Stephen J. Kalkhoff

Fate and transport of glyphosate and aminomethylphosphonic acid in surface waters of agricultural basins

BACKGROUND Glyphosate [N-(phosphonomethyl)glycine] is a herbicide used widely throughout the world in the production of many crops and is heavily used on soybeans, corn and cotton. Glyphosate is used in almost all agricultural areas of the United States, and the agricultural use of glyphosate has increased from less than 10 000 Mg in 1992 to more than 80 000 Mg in 2007. The greatest intensity of glyphosate use is in the midwestern United States, where applications are predominantly to genetically modified corn and soybeans. In spite of the increase in usage across the United States, the characterization of the transport of glyphosate and its degradate aminomethylphosphonic acid (AMPA) on a watershed scale is lacking. RESULTS Glyphosate and AMPA were frequently detected in the surface waters of four agricultural basins. The frequency and magnitude of detections varied across basins, and the load, as a percentage of use, ranged from 0.009 to 0.86% and could be related to three general characteristics: source strength, rainfall runoff and flow route. CONCLUSIONS Glyphosate use in a watershed results in some occurrence in surface water; however, the watersheds most at risk for the offsite transport of glyphosate are those with high application rates, rainfall that results in overland runoff and a flow route that does not include transport through the soil.

Decadal surface water quality trends under variable climate, land use, and hydrogeochemical setting in Iowa, USA

Understanding how nitrogen fluxes respond to changes in agriculture and climate is important for improving water quality. In the midwestern United States, expansion of corn cropping for ethanol production led to increasing N application rates in the 2000s during a period of extreme variability of annual precipitation. To examine the effects of these changes, surface water quality was analyzed in 10 major Iowa Rivers. Several decades of concentration and flow data were analyzed with a statistical method that provides internally consistent estimates of the concentration history and reveals flow-normalized trends that are independent of year-to-year streamflow variations. Flow-normalized concentrations of nitrate+nitrite-N decreased from 2000 to 2012 in all basins. To evaluate effects of annual discharge and N loading on these trends, multiple conceptual models were developed and calibrated to flow-weighted annual concentrations. The recent declining concentration trends can be attributed to both very high and very low discharge in the 2000s and to the long (e.g., 8 year) subsurface residence times in some basins. Dilution of N and depletion of stored N occurs in years with high discharge. Reduced N transport and increased N storage occurs in low-discharge years. Central Iowa basins showed the greatest reduction in flow-normalized concentrations, likely because of smaller storage volumes and shorter residence times. Effects of land-use changes on the water quality of major Iowa Rivers may not be noticeable for years or decades in peripheral basins of Iowa, and may be obscured in the central basins where extreme flows strongly affect annual concentration trends.

Eleven-year trend in acetanilide pesticide degradates in the Iowa River, Iowa.

Trends in concentration and loads of acetochlor, alachlor, and metolachlor and their ethanasulfonic (ESA) and oxanilic (OXA) acid degradates were studied from 1996 through 2006 in the main stem of the Iowa River, Iowa and in the South Fork Iowa River, a small tributary near the headwaters of the Iowa River. Concentration trends were determined using the parametric regression model SEAWAVE-Q, which accounts for seasonal and flow-related variability. Daily estimated concentrations generated from the model were used with daily streamflow to calculate daily and yearly loads. Acetochlor, alachlor, metolachlor, and their ESA and OXA degradates were generally present in >50% of the samples collected from both sites throughout the study. Their concentrations generally decreased from 1996 through 2006, although the rate of decrease was slower after 2001. Concentrations of the ESA and OXA degradates decreased from 3 to about 23% yr. The concentration trend was related to the decreasing use of these compounds during the study period. Decreasing concentrations and constant runoff resulted in an average reduction of 10 to >3000 kg per year of alachlor and metolachlor ESA and OXA degradates being transported out of the Iowa River watershed. Transport of acetochlor and metolachlor parent compounds and their degradates from the Iowa River watershed ranged from <1% to about 6% of the annual application. These trends were related to the decreasing use of these compounds during the study period, but the year-to-year variability cannot explain changes in loads based on herbicide use alone. The trends were also affected by the timing and amount of precipitation. As expected, increased amounts of water moving through the watershed moved a greater percentage of the applied herbicides, especially the relatively soluble degradates, from the soils into the rivers through surface runoff, shallow groundwater inflow, and subsurface drainage.

Effect of variable annual precipitation and nutrient input on nitrogen and phosphorus transport from two Midwestern agricultural watersheds

Precipitation patterns and nutrient inputs affect transport of nitrate (NO3-N) and phosphorus (TP) from Midwest watersheds. Nutrient concentrations and yields from two subsurface-drained watersheds, the Little Cobb River (LCR) in southern Minnesota and the South Fork Iowa River (SFIR) in northern Iowa, were evaluated during 1996-2007 to document relative differences in timings and amounts of nutrients transported. Both watersheds are located in the prairie pothole region, but the SFIR exhibits a longer growing season and more livestock production. The SFIR yielded significantly more NO3-N than the LCR watershed (31.2 versus 21.3kgNO3-Nha(-1)y(-1)). The SFIR watershed also yielded more TP than the LCR watershed (1.13 versus 0.51kgTPha(-1)yr(-1)), despite greater TP concentrations in the LCR. About 65% of NO3-N and 50% of TP loads were transported during April-June, and <20% of the annual loads were transported later in the growing season from July-September. Monthly NO3-N and TP loads peaked in April from the LCR but peaked in June from the SFIR; this difference was attributed to greater snowmelt runoff in the LCR. The annual NO3-N yield increased with increasing annual runoff at a similar rate in both watersheds, but the LCR watershed yielded less annual NO3-N than the SFIR for a similar annual runoff. These two watersheds are within 150 km of one another and have similar dominant agricultural systems, but differences in climate and cropping inputs affected amounts and timing of nutrient transport.

Occurrence of Transformation Products in the Environment

Historically, most environmental occurrence research has focused on the parent compounds of organic contaminants. Research, however, has documented that the environmental transport of chemicals, such as pesticides and emerging contaminants, are substantially underestimated if transformation products are not considered. Although most examples described herein were drawn from research conducted by the U.S. Geological Survey, such results are generally reflective of those found in other parts of the world. Results from a study of 51 streams in the Midwestern United States found that transformation products were seven of the ten most frequently detected pesticide compounds in late spring runoff (after application of pre-emergent herbicides), and nine of the ten most frequently detected compounds in fall season runoff (during and after harvest). In fact, 70% of the total herbicide concentration in water from the Mississippi River Basin was from transformation products. Results from a study of 86 municipal wells in Iowa found the frequency of detection increased from 17%, when pesticide parent compounds were considered, to 53%, when both parents and transformation products were considered. Transformation products were 12 of the 15 most frequently detected compounds for this groundwater study. Although studies on transformation products of synthetic organic compounds other than pesticides are not as common, wastewater treatment plant discharges have repeatedly been shown to contribute such transformation products to streams. In addition, select detergent transformation products have been commonly found in solid waste in the 1000s mg/kg. These findings and many others document that transformation products must be considered to fully assess the potential environmental occurrence of chemical contaminants and their transport and fate in various compartments of the hydrologic system.