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Due to the widespread use of insecticides in agriculture and for urban pest control, there is the potential for contamination of groundwater systems. Five neonicotinoids, fipronil, and nine transformation products (desnitro-imidacloprid, imidacloprid olefin, imidacloprid urea, acetamiprid-n-desmethyl, thiacloprid amide, 6-chloronicotinic acid, fipronil desulfinyl, fipronil sulfide, and fipronil sulfone) were studied in samples from 15 springs and 75 unique wells from 13 counties over four years (2019-2022) in Minnesota. Up to 13 neonicotinoids and fiproles were identified in groundwater samples from springs and 10 from wells. Springs were particularly susceptible to contamination, with clothianidin found in 41 % of springs (maximum concentration: 200 ng/L) followed by thiamethoxam (31 %), imidacloprid (22 %), thiacloprid (19 %), and acetamiprid (12 %). Clothianidin was the most common analyte in well samples (13 %), followed by thiamethoxam (12 %), acetamiprid (14 %), imidacloprid (10 %), and thiacloprid (2 %). Hydrostratigraphy was an important factor in neonicotinoid detection with frequencies of detection highest in sandy or karst aquifers. Regional land use, especially the fraction of agricultural land, and imperviousness influenced observed concentrations within springsheds and well catchment areas. There were several significant correlations between neonicotinoid detections with geochemistry indicators including tritium/groundwater age, dissolved oxygen (DO), and total nitrate plus nitrite (total oxidized nitrogen)., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: William Arnold reports financial support was provided by Environment and Natural Resources Trust Fund. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The Chesapeake Bay watershed has been the focus of pioneering studies of the role of atmospheric nitrogen (N) deposition as a nutrient source and driver of estuarine trophic status. Here, we review the history and evolution of scientific investigations of the role of atmospheric N deposition, examine trends from wet and dry deposition networks, and present century-long (1950-2050) atmospheric N deposition estimates. Early investigations demonstrated the importance of atmospheric deposition as an N source to the Bay, providing 25%-40% among all major N sources. These early studies led to the unprecedented inclusion of targeted decreases in atmospheric N deposition as part of the multi-stakeholder effort to reduce N loads to the Bay. Emissions of nitrogen oxides (NO x ) and deposition of wet nitrate, oxidized dry N, and dry ammonium ( NH 4 + ) sharply and synchronously declined by 60%-73% during 1995-2019. These decreases largely resulted from implementation of Title IV of the 1990 Clean Air Act Amendments, which began in 1995. Wet NH 4 + deposition shows no significant trend during this period. The century-long atmospheric N deposition estimates indicate an increase in total atmospheric N deposition in the Chesapeake watershed from 1950 to a peak of ~15 kg N/ha/yr in 1979, trailed by a slight decline of <10% through the mid-1990s, and followed by a sharp decline of about 40% thereafter through 2019. An additional 21% decline in atmospheric N deposition is projected from 2015 to 2050. A comparison of the Potomac River and James River watersheds indicates higher atmospheric N deposition in the Potomac, likely resulting from greater emissions from higher proportions of agricultural and urban land in this basin. Atmospheric N deposition rose from 30% among all N sources to the Chesapeake Bay watershed in 1950 to a peak of 40% in 1973, and a decline to 28% by 2015. These data highlight the important role of atmospheric N deposition in the Chesapeake Bay watershed and present a potential opportunity for decreases in deposition to contribute to further reducing N loads and improving the trophic status of tidal waters., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Neonicotinoid insecticides cause adverse effects on nontarget organisms, but more information about their occurrence in surface and groundwater is needed across a range of land uses. Sixty-five sites in Minnesota, USA, representing rivers, streams, lakes, groundwater, and treated wastewater, were monitored via collection of 157 water samples to determine variability in spatiotemporal neonicotinoid concentrations. The data were used to assess relations to land use, hydrogeologic condition, and potential effects on aquatic life. Total neonicotinoid concentrations were highest in agricultural watersheds (median = 12 ng/L), followed by urban (2.9 ng/L) and undeveloped watersheds (1.9 ng/L). Clothianidin was most frequently detected in agricultural areas (detection frequency = 100%) and imidacloprid most often in urban waters (detection frequency = 97%). The seasonal trend of neonicotinoid concentrations in rivers, streams, and lakes showed that their highest concentrations coincided with spring planting and elevated streamflow. Consistently low neonicotinoid concentrations were found in shallow groundwater in agricultural regions (<1.2-16 ng/L, median = 1.4 ng/L). Treated municipal wastewater had the highest concentrations across all hydrologic compartments (12-48 ng/L, median = 19 ng/L), but neonicotinoid loads from rivers and streams (median = 4100 mg/d) were greater than in treated wastewater (700 mg/d). No samples exceeded acute aquatic-life benchmarks for individual neonicotinoids, whereas 10% of samples exceeded a chronic benchmark for neonicotinoid mixtures. Although 62% of samples contained 2 or more neonicotinoids, the observed concentrations suggest there were low acute and potential chronic risks to aquatic life. This the first study of its size in Minnesota and is critical to better understanding the drivers of wide-scale environmental contamination by neonicotinoids where urban, agricultural, and undeveloped lands are present. Environ Toxicol Chem 2021;40:1017-1033. © 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC., (© 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.)

Agricultural subsurface drainage can be an important conduit of nitrate from agricultural fields to streams. This study focused on understanding the variability in nitrate concentrations and loads, exported by subsurface drains, into a small, north-central Iowa stream. Ninety-three subsurface drains in this watershed were sampled up to 5 times between 2006 and 2008. Additionally, 2 subsurface drains and the stream draining the study area (South Fork Iowa River near Blairsburg, IA, USA) were sampled frequently during the growing seasons in 2007 and 2008. Spatial variability analysis revealed no distinct spatial pattern in nitrate concentrations. The median nitrate concentrations were not significantly different when the drain outlets were characterized by diameter (17-23 cm, 27-48 cm, 60-108 cm). The eight large subsurface drains (part of the public drainage network) had less variability in nitrate concentration than the smaller drain sizes and generally contributed 70-87% of the total water and nitrate loads exported by subsurface drains to the stream. During high-discharge events, the medium-sized (27-48 cm) subsurface drains discharging to the stream became more important by contributing a higher discharge and nitrate load. The temporal variability examined in this study found that discharge and nitrate loads were influenced by the amount of precipitation that had occurred over the previous months. This paper demonstrates the spatial and within-season homogeneity of nitrate delivery to a stream from an intensely agricultural landscape that has subsurface drainage.

Background: Metolachlor [(RS)-2-Chloro-N-(2-ethyl-6-methyl-phenyl)-N-(1-methoxypropan-2-yl)acetamide] and two degradates (metolachlor ethane-sulfonic acid and metolachlor oxanilic acid) are commonly observed in surface and groundwater. The behavior and fate of these compounds were examined over a 12-year period in seven agricultural watersheds in the United States. They were quantified in air, rain, streams, overland flow, groundwater, soil water, subsurface drain water, and water at the stream/groundwater interface. The compounds were frequently detected in surface and groundwater associated with agricultural areas. A mass budget approach, based on all available data from the study and literature, was used to determine a percentage-wise generalized distribution and fate of applied parent metolachlor in typical agricultural environments., Results: In these watersheds, about 90% of applied metolachlor was taken up by plants or degraded, 10% volatilized, and 0.3% returned as rainfall. One percent was transported to surface water, while an equal amount infiltrated into the unsaturated zone soil water. <0.02% reached the groundwater. Subsurface flow paths resulted in greater degradation of metolachlor because degradation reactions had more time to proceed., Conclusions: An understanding of the residence times of water in the different environmental compartments, and the important processes affecting metolachlor as it is transported along flowpaths among the environmental compartments allows for a degree of predictability of metolachlor's fate. Degradates with long half-lives can be used (in a limited capacity) as tracers of metolachlor, because of their persistence and widespread occurrence in the environment., (Published by Elsevier B.V.)

Background: Genetically modified (GM) varieties of soybean, corn and cotton have largely replaced conventional varieties in the United States. The most widely used applications of GM technology have been the development of crops that are resistant to a specific broad-spectrum herbicide (primarily glyphosate) or that produce insecticidal compounds within the plant itself. With the widespread adoption of GM crops, a decline in the use of conventional pesticides was expected., Results: There has been a reduction in the annual herbicide application rate to corn since the advent of GM crops, but the herbicide application rate is mostly unchanged for cotton. Herbicide use on soybean has increased. There has been a substantial reduction in the amount of insecticides used on both corn and cotton since the introduction of GM crops., Conclusions: The observed changes in pesticide use are likely to be the result of many factors, including the introduction of GM crops, regulatory restrictions on some conventional pesticides, introduction of new pesticide technologies and changes in farming practices. In order to help protect human and environmental health and to help agriculture plan for the future, more detailed and complete documentation on pesticide use is needed on a frequent and ongoing basis. Published 2015. This article is a U.S. Government work and is in the public domain in the USA., (Published 2015. This article is a U.S. Government work and is in the public domain in the USA.)

A variety of current-use pesticides were determined in weekly composite air and rain samples collected during the 1995 and 2007 growing seasons in the Mississippi Delta (MS, USA) agricultural region. Similar sampling and analytical methods allowed for direct comparison of results. Decreased overall pesticide use in 2007 relative to 1995 generally resulted in decreased detection frequencies in air and rain; observed concentration ranges were similar between years, however, even though the 1995 sampling site was 500 m from active fields whereas the 2007 sampling site was within 3 m of a field. Mean concentrations of detections were sometimes greater in 2007 than in 1995, but the median values were often lower. Seven compounds in 1995 and 5 in 2007 were detected in ≥50% of both air and rain samples. Atrazine, metolachlor, and propanil were detected in ≥50% of the air and rain samples in both years. Glyphosate and its degradation product, aminomethyl-phosphonic acid (AMPA), were detected in ≥75% of air and rain samples in 2007 but were not measured in 1995. The 1995 seasonal wet depositional flux was dominated by methyl parathion (88%) and was >4.5 times the 2007 flux. Total herbicide flux in 2007 was slightly greater than in 1995 and was dominated by glyphosate. Malathion, methyl parathion, and degradation products made up most of the 2007 nonherbicide flux., (© 2014 SETAC.)

Carbon is cycled to and from large reservoirs in the atmosphere, on land, and in the ocean. Movement of organic carbon from the terrestrial reservoir to the ocean plays an important role in the global cycling of carbon. The transition from natural to agricultural vegetation can change the storage and movement of organic carbon in and from a watershed. Samples were collected from 13 streams located in hydrologically and agriculturally diverse watersheds, to better understand the variability in the concentrations and loads of dissolved organic carbon (DOC) and particulate organic carbon (POC) in the streams, and the variability in watershed yields. The overall annual median concentrations of DOC and POC were 4.9 (range: 2.1-6.8) and 1.1 (range: 0.4-3.8) mg C L, respectively. The mean DOC watershed yield (± SE) was 25 ± 6.8 kg C ha yr. The yields of DOC from these agricultural watersheds were not substantially different than the DOC yield from naturally vegetated watersheds in equivalent biomes, but were at the low end of the range for most biomes. Total organic carbon (DOC + POC) annually exported from the agricultural watersheds was found to average 0.03% of the organic carbon that is contained in the labile plant matter and top 1 m of soil in the watershed. Since the total organic carbon exported from agricultural watersheds is a relatively small portion of the sequestered carbon within the watershed, there is the great potential to store additional carbon in plants and soils of the watershed, offsetting some anthropogenic CO emissions., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)

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., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)

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., (Copyright © 2011 Society of Chemical Industry.)

This is the first report on the ambient levels of glyphosate, the most widely used herbicide in the United States, and its major degradation product, aminomethylphosphonic acid (AMPA), in air and rain. Concurrent, weekly integrated air particle and rain samples were collected during two growing seasons in agricultural areas in Mississippi and Iowa. Rain was also collected in Indiana in a preliminary phase of the study. The frequency of glyphosate detection ranged from 60 to 100% in both air and rain. The concentrations of glyphosate ranged from <0.01 to 9.1 ng/m(3) and from <0.1 to 2.5 µg/L in air and rain samples, respectively. The frequency of detection and median and maximum concentrations of glyphosate in air were similar or greater to those of the other high-use herbicides observed in the Mississippi River basin, whereas its concentration in rain was greater than the other herbicides. It is not known what percentage of the applied glyphosate is introduced into the air, but it was estimated that up to 0.7% of application is removed from the air in rainfall. Glyphosate is efficiently removed from the air; it is estimated that an average of 97% of the glyphosate in the air is removed by a weekly rainfall ≥ 30 mm., (Copyright © 2011 SETAC.)

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.

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.

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.

This paper is an introduction to the following series of papers that report on in-depth investigations that have been conducted at five agricultural study areas across the United States in order to gain insights into how environmental processes and agricultural practices interact to determine the transport and fate of agricultural chemicals in the environment. These are the first study areas in an ongoing national study. The study areas were selected, based on the combination of cropping patterns and hydrologic setting, as representative of nationally important agricultural settings to form a basis for extrapolation to unstudied areas. The holistic, watershed-scale study design that involves multiple environmental compartments and that employs both field observations and simulation modeling is presented. This paper introduces the overall study design and presents an overview of the hydrology of the five study areas.

We studied the value of serum amyloid A (SAA), a first-class acute-phase protein, as a marker for coronary heart disease (CHD) in a middle-aged male population. In a working population of 16307 men (age, 35-59 years), 446 cases had a history of CHD or prominent Q:QS waves on electrocardiogram. For each case, two matched controls were investigated. SAA, measured by immunonephelometry, was correlated with other acute-phase proteins, cardiovascular risk factors, and infectious serology markers. SAA concentrations were significantly higher in the cases than in controls (P<0.05) and correlated with serum C-reactive protein (CRP) (r=0.61), plasma fibrinogen (r=0.39), serum haptoglobin (r=0.26), and body mass index (r=0.13) (P<0.001). Serum CRP is a better marker for CHD than SAA, which showed discriminative power only in a univariate model comparing highest versus lowest tertile (odds ratio, 1.39; 95% confidence interval, 1.03-1.87). Neither SAA nor other acute-phase proteins correlated with Chlamydia pneumoniae immunoglobulin (Ig)G, Helicobacter pylori IgG and IgA, and cytomegalovirus IgG. In conclusion, although SAA has a discriminative value for CHD, serum CRP is to be preferred as a first-class acute-phase reactant for detection of the disease.