The Lampricide 3-trifluoromethyl-4-nitrophenol Research Articles

Use of an artificial stream to monitor avoidance behavior of larval sea lamprey in response to TFM and niclosamide

The lampricide 3-trifluoromethyl-4-nitrophenol (TFM) has been used in liquid form to control larval sea lamprey (Petromyzon marinus) in Great Lakes tributaries since the late 1950s. In the 1980s a dissolvable TFM bar was developed as a supplemental tool for application to small tributaries as a deterrent to larvae seeking water not activated with TFM. The size, mass, and number of bars needed in some streams, as well as the location of the streams, limit the utility of a TFM bar. The development and use of an alternative niclosamide bar has the potential to use fewer bars to achieve similar results. However, the use of a niclosamide bar is dependent upon its larval deterrent capability compared to the TFM bar. In this study, we developed a laboratory-scale, simulated stream fluvarium with several avoidance areas including two side channels and a seep. The objective was to evaluate the deterrent capabilities of TFM and niclosamide. We found similar behavioral responses, with TFM and niclosamide having similar capabilities to prevent sea lamprey from seeking refuge in side channels and seep avoidance areas. TFM-treated side channels and seep increased sea lamprey occupancy in the main channel 2.56 times more than the untreated-controls (95% CI 1.63–4.14) whereas niclosamide-treated side channels and seep increased sea lamprey occupancy of the main channel 2.68 times more than the untreated-controls (95% CI 1.72–4.32). These responses indicate a niclosamide bar would effectively prevent sea lamprey escapement into freshwater during a lampricide treatment at concentrations unlikely to harm aquatic organisms.

Acute toxicity of the lampricides TFM and niclosamide: Effects on a vascular plant and a chironomid species

The lampricides 3-trifluoromethyl-4-nitrophenol (TFM) and niclosamide have been used for about 60 years to control sea lamprey (Petromyzon marinus) in the Great Lakes Basin and Lake Champlain. To register these chemicals as pesticides in North America, their environmental effects must be reviewed on a periodic basis. As a part of this effort, toxicity of TFM and niclosamide to duckweed (Lemna gibba), and of niclosamide to aquatic midge (Chironomus dilutus), was assessed. Results of these studies indicate that for both lampricides, the no observed and lowest observed effect concentrations (NOEC and LOEC) exceed expected environmental concentrations, with effects only in the highest concentrations tested and the longest exposure times. Duckweed exposed to TFM indicated 7-day LOECs ≥4.88 mg/L for mean specific growth rate and yield, with the half maximal effective concentration (EC50) > 9.74 mg/L. For duckweed exposed to niclosamide, 7-day LOECs for mean specific growth rate and yield ranged from 0.271 to 0.569 mg/L, with the half maximal inhibitory concentration (IC50) 0.725 mg/L or greater depending on the parameter measured. For midge larvae exposed to niclosamide-dosed sediment, the LOEC values based on survival and growth were 26.2 mg/kg and >82.1 mg/kg, respectively, and the EC50 based on survival was 49.6 mg/kg. Based on these data, deleterious effects on aquatic plants and benthic invertebrates are unlikely to result from use of TFM and niclosamide for lamprey control, given that the effect concentrations are in excess of the expected environmental concentrations.

Sea lamprey cardiac mitochondrial bioenergetics after exposure to TFM and its metabolites

Population control of invasive sea lamprey relies heavily on lampricide treatment of infested streams. The lampricide 3-trifluoromethyl-4-nitrophenol (TFM) is thought to impair mitochondrial ATP production through uncoupling oxidative phosphorylation. However, the effect of TFM on the entire electron transport chain (complexes I to V) in the mitochondria is not clear. In addition, TFM is reduced in phase I metabolism by sea lamprey at higher levels than in other fish species. The effects of these TFM reductive metabolites on mitochondria have not been explored. In this study, we sought to examine the effects of TFM and its reductive metabolite amino-TFM (TFMa) on cardiac mitochondrial oxygen consumption and membrane potential to delineate potential mechanisms for toxicity. To determine if molecules with similar structure also exhibit similar effects on mitochondria, we used 4-nitro-3-methylphenol (NMP) and its reductive metabolites 4-amino-3-methylphenol (NMPa) and 4-nitroso-3-methylphenol (NMPn) for comparisons. We found that mitochondrial bioenergetics was heavily affected with increasing concentrations of TFM, NMP, and NMPa when complexes I and II of the electron transport chain were examined, indicating that the toxic action of these compounds was exerted not only by uncoupling complex V, but also affecting complexes I and II.

Metabolism of a sea lamprey pesticide by fish liver enzymes part B: method development and application in quantification of TFM metabolites formed in vivo.

The sea lamprey (Petromyzon marinus) is a destructive invasive species in the Great Lakes. Since the 1960s, tons of the lampricide 3-trifluoromethyl-4-nitrophenol (TFM) has been applied to selected tributaries each year to eliminate or reduce sea lamprey larval populations. Therefore, the environmental impact of TFM needs to be evaluated. However, the metabolism of TFM and its mechanism of selective toxicity in sea lamprey is not yet fully understood. Based upon our previous report on the identification, synthesis, and characterization of TFM metabolites observed in liver incubates from sea lamprey and non-target fishes, we now provide a robust assay for quantifying TFM and its metabolites in fish liver tissue. This method is important for assessing bioaccumulation of TFM in the ecosystems. The compounds purified in our previous report were used to develop and validate a quantitative ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) assay for TFM and TFM metabolites formed in vivo. Several sample preparation techniques were compared, and a protein precipitation method was selected. The unavailability of stable isotopic internal standards was overcome by using a matrix matching method. After a thorough validation, this method was applied to determine the concentrations of TFM and its metabolites in fish liver tissues from animals exposed to TFM, and in the comparison between dead animals and survivors. Seven of eight expected metabolites were observed, some for the first time in vivo. Our results indicate that in vivo nitroreduction, glucuronidation, sulfation, and glutathione conjugation are involved in TFM metabolism in sea lamprey.

Influence of body size, metabolic rate and life history stage on the uptake and excretion of the lampricide 3-trifluoromethyl-4-nitrophenol (TFM) by invasive sea lampreys (Petromyzon marinus)

Invasive sea lamprey (Petromyzon marinus) are controlled in the Great Lakes using the lampricide 3-trifluoromethyl-4-nitrophenol (TFM), which is applied to streams infested with larval lamprey. However, lamprey that survive treatments (residuals) remain a challenge because they may subsequently undergo metamorphosis into parasitic juvenile animals that migrate downstream to the Great Lakes, where they feed on important sport and commercial fishes. The goal of this study was to determine if body size and life stage could potentially influence sea lamprey tolerance to TFM by influencing patterns of TFM uptake and elimination. Because mass specific rates of oxygen consumption (M˙O2) are lower in larger compared to smaller lamprey, we predicted that TFM uptake would be negatively correlated to body size, suggesting that large larvae would be more tolerant to TFM exposure. Accordingly, TFM uptake and M˙O2 were measured in larvae ranging in size from 0.2–4.2g using radio-labelled TFM (14C-TFM) and static respirometry. Both were inversely proportional to wet mass (M), and could be described usingthe allometric power relationship: Y=aMb, in which M˙O2=1.86M0.53 and TFM Uptake=7.24M0.34. We also predicted that body size would extend to rates of TFM elimination, which was measured following the administration of 14C-TFM (via intraperitoneal injection). However, there were no differences in the half-lives of elimination of TFM (T 1/2-TFM). There were also no differences in M˙O2 or TFM uptake amongst size-matched larval, metamorphosing (stages 6–7), or post-metamorphic (juvenile) sea lamprey. However, the T1/2-TFM was significantly lower in larval than post-metamorphic lamprey (juvenile), indicating the larval lamprey cleared TFM more efficiently than juvenile lamprey. We conclude that larger larval sea lamprey are more likely to survive TFM treatments suggesting that body size might be an important variable to consider when treating streams with TFM to control these invasive species.

In situ assessment of lampricide toxicity to age-0 lake sturgeon

Abstract The lampricides 3-trifluoromethyl-4-nitrophenol (TFM) and 2′, 5-dichloro-4′-nitrosalicylanilide (niclosamide) are used to control sea lamprey (Petromyzon marinus), an invasive species in the Great Lakes. Age-0 lake sturgeon (Acipenser fulvescens), a species of conservation concern, share similar stream habitats with larval sea lampreys and these streams can be targeted for lampricide applications on a 3- to 5-year cycle. Previous laboratory research found that lake sturgeon smaller than 100 mm could be susceptible to lampricide treatments. We conducted stream-side toxicity (bioassay) and in situ studies in conjunction with 10 lampricide applications in nine Great Lakes tributaries to determine whether sea lamprey treatments could result in in situ age-0 lake sturgeon mortality, and developed a logistic model to help predict lake sturgeon survival during future treatments. In the bioassays the observed concentrations where no lake sturgeon mortality occurred (no observable effect concentration, NOEC) were at or greater than the observed sea lamprey minimum lethal concentration (MLC or LC99) in 7 of 10 tests. We found that the mean in situ survival of age-0 lake sturgeon during 10 lampricide applications was 80%, with a range of 45–100% survival within streams. Modeling indicated that in age-0 lake sturgeon survival was negatively correlated with absolute TFM concentration and stream alkalinity, and positively correlated with stream pH and temperature. Overall survival was higher than expected based on previous research, and we expect that these data will help managers with decisions on the trade-offs between sea lamprey control and the effect on stream-specific populations of age-0 lake sturgeon.

Direct Photolysis Rates and Transformation Pathways of the Lampricides TFM and Niclosamide in Simulated Sunlight.

The lampricides 3-trifluoromethyl-4-nitrophenol (TFM) and 2',5-dichloro-4'-nitrosalicylanilide (niclosamide) are directly added to many tributaries of the Great Lakes that harbor the invasive parasitic sea lamprey. Despite their long history of use, the fate of lampricides is not well understood. This study evaluates the rate and pathway of direct photodegradation of both lampricides under simulated sunlight. The estimated half-lives of TFM range from 16.6 ± 0.2 h (pH 9) to 32.9 ± 1.0 h (pH 6), while the half-lives of niclosamide range from 8.88 ± 0.52 days (pH 6) to 382 ± 83 days (pH 9) assuming continuous irradiation over a water depth of 55 cm. Both compounds degrade to form a series of aromatic intermediates, simple organic acids, ring cleavage products, and inorganic ions. Experimental data were used to construct a kinetic model which demonstrates that the aromatic products of TFM undergo rapid photolysis and emphasizes that niclosamide degradation is the rate-limiting step to dehalogenation and mineralization of the lampricide. This study demonstrates that TFM photodegradation is likely to occur on the time scale of lampricide applications (2-5 days), while niclosamide, the less selective lampricide, will undergo minimal direct photodegradation during its passage to the Great Lakes.

Exposure to the lampricide 3-trifluoromethyl-4-nitrophenol results in increased expression of carbohydrate transporters in Saccharomyces cerevisiae.

The lampricide 3-trifluoromethyl-4-nitrophenol (TFM) is used to control sea lamprey (Petromyzon marinus) populations in freshwater lakes. Although TFM can have sublethal and lethal effects, little is known about gene expression changes with TFM exposure. Microarray analysis was used to determine differential gene expression over 4 h of exposure in Saccharomyces cerevisiae. Among the most significantly up-regulated genes were regulators of carbohydrate transport, including HXT1, HXT3, HXT4, IMA5, MIG2, and YKR075C. Environ Toxicol Chem 2016;35:1727-1732. © 2015 SETAC.

Effects of Lampricide on Olfaction and Behavior in Young-of-the-Year Lake Sturgeon (Acipenser fulvescens).

The lampricide, 3-trifluoromethyl-4-nitrophenol (TFM), is a primary component to sea lamprey control in the Laurentian Great Lakes. Though the lethal effects of TFM are well-known, the sublethal effects on fishes are virtually unknown. Here we studied the effects of TFM on the olfactory capabilities and behavior of young-of-the-year (YOY) lake sturgeon (Acipenser fulvescens). At ecologically relevant concentrations of TFM there was reduced olfactory response to all three cues (l-alanine, taurocholic acid, food cue) tested, suggesting that TFM inhibits both olfactory sensory neurons tested. Sturgeon exposed to TFM also showed a reduced attraction to the scent of food and reduced consumption of food relative to unexposed fish. Exposed fish were more active than control fish, but with slower acceleration. Fish were able to detect the scent of TFM, but failed to avoid it in behavioral trials. The connection between neurophysiological and behavioral changes, and the commonality of habitats between sturgeon and lamprey ammocoetes, suggests that there may be effects at the ecosystem level in streams that undergo lamprey control treatments.

Evaluation of the short term 12 hour toxicity of 3-trifluoromethyl-4-nitrophenol (TFM) to multiple life stages of Venustaconcha ellipsiformis and Epioblasma triquetra and its host fish (Percina caprodes).

The present study evaluated the risk of 12-h exposures of the lampricide 3-trifluoromethyl-4-nitrophenol (TFM) to multiple life stages of the federally endangered snuffbox (Epioblasma triquetra) and its primary host fish the common logperch (Percina caprodes) as well as a surrogate to the snuffbox, the ellipse (Venustaconcha ellipsiformis). Life stages examined included free glochidia, 1-wk juveniles, and adults of the ellipse; free glochidia, glochidia on host fish, and 1-wk juveniles of the snuffbox; and adult logperch. Larval sea lampreys were also tested alongside adult ellipse and logperch for direct comparison. Survival exceeded 82% among all life stages in both mussel species at levels up to 1.8 times what would be applied during treatments, suggesting that routine sea lamprey control operations would not adversely affect mussels. However, substantial mortality of adult logperch was observed at TFM concentrations typically applied to streams, and loss of host fish could adversely affect snuffbox reproduction. In addition, TFM had no significant effect on the number of glochidia that metamorphosed on adult logperch. Although the snuffbox is not likely to be acutely affected from sea lamprey control operations, mitigation efforts to minimize impacts to the host fish should be considered.

Growth and behavioral effects of the lampricide TFM on non-target fish species

Although the lampricide 3-trifluoromethyl-4-nitrophenol (TFM) has been used for over 60years to control sea lamprey Petromyzon marinus in the Laurentian Great Lakes, its potential non-lethal impacts on non-target species have not been fully evaluated. We exposed juveniles of two species of fish (lake sturgeon Acipenser fulvescens and rainbow trout Oncorhynchus mykiss) and one adult fish species (fathead minnows Pimephales promelas) to various concentrations of TFM (0.25–7.5mg/L) in three sets of experiments examining TFM effects on growth, avoidance of TFM treated water, and predation susceptibility. Lake sturgeon and rainbow trout were monitored for two weeks after a 12hour exposure to TFM to observe differences in instantaneous growth among four treatment levels (0, 2.5, 5, and 7.5mg/L TFM). Growth rates did not differ significantly among control and treated fish of either species. Next, potential avoidance of TFM by rainbow trout was evaluated in a test tank where half the water was contaminated with TFM (0, 0.25, or 2.5mg/L). No avoidance behavior was observed as rainbow trout spent equal amounts of time in TFM and control water. Finally, fathead minnows were exposed at three different concentrations of TFM (0, 2.5, and 7.5mg/L) and placed in mesocosms with a non-exposed largemouth bass Micropterus salmoides predator. Two separate trials were performed, both with no significant differences due to treatments. In summary, results indicate that for the conditions tested, TFM has no detectable sub-lethal effects on growth, avoidance behavior, or predation mortality on the fish species tested.

The effects of the lampricide 3-trifluoromethyl-4-nitrophenol (TFM) on fuel stores and ion balance in a non-target fish, the rainbow trout (Oncorhynchus mykiss)

The pesticide 3-trifluoromethyl-4-nitrophenol (TFM) is used to control sea lamprey (Petromyzon marinus) populations in the Great Lakes through its application to nursery streams containing larval sea lampreys. TFM uncouples oxidative phosphorylation, impairing mitochondrial ATP production in sea lampreys and rainbow trout (Oncorhynchus mykiss). However, little else is known about its sub-lethal effects on non-target aquatic species. The present study tested the hypotheses that TFM exposure in hard water leads to (i) marked depletion of energy stores in metabolically active tissues (brain, muscle, kidney, liver) and (ii) disruption of active ion transport across the gill, adversely affecting electrolyte homeostasis in trout. Exposure of trout to 11.0mgl−1 TFM (12-h LC50) led to increases in muscle TFM and TFM-glucuronide concentrations, peaking at 9h and 12h, respectively. Muscle and brain glycogen was reduced by 50%, while kidney and muscle lactate increased with TFM exposure. Kidney ATP and phosphocreatine decreased by 50% and 70%, respectively. TFM exposure caused no changes in whole body ion (Na+, Cl−, Ca2+, K+) concentrations, gill Na+/K+ ATPase activity, or unidirectional Na+ movements across the gills. We conclude that TFM causes a mismatch between ATP supply and demand in trout, leading to increased reliance on glycolysis, but it does not have physiologically relevant effects on ion balance in hard water.

Failure of ATP supply to match ATP demand: The mechanism of toxicity of the lampricide, 3-trifluoromethyl-4-nitrophenol (TFM), used to control sea lamprey ( Petromyzon marinus) populations in the Great Lakes

Although the pesticide, 3-trifluoromethyl-4-nitrophenol (TFM), has been extensively used to control invasive sea lamprey ( Petromyzon marinus) populations in the Great Lakes, it is surprising that its mechanism(s) of toxicity is unresolved. A better knowledge of the mode of toxicity of this pesticide is needed for predicting and improving the effectiveness of TFM treatments on lamprey, and for risk assessments regarding potential adverse effects on invertebrate and vertebrate non-target organisms. We investigated two hypotheses of TFM toxicity in larval sea lamprey. The first was that TFM interferes with oxidative ATP production by mitochondria, causing rapid depletion of energy stores in vital, metabolically active tissues such as the liver and brain. The second was that TFM toxicity resulted from disruption of gill-ion uptake, adversely affecting ion homeostasis. Exposure of larval sea lamprey to 4.6 mg l −1 TFM (12-h LC50) caused glycogen concentrations in the brain to decrease by 80% after 12 h, suggesting that the animals increased their reliance on glycolysis to generate ATP due to a shortfall in ATP supply. This conclusion was reinforced by a 9-fold increase in brain lactate concentration, a 30% decrease in brain ATP concentration, and an 80% decrease in phosphocreatine (PCr) concentration after 9 and 12 h. A more pronounced trend was noted in the liver, where glycogen decreased by 85% and ATP was no longer detected after 9 and 12 h. TFM led to marginal changes in whole body Na +, Cl −, Ca 2+ and K +, as well as in plasma Na + and Cl −, which were unlikely to have contributed to toxicity. TFM had no adverse effect on Na + uptake rates or gill Na +/K +-ATPase activity. We conclude that TFM toxicity in the sea lamprey is due to a mismatch between ATP consumption and ATP production rates, leading to a depletion of glycogen in the liver and brain, which ultimately leads to neural arrest and death.

The lampricide 3-trifluoromethyl-4-nitrophenol (TFM) interferes with intermediary metabolism and glucose homeostasis, but not with ion balance, in larval sea lamprey (Petromyzon marinus)

Although treatment of streams with the lampricide 3-trifluoromethyl-4-nitrophenol (TFM) has been highly effective for sea lamprey (Petromyzon marinus) population control in the Great Lakes, little is known about its mechanism(s) of toxicity. We investigated two hypotheses of TFM toxicity in larval sea lamprey exposed to TFM for 12 h. The first was that TFM interferes with oxidative ATP production by mitochondria, causing depletion of fuel stores in the body. The second was that TFM interferes with gill-mediated ion exchange, which eventually causes circulatory collapse. While exposure of larvae to TFM (2 mg·L–1) did not disturb tissue ATP stores, it led to a sustained 60% reduction in phosphocreatine (PCr) after 6 h. This was accompanied by 6- to 10-fold increases in plasma and tissue lactate, which persisted through 12 h. By 12 h, plasma glucose was nearly depleted in the five surviving lamprey, but TFM caused no appreciable changes in plasma Cl–, haematocrit, haemoglobin, or ammonia concentration. We conclude that TFM-mediated gill damage and ionic failure are not underlying mechanisms of TFM toxicity. Rather, TFM likely interferes with oxidative ATP production, leading to reduced tissue PCr stores and eventually profound hypoglycaemia that starves the nervous system of glucose, causing death.

Effects of Repeated TFM Applications on Riffle Macroinvertebrate Communities in Four Great Lakes Tributaries

As part of the sea lamprey control program in the Great Lakes, a suite of about 150 sea lamprey producing streams have been regularly treated with the lampricide 3-trifluoromethyl-4-nitrophenol (TFM) every 3 to 5 years since 1958. State, provincial, and tribal agencies in the basin supported the use of TFM and urged that the risk to nontarget organisms be minimized. To determine the response of riffle macroinvertebrate communities to repeated TFM treatments over several years, paired samples were taken at control and treatment sites during 1986 to 1995 on four Great Lakes tributaries: the Bois Brule, West Branch Whitefish, Boardman, and Sturgeon (tributary to Cheboygan River system) rivers. Macroinvertebrates were collected in spring and fall by a standard traveling kick method. The communities were described with several metrics, and general linear models were used to test for different patterns of response in the paired control and treatment sites. Relative abundance of the class Oligochaeta, relative abundance of the genus Ephemerella, the Bray-Curtis similarity index (at the taxonomic level of order), EPT genus richness (the number of genera in the orders Ephemeroptera, Plecoptera, and Trichoptera), and total genus richness all increased more at the treatment sites than at the control sites after TFM application. The greater increase in abundance, similarity, and richness at the treatment sites was an indication of recovery in the treatment sites, where a short-term response to TFM was followed by a several-year rebound. TFM treatments in this study during the 1980s and 1990s had no long-lasting effects on riffle macroinvertebrate communities.

Factors Responsible for the Reduction in Quantity of the Lampricide, TFM, Applied Annually in Streams Tributary to the Great Lakes from 1979 to 1999

Integrated management of sea lampreys ( Petromyzon marinus) in the Great Lakes relies primarily on the application of the lampricide, 3-trifluoromethyl-4-nitrophenol (TFM), into streams to eradicate larval populations. From 1979 to 1999, 1,282 lampricide treatments were conducted on 316 streams. During the period from 1979 to 1989, an average of 52,904 kg active ingredient (kg/yr) of TFM was applied annually. This was reduced to an average of 38,698 kg/yr for the decade of 1990 to 1999. This reduction was enhanced in the years of 1995 to 1999 to an average of 34,120 kg/yr, a 36% reduction from that used in 1979 to 1989. Efforts to minimize non-target mortality and to reduce applications of pesticides into the environment were the impetus for this reduction. The three factors that influenced annual TFM use were number of streams treated and conditions during treatment, the adaptation of several management techniques to reduce TFM use, and alternative control techniques. Changes in streams selected for treatment and scheduling treatments during low stream discharge accounted for about 26% of the reduction in annual TFM use. The management techniques include lampricide treatments with a TFM/niclosamide mixture, pH/alkalinity prediction models to determine minimum TFM requirements, maintaining lampricide concentrations at or near minimum levels, computer modeled treatment planning, and single block treatments, and were responsible for about 70% of the reduction observed in the 1990s. Alternative control techniques (barrier dams) accounted for only 4% of the reduction.

Acute Toxicity of TFM and a TFM/Niclosamide Mixture to Selected Species of Fish, Including Lake Sturgeon ( Acipenser fulvescens) and Mudpuppies ( Necturus maculosus), in Laboratory and Field Exposures

The toxicity of the lampricides 3-trifluoromethyl-4-nitrophenol (TFM) and 2′,5-dichloro-4′-nitrosalicylanilide (niclosamide) to non-target fishes has been a major point of concern since their use to control larval sea lamprey ( Petromyzon marinus) populations began in the early 1960s. The toxicity of TFM to several non-target fish species has been demonstrated in previous studies. However, little information is available on the toxicity of the TFM/1% niclosamide mixture. One species of particular concern is the lake sturgeon ( Acipenser fulvescens). Juvenile lake sturgeon of several size ranges were exposed to determine potential effects of the lampricides to individuals present in treatment streams. Sac fry were most resistant to the lampricides followed by fingerlings in the 200 to 225 mm size range. Swim-up fry and fingerlings less than 100 mm were the most sensitive. Concentrations that produced 50% mortality (LC50 s) in juvenile lake sturgeon of these smaller size ranges were at or near the minimum lethal concentrations (MLCs) required for effective control of larval sea lampreys. The mudpuppy ( Necturus maculosus), an amphibian native to several tributaries of the Great Lakes, have also become a species of interest in recent years. Laboratory tests conducted with TFM and a TFM/1% niclosamide mixture on adult mudpuppies indicate that although the amphibian is sensitive to the lampricides, an adequate margin of safety exists for adult mudpuppies to survive when exposed during stream treatments. Fifteen other fish species native to streams treated with lampricides were investigated in the laboratory to determine their sensitivity to the lampricides. Centrarchids, bluegill ( Lepomis macrochirus) and green sunfish ( Lepomis cyanellus) were the least sensitive to TFM, while ictalurids, black bullhead ( Ictalurus melas), channel catfish ( Ictalurus punctatus), and tadpole madtom ( Notorus gyrinus) were the most sensitive. On-site bioassays conducted before lampricide treatments also revealed that lake sturgeon, channel catfish, and whitefish ( Coregonus clupeaformis) were sensitive to the lampricides although considerably less sensitive compared to sea lamprey.

Development of a pH/Alkalinity Treatment Model for Applications of the Lampricide TFM to Streams Tributary to the Great Lakes

It has long been known that the toxicity of the lampricide 3-trifluoromethyl-4-nitrophenol (TFM) is influenced by chemical and physical properties of water. As the pH, conductivity, and alkalinity of water increase, greater concentrations of TFM are required to kill sea lamprey ( Petromyzon marinus) larvae. Consequently, the concentration of TFM required for effective treatment varies among streams. Brown trout ( Salmo trutta) and sea lamprey larvae were exposed to a series of TFM concentrations in a continuous-flow diluter for 12 h. Twenty five exposures were conducted at various water alkalinities and pHs that treatment personnel encounter during lampricide treatments. Survival/mortality data were analyzed for lampricide concentrations that produced 50 and 99.9% mortality (LC 50 and LC 99.9) for sea lamprey larvae and 25 and 50% mortality (LC 25 and LC 50) for brown trout. Linear regression analyses were performed for each set of tests for each selected alkalinity by comparing the 12-h post exposure LC 99.9 sea lamprey data and LC 25 brown trout data at each pH. Mortality data from on-site toxicity tests conducted by lampricide control personnel were compared to predicted values from the pH/alkalinity prediction model. Of the 31 tests examined, 27 resulted in the LC 100s (lowest TFM concentration where 100% mortality of sea lamprey was observed after 12 h of exposure) falling within 0.2 mg/L of the predicted sea lamprey minimum lethal (LC 99.9) range. The pH/alkalinity prediction model provides managers with an operational tool that reduces the amount of TFM required for effective treatment while minimizing the impact on non-target organisms.

A Case History of Sea Lamprey Control in Lake Michigan: 1979 to 1999

The sea lamprey ( Petromyzon marinus) control program, along with the stocking of native fish species, the introduction of Pacific salmon, and the application of regulations controlling harvest, has allowed the socioeconomic and biological recovery of the Lake Michigan fishery which has been described as “spectacular.” The program is now instrumental in maintaining today's fish community structure. Initial treatment of Lake Michigan tributaries with the lampricide 3-trifluoromethyl-4-nitrophenol (TFM) reduced the number of spawning-phase sea lampreys by 85% and resulted in a noticeable recovery of the Lake Michigan fishery by 1979. Prior to 1979, sea lampreys were present in 115 of the 511 tributaries of Lake Michigan. Sea lampreys were found in four additional streams between 1978 and 1999. The greatest number of parasitic-phase sea lampreys are produced in 34 streams tributary to Lake Michigan. Between 1960 and 1999, 730 treatments were conducted in 113 Lake Michigan tributaries. The six remaining streams were not treated because few sea lampreys were present. The average number of streams treated annually declined from 21 during 1970–1979 to 12 during 1990–1999. Thirty eight percent less TFM (active ingredient) was applied annually, on average, in 1990 to 1999 (192 kg/m 3 of stream discharge) than in 1960 to 1969 (310 kg/m 3 of stream discharge). Barriers specifically constructed or modified to block migrating sea lampreys are currently found on 12 Lake Michigan streams. An additional 27 potential barrier sites have been identified on Lake Michigan streams. The estimated numbers of parasitic-phase sea lampreys in Lake Michigan between 1977 and 1999 ranged from 32,000 (1979) to 105,900 (1998). The incidence of fresh sea lamprey wounds on lake trout ( Salvelinus namaycush) in Lake Michigan was generally less than five per 100 fish in most years since 1971. Sea lampreyinduced mortality increased steadily in the 1990s, especially among large lake trout. Most mortality was in northern Lake Michigan where lake trout are more likely to be attacked by sea lampreys because of the large sea lamprey population.

The Aqueous Photolysis of TFM and Related Trifluoromethylphenols. An Alternate Source of Trifluoroacetic Acid in the Environment

The lampricide 3-trifluoromethyl-4-nitrophenol (TFM) is added annually to the Great Lakes (approximately 50 000 kg/y), with treatment concentrations varying from 1 to 14 mg/L at source. TFM was shown to undergo photohydrolytic degradation, at 365 nm and under actinic radiation, to produce trifluoroacetic acid (TFA). A mechanistic study for the production of TFA from TFM was conducted, and the structural parameters associated with the production of TFA from trifluoromethylated phenols were investigated. It was found that the yield of TFA is clearly dependent on the nature of the trifluoromethylated phenol. The nature of the substituents, the substitution pattern, and the pH strongly effected the photolytic half-life of the parent compound and the yield of TFA. The half-life of TFM at 365 nm was found to be 22 h (pH 9) and yielded 5.1% TFA, and 91.7 h at pH 7, yielding 17.8% TFA. Converting the nitro substituent of TFM to an amino group caused a decrease in the half-life to 2.3 min and yielded 11% TFA. The ...