) deposition in containers of water was studied in fruit orchards in the Western Cape, South Africa. Additionally, attention was given to the contamination in farm streams, as well as to the resulting contamination of the subsequent main channel (Lourens River) approx. 25 km downstream of the tributary stream inlets. Spray deposit decreased with increasing distance downwind and ranged from 4.7 mg m(-2) within the target area to 0.2 mg m(-2) at 15 m downwind (AZI). Measured in-stream concentrations of both pesticides compared well with theoretical values calculated from deposition data for the respective distances. Furthermore, they were in the range of values predicted by an exposure assessment based on 95th-percentile values for basic drift deposition (German Federal Biological Research Centre for Agriculture and Forestry [BBA] and USEPA). Pesticide deposition in the tributaries was followed by a measurable increase of contamination in the Lourens River. Mortality of midges (Chironomus spp.) exposed for 24 h to samples obtained from the AZI trials decreased with decreasing concentrations (estimated LC50 from field samples = 10 microg L(-1) AZI; lethal distance: LD50 = 13 m). Mortality in the tributary samples averaged 11% (0.5-1.7 microg L(-1) AZI), while no mortality was discernible in the Lourens River samples (0.041 microg L(-1)). The sublethal endpoint failure to form tubes from the glass beads provided was significantly increased at all sites in comparison with the control (analysis of variance [ANOVA], Fisher's protected least significant difference [PLSD], p < 0.01).     

Spatial and temporal variation in nutrient parameters in stream water in a rural-urban catchment, Shikoku, Japan: effects of land cover and human impact

Seasonal and spatial variations in major ion chemistry and isotope composition in the rural-urban catchment of the Shigenobu River were monitored to determine the influences of agricultural and urban sewage systems on water quality. Temporal patterns of biochemical oxygen demand (BOD), total nitrogen (TN), total phosphorus (TP), and suspended sediment (SS) were examined at four sites in the rural-urban catchment. Urban land cover, incorporating the effects of increased population, domestic water use, and industrial wastewater, was positively associated with increases in water pollution and was included as an important explanatory variable for the variations in all water quality parameters. Significant trends were found in each parameter. BOD concentrations ranged widely, and were high in urban regions, due to the presence of a waste water treatment plant. TN and SS showed various trends, but did not vary widely, unlike TP. TP concentrations varied greatly, with high concentrations in cultivated areas, due to fertilizer use. Local water quality management or geology could further explain some of the variations in water quality. Non-point-source pollution exhibited strong positive spatial autocorrelation, indicating that incorporating spatial dimensions into water quality assessment enhances our understanding of spatial patterns of water quality. Data from the Ministry of Land Infrastructure and Transport (MLIT) and Environment Ministry (EM) were used to investigate trends in land management. Stepwise regression analysis was used to test the correlation between specific management practises and substance concentrations in surface water and sediment. MLIT and EM data for 1981-2003 showed an increase in TN, TP, and SS concentrations in surface water. High levels of fertilizer in dormant sprays and domestic water use were associated with high pesticide concentrations in water and sediment. This paper presents a novel method of studying the environmental impact of various agricultural management practises and recommends a management strategy that combines the use of reduced-risk pesticides with irrigation and non-irrigation periods in paddy fields.     

PESTICIDES AND PESTICIDE DEGRADATION PRODUCTS IN STORMWATER RUNOFF: SACRAMENTO RWER BASIN,CALIFORNIA1

ABSTRACT: Pesticides in stormwater runoff, within the Sacramento River Basin, California, were assessed during a storm that occurred in January 1994. Two organophosphate insecticides (diazinon and methidathion), two carbamate pesticides (molinate and carbofuran), and one triazine herbicide (simazine) were detected. Organophosphate pesticide concentrations increased with the rising stage of the hydrographs; peak concentrations were measured near peak discharge. Diazinon oxon, a toxic degradation product of diazinon, made up approximately 1 to 3 percent of the diazinon load. The Feather River was the principal source of organophosphate pesticides to the Sacramento River during this storm. The concentrations of molinate and carbofuran, pesticides applied to rice fields during May and June, were relatively constant during and after the storm. Their presence in surface water was attributed to the flooding and subsequent drainage, as a management practice to degrade rice stubble prior to the next planting. A photo-degradation product of molinate, 4-keto molinate, was in all samples where molinate was detected and made up approximately 50 percent of the total molinate load. Simazine, a herbicide used in orchards and to control weeds along the roadways, was detected in the storm runoff, but it was not possible to differentiate the two sources of that pesticide to the Sacramento River.     

A hydrological modeling framework for defining achievable performance standards for pesticides

This paper proposes a hydrological modeling framework to define achievable performance standards (APSs) for pesticides that could be attained after implementation of recommended management actions, agricultural practices, and available technologies (i.e., beneficial management practices [BMPs]). An integrated hydrological modeling system, Gestion Intégrée des Bassins versants à l'aide d'un Système Informatisé, was used to quantify APSs for six Canadian watersheds for eight pesticides: atrazine, carbofuran, dicamba, glyphosate, MCPB, MCPA, metolachlor, and 2,4-D. Outputs from simulation runs to predict pesticide concentration under current conditions and in response to implementation of two types of beneficial management practices (reduced pesticide application rate and 1- to 10-m-wide edge-of-field and/or riparian buffer strips, implemented singly or in combination) showed that APS values for scenarios with BMPs were less than those for current conditions. Moreover, APS values at the outlet of watersheds were usually less than ecological thresholds of good condition, when available. Upstream river reaches were at greater risk of having concentrations above a given ecological thresholds because of limited stream flows and overland loads of pesticides. Our integrated approach of "hydrological modeling-APS estimation-ecotoxicological significance" provides the most effective interpretation possible, for management and education purposes, of the potential biological impact of predicted pesticide concentrations in rivers.     

Pesticides in rain in four agricultural watersheds in the United States

Rainfall samples were collected during the 2003 and 2004 growing seasons at four agricultural locales across the USA in Maryland, Indiana, Nebraska, and California. The samples were analyzed for 21 insecticides, 18 herbicides, three fungicides, and 40 pesticide degradates. Data from all sites combined show that 7 of the 10 most frequently detected pesticides were herbicides, with atrazine (70%) and metolachlor (83%) detected at every site. Dacthal, acetochlor, simazine, alachlor, and pendimethalin were detected in more than 50% of the samples. Chlorpyrifos, carbaryl, and diazinon were the only insecticides among the 10 most frequently detected compounds. Of the remaining pesticide parent compounds, 18 were detected in fewer than 30% of the samples, and 13 were not detected. The most frequently detected degradates were deethylatrazine; the oxygen analogs (OAs) of the organophosphorus insecticides chlorpyrifos, diazinon, and malathion; and 1-napthol (degradate of carbaryl). Deethylatrazine was detected in nearly 70% of the samples collected in Maryland, Indiana, and Nebraska but was detected only once in California. The OAs of chlorpyrifos and diazinon were detected primarily in California. Degradates of the acetanilide herbicides were rarely detected in rain, indicating that they are not formed in the atmosphere or readily volatilized from soils. Herbicides accounted for 91 to 98% of the total pesticide mass deposited by rain except in California, where insecticides accounted for 61% in 2004. The mass of pesticides deposited by rainfall was estimated to be less than 2% of the total applied in these agricultural areas.