The Lampricide 3-trifluoromethyl-4-nitrophenol Research Articles

Hepatic mixed function oxygenase activity and vitellogenin induction in fish following a treatment of the lampricide 3-trifluoromethyl-4-nitrophenol (TFM)

Recent laboratory studies with nontarget fish species have shown that the lampricide 3-trifluoromethyl-4-nitrophenol (TFM) exhibits estrogenic activity through binding to rainbow trout (Oncorhynchus mykiss) hepatic estrogen receptors and induction of vitellogenin in hepatocyte cultures. In addition, mixed function oxygenase (MFO) activity associated with exposure to field formulations has been attributed in part to the presence of chloro-nitro-trifluoromethyl-dibenzo-p-dioxin impurities. To investigate the environmental effects associated with these findings, the temporal and spatial patterns of MFO activity and vitellogenin induction were monitored in three nontarget fish species following a TFM field treatment. Elevated MFO activity was detected as early as 1 day in caged rainbow trout and activity in trout, wild white sucker (Catostomus commersoni), and longnose dace (Rhinichthys cataractae) peaked 2 or 3 days after treatment. Highest activities were observed in fish exposed closest to lampricide application points and declined with increasing distance downstream. After 18 days, MFO activity was reduced but remained almost sevenfold reference values at several sites. Plasma vitellogenin was not detected in caged trout sampled 6 and 18 days post-treatment, and dioxin impurities were not detected in sediments after treatment. It was concluded that laboratory testing underestimated the duration of MFO activity under field conditions and that an assessment of formulation exposure during sensitive life stages represents an area for further study.

Identification of chloro‐nitro‐trifluoromethyl‐substituted dibenzo‐p‐dioxins in lampricide formulations of 3‐trifluoromethyl‐4‐nitrophenol: Assessment to induce mixed function oxidase activity

AbstractThe contamination of field formulations of the lampricide 3‐trifluoromethyl‐4‐nitrophenol (TFM) bya dibenzo‐p‐dioxin containing ‐chloro, ‐nitro, and ‐trifluoromethyl substituents was suspected from chemical fractionations of a TFM formulation that were directed by mixed function oxidase (MFO) induction in rainbow trout. Three dioxin isomers containing these substituents in field formulations were identified by gas chromatography–mass spectrometry (GC‐MS). Short‐term waterborne exposures to a mixture of two isomers, 2‐trifluoromethyl‐3‐nitro‐7‐ (and 8)‐chloro‐dibenzo‐p‐dioxin, elevated MFO activity in trout, with a threshold between 0.148 and 0.745 nM (4.1–20.5 ng/L). Synthetic preparations of other dioxins related to formulation impurities enabled characterizations of this previously unknown family of dioxin congeners by GC‐MS. The elution order of the isomers followed those established for halogenated dioxins except where there was a lone ‐nitro substitution on one ring. The average concentration of these compounds in TFM formulations spanning more than a decade was 288 ± 47 μg/L, which translates into an annual loading of approximately 40 g to the Great Lakes Basin. Using mammalian (H4IIE) and fish (PLHC‐1) in vitro assays, a 2,3,7‐substituted chloro‐nitro‐trifluoromethyl isomer was a four to five times more potent inducer of MFO activity than 2,3,7‐trichlorodibenzo‐p‐dioxin. Characterizations of the synthetic isomers indicate that the isomers present in the formulation are not substituted in the 2,3,7‐ positions and are relatively weak inducers of MFO activity.

Hepatic mixed function oxygenase activity and vitellogenin induction in fish following a treatment of the lampricide 3-trifluoromethyl-4-nitrophenol (TFM)

Hepatic mixed function oxygenase activity and vitellogenin induction in fish following a treatment of the lampricide 3-trifluoromethyl-4-nitrophenol (TFM)

Evaluation of Piscicides for Control of Ruffe

Abstract Ruffe Gymnocephalus cernuus, a Eurasian species, was introduced into Duluth Harbor, Minnesota, in the 1980s, probably in releases of ballast water from seagoing freighters. Ruffe is now the most abundant species in the fish community; native species, such as the yellow perch Perca flavescens, trout-perch Percopsis omiscomaycus, black bullhead Ameiurus melas, and most endemic minnows, have declined. Toxicity tests of antimycin and rotenone (registered piscicides) and the lampricide 3-trifluoromethyl-4-nitrophenol (TFM) were conducted with ruffe and other fish species in water from several tributaries to Lake Superior. Ruffe and brown trout Salmo trutta were similar in their sensitivity to antimycin and rotenone; they were about five times more sensitive to antimycin and two times more sensitive to rotenone than yellow perch. However, ruffe were about three to six times more sensitive to TFM than either brown trout or yellow perch. The effects of control treatments for sea lamprey Petromyzon marinu...

Use of the Lampricide 3-Trifluoromethyl-4-Nitrophenol (TFM) to Control Tadpoles in Warmwater Ornamental Fish Ponds

Abstract Laboratory-based static acute toxicity tests were performed to determine the relative toxicity of TFM to selected species of tadpoles and ornamental fish in soft (mean, 45 mg/L as CaCO3) and hard (mean, 177 mg/L) freshwater. Sensitivity was measured as the 96-h LC50, the concentration lethal to half the test animals in 96 h, The sensitivity of larval bullfrogs Rana catesbeiana to TFM was 1.50 mg/L in soft water and 4.20 mg/L in hard water. The 96-h LC50 of TFM for larval southern toads Bufo terrestris was 0.51 mg/L in soft water and 0.70 mg/L in hard water. Toxicity of TFM (96-h LC50) to the fish tested ranged from 1.02 to 7.73 mg/L in soft water and 1.83 to 18.05 mg/L in hard water. Probit analysis indicated that the amount of TFM required to kill 99% of bullfrog larvae was 3.35 mg/L. A 96-h exposure to 3.35 mg!L TFM would also kill 99% of suckermouth catfish Hypostomus plecostomus, 92% of black neon tetras Hyphessobrycon herbertaxelrodi, 90% of tiger barbs Puntius tetrazona, 50% of freshwater angelfish Pterophyllurn scalare, 25% of dwarf gouramis Colisa lalia, and 5% of southern platyfish Xiphophorus maculatus. Although there was apparent selectivity when used with certain ornamental fish species, the use of TFM as a tadpole control agent can be nonselective, unpredictable, and expensive.

Photodegradation of the Lampricide 3-Trifluoromethyl-4-Nitrophenol(TFM). 2. Field Confirmation of Direct Photolysis and Persistence of Formulation Impurities in a Stream During Treatment

The persistence of TFM in a stream receiving a lampricide treatment was evaluated. Mass balances indicated that a significant amount of TFM was unaccounted for during the treatment. The presence of five known photoproducts in the downstream samples confirmed that photo-degradation of TFM was occurring. A new TFM transformation product 4,4′-dinitro-2,2′-bistrifluoromethylazobenzene, was identified by mass spectrometry and confirmed by synthesis. Most of the impurities in the TFM formulation were less persistent than TFM. However, hydroxynitrobenzoic acid was more persistent than TFM.

Toxicity of TFM Lampricide to Early Life Stages of Walleye

Abstract We studied the effects of the lampricide 3-trifluoromethyl-4-nitrophenol (TFM) on gametes, newly fertilized eggs, eyed eggs, larvae, and swim-up fry of the walleye Stizostedion vitreum. When gametes from sexually mature walleyes were stripped into solutions of TFM, no effects were observed during the fertilization process at concentrations up to 3.0 mg/L—three times the concentration lethal to 99.9% of larval sea lampreys Petromyzon marinus held 12 h (LC99.9) under the same test conditions. Newly fertilized eggs likewise were unaffected during water hardening by concentrations of TFM that were lethal to sea lamprey ammocoetes. Eyed eggs, sac fry, and swim-up fry yielded LC25 values that were 2.5 to 5 times greater than the 12-h LC99.9 for sea lamprey ammocoetes. The data thus indicated that all of the early life stages of walleyes tested were considerably more resistant than sea lamprey ammocoetes to TFM, and that it is unlikely they would be adversely affected by standard stream treatments to ki...

Effects of the lampricide, 3-trifluoromethyl-4-nitrophenol (TFM) on the macroinvertebrates of Wilmot Creek

The effects of the lampricide, TFM, on the abundance of macroinvertebrates in the benthos of Wilmot Creek, a hardwater tributary to Lake Ontario, was examined over 1 year. Drifting macroinvertebrates were also collected before, during and after TFM treatment. Significant decreases in benthic abundance were exhibited by Dolophilodes sp., Tubificoidea, Cricotopus sp. and Macrotendipes sp. throughout the 350 days following treatment. Only the decrease in abundance of Dolophilodes sp. and Tubificoidea could be attributed to TFM treatment. Increases in drift abundance observed during treatment were generally an accurate indicator of TFM-sensitive macroinvertebrates. The most sentive taxa (Dolophilodes sp., Dugesia sp. and Tubificoidea) responded immediately following the introduction of TFM. Branchiobdellida, Diamesa sp., Dicranota sp., Lumbricidae and Nemouridae exhibited increases in drift abundance 8–10 h after the introduction of TFM, however, were considered less sensitive than the former taxa because a decline in their abundance in the benthos was not detected.

Effects of the lampricide, 3-trifluoromethyl-4-nitrophenol (TFM) on the macroinvertebrates of a hardwater river

The effects of the lampricide, TFM, on the benthic macroinvertebrates in the Rouge River, a hardwater tributary to Lake Ontario was examined at 1 untreated and 2 treated sites over a 7 month period. Drift samples were collected from one one of the treated sites during the 5 days bracketing treatment. Significant decreases in relative abundance attributable to TFM were recorded for Chimarra sp., Dugesia sp. and Tubificoidea 2–19 d following treatment. Large reductions were also exhibited by Caenis sp. and Lumbricidae. Two-thirds of the Chironomidae genera and Nematoda tended to decline in abundance 2 d after treatment at only one of the treated sites, probably due to a 2.5 h longer treatment. This decline was followed by a significant increase to greater than pretreatment abundances 17 d later undoubtedly as a result of an upward migration of macroinvertebrates from within the hyporheos. Partial recolonization of the TFM-sensitive benthic taxa was evident 19 d after lampricide treatment with complete recolonization 6.5 months later. With the exception of Caenis sp. those taxa in the present study found to be TFM-sensitive were in accordance with those found in softwater field studies.

Effects of the lampricide, 3-trifluoromethyl-4-nitrophenol (TFM) on the macroinvertebrates within the hyporheic region of a small stream

The effect of the lampricide, 3-trifluoromethyl-4-nitrophenol (TFM), on the benthic macroinvertebrates within the hyporheic region of Dam Creek, Ontario was investigated. Organisms were regularly found to a depth of 70 cm in the substrate throughout the study period. Of the eight major taxa found at both the treated and untreated sites only Tubificoidea exhibited a decrease in abundance attributable to TFM. One day after treatment, TFM concentrations were greatest at a depth of 55 cm, the greatest depth to which water samples were taken. The movement of TFM into the hyporheic region during the present study may be due to the large convective forces created by the rapid decrease in surface water temperature. These convective forces are usually greatest in the late fall and winter when TFM is not applied. The greater part of TFM stream treatments are carried out during the summer when surface water temperatures remain fairly constant. It is suggested that the hyporheic region may act as a refuge zone for benthic macroinvertebrates against the lampricide during most of the TFM application season.

Loss of Lampricides by Adsorption on Bottom Sediments

Problems have been encountered in maintaining effective concentrations of the lampricides 3-trifluoromethyl-4-nitrophenol (TFM) and 5,2′-dichloro-4′-nitrosalicylanilide (Bayer 73) during treatments of certain Great Lakes tributaries. Concentrations of Bayer 73 decreased by more than 80% in a portion of the Ford River, Michigan, during treatment in 1980. Adsorption of Bayer 73 on sediments was hypothesized as the primary mechanism of this excessive loss. Subsequent laboratory studies demonstrated that lampricides are adsorbed by silt-type sediments that are high in organic content, including those collected from the treated portion of the Ford River. Un-ionized lampricides (acidic solution) were more readily adsorbed than ionized forms (basic solution). Adsorption onto sediments was proportionally greater, and desorption proportionally less, for Bayer 73 than for TFM. When Ford River sediments were mixed with lampricide-free water, less than 10% of the adsorbed Bayer 73, but more than 60% of the TFM, was released. The extensive adsorption of the lampricides (especially Bayer 73) from solution by silt-type sediments explains much of the loss of effective concentrations in certain streams.

Photodegradation of the Lampricide 3-Trifluoromethyl-4-Nitrophenol (TFM) 1. Pathway of the Direct Photolysis in Solution

Solutions of TFM (3-trifluoromethyl-4-nitrophenol) in distilled and in two Lake Ontario tributary stream waters were exposed to spring and fall natural sunlight in Pyrex glass containers. TFM degraded in the natural stream waters with a half-life of about 3 days. The principle identified photoproduct is shown to be gentisic acid (2,5-dihydroxybenzoic acid). A second major photoproduct is believed to be a condensation product of TFM and gentisic acid (molecular weight 371). Structures based on mass spectra are proposed for four other photoproducts. A photolysis pathway is proposed in which the primary degrdation route leads to polymeric, humic acid-like material.

Sea Lamprey (Petromyzon marinus) in Lakes Huron, Michigan, and Superior: History of Invasion and Control, 1936–78

Sea lamprey (Petromyzon marinus) entered the upper three Great Lakes in the late 1930s and began making sharp inroads into the fish stocks by the mid-1940s in lakes Huron and Michigan and the mid-1950s in Lake Superior. The first serious attempts to control the parasite began in 1950 with the installation of mechanical barriers along the United States shore of Lake Huron to block spawning runs. Electrical barriers, developed in 1952, were installed in 132 tributaries of the Great Lakes by 1960, but control measures did not become effective until after 1958, when a selective toxicant — the lampricide 3-trifluoromethyl-4-nitrophenol (TFM) — was used to destroy larval lampreys in streams. In the 21 years, 1958–78, 1223 treatments of tributaries of the upper three lakes with TFM were completed in 334 streams — 91 in Canada and 243 in the United States. Evidence of the success of the control program was soon obvious: first by reduced sea lamprey spawning runs as measured by the numbers of adults taken at electrical barriers; second by significant decreases in the incidence of sea lamprey wounds on lake trout (Salvelinus namaycush); and finally by the excellent responses of major fish stocks to sea lamprey control. All three of the upper lakes have large numbers of lake trout, coho salmon (Oncorhynchus kisutch), chinook salmon (O. tshawytscha), and other salmonids available to the sport fishery and in some areas to the commercial fishing industry. Although the sea lamprey control program has been successful, it is important that emphasis be placed on developing new and innovative methods to reduce the dependence on lampricides. It is expected that a fully integrated program will eventually comprise several methods, including permanent barrier dams on selected streams and the use of sterilants, attractants, repellents, and biological controls, as well as chemical lampricides.Key words: sea lamprey, distribution, abundance, history, predation, integrated controls, Huron, Michigan, Superior

Rapid Method for Determining Concentrations of Bayer 73 in Water During Lampricide Treatments

Two simple, rapid, sensitive methods were developed for determining the concentration of the lampricide 2′,5-dichloro-4′-nitrosalicylanilide (Bayer 73) in stream water. Bayer 73 was extracted from acidified water samples with chloroform and then hydrolyzed to 2-chloro-4-nitroaniline (CNA) with either acid or base. The CNA was diazotized with sodium nitrite, and an azo dye was formed with either N-(1-naphthyl) ethylenediamine dihydrochloride (after acid hydrolysis) or 1-naphthol (after base hydrolysis). There was no interference from the lampricide 3-trifluoromethyl-4-nitrophenol (TFM) in either method. Standard curves were prepared with untreated water to compensate for interfering substances that occurred naturally in some streams. The methods were sensitive to about 0.005 mg/L (ppm). Time required for analysis of a sample ranged from 25 min to 1 h. Key words: Bayer 73, Bayluscide®, 2′,5-dichloro-4′-nitrosalicylanilide, lampricide, phenylamide, analysis, water, colorimetric, sea lamprey, Great Lakes

Uptake, elimination, and biotransformation of the lampricide 3-trifluoromethyl-4-nitrophenol (TFM) by larvae of the aquatic midge chironomus tentans

Accumulation of [ 14C]3-trifluoromethyl-4-nitrophenol ([ 14C] TFM) by chironomid larvae from sublethal aqueous concentrations is rapid and dependent on hardness of exposure water. TFM is readily biotransformed to at least two more polar derivatives, including sulfated TFM and TFM-glucuronide or galacturonide. Some TFM is also reduced to the phenol amine. Chironomids can quickly eliminate all TFM derivatives as well as the parent [ 14C] TFM.

BODY SIZE AND METABOLIC RATE

BODY SIZE AND METABOLIC RATE