Atmospherically deposited contaminants in the Sierra Nevada mountains of California, USA have been implicated as adversely affecting amphibians and fish, yet little is known about the distributions of contaminants within the mountains, particularly at high elevation. We tested the hypothesis that contaminant concentrations in a high-elevation portion of the Sierra Nevada decrease with distance from the adjacent San Joaquin Valley. We sampled air, sediment, and tadpoles twice at 28 water bodies in 14 dispersed areas in Sequoia and Kings Canyon National Parks (2785 – 3375 m elevation; 43 – 82 km from Valley edge). We detected up to 15 chemicals frequently in sediment and tadpoles, including current- and historic-use pesticides, polychlorinated biphenyls, and polycyclic aromatic hydrocarbons. Only β-endosulfan was found frequently in air. Concentrations of all chemicals detected were very low, averaging in the parts-per-billion range or less in sediment and tadpoles, and on the order of 10 pg/m3 for β-endosulfan in air. Principal components analysis indicated that chemical compositions were generally similar among sites, suggesting that chemical transport patterns were likewise similar among sites. In contrast, transport processes did not appear to strongly influence concentration differences among sites because variation in concentrations among nearby sites was high relative to sites far from each other. Moreover, a general relationship for concentrations as a function of distance from the valley was not evident across chemical, medium, and time. Nevertheless, concentrations for some chemical/medium/time combinations showed significant negative relationships with metrics for distance from the Valley. However, the magnitude of these distance effects among high-elevation sites was small relative to differences found in other studies between the valley edge and the nearest high-elevation sites.
Fish in agricultural and remote areas may be exposed to endosulfan and its degradation products as a result of direct runoff, atmospheric transport and deposition. The following study used the zebrafish developmental model to investigate the responses to endosulfan I and endosulfan sulfate, the major degradation product of endosulfan I and II. Embryos were dechorionated and waterborne exposed to the endosulfan I or endosulfan sulfate from 6 to 120 hours post fertilization (hpf). Endosulfan I exposure concentrations ranged from 0.01 to 10 μg/L and endosulfan sulfate from 1 to 100 μg/L. Water solutions were renewed every 24 hours and fish were scored for overt developmental and behavioral abnormalities. Chemical analysis was performed on water, whole embryo, and larvae samples to determine waterborne exposure concentrations and tissue concentrations throughout the 5-day period. The most sensitive toxicity endpoint for both endosulfan I and endosulfan sulfate was an abnormal response of the embryo/larvae to touch, suggesting that endosulfan I and sulfate are developmentally neurotoxic. The waterborne exposure EC 50 s for inhibition of touch response for endosulfan I and endosulfan sulfate were 2.2 μg/L and 23 μg/L, respectively. The endosulfans were highly concentrated by the organisms, and the inhibition of touch response tissue EC 50 , determined from the measured tissue concentrations, was 367 ng/g for endosulfan I and 4552 ng/g for endosulfan sulfate.
Atmospherically deposited pesticides from the intensively cultivated Central Valley of California, USA, have been implicated as a cause for population declines of several amphibian species, with the strongest evidence for the frogs Rana muscosa and Rana sierrae at high elevation in the Sierra Nevada mountains. Previous studies on these species have relied on correlations between frog population status and either a metric for amount of upwind pesticide use or limited measurements of pesticide concentrations in the field. The present study tested the hypothesis that pesticide concentrations are negatively correlated with frog population status (i.e., fraction of suitable water bodies occupied within 2 km of a site) by measuring pesticide concentrations in multiple media twice at 28 sites at high elevation in the southern Sierra Nevada. Media represented were air, sediment, and Pseudacris sierra tadpoles. Total cholinesterase (ChE), which has been used as an indicator for organophosphorus and carbamate pesticide exposure, was also measured in P. sierra tadpoles. Results do not support the pesticide-site occupancy hypothesis. Among 46 pesticide compounds analyzed, nine were detected with ≥ 30% frequency, representing both historically and currently used pesticides. In stepwise regressions with a chemical metric and linear distance from the Central Valley as predictor variables, no negative association was found between frog population status and the concentration of any pesticide or tadpole ChE activity level. By contrast, frog population status showed a strong positive relationship with linear distance from the Valley, a pattern that is consistent with a general west-to-east spread across central California of the amphibian disease chytridiomycosis observed by other researchers.
Populations of Cascades frogs (Rana cascadae) have declined precipitously in the Mount Lassen area, but remain abundant in the other half of their California range in the Klamath Mountains. To evaluate the role of contaminants in Cascade frog declines, we sampled sediment and frog tadpole tissue at 31 sites where Cascades frogs had disappeared and sites where Cascades frogs are still present across the Lassen and Klamath regions. Pacific chorus frogs (Pseudacris regilla) were tested and used as surrogates for residue concentrations in Cascades frogs. We analyzed a total of 79 tadpole samples for 73 semivolatile contaminants including pesticides, polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs). The most frequently detected residue was endosulfan sulfate, followed by dacthal, chlorpyrifos, PCB 187, endosulfan II, trans-chlordane, and trans-nonachlor. Chorus frogs had similar residue concentrations as Cascades frogs for most but not all chemicals, indicating that chorus frogs can serve as a reasonable proxy for chemical concentrations in Cascades frogs. None of the contaminants in tissue or sediment had significantly higher concentrations at sites where Cascades frogs have disappeared than at sites where Cascades frogs are still present. We found no evidence to support the hypothesis that the contaminants analyzed have contributed to the decline of Cascades frogs in northern California, although we were able to analyze only a handful of the over 300 pesticides currently used in the area.
Atrazine (ATZ) is a selective triazine herbicide used primarily for pre-emergent weed control in corn, sorghum and sugar cane production. It is one of the most widely used herbicides in North America. Some research published over the last decade suggests that chronic exposure to environmentally relevant ATZ concentrations can adversely impact gonadal development and/or sexual differentiation in amphibians and fish, while other studies report no effect, or moderate effects. As a result, contrasting conclusions have been published regarding the potential effects of the herbicide ATZ on aquatic species. Two near-identical four-month studies in 2009 (Study I) and 2010 (Study II), were performed investigating the potential for chronic ATZ exposure to affect zebrafish (Danio rerio) sexual development and differentiation. Zebrafish, were chronically exposed to 0, 0.1, 1, 10 µM ATZ or 1 nM 17α-estradiol (E2). Fish were histologically examined to assign gender and to evaluate potential impacts of E2 or ATZ on gonadal development. Exposure to E2 consistently resulted in a significantly higher proportion of female fish to normal male fish when compared to unexposed fish (both studies). In both studies, ATZ exposure did not significantly influence the percentage of female or male fish when compared to unexposed fish. A greater percentage of abnormally developed male fish and fish lacking differentiated gonadal tissue was observed in Study II E2 exposures but not in ATZ exposures. Together, these studies indicate that long-term exposure to ATZ at or above environmentally relevant concentrations does not significantly impact zebrafish gonadal development or sexual differentiation.
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