GROUND WATER AS A SOURCE OF NUTRIENTS AND ATRAZINE TO STREAMS IN THE SOUTH PLATTE RIVER BASIN1

ABSTRACT: Concentrations of nitrite plus nitrate, ammonia, orthophosphate, and atrazine were measured in streams and ground water beneath the streams at 23 sites in the South Platte River basin of Colorado, Nebraska, and Wyoming to assess: (1) the role of ground water as a source of nutrients and atrazine to streams in the basin, and (2) the effect of land-use setting on this process. Concentrations of nitrite plus nitrate, ammonia, orthophosphate, and atrazine were higher in ground water than in the overlying streams at 2, 12, 12, and 3 of 19 sites, respectively, where there was not a measurable hydraulic gradient directed from the stream to the ground water. Orthophosphate was the only constituent that had a significantly higher (p ≤ 0.05) concentration in ground water than in surface water for a given land-use setting (range land). Redox conditions in ground water were more important than land-use setting in influencing whether ground water was a source of elevated nitrite plus nitrate concentrations to streams in the basin. The ratios of nitrite plus nitrate in ground water/surface were were significantly lower (p ≤ 0.05) at sites having concentrations of dissolved oxygen in ground water ≤ 0.5 mg/L than at sites having dissolved oxygen concentrations ≥ 0.5 mg/L. Elevated concentrations of ammonia or atrazine in ground water occurred at sites in close proximity to likely sources of ammonia or atrazine, regardless of land-use setting. These results indicate that land-use setting is not the only factor that influences whether ground water is a source of elevated nutrient and atrazine concentrations to streams in the South Platte River Basin.     

Exposure Times to the Spring Atrazine Flush Along a Stream-Reservoir System1

Stoeckel, James A., Jade Morris, Elizabeth Ames, David C. Glover, Michael J. Vanni, William Renwick, and María J. González, 2012. Exposure Times to the Spring Atrazine Flush Along a Stream-Reservoir System. Journal of the American Water Resources Association (JAWRA) 48(3): 616-634. DOI: 10.1111/j.1752-1688.2011.00633.x Abstract: We used enzyme-linked immunosorbent assay to examine reservoir-mediated shifts in spring to fall exposure of aquatic organisms to the spring atrazine pulse over four years in a Midwestern stream-reservoir system. Peak atrazine concentrations in the major inflowing stream exceeded 10 μg/l in all four years. The reservoir had a beneficial effect in two of four years by diluting atrazine below the 10 μg/l threshold. However, during the other two years, exposure times above 10 μg/l were approximately doubled in the reservoir compared to the major inflowing stream. Thresholds of 3 and 5 μg/l were exceeded during all four years in the reservoir. The uplake and downlake reservoir sites were four to five times more likely to exceed these thresholds and aquatic organisms were subjected to longer exposure times above these thresholds compared to the inflowing stream. Release of elevated atrazine concentrations from the reservoir extended exposure times in the outflowing stream. This effect was most pronounced just below the dam. Aquatic organisms upstream of the reservoir were most likely to experience acute exposures whereas organisms within and immediately downstream of the reservoir were more likely to experience chronic exposures. The ubiquity of reservoirs and the annual spring herbicide flush highlight the importance of considering the presence and relative location of reservoirs when assessing risk to aquatic communities as well as locations of drinking water intakes.     

Pesticide transport pathways from a sloped Litchi orchard to an adjacent tropical stream as identified by hydrograph separation

This study was performed to identify the transport pathways of pesticides from a sloped litchi ( Sonn.) orchard to a nearby stream based on a three-component hydrograph separation (baseflow, interflow, surface runoff). Dissolved silica and electrical conductivity were chosen as representative tracers. During the study period (30 d), 0.4 and 0.01% of the applied mass of atrazine and chlorpyrifos, respectively, were detected in the stream after 151 mm of rainfall. Baseflow (80-96%) was the dominant hydrological flow component, followed by interflow (3-18%) and surface runoff (1-7%). Despite its small contribution to total discharge, surface runoff was the dominant atrazine transport pathway during the first days after application because pesticide concentrations in the surface runoff flow component declined quickly within several days. Preferential transport with interflow became the dominant pathway of atrazine. Because chlorpyrifos was detected in the stream water only twice, it was not included in the hydrograph separation. A feature of the surface runoff pathway was the coincidence of pesticide and discharge peaks. In contrast, peak concentrations of pesticides transported by interflow occurred during the hydrograph recession phases. Stormflow generation and pesticide transport depended on antecedent rainfall. The combination of high-resolution pesticide concentration measurements with a three-component hydrograph separation has been shown to be a suitable method to identify pesticide transport pathways under tropical conditions.     

Time Series Analysis of Nebraska Daily Rainfall Data to Simulate Atrazine Runoff1

Abstract: Measured atrazine concentrations in Nebraska surface water have been shown to exceed water‐quality standards, posing risks to humans and to the ecosystem. To assess this risk, atrazine runoff was simulated at the field‐scale in Nebraska based on the pesticide component of the AGNPS model. This project’s objective was to determine the frequency that the atrazine concentration at the field outlet exceeded three different atrazine water‐quality criteria. The simulation was conducted for different farm management practices, soil moisture conditions, and five Nebraska topographic regions. If the criteria were exceeded, a risk to the drinking water consumer or freshwater aquatic life was hypothesized to exist. Three pesticide fate and transport processes were simulated with the model. Degradation was simulated using first‐order kinetics. Adsorption/desorption was modeled assuming a linear soil‐water partitioning coefficient. Advection (runoff) was based primarily on the USDA‐NRCS curve number method. Daily rainfall from the National Weather Service was used to compute the soil moisture conditions for the 1985‐2000 growing seasons. After each runoff event, the pesticide runoff concentration was compared with each of the three atrazine water‐quality criteria. The results show that environmental receptors (i.e., freshwater aquatic species) are exposed to unacceptable atrazine runoff concentrations in 20‐50% of the runoff events.     

Atrazine dissipation in s-triazine-adapted and nonadapted soil from Colorado and Mississippi: implications of enhanced degradation on atrazine fate and transport parameters

Soil bacteria have developed novel metabolic abilities resulting in enhanced atrazine degradation. Consequently, there is a need to evaluate the effects of enhanced degradation on parameters used to model atrazine fate and transport. The objectives of this study were (i) to screen Colorado (CO) and Mississippi (MS) atrazine-adapted and non-adapted soil for genes that code for enzymes able to rapidly catabolize atrazine and (ii) to compare atrazine persistence, Q(10), beta, and metabolite profiles between adapted and non-adapted soils. The atzABC and/or trzN genes were detected only in adapted soil. Atrazine's average half-life in adapted soil was 10-fold lower than that of the non-adapted soil and 18-fold lower than the USEPA estimate of 3 to 4 mo. Q(10) was greater in adapted soil. No difference in beta was observed between soils. The accumulation and persistence of mono-N-dealkylated metabolites was lower in adapted soil; conversely, under suboptimal moisture levels in CO adapted soil, hydroxyatrazine concentrations exceeded 30% of the parent compounds' initial mass. Results indicate that (i) enhanced atrazine degradation and atzABC and/or trzN genes are likely widespread across the Western and Southern corn-growing regions of the USA; (ii) persistence of atrazine and its mono-N-dealkylated metabolites is significantly reduced in adapted soil; (iii) hydroxyatrazine can be a major degradation product in adapted soil; and (iv) fate, transport, and risk assessment models that assume historic atrazine degradation pathways and persistence estimates will likely overpredict the compounds' transport potential in adapted soil.     

Prediction of the Fate and Transport Processes of Atrazine in a Reservoir

The fate and transport processes of a toxic chemical such as atrazine, an herbicide, in a reservoir are significantly influenced by hydrodynamic regimes of the reservoir. The two-dimensional (2D) laterally-integrated hydrodynamics and mass transport model, CE-QUAL-W2, was enhanced by incorporating a submodel for toxic contaminants and applied to Saylorville Reservoir, Iowa. The submodel describes the physical, chemical, and biological processes and predicts unsteady vertical and longitudinal distributions of a toxic chemical. The simulation results from the enhanced 2D reservoir model were validated by measured temperatures and atrazine concentrations in the reservoir. Although a strong thermal stratification was not identified from both observed and predicted water temperatures, the spatial variation of atrazine concentrations was largely affected by seasonal flow circulation patterns in the reservoir. In particular, the results showed the effect of flow circulation on spatial distribution of atrazine during summer months as the river flow formed an underflow within the reservoir and resulted in greater concentrations near the surface of the reservoir. Atrazine concentrations in the reservoir peaked around the end of May and early June. A good agreement between predicted and observed times and magnitudes of peak concentrations was obtained. The use of time-variable decay rates of atrazine led to more accurate prediction of atrazine concentrations, while the use of a constant half-life (60 days) over the entire period resulted in a 40% overestimation of peak concentrations. The results provide a better understanding of the fate and transport of atrazine in the reservoir and information useful in the development of reservoir operation strategies with respect to timing, amount, and depth of withdrawal.     

INFILTRATION OF ATRAZINE AND METABOLITES FROM A STREAM TO AN ALLUVIAL AQUIFER1

ABSTRACT: The infiltration of atrazine, deethylatrazine, and deisopropylatrazine from Walnut Creek, a tributary stream, to the alluvial valley aquifer along the South Skunk River in central Iowa occurred where the stream transects the river's flood plain. A preliminary estimate indicated that the infiltration was significant and warrants further investigation. Infiltration was estimated by measuring the loss of stream discharge in Walnut Creek and the concentrations of atrazine and its metabolites deethylatrazine and deisopropylatrazine, in ground water 1 m beneath the streambed. Infiltration was estimated before application of agrichemicals to the fields during a dry period on April 7, 1994, and after application of agrichemicals during a period of small runoff on June 8, 1994. On April 7, the flux of atrazine, deethylatrazine, and deisopropylatrazine from Walnut Creek into the alluvial valley aquifer ranged from less than 10 to 60 (μg/d)/m², whereas on June 8 an increased flux ranged from 270 to 3060 (μg/d)/m². By way of comparison, the calculated fluxes of atrazine beneath Walnut Creek, for these two dates, were two to five orders of magnitude greater than an estimated flux of atrazine to ground water caused by leaching from a field on a per-unit-area basis. Furthermore, the unit-area flux rates of water from Walnut Creek to the alluvial valley aquifer were about three orders of magnitude greater than estimated recharge to the alluvial aquifer from precipitation. The large flux of chemicals from Walnut Creek to the alluvial valley aquifer was due in part to the conductive streambed and rather fast ground water velocities; average vertical hydraulic conductivity through the streambed was calculated as 35 and 90 m/d for the two sampling dates, and estimated ground water velocities ranged from 1 to 5 m/d.     

HERBICIDE AND NITRATE VARIATION IN ALLUVIUM UNDERLYING A CORN FIELD AT A SITE IN IOWA COUNTY,IOWA1

ABSTRACT: A hydrologic investigation to determine vertical and seasonal variation of atrazine, alachlor, cyanazine, and nitrate at one location and to relate the variation to ground-water movement in the Iowa River alluvium was conducted in Iowa County, Iowa, from March 1986 to December 1987. Water samples were collected at discrete intervals through the alluvial sequence from the soil zone to the base of the aquifer. Alachlor, atrazine, and cyanazine were detected most frequently in the soil zone but also were present in the upper part of the alluvial aquifer. Alachlor was detected sporadically, whereas, atrazine, cyanazine, and nitrate were present throughout the year. In the alluvial aquifer, the herbicides generally were not detected during 1986 and were present in detectable concentrations for only a short period of time in the upper 1.6 meters of the aquifer during 1987. Nitrate was present throughout the alluvium and was stratified in the alluvial aquifer. The largest nitrate concentrations were detected in the middle part of the aquifer. Nitrate concentrations were variable only in the upper 2 meters of the aquifer. Vertical movement of herbicides and nitrate in the soil correlated with precipitation and degree of saturation. A clay layer retarded vertical movement of atrazine but not nitrate from the soil layer to the aquifer. Vertical movement could not account for the chemical variation in the alluvial aquifer.     

ATRAZINE IN SPRING RUNOFF AS RELATED TO ENVIRONMENTAL SETTING EBRASKA, 19921

ABSTRACT: A synoptic sampling of five surface-water sites in central Nebraska was conducted by the U.S. Geological Survey as part of its National Water-Quality Assessment Program during storm runoff in May 1992 to relate transport, yields, and concentrations of atrazine to environmental setting. Atrazine was the most extensively applied pesticide in the study unit. Atrazine transport was related to the size of contributing drainage area, quantity of atrazine applied, amount of precipitation, and volume of stream-flow. Estimated yields and mean concentrations of atrazine were related to the percentage of cropland in a drainage area. The largest estimated yields and mean concentrations of atrazine in surface water were associated from drainage areas with the highest percentage of cropland, and the smallest was associated with the smallest amount of cropland. Atrazine concentrations increased as streamflow increased but decreased at or near the time of peak streamflows, perhaps due to dilution. Atrazine concentrations then increased and remained elevated far into the stream recession. Atrazine is a regulated contaminant in finished public-water supplies. Large concentrations of atrazine could affect the management of public-water supplies because atrazine remains in solution in contrast to many other pesticides that are more easily removed.     

Stream transport of herbicides and metabolites in a tile-drained, agricultural watershed

The occurrence of metabolites of many commonly used herbicides in streams has not been studied extensively in tile-drained watersheds. We collected water samples throughout the Upper Embarras River watershed [92% corn, Zea mays L., and soybean, Glycine max (L.) Merr.] in east-central Illinois from March 1999 through September 2000 to study the occurrence of atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine), metolachlor 12-chloro-N-(2-ethyl-6-methylphenyl)-N-(methoxy-1-methylethyl) acetamide], alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl) acetamide], acetochlor [2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl) acetamide], and their metabolites. River water samples were collected from three subwatersheds of varying tile density (2.8-5.3 km tile km(-2)) and from the outlet (United States Geological Survey [USGS] gage site). Near-record-low totals for stream flow occurred during the study, and nearly all flow was from tiles. Concentrations of atrazine at the USGS gage site peaked at 15 and 17 microg L(-1) in 1999 and 2000, respectively, and metolachlor at 2.7 and 3.2 microg L(-1); this was during the first significant flow event following herbicide applications. Metabolites of the chloroacetanilide herbicides were detected more often than the parent compounds (evaluated during May to July each year, when tiles were flowing), with metolachlor ethanesulfonic acid [2-[(2-ethyl-6-methylphenyl)(2-methoxy-1-methylethyl)amino]-2-oxoethanesulfonic acid] detected most often (> 90% from all sites), and metolachlor oxanilic acid [2-[(2-ethyl-6-methylphenyl)(2-methoxy-1-methylethyl)amino]-2-oxoacetic acid] second (40-100% of samples at the four sites). When summed, the median concentration of the three chloroacetanilide parent compounds (acetochlor, alachlor, and metolachlor) at the USGS gage site was 3.4 microg L(-1), whereas it was 4.3 microg L(-1) for the six metabolites. These data confirm the importance of studying chloroacetanilide metabolites, along with parent compounds, in tile-drained watersheds.     

Phosphorus transport pathways to streams in tile-drained agricultural watersheds

Agriculture is a major nonpoint source of phosphorus (P) in the Midwest, but how surface runoff and tile drainage interact to affect temporal concentrations and fluxes of both dissolved and particulate P remains unclear. Our objective was to determine the dominant form of P in streams (dissolved or particulate) and identify the mode of transport of this P from fields to streams in tile-drained agricultural watersheds. We measured dissolved reactive P (DRP) and total P (TP) concentrations and loads in stream and tile water in the upper reaches of three watersheds in east-central Illinois (Embarras River, Lake Fork of the Kaskaskia River, and Big Ditch of the Sangamon River). For all 16 water year by watershed combinations examined, annual flow-weighted mean TP concentrations were >0.1 mg L(-1), and seven water year by watershed combinations exceeded 0.2 mg L(-1). Concentrations of DRP and particulate P (PP) increased with stream discharge; however, particulate P was the dominant form during overland runoff events, which greatly affected annual TP loads. Concentrations of DRP and PP in tiles increased with discharge, indicating tiles were a source of P to streams. Across watersheds, the greatest DRP concentrations (as high as 1.25 mg L(-1)) were associated with a precipitation event that followed widespread application of P fertilizer on frozen soils. Although eliminating this practice would reduce the potential for overland runoff of P, soil erosion and tile drainage would continue to be important transport pathways of P to streams in east-central Illinois.     

Impact of climatic and soil conditions on environmental fate of atrazine used under plantation forestry in Australia

We studied the leaching and dissipation of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1, 3, 5-s-triazine) and its two principal metabolites (desethylatrazine and desisopropylatrazine) for more than two years through soil profiles at five forestry sites across Australia (representing subtropical, temperate and Mediterranean climatic conditions with rainfall ranging from 780 to 1536 mm yr^?1). Following atrazine applications at local label rates, soil cores were collected at regular intervals (up to depths of 90–150 cm), and the residues of the three compounds in soil were analysed in composite samples using liquid chromatography. Bromide was applied simultaneously with atrazine to follow the movement of the soil water. While bromide ion rapidly leached through the entire profile, in most cases the bulk of atrazine, desethylatrazine and desisopropylatrazine remained in the top 45 cm of the soil profile. However, a small fraction of residue moved deeper into the soil profile and at a subtropical site (Toolara) trace levels (ng L^?1) of atrazine and one of its metabolites (DEA) were detected in perched groundwater located at a depth of 1.8 m. Data on the total residues of atrazine in soil profiles from all sites except the Tasmanian site fitted a first-order decay model. The half-life of atrazine in surface soils at the subtropical sites (Toolara and Imbil) ranged from 11 to 21 days. Four separate applications of atrazine at Toolara resulted in a narrow range of half-lives (16 ± 3.6 days), confirming relatively rapid dissipation of atrazine under subtropical conditions (Queensland). In contrast, a prominent biphasic pattern of initial rapid loss followed by very slow phase of degradation of atrazine was observed under the colder temperate climate of Highclere (Tasmania). The data showed that while its 50% (DT₅₀) loss occurred relatively rapidly (36 days), more than 10% of herbicide residue was still detectable in the profile even a year after application (DT₉₀ = 375 days). The rate of dissipation of atrazine at warm subtropical Queensland sites (Imbil and Toolara) was 2–3 times faster than sites located in colder climate of Tasmania. The marked contrast in DT₅₀ values between subtropical and temperate sites suggest that climatic conditions (soil temperature) is one of the key factors affecting atrazine dissipation. At the Tasmanian site, the combination of leaching of the herbicide in subsoil and slower microbial activity at cooler temperatures would have caused a longer persistence of atrazine.     

Grazing management effects on sediment, phosphorus, and pathogen loading of streams in cool-season grass pastures

Erosion and runoff from pastures may lead to degradation of surface water. A 2-yr grazing study was conducted to quantify the effects of grazing management on sediment, phosphorus (P), and pathogen loading of streams in cool-season grass pastures. Six adjoining 12.1-ha pastures bisected by a stream in central Iowa were divided into three treatments: continuous stocking with unrestricted stream access (CSU), continuous stocking with restricted stream access (CSR), and rotational stocking (RS). Rainfall simulations on stream banks resulted in greater ( < 0.10) proportions of applied precipitation and amounts of sediment and P transported in runoff from bare sites than from vegetated sites across grazing treatments. Similar differences were observed comparing vegetated sites in CSU and RS pastures with vegetated sites in CSR pastures. Bovine enterovirus was shed by an average of 24.3% of cows during the study period and was collected in the runoff of 8.3 and 16.7% of runoff simulations on bare sites in CSU pastures in June and October of 2008, respectively, and from 8.3% of runoff simulations on vegetated sites in CSU pastures in April 2009. Fecal pathogens (bovine coronavirus [BCV], bovine rotavirus group A, and O157:H7) shed or detected in runoff were almost nonexistent; only BCV was detected in feces of one cow in August of 2008. Erosion of cut-banks was the greatest contributor of sediment and P loading to the stream; contributions from surface runoff and grazing animals were considerably less and were minimized by grazing management practices that reduced congregation of cattle by pasture streams.     

Nutrient retention efficiency in streams receiving inputs from wastewater treatment plants

We tested the effect of nutrient inputs from wastewater treatment plants (WWTPs) on stream nutrient retention efficiency by examining the longitudinal patterns of ammonium, nitrate, and phosphate concentrations downstream of WWTP effluents in 15 streams throughout Catalonia (Spain). We hypothesized that large nutrient loadings would saturate stream communities, lowering nutrient retention efficiency (i.e., nutrient retention relative to nutrient flux) relative to less polluted streams. Longitudinal variation in ambient nutrient concentration reflected the net result of physical, chemical, or biological uptake and release processes. Therefore, gradual increases in nutrient concentration indicate that the stream acts as a net source of nutrients to downstream environments, whereas gradual declines indicate that the stream acts as a net sink. In those streams where gradual declines in nutrient concentration were observed, we calculated the nutrient uptake length as an indicator of the stream nutrient retention efficiency. No significant decline was found in dilution-corrected concentrations of dissolved inorganic nitrogen (DIN) and phosphate in 40 and 45% of streams, respectively. In the remaining streams, uptake length (estimated based on the decline of nutrient concentrations at ambient levels) ranged from 0.14 to 29 km (DIN), and from 0.14 to 14 km (phosphate). Overall, these values are longer (lower retention efficiency) than those from nonpolluted streams of similar size, supporting our hypothesis, and suggest that high nutrient loads affect fluvial ecosystem function. This study demonstrates that the efficiency of stream ecosystems to remove nutrients has limitations because it can be significantly altered by the quantity and quality of the receiving water.     

Impact of glyphosate-tolerant soybean and glufosinate-tolerant corn production on herbicide losses in surface runoff

Residual herbicides used in the production of soybean [Glycine max (L.) Merr] and corn (Zea mays L.) are often detected in surface runoff at concentrations exceeding their maximum contaminant levels (MCL) or health advisory levels (HAL). With the advent of transgenic, glyphosate-tolerant soybean and glufosinate-tolerant corn this concern might be reduced by replacing some of the residual herbicides with short half-life, strongly sorbed, contact herbicides. We applied both herbicide types to two chiseled and two no-till watersheds in a 2-yr corn-soybean rotation and at half rates to three disked watersheds in a 3-yr corn/soybean/wheat (Triticum aestivum L.)-red clover (Trifolium pratense L.) rotation and monitored herbicide losses in runoff water for four crop years. In soybean years, average glyphosate loss (0.07%) was approximately 1/7 that of metribuzin (0.48%) and about one-half that of alachlor (0.12%), residual herbicides it can replace. Maximum, annual, flow-weighted concentration of glyphosate (9.2 microg L(-1)) was well below its 700 microg L(-1) MCL and metribuzin (9.5 microg L(-1)) was well below its 200 microg L(-1) HAL, whereas alachlor (44.5 microg L(-1)) was well above its 2 microg L(-1) MCL. In corn years, average glufosinate loss (0.10%) was similar to losses of alachlor (0.07%) and linuron (0.15%), but about one-fourth that of atrazine (0.37%). Maximum, annual, flow-weighted concentration of glufosinate (no MCL) was 3.5 microg L(-1), whereas atrazine (31.5 microg L(-1)) and alachlor (9.8 microg L(-1)) substantially exceeded their MCLs of 3 and 2 microg L(-1), respectively. Regardless of tillage system, flow-weighted atrazine and alachlor concentrations exceeded their MCLs in at least one crop year. Replacing these herbicides with glyphosate and glufosinate can reduce the occurrence of dissolved herbicide concentrations in runoff exceeding drinking water standards.     

RELATION BETWEEN STREAM-WATER QUALITY AND GEOHYDROLOGY DURING BASE-FLOW CONDITIONS,ROBERTS CREEK WATERSHED,CLAYTON COUNTY,IOWA1

ABSTRACT: An investigation to determine the relation between stream water quality and geohydrology in the Roberts Creek watershed, Clayton County, Iowa, was conducted during selected base-flow periods in 1988–90. Discharge measurements were made and water samples collected for analyses of nutrients and selected herbicides in 19 subbasins along the main stem and tributaries of Roberts Creek. The areal extent of unconsolidated and bedrock units subcropping in each subbasin was quantified. The hydrologic data were correlated statistically with the geologic data to determine relations. Roberts Creek generally gained water and had larger nitrogen concentrations in subbasins in which bess and alluvial material were underlain primarily by low-permeability till and shale units. Roberts Creek generally lost water and had lower nitrate concentrations in subbasins with subcroppmg karstic units. Nitrogen concentrations decreased in streams underlain by the karstic units because the nitrogen removed by biological processes was not replaced by ground-water inflow. Seepage from Roberts Creek to ground water in areas of subcropping karstic carbonate rocks reduced the flow, which reduced the velocity, causing increased residence time of water in the stream. The additional residence time may allow additional time for biological processes to remove nitrogen from solution. There was no significant relation between dissolved orthophosphate or atrazine and the underlying geology.     

Iowa Statewide Stream Nitrate Load Calculated Using In Situ Sensor Network

Various techniques exist to estimate stream nitrate loads when measured concentration data are sparse. The inherent uncertainty associated with load estimation, however, makes tracking progress toward water quality goals more difficult. We used high‐frequency, in situ nitrate sensors strategically deployed across the agricultural state of Iowa to evaluate 2016 stream concentrations at 60 sites and loads at 35 sites. The generated data, collected at an average of 225 days per site, show daily average nitrate‐N yields ranging from 12 to 198 g/ha, with annual yields as high as 53 kg/ha from the intensely drained Des Moines Lobe. Thirteen of the sites that capture water from 82.5% of Iowa's area show statewide nitrate‐N loading in 2016 totaled 477 million kg, or 41% of the load delivered to the Mississippi–Atchafalaya River Basin (MARB). Considering the substantial private and public investment being made to reduce nitrate loading in many states within the MARB, networks of continuous, in situ measurement devices as described here can inform efforts to track year‐to‐year changes in nitrate load related to weather and conservation implementation. Nitrate and other data from the sensor network described in this study are made publicly available in real time through the Iowa Water Quality Information System.     

Regression models for estimating concentrations of atrazine plus deethylatrazine in shallow groundwater in agricultural areas of the United States

Tobit regression models were developed to predict the summed concentration of atrazine [6-chloro--ethyl--(1-methylethyl)-1,3,5-triazine-2,4-diamine] and its degradate deethylatrazine [6-chloro--(1-methylethyl)-1,3,5,-triazine-2,4-diamine] (DEA) in shallow groundwater underlying agricultural settings across the conterminous United States. The models were developed from atrazine and DEA concentrations in samples from 1298 wells and explanatory variables that represent the source of atrazine and various aspects of the transport and fate of atrazine and DEA in the subsurface. One advantage of these newly developed models over previous national regression models is that they predict concentrations (rather than detection frequency), which can be compared with water quality benchmarks. Model results indicate that variability in the concentration of atrazine residues (atrazine plus DEA) in groundwater underlying agricultural areas is more strongly controlled by the history of atrazine use in relation to the timing of recharge (groundwater age) than by processes that control the dispersion, adsorption, or degradation of these compounds in the saturated zone. Current (1990s) atrazine use was found to be a weak explanatory variable, perhaps because it does not represent the use of atrazine at the time of recharge of the sampled groundwater and because the likelihood that these compounds will reach the water table is affected by other factors operating within the unsaturated zone, such as soil characteristics, artificial drainage, and water movement. Results show that only about 5% of agricultural areas have greater than a 10% probability of exceeding the USEPA maximum contaminant level of 3.0 μg L. These models are not developed for regulatory purposes but rather can be used to (i) identify areas of potential concern, (ii) provide conservative estimates of the concentrations of atrazine residues in deeper potential drinking water supplies, and (iii) set priorities among areas for future groundwater monitoring.     

Estimation of upper centile concentrations using historical atrazine monitoring data from community water systems

A survey sampling approach is presented for estimating upper centiles of aggregate distributions of surface water pesticide measurements obtained from datasets with large sample sizes but variable sampling frequency. It is applied to three atrazine monitoring programs of Community Water Systems (CWS) that used surface water as their drinking water source: the nationwide Safe Drinking Water Act (SDWA) data, the Syngenta Voluntary Monitoring Program (VMP), and the Atrazine Monitoring Program (AMP).The VMP/AMP CWS were selected on the basis of atrazine monitoring history (CWS having at least one annual average concentration from SDWA ≥ 1.6 ppb atrazine since 1997 in the AMP). Estimates of the raw water 95th, 99th, and 99.9th centile atrazine concentrations for the VMP/AMP CWS are 4.82, 11.85, and 34.00 ppb, respectively. The corresponding estimates are lower for the finished drinking water samples, with estimates of 2.75, 7.94, and 22.66 ppb, respectively. Finished water centile estimates for the VMP/AMP CWS using only the SDWA data for these sites are consistent with the results. Estimates are provided for the April through July period and for CWS based on surface water source type (static, flowing, or mixed). Requisite sample sizes are determined using statistical tolerance limits, relative SE, and the Woodruff interval sample size criterion. These analyses provide 99.9% confidence that the existing data include the 99.9th centile atrazine concentration for CWS raw and finished water in the Midwest atrazine high-use areas and in the nationwide SDWA dataset. The general validity of this approach is established by a simulation that shows estimates to be close to target quantities for weights based on sampling probabilities or time intervals between samples. Recommendations are given for suitable effective sample sizes to reliably determine interval estimates.     

Wastewater reuse and predicted ecological risk posed by contaminant mixtures in Potomac River watershed streams

A wastewater model was applied to the Potomac River watershed to provide (i) a means to identify streams with a high likelihood of carrying elevated effluent-derived contaminants and (ii) risk assessments to aquatic life and drinking water. The model linked effluent discharges along stream networks, accumulated wastewater, and predicted contaminant loads of municipal wastewater constituents while accounting for instream dilution and attenuation. Simulations using 2016 data suggested that nearly 30% (8281 km) of streams were wastewater impacted. Low- to medium-order streams had the largest range of accumulated wastewater (ACCWW%) values. ACCWW% exceeded a 1% threshold at >39% of drinking-water intakes (varied by temporal condition). Risk assessments of municipal wastewater-contaminant mixtures indicated that 22% (1479 km) of streams impacted by municipal wastewater (5.5% of all reaches modeled) may pose high risk to aquatic organisms under mean-annual conditions, with fish more susceptible to chronic-exposure effects relative to other taxa. Risk varied temporally and by stream order, with the greatest risk occurring in the summer in small streams. These findings suggest that wastewater may be an important factor contributing to environmental degradation in the Potomac River watershed.