Jonathan D. Maul

Acute effects of Fe2O3, TiO2, ZnO and CuO nanomaterials on Xenopus laevis

Metal oxide nanomaterials have exhibited toxicity to a variety of aquatic organisms, especially microbes and invertebrates. To date, few studies have evaluated the toxicity of metal oxide nanomaterials on aquatic vertebrates. Therefore, this study examined effects of ZnO, TiO(2), Fe(2)O(3), and CuO nanomaterials (20-100 nm) on amphibians utilizing the Frog Embryo Teratogenesis Assay Xenopus (FETAX) protocol, a 96 h exposure with daily solution exchanges. Nanomaterials were dispersed in reconstituted moderately hard test medium. These exposures did not increase mortality in static renewal exposures containing up to 1,000 mg L(-1) for TiO(2), Fe(2)O(3), CuO, and ZnO, but did induce developmental abnormalities. Gastrointestinal, spinal, and other abnormalities were observed in CuO and ZnO nanomaterial exposures at concentrations as low as 3.16 mg L(-1) (ZnO). An EC(50) of 10.3 mg L(-1) ZnO was observed for total malformations. The minimum concentration to inhibit growth of tadpoles exposed to CuO or ZnO nanomaterials was 10 mg L(-1). The results indicate that select nanomaterials can negatively affect amphibians during development. Evaluation of nanomaterial exposure on vertebrate organisms are imperative to responsible production and introduction of nanomaterials in everyday products to ensure human and environmental safety.

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.

Uptake of 17α-ethynylestradiol and triclosan in pinto bean, Phaseolus vulgaris.

Pharmaceuticals and personal care products (PPCPs) have emerged as a group of potential environmental contaminants of concern. PPCPs in soil may enter terrestrial food webs via plant uptake. We evaluated uptake of 17α-ethynylestradiol (EE2) and triclosan in bean plants (Phaseolus vulgaris) grown in sand and soil. The extent of uptake and accumulation of EE2 and triclosan in plants grown in sand was higher than in plants grown in soil. In sand (conditions of maximum contaminant bioavailability), bioconcentration factors (BCFs) of EE2 and triclosan in roots (based on dry weights) were 1424 and 16,364, respectively, whereas BCFs in leaves were 55 for EE2 and 85 for triclosan. In soil, the BCF of EE2 decreased from 154 in the first week to 32 in the fourth week while it fluctuated in leaves from 18 to 20. The BCF for triclosan in plants grown in soil increased over time to 12 in roots and 8 in leaves. These results indicate that the potential for uptake and accumulation of PPCPs in plants exists. This trophic transfer pathway should be considered when assessing exposure to certain PPCPs, particularly with the use of recycled wastewater for irrigation.

Effects of the antibiotic ciprofloxacin on stream microbial communities and detritivorous macroinvertebrates

Microbial communities play an important role in stream ecosystem processes, such as breakdown of senescent leaf litter, and as a primary nutritional source for detritivorous macroinvertebrates. Antibiotics may affect stream microbial communities and associated ecosystem processes, especially because recent stream and river monitoring programs have indicated the presence of antibiotics downstream of wastewater treatment plants. In the current study, effects of chronic exposure to the fluoroquinolone antibiotic ciprofloxacin (Cipro) were examined on stream microbial community-level physiological profiles and growth indices of detritivorous amphipods (Gammarus spp.) and caddisflies (Lepidostoma liba). Microcosm experiments were conducted using stream sediments and water, senesced leaf material (Acer saccharum), and macroinvertebrates. A shift in function of leaf-associated microbial communities (based on carbon source utilization) was observed for samples exposed to 100 microg/L of Cipro for 12 d compared to control and treatments exposed to 1 and 10 microg/L of Cipro. This was attributable to carbohydrate substrates, which had 2.7- to 3.5-fold lower microbial respiration than the lower concentrations and control (p < 0.001). For detritivores, Gammarus spp. condition index did not differ among control, 0.1, and 1.0 microg/L treatments after 30-d exposures (p > 0.05). Similarly, L. liba growth rate did not vary among control, 10, and 100 microg/L treatments after 45-d exposures (p > 0.05). These results suggest that Cipro may affect leaf-associated microbial communities, but at concentrations four orders of magnitude above those detected in streams. However, effects of the antibiotic on growth and condition of detritivores were not observed. Future work should focus on identifying specific changes in stream microbial communities as a result of Cipro exposure and impacts on other aquatic species.

Bioaccumulation and trophic transfer of polychlorinated biphenyls by aquatic and terrestrial insects to tree swallows (Tachycineta bicolor)

Insectivorous passerines often bioaccumulate polychlorinated biphenyls (PCBs) via trophic transfer processes. Tree swallows (Tachycineta bicolor) frequently are used for estimating PCB bioaccumulation, yet the focus on specific trophic links between contaminated sediment and bird has been limited. Bioaccumulation of PCBs from sediment to tree swallows was examined with focus on trophic pathways by simultaneously examining PCBs in emergent aquatic and terrestrial insects and gut contents of nestlings. Total PCB concentrations increased from sediment (123.65 +/- 15.93 microg/kg) to tree swallow nestlings (2,827.76 +/- 505.67 microg/kg), with emergent aquatic insects, terrestrial insects, and gut content samples having intermediate concentrations. Biota-sediment accumulation factors (BSAFs) varied among congeners for tree swallow nestlings and for male and female Chironomus spp. For nestlings, the highest BSAF was for the mono-ortho-substituted congener 118. Nestling biomagnification values were similar for gut contents and female Chironomus spp., suggesting this diet item may be the main contributor to the overall PCB transfer to nestlings. However, gut content samples were highly variable and, on a PCB congener pattern basis, may have been influenced by other taxa, such as terrestrial insects. Considering dietary plasticity of many insectivorous birds, the present study suggests that a variety of potential food items should be considered when examining PCB accumulation in insectivorous passerines.

Effect of titanium dioxide nanomaterials and ultraviolet light coexposure on African clawed frogs (Xenopus laevis)

Titanium dioxide nanomaterials (nano-TiO(2) ) exhibit stronger photochemical oxidation/reduction capacity compared with their bulk counterparts, but the effectiveness of nano-TiO(2) interaction with ultraviolet (UV) light strongly depends on particle size. In this study, the dependence of nano-TiO(2) toxicity on particle size and interaction with UV light were investigated. Toxicity tests with Xenopus laevis included eight concentrations of nano-TiO(2) in the presence of either white light or UVA (315-400 nm). We quantified viability and growth of Xenopus laevis. Results showed that, regardless of UV light exposure, increasing TiO(2) concentration decreased X. laevis survival (p < 0.05). Coexposure to 5-nm TiO(2) and UVA caused near-significant decreases in X. laevis survival (p = 0.08). Coexposure to 10-nm TiO(2) and UVA significantly decreased X. laevis survival (p = 0.005). However, coexposure to 32-nm TiO(2) and UVA had no statistical effect on X. laevis survival (p = 0.8). For all three particle sizes, whether alone or with UV light, the nano-TiO(2) concentrations significantly affected growth of tadpoles as determined by total body length, snout-vent length, and developmental stage. High-concentration TiO(2) solutions suppressed tadpole body length and delayed developmental stages. Further research to explore reasons for the growth and mortality in tadpoles is still underway in our laboratory. Given the widespread application of nano-TiO(2) , our results may be useful in the management of nano-TiO(2) released from industrial, municipal, and nonpoint sources.

Effects of ZnO nanomaterials on Xenopus laevis growth and development

The objectives of this study were to quantify uptake and developmental effects of zinc oxide nanomaterials (nano-ZnO) on Xenopus laevis throughout the metomormosis process. To accomplish this, X. laevis were exposed to aqueous suspensions of 40-100 nm nano-ZnO beginning in-ovo and proceeding through metamorphosis. Nanomaterials were dispersed via sonication methods into reconstituted moderately hard water test solutions. A flow-through system was utilized to decrease the likelihood of depletion in ZnO concentration. Exposure to 2 mg/L nano-ZnO significantly increased mortality incidence to 40% and negatively affected metamorphosis of X. laevis. Tadpoles exposed to 2 mg/L nano-ZnO developed slower as indicated by tadpoles with an average stage of 56 at the conclusion of the study which was significantly lower than the control tadpole stages. No tadpoles exposed to 2 mg/L of nano-ZnO completed metamorphosis by the conclusion of the study. Tadpoles exposed to 0.125 mg/L nano-ZnO experienced faster development along with larger body measurements indicating that low dose exposure to nano-ZnO can stimulate growth and metamorphosis of X. laevis.

Effects of predator cues on pesticide toxicity: Toward an understanding of the mechanism of the interaction

Pesticide toxicity may be modified by a number of co-occurring environmental and ecological stressors. Coexposure to predator cues has been shown to potentiate and/or synergize toxicity of pesticides. However, the mechanisms behind these interactions are not well understood. Here we examine the effects of fish predator (bluegill, Lepomis macrochirus) cues on toxicity of five different pesticides to the freshwater cladoceran, Ceriodaphnia dubia. The purpose for examining patterns among pesticides was to test the idea that the mechanism of the interaction could be explained by a general stress response; that is, the interaction patterns would be similar regardless of the pesticides mechanism of action [MOA]). Acute 96-h concentration-response experiments were conducted for pesticides with and without fish cues. Predator cues influenced the toxicity of pesticides and the interaction patterns varied among pesticides. Fipronil exhibited a synergistic interaction, while predator cues interacted antagonistically for bifenthrin and thiacloprid. Other compounds previously reported to potentiate toxicity (malathion) were found to act additively. The results demonstrate that factors such as pesticide bioavailability, K(OC) , and exposure concentration may be important for predicting the occurrence of these interactions and that patterns were not consistent among pesticides varying in MOA. Predator stress is an important component for structuring communities and ecosystem processes. Fully understanding how this process may interact with organic contaminants may best be achieved by examination at toxicokinetic and toxicodynamic scales.

Partitioning and matrix-specific toxicity of bifenthrin among sediments and leaf-sourced organic matter†‡

Synthetic pyrethroids readily partition from the aqueous to the solid phase in aquatic systems. Previous work has focused on pyrethroid partitioning to sediment matrices. Within many aquatic systems, however, other carbon-containing materials are present and can be critically important to certain invertebrate species and ecosystem functioning. For example, some invertebrates readily process leaf material, and these processes may represent an additional route of contaminant exposure. To our knowledge, estimates for partitioning of pyrethroids to these nondissolved organic matter matrices and associated toxicity have not been examined. The objectives of the present study were to examine variation in organic carbon (OC)-based partition coefficient (K(OC)) among three size fractions of particulate organic matter from sugar maple (Acer saccharum) leaf litter and sediments for the pyrethroid insecticide bifenthrin and to examine variation in toxicity to Hyalella azteca among bifenthrin-bound organic matter matrices and sediment. Log K(OC) of [(14)C]bifenthrin was greatest within sediment (6.63+/-0.23; mean +/- standard deviation throughout) and lowest in coarse particulate leaf material (4.86+/-0.03). The H. azteca median lethal concentration was 0.07, 0.11, and 0.15 microg/g OC for leaf material, sediment, and a 50% mix of leaf and sediment, respectively. Nonoverlapping 95% confidence intervals occurred between the leaf treatment and the leaf-sediment treatment. This pattern was supported in an additional experiment, and at 0.22 microg/g OC, H. azteca survival was greater in the leaf-sediment mixture than in sediment or in leaf material alone (F=29.5, p<0.0001). In systems that contain sediment and leaf material, both greater partitioning of bifenthrin to the sediment fraction and preferential use of leaf substrates may drive H. azteca survival.

Subchronic and chronic developmental effects of copper oxide (CuO) nanoparticles on Xenopus laevis

Metal oxide nanoparticles, such as copper oxide (CuO), are mass produced for use in a variety of products like coatings and ceramics. Acute exposure to CuO nanoparticles has caused toxicity to many aquatic organisms, yet there is no information on the effect of prolonged CuO nanomaterial exposures. This study examined effects of chronic exposure to CuO nanoparticles on Xenopus laevis growth and development. Experiments included a 14 d subchronic exposure and a 47 d chronic exposure throughout metamorphosis. The subchronic exposure caused mortality in all tested CuO concentrations, and significant growth effects occurred after exposure to 2.5 mg L(-1) CuO. Chronic exposure to 0.3 mg L(-1) CuO elicited significant mortality and affected the rate of metamorphosis. Exposure to lower concentrations of CuO stimulated metamorphosis and growth, indicating that low dose exposure can have hormetic effects.