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.     

Sources and Transport of Phosphorus to Rivers in California and Adjacent States,U.S., as Determined by SPARROW Modeling

The SPARROW (SPAtially Referenced Regression on Watershed attributes) model was used to simulate annual phosphorus loads and concentrations in unmonitored stream reaches in California, U.S., and portions of Nevada and Oregon. The model was calibrated using de‐trended streamflow and phosphorus concentration data at 80 locations. The model explained 91% of the variability in loads and 51% of the variability in yields for a base year of 2002. Point sources, geological background, and cultivated land were significant sources. Variables used to explain delivery of phosphorus from land to water were precipitation and soil clay content. Aquatic loss of phosphorus was significant in streams of all sizes, with the greatest decay predicted in small‐ and intermediate‐sized streams. Geological sources, including volcanic rocks and shales, were the principal control on concentrations and loads in many regions. Some localized formations such as the Monterey shale of southern California are important sources of phosphorus and may contribute to elevated stream concentrations. Many of the larger point source facilities were located in downstream areas, near the ocean, and do not affect inland streams except for a few locations. Large areas of cultivated land result in phosphorus load increases, but do not necessarily increase the loads above those of geological background in some cases because of local hydrology, which limits the potential of phosphorus transport from land to streams.     

Trends in Pesticide Concentrations in Streamsof the Western United States, 1993‐20051

Johnson, Henry M., Joseph L. Domagalski, and Dina K. Saleh, 2010. Trends in Pesticide Concentrations in Streams of the Western United States, 1993‐2005. Journal of the American Water Resources Association (JAWRA) 00(0):1‐22. DOI: 10.1111/j.1752‐1688.2010.00507.x Abstract: Trends in pesticide concentrations for 15 streams in California, Oregon, Washington, and Idaho were determined for the organophosphate insecticides chlorpyrifos and diazinon and the herbicides atrazine, s‐ethyl diproplythiocarbamate (EPTC), metolachlor, simazine, and trifluralin. A parametric regression model was used to account for flow, seasonality, and antecedent hydrologic conditions and thereby estimate trends in pesticide concentrations in streams arising from changes in use amount and application method in their associated catchments. Decreasing trends most often were observed for diazinon, and reflect the shift to alternative pesticides by farmers, commercial applicators, and homeowners because of use restrictions and product cancelation. Consistent trends were observed for several herbicides, including upward trends in simazine at urban‐influenced sites from 2000 to 2005, and downward trends in atrazine and EPTC at agricultural sites from the mid‐1990s to 2005. The model provided additional information about pesticide occurrence and transport in the modeled streams. Two examples are presented and briefly discussed: (1) timing of peak concentrations for individual compounds varied greatly across this geographic gradient because of different application periods and the effects of local rain patterns, irrigation, and soil drainage and (2) reconstructions of continuous diazinon concentrations at sites in California are used to evaluate compliance with total maximum daily load targets.     

SPARROW Modeling of Nitrogen Sources and Transport in Rivers and Streams of California and Adjacent States,U.S.

The SPARROW (SPAtially Referenced Regressions On Watershed attributes) model was used to evaluate the spatial distribution of total nitrogen (TN) sources, loads, watershed yields, and factors affecting transport and decay in the stream network of California and portions of adjacent states for the year 2002. The two major TN sources to local catchments on a mass basis were fertilizers and manure (51.7%) and wastewater discharge (15.9%). Other sources contributed < 12%. Fertilizer use is widespread in the Central Valley region of California, and also important in several other regions because of the diversity of California agriculture. Precipitation, sand content of surficial soils, wetlands, and tile drains were important for TN movement to stream reaches. Median streamflow in the study area is about 0.04 m³/s. Aquatic losses of nitrogen were found to be most important in intermittent and small to medium sized streams (0.2‐14 m³/s), while larger streams showed less loss, and therefore are important for TN transport. Nitrogen loss in reservoirs was found to be insignificant, possibly because most of the larger ones are located upstream of nitrogen sources. The model was used to show loadings, sources, and tributary inputs to several major rivers. The information provided by the SPARROW model is useful for determining both the major sources contributing nitrogen to streams and the specific tributaries that transport the load.     

Comparative study of transport processes of nitrogen, phosphorus, and herbicides to streams in five agricultural basins, USA

Agricultural chemical transport to surface water and the linkage to other hydrological compartments, principally ground water, was investigated at five watersheds in semiarid to humid climatic settings. Chemical transport was affected by storm water runoff, soil drainage, irrigation, and how streams were linked to shallow ground water systems. Irrigation practices and timing of chemical use greatly affected nutrient and pesticide transport in the semiarid basins. Irrigation with imported water tended to increase ground water and chemical transport, whereas the use of locally pumped irrigation water may eliminate connections between streams and ground water, resulting in lower annual loads. Drainage pathways in humid environments are important because the loads may be transported in tile drains, or through varying combinations of ground water discharge, and overland flow. In most cases, overland flow contributed the greatest loads, but a significant portion of the annual load of nitrate and some pesticide degradates can be transported under base-flow conditions. The highest basin yields for nitrate were measured in a semiarid irrigated system that used imported water and in a stream dominated by tile drainage in a humid environment. Pesticide loads, as a percent of actual use (LAPU), showed the effects of climate and geohydrologic conditions. The LAPU values in the semiarid study basin in Washington were generally low because most of the load was transported in ground water discharge to the stream. When herbicides are applied during the rainy season in a semiarid setting, such as simazine in the California basin, LAPU values are similar to those in the Midwest basins.     

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.