Michael J. Lydy

Toxicity of fluoroquinolone antibiotics to aquatic organisms

Toxicity tests were performed with seven fluoroquinolone antibiotics, ciprofloxacin, lomefloxacin, ofloxacin, levofloxacin, clinafloxacin, enrofloxacin, and flumequine, on five aquatic organisms. Overall toxicity values ranged from 7.9 to 23,000 microg/L. The cyanobacterium Microcystis aeruginosa was the most sensitive organism (5-d growth and reproduction, effective concentrations [EC50s] ranging from 7.9 to 1,960 microg/L and a median of 49 microg/L), followed by duckweed (Lemna minor, 7-d reproduction, EC50 values ranged from 53 to 2,470 microg/L with a median of 106 microg/L) and the green alga Pseudokirchneriella subcapitata (3-d growth and reproduction, EC50 values ranged from 1,100 to 22,700 microg/L with a median 7,400 microg/L). Results from tests with the crustacean Daphnia magna (48-h survival) and fathead minnow (Pimephales promelas, 7-d early life stage survival and growth) showed limited toxicity with no-observed-effect concentrations at or near 10 mg/L. Fish dry weights obtained in the ciprofloxacin, levofloxacin, and ofloxacin treatments (10 mg/L) were significantly higher than in control fish. The hazard of adverse effects occurring to the tested organisms in the environment was quantified by using hazard quotients. An estimated environmental concentration of 1 microg/L was chosen based on measured environmental concentrations previously reported in surface water; at this level, only M. aeruginosa may be at risk in surface water. However, the selective toxicity of these compounds may have implications for aquatic community structure.

Challenges in regulating pesticide mixtures

This paper introduces the field of mixture toxicity and the challenges in regulating pesticide mixtures. Even though pesticides are unique chemical stressors designed to have biological activity that can affect a number of nontarget species, they are intentionally placed into the environment in large quantities. Currently, methods and terminology for evaluating mixture toxicity are poorly established. The most common approach used is the assumption of additive concentration, with the concentrations adjusted for potency to a reference toxicant. Using this approach, the joint action of pesticides that have similar chemical structures and modes of toxic action can be predicted. However, this approach and other modeling techniques often provide little insight into the observed toxicity produced by mixtures of pesticides from different classes. Particularly difficult to model are mixtures that involve a secondary toxicant that changes the toxicokinetics of a primary toxicant. This may result in increased activation or a change in the persistence of the primary toxicant within the organism and may be responsible for a several-fold increase or decrease in toxicity. At present, the ecological effects caused by mixtures of pesticides are given little consideration in the regulatory process. However, mixtures are being considered in relation to human health in the pesticide registration process, setting a precedent that could be followed for ecological protection. Additionally, pesticide mixtures may be regulated through toxicity testing of surface water under the Clean Water Act. The limits of our basic knowledge of how mixtures interact are compromising both these avenues for regulating mixtures. We face many challenges to adequately protecting the environment from mixture toxicity; these challenges include understanding the interactions of toxicants within an organism, identifying the mixtures that most commonly occur and cause adverse effects, and developing a regulatory structure capable of minimizing environmental impacts.

Residential runoff as a source of pyrethroid pesticides to urban creeks

Pyrethroid pesticides occur in urban creek sediments at concentrations acutely toxic to sensitive aquatic life. To better understand the source of these residues, runoff from residential neighborhoods around Sacramento, California was monitored over the course of a year. Pyrethroids were present in every sample. Bifenthrin, found at up to 73 ng/L in the water and 1211 ng/g on suspended sediment, was the pyrethroid of greatest toxicological concern, with cypermethrin and cyfluthrin of secondary concern. The bifenthrin could have originated either from use by consumers or professional pest controllers, though the seasonal pattern of discharge from the drain was more consistent with professional use as the dominant source. Stormwater runoff was more important than dry season irrigation runoff in transporting pyrethroids to urban creeks. A single intense storm was capable of discharging as much bifenthrin to an urban creek in 3h as that discharged over 6 months of irrigation runoff.

Urban and Agricultural Sources of Pyrethroid Insecticides to the Sacramento-San Joaquin Delta of California

While studies have documented the presence of pyrethroid insecticides at acutely toxic concentrations in sediments, little quantitative data on sources exist. Urban runoff, municipal wastewater treatment plants and agricultural drains in Californias Sacramento-San Joaquin River Delta were sampled to understand their importance as contributors of these pesticides to surface waters. Nearly all residential runoff samples were toxic to the amphipod, Hyalella azteca, and contained pyrethroids at concentrations exceeding acutely toxic thresholds, in many cases by 10-fold. Toxicity identification evaluation data were consistent with pyrethroids, particularly bifenthrin and cyfluthrin, as the cause of toxicity. Pyrethroids passed through secondary treatment systems at municipal wastewater treatment facilities and were commonly found in the final effluent, usually near H. azteca 96-h EC(50) thresholds. Agricultural discharges in the study area only occasionally contained pyrethroids and were also occasional sources of toxicity related to the organophosphate insecticide chlorpyrifos. Discharge of the pyrethroid bifenthrin via urban stormwater runoff was sufficient to cause water column toxicity in two urban creeks, over at least a 30 km reach of the American River, and at one site in the San Joaquin River, though not in the Sacramento River.

Occurrence and potential toxicity of pyrethroids and other insecticides in bed sediments of urban streams in central Texas.

Despite heavy insecticide usage in urban areas, only a few studies have investigated the impact of current-use insecticides on benthic invertebrates in urban streams. The objective of this study was to measure the presence and concentration of current-use pesticides in sediments of residential streams in central Texas. Additionally, toxicity of these sediments to Hyalella azteca was evaluated. Sediment samples were collected from several sites in urban streams over the course of a year, of which, 66% had greater than one toxic unit (TU) of insecticide. Bifenthrin was the greatest contributor accounting for 65% of the TUs, and sediment toxicity to H. azteca correlated with the magnitude of total insecticides and bifenthrin TUs. The results of this study further raise concerns over the environmental consequences posed by many current-use insecticides, especially pyrethroids, in urban settings.

Distribution and toxicity of sediment-associated pesticides in urban and agricultural waterways from Illinois, USA.

A statewide investigation of insecticide presence and sediment toxicity was conducted in Illinois, USA, from June to August 2008. Twenty sediment samples were collected from urban areas throughout Illinois, and 49 sediment samples were collected from 14 agriculture-dominated counties in central and southern Illinois. Ten-day sediment toxicity tests were conducted using the amphipod Hyalella azteca, and 59% of the urban sites and 2% of the agricultural locations sampled caused significant mortality in the amphipods. The field sediments were analyzed for 29 pesticides, including 19 organochlorines, one organophosphate, and nine pyrethroids. The detection frequencies of organochlorines, chlorpyrifos, and pyrethroids were 95, 65, and 95%, respectively, for urban sites, and 45, 6.1, and 47%, respectively, for agricultural sites. Based on toxic unit analysis, bifenthrin was the main contributor to the detected mortality in urban sediments. The present study provides the first broad assessment of pesticide prevalence in both urban and agriculture areas in Illinois.

Temperature as a toxicity identification evaluation tool for pyrethroid insecticides: Toxicokinetic confirmation

Toxicity identification evaluation (TIE) methods can be used to identify toxic compounds in environmental samples using a variety of laboratory techniques. Whereas TIEs exist for nonpolar organics, relatively few methods are established for individual contaminant classes. Toxicity identification evaluations have shown pesticides to be the cause of toxicity in agricultural waters and effluents, and more recent studies have shown that the insecticide class of concern is pyrethroids. The primary objectives of the present study were to confirm a temperature TIE model and mechanistically explain these trends. This was achieved by comparing the relative toxicity and influence of temperature (13 vs. 23 degrees C) on Chironomus dilutus exposed to four insecticides, including two pyrethroids, an organophosphate, and an organochlorine, and then explaining these changes using toxicokinetics. A 10 degrees C temperature decrease increased the toxicity of pyrethroids and DDT but decreased the toxicity of chlorpyrifos. The decrease in chlorpyrifos toxicity was driven primarily by the reduction of the formation of more toxic products via decreased biotransformation. The increase in DDT toxicity, in contrast, can be attributed to increased nerve sensitivity at 13 versus 23 degrees C. The pyrethroid toxicity change, however, resulted from a combination of increased accumulation of parent compound and increased nerve sensitivity, exacerbating the toxicity of pyrethroids at 13 degrees C. These trends also held true in sediment exposures with chlorpyrifos and permethrin, indicating that water-only exposures were adequate substitutes for examining this mechanism.

EFFECT OF SEDIMENT-ASSOCIATED PYRETHROIDS, FIPRONIL, AND METABOLITES ON CHIRONOMUS TENTANS GROWTH RATE, BODY MASS, CONDITION INDEX, IMMOBILIZATION, AND SURVIVAL

Pyrethroids and fipronil insecticides partition to sediment and organic matter in aquatic systems and may pose a risk to organisms that use these matrices. It has been suggested that bioavailability of sediment-sorbed pesticides is reduced, but data on toxicity of sediment-associated pesticides for pyrethroids and fipronil are limited. In the current study, 10-d sediment exposures were conducted with larval Chironomus tentans for bifenthrin, lambda-cyhalothrin, permethrin, fipronil, fipronil-sulfide, and fipronil-sulfone, the last two being common fipronil metabolites. Sublethal endpoints included immobilization, instantaneous growth rate (IGR), body condition index, and growth estimated by ash-free dry mass (AFDM). Pyrethroid lethal concentrations to 50% of the population (LC50s) were 6.2, 2.8, and 24.5 microg/g of organic carbon (OC) for bifenthrin, lambda-cyhalothrin, and permethrin, respectively; with the former two lower than previously published estimates. Fipronil, fipronil-sulfide, and fipronil-sulfone LC50 values were 0.13, 0.16, and 0.12 microg/g of OC, respectively. Ratios of LC50s to sublethal endpoints (immobilization, IGR, and AFDM) ranged from 0.90 to 9.03. The effects on growth observed in the present study are important because of the unique dipteran life cycle involving pupation and emergence events. Growth inhibition would likely lead to ecological impacts similar to mortality (no emergence and thus not reproductively viable) but at concentrations up to 4.3 times lower than the LC50 for some compounds. In addition, C. tentans was highly sensitive to fipronil and metabolites, suggesting that dipterans may be important for estimating risk and understanding effects of phenylpyrazole-class insecticides on benthic macroinvertebrate communities.

Method development for the analysis of organophosphate and pyrethroid insecticides at low parts per trillion levels in water.

In the current study, organophosphate and pyrethroid insecticides including diazinon, chlorpyrifos, bifenthrin, fenpropathrin, permethrin, lambda-cyhalothrin, cyfluthrin, cypermethrin, esfenvalerate and deltamethrin were analyzed in laboratory and field-collected water samples. Water samples were extracted and analyzed by gas chromatography/electron capture detector (GC/ECD) and gas chromatography/nitrogen-phosphorous detector (GC/NPD). Comparison of results from liquid-liquid extraction and subsequent normal phase solid-phase extraction cleanup (LLE-NPSPE), and reversed phase solid-phase extraction (RPSPE) showed that LLE-NPSPE was the better choice to extract trace amounts of pesticides from water. Pesticide recoveries from four spiked water samples using LLE-NPSPE ranged from 63.2 to 148.8% at four spiking concentrations. Method detection limits were 0.72-1.69 ng/L using four different water sources. The stability of the target pesticides in lake water was investigated at 4 degrees C for 1h, 1d, 4d, and 7d under three conditions: (1) water samples only; (2) with 20 mL hexane used as a keeper solvent; and (3) with acidification to pH 2 with HCl. Results showed that water storage without treatment resulted in slow degradation of some pesticides with storage time, storage using water acidification led to significant degradation and loss of diazinon and chlorpyrifos, while water storage with hexane as a keeper solvent showed good stability for all of the target pesticides over the 7d storage period.

Joint toxicity of chlorpyrifos and esfenvalerate to fathead minnows and midge larvae

The joint toxicity of esfenvalerate and chlorpyrifos to the fathead minnow (Pimephales promelas) and the aquatic midge larvae (Chironomus tentans) was determined using comparisons to independent action (IA) and concentration addition (CA) models. Equipotent mixtures of the two insecticides were used for initial testing of both species. A secondary study evaluating the effects of low-level chlorpyrifos on esfenvalerate toxicity also was performed. For fathead minnows, the equipotent mixture and the low-level chlorpyrifos exposure resulted in toxicity greater than that predicted by either model. In both studies, however, the observed concentrations causing 50% effect (EC50) were within a factor of two of the values predicted by the CA model. For midges, the observed EC50s were similar to the values predicted by the CA model, whereas the IA model slightly underpredicted toxicity. The observance of toxicity that was not predicted by either of the conceptual models tested likely results from a toxicokinetic interaction occurring between the toxicants.