Rotenone formulation fate in Lake Davis following the 2007 treatment.

In September 2007, Lake Davis (near Portola, California) was treated by the California Department of Fish and Game with CFT Legumine, a rotenone formulation, to eradicate the invasive northern pike (Esox lucius). The objective of this report is to describe the fate of the five major formulation constituents-rotenone, rotenolone, methyl pyrrolidone (MP), diethylene glycol monethyl ether (DEGEE), and Fennedefo 99-in water, sediment, and brown bullhead catfish (Ameiurus nebulosus; a rotenone-resistant species) by determination of their half-lives (t(1/2)) and pseudo first-order dissipation rate constants (k). The respective t(1/2) values in water for rotenone, rotenolone, MP, DEGEE, and Fennedefo 99 were 5.6, 11.1, 4.6, 7.7, and 13.5 d; in sediments they were 31.1, 31.8, 10.0, not able to calculate, and 48.5 d; and in tissues were 6.1, 12.7, 3.7, 3.2, and 10.4 d, respectively. Components possessing low water solubility values (rotenone and rotenolone) persisted longer in sediments (not detectable after 157 d) and tissues (<212 d) compared with water, whereas the water-miscible components (MP and DEGEE) dissipated more quickly from all matrices, except for Fennedefo 99, which was the most persistent in water (83 d). None of the constituents was found to bioaccumulate in tissues as a result of treatment. In essence, the physicochemical properties of the chemical constituents effectively dictated their fate in the lake following treatment.

Use of vegetated agricultural drainage ditches to decrease toxicity of irrigation runoff from tomato and alfalfa fields in California, USA.

The current study investigated the potential of vegetated drainage ditches for mitigating the impact of agricultural irrigation runoff on downstream aquatic ecosystems. Water column toxicity to larval fathead minnow (Pimephales promelas),and the amphipod Hyalella azteca was measured for 12 h or less at the ditch inflow and outflow, using custom-built in situ exposure systems. In addition, water and sediment samples were subject to standard toxicity tests with Ceriodaphnia dubia and H. azteca, respectively. No acute toxicity to larval fathead minnow was observed; however, runoff was highly toxic to invertebrates. Passage through a 389- to 402-m section of vegetated ditch had a mitigating effect and reduced toxicity to some degree. However, runoff from an alfalfa field treated with chlorpyrifos remained highly toxic to both invertebrate species, and runoff from a tomato field treated with permethrin remained highly toxic to H. azteca after passage through the ditch. Predicted toxic units calculated from insecticide concentrations in runoff and 96-h median lethal concentration (LC50) values generally agreed with C. dubia toxicity measured in the laboratory but significantly underestimated in situ toxicity to H. azteca. Sediments collected near the ditch outflow were toxic to H. azteca. Results from the current study demonstrate that experimental vegetated ditches were unable to eliminate the risk of irrigation runoff to aquatic ecosystems. In addition, protective measures based on chemical concentrations or laboratory toxicity tests with C. dubia do not ensure adequate protection of aquatic ecosystems from pyrethroid-associated toxicity.

Evaluation of methods to determine causes of sediment toxicity in San Diego Bay, California, USA.

Regulation of waterbodies impaired due to sediment toxicity may require development of Total Maximum Daily Load (TMDL) allocations to reduce chemicals of concern. A key step in this process is the identification of chemicals responsible for toxicity, and sediment toxicity identification evaluation procedures (TIEs) are the primary tools used to accomplish this. Several sites in San Diego Bay (CA, USA) are listed as impaired due to sediment toxicity associated with organic chemicals and metals, and due to degraded benthic macroinvertebrate communities. Sediment was collected from one of these sites, at the confluence of Switzer Creek in San Diego Harbor. The sediment was subjected to selected whole-sediment TIE treatments to evaluate the efficacy of these procedures for identifying the causes of toxicity at Switzer Creek. Toxicity was assessed using the estuarine amphipod Eohaustorius estuarius. The results indicated that toxicity of San Diego Bay sediment was likely partly due to mixtures of pyrethroid pesticides. These experiments showed that the effectiveness of the individual TIE procedures varied by treatment. Variability was mainly due to inconsistency between results of samples subjected to various Phase II TIE procedures, including chemical analyses of samples subjected to high-pressure liquid chromatography and direct analyses of acetone extractions of carbonaceous resin. The procedures require further refinement to ensure maximum sorption and complete elution and detection of sorbed chemicals. Despite these inconsistencies, the results indicate the utility of these procedures for identifying chemicals of concern in this system.

Mass stranding of marine birds caused by a surfactant-producing red tide.

In November-December 2007 a widespread seabird mortality event occurred in Monterey Bay, California, USA, coincident with a massive red tide caused by the dinoflagellate Akashiwo sanguinea. Affected birds had a slimy yellow-green material on their feathers, which were saturated with water, and they were severely hypothermic. We determined that foam containing surfactant-like proteins, derived from organic matter of the red tide, coated their feathers and neutralized natural water repellency and insulation. No evidence of exposure to petroleum or other oils or biotoxins were found. This is the first documented case of its kind, but previous similar events may have gone undetected. The frequency and amplitude of red tides have increased in Monterey Bay since 2004, suggesting that impacts on wintering marine birds may continue or increase.

Statewide investigation of the role of pyrethroid pesticides in sediment toxicity in California's urban waterways.

A statewide investigation of urban creek sediment toxicity was conducted in California in recognition of increased incidences of toxicity linked to pyrethroid pesticides. The goals were to examine the spatial occurrence and magnitude of sediment toxicity in California urban creeks, and to examine the role of pyrethroids in toxic urban creek sediment samples. After a preliminary screening of 90 sites, 30 creeks were sampled in eight geographical regions. Sediment toxicity was assessed using 10 day bioassays with the resident amphipod Hyalella azteca. Bioassays were conducted at two test temperatures of 23 degrees C and at 15 degrees C to provide evidence of the cause of toxicity, and to more accurately reflect ambient environmental temperatures. Twenty-five of 30 samples were toxic when tested at 23 degrees C, and all 30 samples were toxic when tested at 15 degrees C. The magnitude of toxicity increased in samples tested at 15 degrees C suggesting the influence of pyrethroids, which are more toxic at colder temperatures. Pyrethroids were present in all sediment samples and were the only compounds detected at concentrations toxic to H. azteca. Bifenthrin was the pyrethroid of greatest toxicological concern, occurring in all 30 samples at concentrations up to 219 ng/g. Pyrethroid contamination of urban creeks was most severe in the Los Angeles, Central Valley, and San Diego regions, respectively. However, pyrethroids were also linked to urban creek aquatic toxicity in all regions sampled, including the less urbanized areas of the North Coast and Lake Tahoe.

Aquatic effects of aerial spraying for mosquito control over an urban area.

In an effort to combat West Nile Virus, planes dispersed insecticide over Sacramento, CA, treating nearly 50,000 hectares with pyrethrins and the synergist piperonyl butoxide (PBO). Widespread dispersal of insecticide over a metropolitan area, coupled with extensive pretreatment data on the area's urban creeks, provided a unique opportunity to study effects of mosquito control agents on aquatic habitats within an urban setting. There was no evidence of aquatic toxicity from the two active ingredients in the product applied. However, PBO concentrations were high enough to enhance toxicity of pyrethroids already existing in creek sediments from general urban pesticide use. PBO concentrations of 2-4 microg/L were high enough to nearly double the toxicity of sediments to the amphipod Hyalella azteca. Though the increase in toxicity was modest, it was unexpected to find environmental synergy at all. Risk assessments for mosquito control agents have focused on the active ingredients but have failed to recognize the potential for interactions with pesticides previously existing in the environment, which in this case appeared to represent a risk to aquatic life greater than that of the active ingredients themselves.

Evaluation of estrogenic activities of aquatic herbicides and surfactants using an rainbow trout vitellogenin assay.

Estrogenic potencies of four herbicides (triclopyr, 2,4-dichlorophenoxyacetic acid (2,4-D), diquat dibromide, glyphosate), two alkylphenol ethoxylate-containing surfactants (R-11 and Target Prospreader Activator (TPA)), and the binary mixture of surfactants with the herbicides were evaluated using an in vivo rainbow trout vitellogenin assay. Juvenile rainbow trout exposed to 2,4-D (1.64 mg/l) for 7 days had a 93-fold increase in plasma vitellogenin (Vtg) levels compared with untreated fish, while rainbow trout exposed to other pesticides alone did not show elevated vitellogenin levels compared to the control fish. When combined with surfactants, trends indicated enhanced estrogenicity for all combinations, but only 2,4-D and triclopyr caused significant induction of Vtg. Concentration-response studies demonstrated that the lowest observed effect concentrations (LOECs) for 2,4-D and triclopyr were 0.164 mg/l and 1 mg/l, respectively. In terms of measured 4-nonylphenol (4-NP), the LOECs of R-11 and TPA were 20 micro/l and 9.5 microg/l, respectively. Binary mixtures of TPA and 2,4-D showed a greater than additive estrogenic response at the lowest concentrations tested, but a less than additive response at the highest combined concentrations. Binary mixtures of TPA with triclopyr also caused greater than additive Vtg responses in two middle concentrations when compared to TPA or triclopyr alone. When trout were exposed to water collected from a site where triclopyr was used in combination with TPA, a concentration-dependent increase in Vtg expression was observed. Measured values of 4-NP were 3.7 microg/l, and triclopyr concentrations were below detection (<5 ng/l). Estradiol equivalents (EEQs) of the lake water were calculated from an estradiol concentration-response curve and were similar (8.5 +/- 7.7 ng/l) to the mean values for the combined triclopyr + TPA treatments (9.9-12.2 ng/l) in the laboratory, suggesting the estrogenicity of the water may have been due to the treatment. These results demonstrated the binary mixture of alkylphenol ethoxylate-containing surfactants with two aquatic pesticides possessed greater than additive estrogenic responses in fish under laboratory conditions and in a field setting.