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USGS2009

Environmental exposures to agrochemicals in the Sierra Nevada mountain range

The release of pesticides into the environment may impact human and environmental health. Despite the need for environmental exposure data, few studies quantify exposures in urban areas and even fewer determine exposures to wildlife in remote areas. Although it is expected that concentrations in remote regions will be low, recent studies suggest that even low concentrations may have deleterious effects on wildlife. Many pesticides are known to interfere with the endocrine systems of humans and wildlife, adversely affecting growth, development, and behavior. This chapter reviews the fate and transport of pesticides applied in the Central Valley of California and quantifies their subsequent deposition into the relatively pristine Sierra Nevada Mountain Range.

California↗

USGS2005

Individual variability in esterase activity and CYP1A levels in Chinook salmon (Oncorhynchus tshawytscha) exposed to esfenvalerate and chlorpyrifos

Acetylcholinesterase (AChE) activity has traditionally been monitored as a biomarker of organophosphate (OP) and/or carbamate exposure. However, AChE activity may not be the most sensitive endpoint for these agrochemicals, because OPs can cause adverse physiological effects at concentrations that do not affect AChE activity. Carboxylesterases are a related family of enzymes that have higher affinity than AChE for some OPs and carbamates and may be more sensitive indicators of environmental exposure to these pesticides. In this study, carboxylesterase and AChE activity, cytochrome P4501A (CYP1A) protein levels, and mortality were measured in individual juvenile Chinook salmon (Oncorhynchus tshawytscha) following exposure to an OP (chlorpyrifos) and a pyrethroid (esfenvalerate). As expected, high doses of chlorpyrifos and esfenvalerate were acutely toxic, with nominal concentrations (100 and 1 ??g/l, respectively) causing 100% mortality within 96 h. Exposure to chlorpyrifos at a high dose (7.3 ??g/l), but not a low dose (1.2 ??g/l), significantly inhibited AChE activity in both brain and muscle tissue (85% and 92% inhibition, respectively), while esfenvalerate exposure had no effect. In contrast, liver carboxylesterase activity was significantly inhibited at both the low and high chlorpyrifos dose exposure (56% and 79% inhibition, respectively), while esfenvalerate exposure still had little effect. The inhibition of carboxylesterase activity at levels of chlorpyrifos that did not affect AChE activity suggests that some salmon carboxylesterase isozymes may be more sensitive than AChE to inhibition by OPs. CYP1A protein levels were ???30% suppressed by chlorpyrifos exposure at the high dose, but esfenvalerate had no effect. Three teleost species, Chinook salmon, medaka (Oryzias latipes) and Sacramento splittail (Pogonichthys macrolepidotus), were examined for their ability to hydrolyze a series of pyrethroid surrogate substrates and in all cases hydrolysis activity was undetectable. Together these data suggest that (1) carboxylesterase activity inhibition may be a more sensitive biomarker for OP exposure than AChE activity, (2) neither AChE nor carboxylesterase activity are biomarkers for pyrethroid exposure, (3) CYP1A protein is not a sensitive marker for these agrochemicals and (4) slow hydrolysis rates may be partly responsible for acute pyrethroid toxicity in fish. ?? 2005 Elsevier B.V. All rights reserved.

Aquatic Toxicology↗

USGS2024

Characterizing the areal extent of PFAS contamination in fish species downgradient of AFFF source zones

Most monitoring programs next to large per- and polyfluoroalkyl substances (PFAS) sources focus on drinking water contamination near source zones. However, less is understood about how these sources affect downgradient hydrological systems and food webs. Here, we report paired PFAS measurements in water, sediment, and aquatic biota along a hydrological gradient away from source zones contaminated by the use of legacy aqueous film-forming foam (AFFF) manufactured using electrochemical fluorination. Clustering analysis indicates that the PFAS composition characteristic of AFFF is detectable in water and fishes >8 km from the source. Concentrations of 38 targeted PFAS and extractable organofluorine (EOF) decreased in fishes downgradient of the AFFF-contaminated source zones. However, PFAS concentrations remained above consumption limits at all locations within the affected watershed. Perfluoroalkyl sulfonamide precursors accounted for approximately half of targeted PFAS in fish tissues, which explain >90% of EOF across all sampling locations. Suspect screening analyses revealed the presence of a polyfluoroketone pharmaceutical in fish species, and a fluorinated agrochemical in water that likely does not accumulate in biological tissues, suggesting the presence of diffuse sources such as septic system and agrochemical inputs throughout the watershed in addition to AFFF contamination. Based on these results, monitoring programs that consider all hydrologically connected regions within watersheds affected by large PFAS sources would help ensure public health protection.

Massachusetts↗

USGS2010

Exposure of nonbreeding migratory shorebirds to cholinesterase-inhibiting contaminants in the western hemisphere

Migratory shorebirds frequently forage and roost in agricultural habitats, where they may be exposed to cholinesterase-inhibiting pesticides. Exposure to organophosphorus and carbamate compounds, common anti-cholinesterases, can cause sublethal effects, even death. To evaluate exposure of migratory shorebirds to organophosphorus and carbamates, we sampled birds stopping over during migration in North America and wintering in South America. We compared plasma cholinesterase activities and body masses of individuals captured at sites with no known sources of organophosphorus or carbamates to those captured in agricultural areas where agrochemicals were recommended for control of crop pests. In South America, plasma acetylcholinesterase and butyrylcholinesterase activity in Buff-breasted Sandpipers was lower at agricultural sites than at reference sites, indicating exposure to organophosphorus and carbamates. Results of plasma cholinesterase reactivation assays and foot-wash analyses were inconclusive. A meta-analysis of six species revealed no widespread effect of agricultural chemicals on cholinesterase activity. however, four of six species were negative for acetylcholinesterase and one of six for butyrylcholinesterase, indicating negative effects of pesticides on cholinesterase activity in a subset of shorebirds. Exposure to cholinesterase inhibitors can decrease body mass, but comparisons between treatments and hemispheres suggest that agrochemicals did not affect migratory shorebirds' body mass. Our study, one of the first to estimate of shorebirds' exposure to cholinesterase-inhibiting pesticides, suggests that shorebirds are being exposed to cholinesterase- inhibiting pesticides at specific sites in the winter range but not at migratory stopover sites. future research should examine potential behavioral effects of exposure and identify other potential sitesand levels of exposure. ?? The Cooper Ornithological Society 2010.

Condor↗

USGS2001

An interdisciplinary assessment of regional-scale nonpoint source ground-water vulnerability: Theory and application

An integrated earth science-economics model, developed within a geographic information system (GIS), combines a regional-scale nonpoint source vulnerability assessment with a specific remediation measure to avoid unnecessary agricultural production costs associated with the use of agrochemicals in the Pearl Harbor basin on the island of Oahu, Hawaii. This approach forms the core of a risk-based regulation for the application of agrochemicals and estimates the benefits of an information-based approach to decisionmaking.

Hawaii↗

USGS2024

Methods of analysis—Determination of pesticides in filtered water and suspended sediment using liquid chromatography- and gas chromatography-tandem mass spectrometry

The widespread application of pesticides in agricultural and urban areas leads to their presence in surface waters. Presence of these biologically active chemicals in environmental waters potentially has adverse effects on nontarget organisms. To better understand the environmental fate of these contaminants, a robust method to capture chemicals with wide-ranging physicochemical properties has been developed. The method was developed by the U.S. Geological Survey’s Organic Chemistry Research Laboratory to monitor pesticides, pesticide degradates, and other agrochemicals in environmental surface waters throughout the country. The analysis involves a multiresidue method to determine 183 pesticides and pesticide degradates in filtered water samples and 178 pesticides and pesticide degradates in paired suspended sediment samples. After the filtration of whole water, contaminants are individually measured in the filtered water and the collected suspended sediment. Filtered water is extracted via solid-phase extraction, whereas suspended sediment is extracted using an ultrasonication, solid-liquid extraction. Samples are analyzed by liquid chromatography-tandem mass spectrometry using an electrospray ionization source in positive and negative modes and analyzed by gas chromatography-tandem mass spectrometry using an advanced electron ionization source in positive mode. Instrument parameters were optimized for the highest sensitivity, and at least two transitions (quantifier and qualifier) were monitored for each analyte. Recoveries in test filtered water ( n =9; 183 analytes) from the American River, California, and suspended sediment ( n =9; 178 analytes) samples fortified at 15 nanograms per liter (ng/L) ranged from 70.1 to 121.0 and 71.1 to 117.0 percent in water and suspended sediment filter samples, respectively. Method detection limits of pesticides and pesticide degradates ranged from 0.5 to 10.6 ng/L in water and 0.7 to 11.8 ng/L in suspended sediment filters. Reporting limits were 1.1–21.1 ng/L and 1.5–23.7 ng/L in water and filter samples, respectively. The developed method is applied to surface-water samples for the analysis of pesticides, pesticide degradates, and other agrochemicals.

Techniques and Methods↗

USGS2017

A pesticide paradox: Fungicides indirectly increase fungal infections

There are many examples where the use of chemicals have had profound unintended consequences, such as fertilizers reducing crop yields (paradox of enrichment) and insecticides increasing insect pests (by reducing natural biocontrol). Recently, the application of agrochemicals, such as agricultural disinfectants and fungicides, has been explored as an approach to curb the pathogenic fungus, Batrachochytrium dendrobatidis ( Bd ), which is associated with worldwide amphibian declines. However, the long-term, net effects of early-life exposure to these chemicals on amphibian disease risk have not been thoroughly investigated. Using a combination of laboratory experiments and analysis of data from the literature, we explored the effects of fungicide exposure on Bd infections in two frog species. Extremely low concentrations of the fungicides azoxystrobin, chlorothalonil, and mancozeb were directly toxic to Bd in culture. However, estimated environmental concentrations of the fungicides did not reduce Bd on Cuban tree frog ( Osteopilus septentrionalis ) tadpoles exposed simultaneously to any of these fungicides and Bd , and fungicide exposure actually increased Bd -induced mortality. Additionally, exposure to any of these fungicides as tadpoles resulted in higher Bd abundance and greater Bd -induced mortality when challenged with Bd post-metamorphosis, an average of 71 d after their last fungicide exposure. Analysis of data from the literature revealed that previous exposure to the fungicide itraconazole, which is commonly used to clear Bd infections, made the critically endangered booroolong frog ( Litoria booroolongensis ) more susceptible to Bd . Finally, a field survey revealed that Bd prevalence was positively associated with concentrations of fungicides in ponds. Although fungicides show promise for controlling Bd , these results suggest that, if fungicides do not completely eliminate Bd or if Bd recolonizes, exposure to fungicides has the potential to do more harm than good. To ensure that fungicide applications have the intended consequence of curbing amphibian declines, researchers must identify which fungicides do not compromise the pathogen resistance mechanisms of amphibians.

Ecological Applications↗

USGS2017

Long-term and widespread changes in agricultural practices influence ring-necked pheasant abundance in California

Declines in bird populations in agricultural regions of North America and Europe have been attributed to agricultural industrialization, increases in use of agrochemical application, and increased predation related to habitat modification. Based on count data compiled from Breeding Bird Survey (BBS) from 1974 to 2012, Christmas Bird Count (CBC) collected from 1914 to 2013, and hunter data from Annual Game Take Survey (AGTS) for years 1948–2010, ring-necked pheasants ( Phasianus colchicus ) in California have experienced substantial declines in agricultural environments. Using a modeling approach that integrates all three forms of survey data into a joint response abundance index, we found pheasant abundance was related to the amount of harvested and unharvested crop land, types of crops produced, amount of total pesticide applied, minimum temperature, precipitation, and numbers of avian competitors and predators. Specifically, major changes in agricultural practices over the last three decades were associated with declines in pheasant numbers and likely reflected widespread loss of habitat. For example, increases in cropland were associated with increased pheasant abundance during early years of study but this effect decreased through time, such that no association in recent years was evidenced. A post hoc analysis revealed that crops beneficial to pheasant abundance (e.g., barley) have declined substantially in recent decades and were replaced by less advantageous crops (e.g., nut trees). An additional analysis using a restricted data set (1990–2013) indicated recent negative impacts on pheasant numbers associated with land use practices were also associated with relatively high levels of pesticide application. Our results may provide valuable information for management policies aimed at reducing widespread declines in pheasant populations in California and may be applicable to other avian species within agricultural settings. Furthermore, this general analytical approach is not limited to pheasants and could be applied to other taxa for which multiple survey data sources exist.

California↗

USGS2006

Future trends in transport and fate of diffuse contaminants in catchments, with special emphasis on stable isotope applications

A summary is provided of the first of a series of proposed Integrated Science Initiative workshops supported by the UNESCO International Hydrological Programme. The workshop brought together hydrologists, environmental chemists, microbiologists, stable isotope specialists and natural resource managers with the purpose of communicating new ideas on ways to assess microbial degradation processes and reactive transport at catchment scales. The focus was on diffuse contamination at catchment scales and the application of compound-specific isotope analysis (CSIA) in the assessment of biological degradation processes of agrochemicals. Major outcomes were identifying the linkage between water residence time distribution and rates of contaminant degradation, identifying the need for better information on compound specific microbial degradation isotope fractionation factors and the potential of CSIA in identifying key degradative processes. In the natural resource management context, a framework was developed where CSIA techniques were identified as practically unique in their capacity to serve as distributed integrating indicators of process across a range of scales (micro to diffuse) of relevance to the problem of diffuse pollution assessment. Copyright ?? 2006 John Wiley & Sons, Ltd.

Hydrological Processes↗

USGS2015

Corn stover harvest increases herbicide movement to subsurface drains: RZWQM simulations

BACKGROUND Crop residue removal for bioenergy production can alter soil hydrologic properties and the movement of agrochemicals to subsurface drains. The Root Zone Water Quality Model (RZWQM), previously calibrated using measured flow and atrazine concentrations in drainage from a 0.4 ha chisel-tilled plot, was used to investigate effects of 50 and 100% corn ( Zea mays L.) stover harvest and the accompanying reductions in soil crust hydraulic conductivity and total macroporosity on transport of atrazine, metolachlor, and metolachlor oxanilic acid (OXA). RESULTS The model accurately simulated field-measured metolachlor transport in drainage. A 3-yr simulation indicated that 50% residue removal decreased subsurface drainage by 31% and increased atrazine and metolachlor transport in drainage 4 to 5-fold when surface crust conductivity and macroporosity were reduced by 25%. Based on its measured sorption coefficient, ~ 2-fold reductions in OXA losses were simulated with residue removal. CONCLUSION RZWQM indicated that if corn stover harvest reduces crust conductivity and soil macroporosity, losses of atrazine and metolachlor in subsurface drainage will increase due to reduced sorption related to more water moving through fewer macropores. Losses of the metolachlor degradation product OXA will decrease due to the more rapid movement of the parent compound into the soil.

Pest Management Science↗

USGS2019

Review: Endophytic microbes and their potential applications in crop management

Endophytes are microbes (mostly bacteria and fungi) present in plants. Endophytic microbes are often functional in that they may carry nutrients from the soil into plants, modulate plant development, increase stress tolerance of plants, suppress virulence in pathogens, increase disease resistance in plants, and suppress development of competitor plant species. Endophytic microbes have been shown: 1) obtain nutrients in soils and transfer nutrients to plants in the rhizophagy cycle and other nutrient‐transfer symbioses; 2) increase plant growth and development; 3) reduce oxidative stress of hosts; 4) protect plants from disease; 5) deter feeding by herbivores; and 6) suppress growth of competitor plant species. Because of the effective functions of endophytic microbes, we suggest that endophytic microbes may significantly reduce use of agrochemicals (fertilizers, fungicides, insecticides, and herbicides) in the cultivation of crop plants. The loss of endophytic microbes from crop plants during domestication and long‐term cultivation could be remedied by transfer of endophytes from wild relatives of crops to crop species. Increasing atmospheric carbon dioxide levels could reduce the efficiency of the rhizophagy cycle due to repression of reactive oxygen used to extract nutrients from microbes in roots.

Pest Management Science↗

USGS2026

Cotton farming pesticides affect ileal microbiota activity expressions of virulome but not resistome or metabolic pathways in a sedentary wild passerine

The increased use of agrochemicals to enhance crop production has had detrimental environmental effects including implication in the sharp decline of North American farmland-breeding birds. Here, using a combination of deep shotgun metatranscriptomics and pesticide exposure data, we sought to assess whether exposure to cotton ( Gossypium spp.) production had a differential effect on ileum multi-kingdom microbial activity, metabolism, anti-microbial resistance, and virulence factors of sedentary northern mockingbirds ( Mimus polyglottos ) sampled from two cotton-producing areas (16 birds in total) and one uncultivated area (7 birds) in Texas, USA. Both Shannon Index values (Adj. r 2 = 0.174, F (1,21) = 5.633, p = 0.027) and a Mantel test (Spearman ρ = 0.184, p = 0.013) supported a relationship between metabolically active microbiota Bray–Curtis dissimilarities and differences in pesticide mixtures among study areas. Virulence factor richness (Adj. r 2 = 0.182, F (1,21) = 5.890, p = 0.024), Shannon Index (Adj. r 2 = 0.231, F (1,21) = 7.612, p = 0.012), and load (sum of virulence factor abundances; Adj. r 2 = 0.160, F (1,21) = 5.194, p = 0.033) were related to total pesticide load (total quantity of pesticides). We found no pesticide effects on expression of either antimicrobial resistance genes or metabolic pathways.

Texas↗

USGS2006

Solute transport processes

Soils and aquifers are major compartments of the subsurface environment, which together control the terrestrial hydrological cycle. This subsurface is important for water resources and also as repository for municipal, industrial, and government waste. Aquifers are typically recharged by natural rainfall entering the soil profile and leaching into deeper soil layers. Due to intensive agricultural or industrial activities the leachate leaving the soil profile and entering the aquifer may contain concentrations of toxic substances such as agrochemicals, heavy metals, and polycyclic aromatic hydrocarbons. At contaminated industrial sites light and dense non-aqueous phase liquids (LNAPLs, DNAPLs) may be transported as a separate phase to the underlying aquifer systems. Once any of these chemicals have entered the aquifer they can be transported over large horizontal distances thus contaminating large parts of the aquifer and threateningwater supplywells. Remediation of highly contaminated aquifer systems is commonly a long-term and expensive proposition. As safe and effective use of the subsurface environment is a major challenge facing our society, there is a great need to improve our understanding of the shallow subsurface and the groundwater systems. This particularly includes the understanding of transport processes, which are responsible for the fate of contaminants.

Book chapter↗

USGS2009

Identifying sources of dissolved organic carbon in agriculturally dominated rivers using radiocarbon age dating: Sacramento-San Joaquin River Basin, California

We used radiocarbon measurements of dissolved organic carbon (DOC) to resolve sources of riverine carbon within agriculturally dominated landscapes in California. During 2003 and 2004, average Δ 14 C for DOC was −254‰ in agricultural drains in the Sacramento–San Joaquin Delta, −218‰ in the San Joaquin River, −175‰ in the California State Water Project and −152‰ in the Sacramento River. The age of bulk DOC transiting the rivers of California’s Central Valley is the oldest reported for large rivers and suggests wide-spread loss of soil organic matter caused by agriculture and urbanization. Using DAX 8 adsorbent, we isolated and measured 14 C concentrations in hydrophobic acid fractions (HPOA); river samples showed evidence of bomb-pulse carbon with average Δ 14 C of 91 and 76‰ for the San Joaquin and Sacramento Rivers, respectively, with older HPOA, −204‰, observed in agricultural drains. An operationally defined non-HPOA fraction of DOC was observed in the San Joaquin River with seasonally computed Δ 14 C values of between −275 and −687‰; the source of this aged material was hypothesized to be physically protected organic-matter in high clay-content soils and agrochemicals (i.e., radiocarbon-dead material) applied to farmlands. Mixing models suggest that the Sacramento River contributes about 50% of the DOC load in the California State Water Project, and agricultural drains contribute approximately one-third of the load. In contrast to studies showing stabilization of soil carbon pools within one or two decades following land conversion, sustained loss of soil organic matter, occurring many decades after the initial agricultural-land conversion, was observed in California’s Central Valley.

California↗

USGS2025

Pyrethroid insecticide pollution of wetlands reduces amphipod density

Freshwater amphipods play a key role as forage for breeding and migrating waterfowl in wetlands throughout the Prairie Pothole Region (PPR) of North America. Amphipod populations declined in recent decades, but there is a limited understanding of mechanisms for their decline and their uneven distribution across the landscape. Row crop agriculture is abundant in the PPR, but the sensitivity of amphipods and wetland ecosystems to agrochemical pollution has rarely been studied. We investigated relationships among amphipod abundances (specifically, Gammarus lacustris and Hyalella azteca ), land uses, water quality, and pyrethroid insecticide contamination of wetland sediments. Our study design targeted a large gradient of amphipod abundances and accounted for water quality, hydrology, and habitat metrics that commonly influence amphipods. We found a significant, negative relationship between pyrethroid concentrations and the abundance of the two amphipod species. Pyrethroids were detected at relatively low concentrations (<2.5 ng/g sediment) in 44% of study wetlands and occurred most frequently in intensively cropped watersheds with low vegetative filter strip coverage. Interestingly, wetlands on state and federal wildlife reserves had regular occurrence of pyrethroids, demonstrating the pervasive transport of these compounds and the intensity of agriculture in the PPR. The pyrethroids are likely entering these wetlands through overland transport during rain events or aerial spray drift, and our results show that forest patches and vegetative filter strips may reduce pyrethroid exposure to both wetlands and amphipods.

Ecotoxicology↗

USGS2022

Seed treatments containing neonicotinoids and fungicides reduce aquatic insect richness and abundance in midwestern USA–managed floodplain wetlands

Agrochemicals including neonicotinoid insecticides and fungicides are frequently applied as seed treatments on corn, soybeans, and other common row crops. Crops grown from pesticide-treated seed are often directly planted in managed floodplain wetlands and used as a soil disturbance or food resource for wildlife. We quantified invertebrate communities within mid-latitude floodplain wetlands and assessed their response to use of pesticide-treated seeds within the floodplain. We collected and tested aqueous and sediment samples for pesticides in addition to sampling aquatic invertebrates from 22 paired wetlands. Samples were collected twice in 2016 (spring [pre-water level drawdown] and autumn [post-water level flood-up]) followed by a third sampling period (spring 2017). Meanwhile, during the summer of 2016, a portion of study wetlands were planted with either pesticide-treated or untreated corn seed. Neonicotinoid toxic equivalencies (NI-EQs) for sediment ( X̅ = 0.58 μg/kg), water ( X̅ = 0.02 μg/L), and sediment fungicide concentrations ( X̅ = 0.10 μg/kg) were used to assess potential effects on wetland invertebrates. An overall decrease in aquatic insect richness and abundance was associated with greater NI-EQs in wetland water and sediments, as well as with sediment fungicide concentration. Post-treatment, treated wetlands displayed a decrease in insect taxa-richness and abundance before recovering by the spring of 2017. Information on timing and magnitude of aquatic insect declines will be useful when considering the use of seed treatments for wildlife management. More broadly, this study brings attention to how agriculture is used in wetland management and conservation planning.

Missouri↗

USGS2019

Evidence for widespread microbivory of endophytic bacteria in roots of vascularplants through oxidative degradation in root cell periplasmic spaces

In this chapter we present a hypothesis, and data supporting it, that vascular plants in diverse families possess symbiotic/endophytic bacteria that frequently vector on or within their seeds; seedlings degrade symbiotic bacteria within roots. Evidence of widespread microbivory was found in a survey for intracellular bacteria that we conducted including seedlings in 36 species of vascular plants distributed in 20 plant families. Experiments indicate that when seeds germinate, bacteria colonize seedlings and internalize into root cells where they are oxidatively-degraded in the periplasmic spaces of cells. The process of degradation of microbes in roots has been termed “rhizophagy”, and “rhizophagy cycle” or “rhizophagy symbiosis” in the case of symbiotic bacteria that alternate between a free-living soil phase and intracellular/endophytic phase. We hypothesize that microbivory could account for a significant portion of nutrients acquired by plants from soils—with one estimate suggesting that as much as 30% of the nutrients acquired by seedlings may stem from rhizophagy symbiosis. Developing a better understanding of rhizophagy symbiosis could lead to new ways to cultivate crops without reliance on excessive agrochemical applications. Learning how to manipulate rhizophagy symbiosis could result in new technologies for reducing growth of weedy or invasive plant species by inhibiting rhizophagy symbiosis.

Book chapter↗

USGS2011

Relating nutrient and herbicide fate with landscape features and characteristics of 15 subwatersheds in the Choptank River watershed

Excess nutrients and agrochemicals from non-point sources contribute to water quality impairment in the Chesapeake Bay watershed and their loading rates are related to land use, agricultural practices, hydrology, and pollutant fate and transport processes. In this study, monthly baseflow stream samples from 15 agricultural subwatersheds of the Choptank River in Maryland USA (2005 to 2007) were characterized for nutrients, herbicides, and herbicide transformation products. High-resolution digital maps of land use and forested wetlands were derived from remote sensing imagery. Examination of landscape metrics and water quality data, partitioned according to hydrogeomorphic class, provided insight into the fate, delivery, and transport mechanisms associated with agricultural pollutants. Mean Nitrate-N concentrations (4.9 mg/L) were correlated positively with percent agriculture (R 2 = 0.56) and negatively with percent forest (R 2 = 0.60). Concentrations were greater ( p = 0.0001) in the well-drained upland (WDU) hydrogeomorphic region than in poorly drained upland (PDU), reflecting increased denitrification and reduced agricultural land use intensity in the PDU landscape due to the prevalence of hydric soils. Atrazine and metolachlor concentrations (mean 0.29 μg/L and 0.19 μg/L) were also greater ( p = 0.0001) in WDU subwatersheds than in PDU subwatersheds. Springtime herbicide concentrations exhibited a strong, positive correlation (R 2 = 0.90) with percent forest in the WDU subwatersheds but not in the PDU subwatersheds. In addition, forested riparian stream buffers in the WDU were more prevalent than in the PDU where forested patches are typically not located near streams, suggesting an alternative delivery mechanism whereby volatilized herbicides are captured by the riparian forest canopy and subsequently washed off during rainfall. Orthophosphate, CIAT (6-chloro- N -(1-methylethyl)-1,3,5-triazine-2,4-diamine), CEAT (6-chloro- N -ethyl-1,3,5-triazine-2,4-diamine), and MESA (2-[(2-ethyl-6-methylphenyl) (2-methoxy-1-methylethyl)amino]-2-oxoethanesulfonic acid) were also analyzed. These findings will assist efforts in targeting implementation of conservation practices to the most environmentally-critical areas within watersheds to achieve water quality improvements in a cost-effective manner.

Delaware, Maryland↗