Trends in Pesticide Concentrations in Streams of the Western United States, 1993-2005.

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.

Trends in nitrogen, phosphorus, and sediment concentrations and loads in streams draining to Lake Tahoe, California, Nevada, USA.

Lake Tahoe, a large freshwater lake of the eastern Sierra Nevada in California and Nevada, has 63 tributaries that are sources of nutrients and sediment to the lake. The Tahoe watershed is relatively small, and the surface area of the lake occupies about 38% of the watershed area (1313 km2). Only about 6% of the watershed is urbanized or residential land, and as part of a plan to maintain water clarity, wastewater is exported out of the basin. The lake's clarity has been diminishing due to algae and fine sediment, prompting development of management plans. Much of the annual discharge and nutrient load to the lake results from snowmelt in the spring and summer months. To understand the relative importance of land use, climate, forest management, and other factors affecting trends in nutrient stream concentrations and loads, a Weighted Regression on Time Discharge and Season (WRTDS) model simulated these trends over a time frame of >25 years (mid-1970s to 2017). All studied locations generally show nitrate concentration and load trending down. Ammonium concentration and load initially trended down then increased continuously after 2005. Some locations show initially decreasing orthophosphate trends, followed by small significant increases in concentration and loads starting around 2000 to 2005. Total Kjeldahl nitrogen, total phosphorus and suspended sediment mostly trended downward. Overall, the trends in various forms of nitrogen were observed at most sites irrespective of the degree of development and indicate a change in ecological conditions is affecting the nitrogen cycle throughout the watershed, most likely attributable to forest aggradation and fire suppression. Ratios of bioavailable nitrogen in the form of nitrate and ammonium to orthophosphate have also trended downward during the period of record suggesting a shift of these streams from phosphorus limited to nitrogen limited.

Pyrethroid insecticide concentrations and toxicity in streambed sediments and loads in surface waters of the San Joaquin Valley, California, USA.

Pyrethroid insecticide use in California, USA, is growing, and there is a need to understand the fate of these compounds in the environment. Concentrations and toxicity were assessed in streambed sediment of the San Joaquin Valley of California, one of the most productive agricultural regions of the United States. Concentrations were also measured in the suspended sediment associated with irrigation or storm-water runoff, and mass loads during storms were calculated. Western valley streambed sediments were frequently toxic to the amphipod, Hyalella azteca, with most of the toxicity attributable to bifenthrin and cyhalothrin. Up to 100% mortality was observed in some locations with concentrations of some pyrethroids up to 20 ng/g. The western San Joaquin Valley streams are mostly small watersheds with clay soils, and sediment-laden irrigation runoff transports pyrethroid insecticides throughout the growing season. In contrast, eastern tributaries and the San Joaquin River had low bed sediment concentrations (<1 ng/g) and little or no toxicity because of the preponderance of sandy soils and sediments. Bifenthrin, cyhalothrin, and permethrin were the most frequently detected pyrethroids in irrigation and storm water runoff. Esfenvalerate, fenpropathrin, and resmethrin were also detected. All sampled streams contributed to the insecticide load of the San Joaquin River during storms, but some compounds detected in the smaller creeks were not detected in the San Joaquin River. The two smallest streams, Ingram and Hospital Creeks, which had high sediment toxicity during the irrigation season, accounted for less than 5% of the total discharge of the San Joaquin River during storm conditions, and as a result their contribution to the pyrethroid mass load of the larger river was minimal.

Hydrologic and biogeochemical controls of river subsurface solutes under agriculturally enhanced ground water flow.

The relative influences of hydrologic processes and biogeochemistry on the transport and retention of minor solutes were compared in the riverbed of the lower Merced River (California, USA). The subsurface of this reach receives ground water discharge and surface water infiltration due to an altered hydraulic setting resulting from agricultural irrigation. Filtered ground water samples were collected from 30 drive point locations in March, June, and October 2004. Hydrologic processes, described previously, were verified by observations of bromine concentrations; manganese was used to indicate redox conditions. The separate responses of the minor solutes strontium, barium, uranium, and phosphorus to these influences were examined. Correlation and principal component analyses indicate that hydrologic processes dominate the distribution of trace elements in the ground water. Redox conditions appear to be independent of hydrologic processes and account for most of the remaining data variability. With some variability, major processes are consistent in two sampling transects separated by 100 m.

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.

Mercury and methylmercury concentrations and loads in the Cache Creek watershed, California.

Concentrations and loads of total mercury and methylmercury were measured in streams draining abandoned mercury mines and in the proximity of geothermal discharge in the Cache Creek watershed of California during a 17-month period from January 2000 through May 2001. Rainfall and runoff were lower than long-term averages during the study period. The greatest loading of mercury and methylmercury from upstream sources to downstream receiving waters, such as San Francisco Bay, generally occurred during or after winter rainfall events. During the study period, loads of mercury and methylmercury from geothermal sources tended to be greater than those from abandoned mining areas, a pattern attributable to the lack of large precipitation events capable of mobilizing significant amounts of either mercury-laden sediment or dissolved mercury and methylmercury from mine waste. Streambed sediments of Cache Creek are a significant source of mercury and methylmercury to downstream receiving bodies of water. Much of the mercury in these sediments is the result of deposition over the last 100-150 years by either storm-water runoff, from abandoned mines, or continuous discharges from geothermal areas. Several geochemical constituents were useful as natural tracers for mining and geothermal areas, including the aqueous concentrations of boron, chloride, lithium and sulfate, and the stable isotopes of hydrogen and oxygen in water. Stable isotopes of water in areas draining geothermal discharges showed a distinct trend toward enrichment of (18)O compared with meteoric waters, whereas much of the runoff from abandoned mines indicated a stable isotopic pattern more consistent with local meteoric water.

Concentrations and loads of suspended sediment-associated pesticides in the San Joaquin River, California and tributaries during storm events.

Current-use pesticides associated with suspended sediments were measured in the San Joaquin River, California and its tributaries during two storm events in 2008. Nineteen pesticides were detected: eight herbicides, nine insecticides, one fungicide and one insecticide synergist. Concentrations for the herbicides (0.1 to 3,000 ng/g; median of 6.1 ng/g) were generally greater than those for the insecticides (0.2 to 51 ng/g; median of 1.5 ng/g). Concentrations in the tributaries were usually greater than in the mainstem San Joaquin River and the west side tributaries were higher than the east side tributaries. Estimated instantaneous loads ranged from 1.3 to 320 g/day for herbicides and 0.03 to 53 g/day for insecticides. The greatest instantaneous loads came from the Merced River on the east side. Instantaneous loads were greater for the first storm of 2008 than the second storm in the tributaries while the instantaneous loads within the San Joaquin River were greater during the second storm. Pesticide detections generally reflected pesticide application, but other factors such as physical-chemical properties and timing of application were also important to pesticide loads.