The triazine herbicide atrazine (2-chloro-4-ethylamino-6-isopropyl-amino-s-triazine) is one of the most used pesticides in North America. Atrazine is principally used for control of certain annual broadleaf and grass weeds, primarily in corn but also in sorghum, sugarcane, and, to a lesser extent, other crops and landscaping. Atrazine is found in many surface and ground waters in North America, and aquatic ecological effects are a possible concern for the regulatory and regulated communities. To address these concerns an expert panel (the Panel) was convened to conduct a comprehensive aquatic ecological risk assessment. This assessment was based on several newly suggested procedures and included exposure and hazard subcomponents as well as the overall risk assessment. The Panel determined that use of probabilistic risk assessment techniques was appropriate. Here, the results of this assessment are presented as a case study for these techniques. The environmental exposure assessment concentrated on monitoring data from Midwestern watersheds, the area of greatest atrazine use in North America. This analysis revealed that atrazine concentrations rarely exceed 20 μg/L in rivers and streams that were the main focus of the aquatic ecological risk assessment. Following storm runoff, biota in lower-order streams may be exposed to pulses of atrazine greater than 20 μg/L, but these exposures are short-lived. The assessment also considered exposures in lakes and reservoirs. The principal data set was developed by the U.S. Geological Survey, which monitored residues in 76 Midwestern reservoirs in 11 states in 1992-1993. Residue concentrations in some reservoirs were similar to those in streams but persisted longer. Atrazine residues were widespread in reservoirs (92% occurrence), and the 90th percentile of this exposure distribution for early June to July was about 5 μg/L. Mathematical simulation models of chemical fate were used to generalize the exposure analysis to other sites and to assess the potential effects of reduction in the application rates. Models were evaluated, modified, and calibrated against available monitoring data to validate that these models could predict atrazine runoff. PRZM-2 overpredicted atrazine concentrations by about an order of magnitude, whereas GLEAMS underpredicted by a factor of 2 to 5. Thus, exposure models were not used to extrapolate to other regions of atrazine use in this assessment. The effects assessment considered both freshwater and saltwater toxicity test results. Phytoplankton were the most sensitive organisms, followed, in decreasing order of sensitivity, by macrophytes, benthic invertebrates, zooplankton, and fish. Atrazine inhibits photophosphorylation but typically does not result in lethality or permanent cell damage in the short term. This characteristic of atrazine required a different model than typically used for understanding the potential impact in aquatic systems, where lethality or nonreversible effects are usually assumed. In addition, recovery of phytoplankton from exposure to 5 to 20 μg/L atrazine was demonstrated. In some mesocosm field experiments, phytoplankton and macrophytes were reduced after atrazine exposures greater than 20 μg/L. However, populations were quickly reestablished, even while atrazine residues persisted in the water. Effects in field studies were judged to be ecologically important only at exposures of 50 μg/L or greater. Mesocosm experiments did not reveal disruption of either ecosystem structure or function at atrazine concentrations typically encountered in the environment (generally 5 μg/L or less). Based on an integration of laboratory bioassay data, field effects studies, and environmental monitoring data from watersheds in high-use areas in the Midwestern United States, the Panel concluded that atrazine does not pose a significant risk to the aquatic environment. Although some inhibitory effects on algae, phytoplankton, or macrophyte production may occur in small streams vulnerable to agricultural runoff, these effects are likely to be transient, and quick recovery of the ecological system is expected. A subset of surface waters, principally small reservoirs in areas with intensive use of atrazine, may be at greater risk of exposure to atrazine. Therefore, it is recommended that site-specific risk assessments be conducted at these sites to assess possible ecological effects in the context of the uses to which these ecosystems are put and the effectiveness and cost-benefit aspect of any risk mitigation measures that may be applied.

https://setac.onlinelibrary.wiley.com/doi/pdf/10.1002/etc.5620150105

Ecological risk assessment of atrazine in North American surface waters.

We analyzed management policies for ecosystems subject to alternate states, thresholds, and irreversible changes. We focused on the problem of lake eutrophication by excessive phosphorus (P) input. Eutrophic lakes may be classified, with respect to their response to reduced P input alone, as reversible (recovery is immediate and proportional to the reduction in P input), hysteretic (recovery requires extreme reductions in P input for a period of time), or irreversible (recovery cannot be accomplished by reducing P input alone). A model with one state variable and one control variable describes the responses of lake trophic state to changes in P input and other management interventions. Activities that generate P input to the lake are assumed to create profits, while the value of ecosystem services provided by the lake declines at high P levels. We then calculated P input policies that maximize the discounted net benefits from polluting activities and ecosystem services. If “optimality” is defined as maxim...

Management of eutrophication for lakes subject to potentially irreversible change

The water quality response to implementation of conservation measures across watersheds has been slower and smaller than expected. This has led many to question the efficacy of these measures and to call for stricter land and nutrient management strategies. In many cases, this limited response has been due to the legacies of past management activities, where sinks and stores of P along the land-freshwater continuum mask the effects of reductions in edge-of-field losses of P. Accounting for legacy P along this continuum is important to correctly apportion sources and to develop successful watershed remediation. In this study, we examined the drivers of legacy P at the watershed scale, specifically in relation to the physical cascades and biogeochemical spirals of P along the continuum from soils to rivers and lakes and via surface and subsurface flow pathways. Terrestrial P legacies encompass prior nutrient and land management activities that have built up soil P to levels that exceed crop requirements and modified the connectivity between terrestrial P sources and fluvial transport. River and lake P legacies encompass a range of processes that control retention and remobilization of P, and these are linked to water and sediment residence times. We provide case studies that highlight the major processes and varying timescales across which legacy P continues to contribute P to receiving waters and undermine restoration efforts, and we discuss how these P legacies could be managed in future conservation programs.

Phosphorus legacy: overcoming the effects of past management practices to mitigate future water quality impairment.

Eutrophication (the overenrichment of aquatic ecosystems with nutrients leading to algal blooms and anoxic events) is a persistent condition of surface waters and a widespread environmental problem. Some lakes have recovered after sources of nutrients were reduced. In others, recycling of phosphorus from sediments enriched by years of high nutrient inputs causes lakes to remain eutrophic even after external inputs of phosphorus are decreased. Slow flux of phosphorus from overfertilized soils may be even more important for maintaining eutrophication of lakes in agricultural regions. This type of eutrophication is not reversible unless there are substantial changes in soil management. Technologies for rapidly reducing phosphorus content of overenriched soils, or reducing erosion rates, are needed to improve water quality.

/pdf/eutrophication-of-aquatic-ecosystems-bistability-and-soil-5dvxxxy4e7.pdf

Eutrophication of aquatic ecosystems: Bistability and soil phosphorus

Nonpoint source (NPS) watershed projects often fail to meet expectations for water quality improvement because of lag time, the time elapsed between adoption of management changes and the detection of measurable improvement in water quality in the target water body. Even when management changes are well-designed and fully implemented, water quality monitoring efforts may not show definitive results if the monitoring period, program design, and sampling frequency are not sufficient to address the lag between treatment and response. The main components of lag time include the time required for an installed practice to produce an effect, the time required for the effect to be delivered to the water resource, the time required for the water body to respond to the effect, and the effectiveness of the monitoring program to measure the response. The objectives of this review are to explore the characteristics of lag time components, to present examples of lag times reported from a variety of systems, and to recommend ways for managers to cope with the lag between treatment and response. Important processes influencing lag time include hydrology, vegetation growth, transport rate and path, hydraulic residence time, pollutant sorption properties, and ecosystem linkages. The magnitude of lag time is highly site and pollutant specific, but may range from months to years for relatively short-lived contaminants such as indicator bacteria, years to decades for excessive P levels in agricultural soils, and decades or more for sediment accumulated in river systems. Groundwater travel time is also an important contributor to lag time and may introduce a lag of decades between changes in agricultural practices and improvement in water quality. Approaches to deal with the inevitable lag between implementation of management practices and water quality response lie in appropriately characterizing the watershed, considering lag time in selection, siting, and monitoring of management measures, selection of appropriate indicators, and designing effective monitoring programs to detect water quality response.

Lag time in water quality response to best management practices: a review

The effect of wastewater phosphorus removal on shagawa lake, Minnesota: phosphorus supplies, lake phosphorus and chlorophyll a

Fate and effects of atrazine in small aquatic microcosms.

The enantiomeric composition of polychlorinated biphenyl (PCB) atropisomers was measured in river and riparian biota (fish, bivalves, crayfish, water snakes, barn swallows) from selected sites throughout the United States by using chiral gas chromatography/mass spectrometry. Nonracemic enantiomeric fractions (EFs) were observed for PCBs 91, 95, 136, and 149 for aquatic and riparian biota from Lake Hartwell, SC, a reservoir heavily contaminated with PCBs, and for these congeners and PCBs 132, 174, 176, and 183 in river fish and bivalves nationwide. Fish and bivalves showed marked differences in EFs as compared to sediment found at the same sampling sites, thus suggesting that PCBs are bioprocessed in biota in a different manner from those found in sediment (e.g., reductive dechlorination). Species-dependent patterns in PCB EFs were observed, which suggest differences in the ability of different species to bioprocess PCBs enantioselectively, most likely by metabolism. The presence of nonracemic PCBs in fish...

Enantiomeric composition of chiral polychlorinated biphenyl atropisomers in aquatic and riparian biota

The toxicity of pentachlorophenol (PCP) to Selenastrum capricornutum was examined in three different culture media: a hard and a soft form of Freeman's reference water and the algal assay bottle test (AABT) medium (a soft water). The 96-h growth potentials of the media were equal (28–29 mg/L dry wt.) but 96-h EC50s ranged sevenfold: 0.11 mg/L (AABT), 0.15 mg/L (Freeman's soft water) and 0.76 mg/L (Freeman's hard water). Culture media equilibrium pH and 96-h EC50 were strongly correlated (r = 1.00). Evidence is presented that supports the hypothesis that the toxicity of PCP, a weak acid, is due primarily to the concentration of the undissociated species.

Paul D. Smith

Papers

The effect of wastewater phosphorus removal on shagawa lake, Minnesota: phosphorus supplies, lake phosphorus and chlorophyll a

Fate and effects of atrazine in small aquatic microcosms.

Enantiomeric composition of chiral polychlorinated biphenyl atropisomers in aquatic and riparian biota

Effects of hardness, alkalinity and pH on the toxicity of pentachlorophenol to selenastrum capricornutum (printz)

Fate and effects of pentachlorophenol in hard- and soft-water microcosms