The effects of commercial 2,4-D herbicide on game fish species: Natural lake water vs. laboratory system water.

Aquatic herbicides with active ingredient 2,4-dichlorophenoxyacteic acid (2,4-D) are commonly used to control and combat aquatic non-native species that cause detrimental impacts including habitat destruction, strained resources among biota, and biodiversity loss. While many (eco)toxicology studies are performed in the laboratory under highly controlled circumstances, these studies may disregard the nuances and disorder that come with the complexity of natural aquatic ecosystems. Therefore, we conducted a series of laboratory experiments using laboratory system water, different lake waters, and different water parameters to determine the effects of ecologically relevant concentrations of 2,4-D (0.00-4.00 ppm a.e.) on the development and survival of two freshwater game species (Sander vitreus and Esox lucius). For 2,4-D exposures using different water sources, there were significant main effects of 2,4-D concentration and water source on walleye embryo and larval survival, however, there was no significant interaction between 2,4-D exposure and water source. For 2,4-D exposures and pH (5-9 pH), there were significant main effects of 2,4-D concentration and pH on walleye and northern pike embryo survival and a significant interaction between 2,4-D exposure and pH. Our results indicate that 2,4-D exposures in controlled laboratory system water can predict similar outcomes as 2,4-D exposures in natural lake water. Moreover, individual water parameters, such as pH, play a significant role in the toxicity of 2,4-D. Taken together, these results suggest that highly controlled laboratory studies are a useful tool for predicting impacts on survival of non-target fish in natural waters, but it is crucial for management agencies to consider individual water sources and specific lake water parameters in herbicide risk assessments to minimize the impacts to non-target organism.

Laboratory measurements underestimate persistence of the aquatic herbicide fluridone in lakes.

Fluridone is an aquatic herbicide commonly used to treat invasive freshwater plant species such as Eurasian watermilfoil, hydrilla, and curly-leaf pondweed. However, required exposures times are very long and often exceed 100 days. Thus, understanding the mechanisms that determine the fate of fluridone in lakes is critical for supporting effective herbicide treatments and minimizing impacts to non-target species. We use a combination of laboratory and field studies to quantify fluridone photodegradation, as well as sorption and microbial degradation in water and sediment microcosms. Laboratory irradiation studies demonstrate that fluridone is susceptible to direct photodegradation with negligible indirect photodegradation, with predicted half-lives in sunlight ranging from 2.3 days (1 cm path length) to 118 days (integrated over 1 meter). Biodegradation is attributable to microbes in sediment with an observed half-life of 57 days. Lastly, fluridone sorbs to sediments (Koc = 340 ± 28 L kg-1); sorption accounts for 16% of fluridone loss in the microcosm experiments. While the laboratory results indicate that all three loss pathways can influence fluridone fate, these controlled studies oversimplify herbicide behavior due to their inability to replicate field conditions. Fluridone concentration measurements in a lake following commercial application demonstrate a half-life of >150 days, indicating that the herbicide is very persistent in water. This study illustrates why caution should be used when relying on laboratory studies to predict the fate of pesticides and other polar organic compounds in the environment.

Quantifying the Role of Simultaneous Transformation Pathways in the Fate of the Novel Aquatic Herbicide Florpyrauxifen-Benzyl.

Predicting the fate of organic compounds in the environment is challenging due to the inability of laboratory studies to replicate field conditions. We used the intentionally applied aquatic herbicide florpyrauxifen-benzyl (FPB) as a model compound to investigate the contribution of multiple transformation pathways to organic compound fate in lakes. FPB persisted in five Wisconsin lakes for 5-7 days with an in-lake half-life of <2 days. FPB formed four transformation products, with the bioactive product florpyrauxifen persisting up to 30 days post-treatment. Parallel laboratory experiments showed that FPB degrades to florpyrauxifen via base-promoted hydrolysis. Hydroxy-FPB and hydroxy-florpyrauxifen were identified as biodegradation products, while dechloro-FPB was identified as a photoproduct. Material balance calculations using both laboratory rates and field product concentrations demonstrated that hydrolysis (∼47% of loss), biodegradation (∼20%), sorption (∼13%), and photodegradation (∼4%) occurred on similar timescales. Furthermore, the combined results demonstrated that abiotic and plant-catalyzed hydrolysis of FPB to florpyrauxifen, followed by biodegradation of florpyrauxifen to hydroxy-florpyrauxifen, was the dominant transformation pathway in lakes. This study demonstrates how combined field and laboratory studies can be used to elucidate the role of simultaneous and interacting pathways in the fate of organic compounds in aquatic environments.

Elucidating the effects of acute and chronic exposure to 2,4-Dichlorophenoxyacetic acid on fathead minnow (Pimephales promelas) innate immunity.

Aquatic herbicides, such as 2,4-dichlorophenoxyacetic acid (2,4-D) formulations, are commonly used for invasive species management throughout the United States. Ecologically relevant concentrations of 2,4-D can impair essential behaviors, reduce survival, and act as an endocrine disruptor; however, there is limited knowledge of its effects on the health of non-target organisms. Here, we investigate the acute and chronic exposure impacts of 2,4-D on adult male and female fathead minnow (Pimephales promelas) innate immune function. We exposed both adult male and female fathead minnows to three different ecologically relevant concentrations of 2,4-D (0.00, 0.40, and 4.00 mg/L) and took blood samples at three acute time points (6, 24, and 96 h) and one chronic time point (30 days). We found that male fatheads had higher total white blood cell concentrations when exposed to 2,4-D at the acute time points. For the females, only proportions of specific cell types were altered when exposed to 2,4-D at the acute time points. However, we did not observe any significant impacts of chronic exposure to 2,4-D on any innate immune responses for either males or females. Overall, this study is the first step in answering an important question for game fisheries and management agencies while providing insight to future studies that investigate the impacts of herbicide exposure to freshwater fish health and immunity.

Synthesizing Laboratory and Field Experiments to Quantify Dominant Transformation Mechanisms of 2,4-Dichlorophenoxyacetic Acid (2,4-D) in Aquatic Environments.

Laboratory studies used to assess the environmental fate of organic chemicals such as pesticides fail to replicate environmental conditions, resulting in large errors in predicted transformation rates. We combine laboratory and field data to identify the dominant loss processes of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) in lakes for the first time. Microbial and photochemical degradation are individually assessed using laboratory-based microcosms and irradiation studies, respectively. Field campaigns are conducted in six lakes to quantify 2,4-D loss following large-scale herbicide treatments. Irradiation studies show that 2,4-D undergoes direct photodegradation, but modeling efforts demonstrated that this process is negligible under environmental conditions. Microcosms constructed using field inocula show that sediment microbial communities are responsible for degradation of 2,4-D in lakes. Attempts to quantify transformation products are unsuccessful in both laboratory and field studies, suggesting that their persistence is not a major concern. The synthesis of laboratory and field experiments is used to demonstrate best practices in designing laboratory persistence studies and in using those results to mechanistically predict contaminant fate in complex aquatic environments.

Effects of subchronic exposure to environmentally relevant concentrations of a commercial fluridone formulation on fathead minnows (Pimephales promelas).

Invasive aquatic plants are a widespread problem in United States' waterways, and aquatic herbicide treatments are a common tool used in their management. Fluridone is an active ingredient in aquatic herbicides used globally to control aquatic plants. In order to be effective, fluridone requires a long contact time with plants resulting in extended exposure to non-target organisms. While there has been limited studies exploring the effects of fluridone on non-target aquatic organisms, the effects of subchronic commercial fluridone exposure at concentrations representative of operational use rates for plant management on fish are poorly understood. Therefore, we conducted a series of three exposure experiments using environmentally relevant concentrations on different life stages of the fathead minnow (Pimephales promelas). We exposed fathead minnows to a commercial fluridone formulation, Spritflo®, at environmentally relevant concentrations of 0.00, 3.00, 12.00, 25.00, and 100.00 µg/L. Exposure times included subchronic periods up to 35 days and a trans-generation exposure of 65 days, which is a likely residence time of fluridone when applied for plant management. Following 30 days of fluridone exposure, adult male fish had an increased presence of nuptial tubercules, an indicator of endocrine disruption, and an enlarged liver compared to the control. Additionally, we conducted larval fish behavior experiments and found fluridone exposure negatively affected prey capture ability, locomotion, and position preference. Our findings suggest fluridone treatment concentrations used in aquatic plant management do not directly cause mortality in fathead minnows, though sub-lethal effects observed could cause a decline in biological fitness and pose potential ecological implications.