Photo-induced toxicity of titanium dioxide nanoparticles to Daphnia magna under natural sunlight.

Titanium dioxide nanoparticles (TiO2 NP) are one of the most abundantly utilized nanoparticles in the world. Studies have demonstrated the ability of the anatase crystal of TiO2 NP to produce reactive oxygen species (ROS) in the presence of ultraviolet radiation (UVR), a co-exposure likely to occur in aquatic ecosystems. The goal of this study was to examine the photo-induced toxicity of anatase TiO2 NP under natural sunlight to Daphnia magna. D. magna were exposed to a range of UVR intensities and anatase TiO2 concentrations in an outdoor exposure system using the sun as the source of UVR. Different UVR intensities were achieved using UVR opaque and transparent plastics. AnataseTiO2-NP demonstrated the reciprocal relationship seen in other phototoxic compounds such as polycyclic aromatic hydrocarbons (PAHs) at higher UVR treatments. The calculated 8h LC50 of anatase TiO2 NP was 139 ppb under full intensity ambient natural sunlight, 778 ppb under 50% natural sunlight, and >500 ppm under 10% natural sunlight. Mortality was also compared between animals allowed to accumulate a body burden of anatase TiO2 for 1h and organisms whose first exposure to anatase TiO2 aqueous suspensions occurred under UVR. A significantly greater toxic effect was observed in aqueous, low body burden suspensions than that of TiO2 1h body burdens, which is dissimilar from the model presented in PAHs. Anatase TiO2 presents a unique photo-induced toxic model that is different than that of established phototoxic compounds.

Physiological responses of hybrid striped bass to aqueous copper in freshwater and saltwater.

Copper (Cu) is an abundant trace metal, and although essential at low levels, it is also potentially toxic to aquatic organisms. Mechanisms of toxicity and consequences of exposure vary depending on ionoregulatory status (acclimated to freshwater or salt water). The goal of this research was to examine the responses of hybrid striped bass (Morone chrysops x Morone saxatilis) exposed to Cu in freshwater and 15 g/L salt water. In freshwater, a general dose- and time-dependent pattern of increasing Cu accumulation in gill tissue was evident in fish exposed to aqueous Cu (220 and 447 mg/L) for up to 96 hours. The 96-hour acute median lethal concentration for freshwater-acclimated hybrid striped bass exposed to Cu was 94 mg/L (confidence interval = 62 to 144 mg/L). Plasma osmolality and Na(+) concentrations decreased in Cu-exposed fish. Freshwater-acclimated hybrid striped bass exposed to aqueous Cu (60 mg/L) for 3 weeks decreased in mass and accumulated Cu in gill, intestine, and liver. In salt water, no mortality occurred, and there were no statistical differences in growth, tissue Cu, or plasma ion concentrations in hybrid striped bass exposed to Cu compared with control fish. Freshwater-acclimated hybrid striped bass were very sensitive to Cu exposure and exhibited responses typical of commonly tested teleost fishes; however, the same sensitivity was not observed in salt water-acclimated fish.

Influence of plant age and size on simazine toxicity and uptake.

Improper pesticide management can lead to environmental problems such as water quality degradation and ecological stress. Recent research in our laboratory has focused on development of constructed wetlands to assimilate pesticide-contaminated water. For improved aesthetics, these wetlands have been established with ornamental plant species. The effectiveness of a plant species for phytoremediation depends in part on its tolerance for the contaminant. Plant tolerance for pesticides may vary depending on plant age and size. This study examined the influence of plant age and size on the uptake, distribution, and toxicity of the herbicide simazine [2-chloro-4,6-bis(ethylamino)-1,3,5-triazine] in two ornamental wetland plants: parrot feather [Myriophyllum aquaticum (Vell.) Verdc.] and canna (Canna x hybrida L. 'Yellow King Humbert'). Plants of different ages and sizes were exposed to simazine in 10% Hoagland's nutrient solution. Toxicity was characterized using plant growth, water uptake, and photosynthetic yield during exposure and postexposure periods. In addition, other plants were exposed to [14C] simazine in nutrient medium to characterize pesticide uptake and translocation. Four-week-old parrot feather and canna were more tolerant of simazine than two-week-old plants. The two-week-old plant tissues of both species had higher tissue burdens of simazine than four-week-old plants. Simazine was primarily accumulated in the leaves of both parrot feather and canna. These results suggest that plants in a constructed wetland designed for simazine assimilation would be more vulnerable to simazine toxicity shortly after emergence.

Nutrient attenuation by a riparian wetland during natural and artificial runoff events.

Due to chronic nutrient enrichment of surface water, wetlands adjacent to land managed with fertilizer have been studied to determine their role in nutrient dynamics. We sampled golf course runoff and determined the loads of NO3- and PO4(-3) transported during storms and the attenuation of those loads when runoff passed through a riparian wetland. All sampled storm events contained NO3- (2 to 1470 g NO3-N per event) and PO4(-3) (1 to 4156 g PO4-P per event). Extensive nutrient attenuation occurred when water passed through the riparian wetland. In 11 events, NO3- and PO4(-3) attenuation averaged 80 and 74%, respectively. In subsequent experiments, we created a stream of water flowing into the wetland and amended it with NO3-, PO4(-3) and Br-, creating an artificial runoff event. The experiments were conducted using conditions similar to those of natural runoff events. We observed rapid and complete attenuation of PO4(-3) immediately after runoff water infiltrated into the wetland subsurface. No PO4(-3) was observed in discharge from the wetland. Nitrate attenuation occurred following a lag phase of several hours that was probably due to reactivation of denitrifying enzymes. Nitrate attenuation was initially less than 60% but increased to 100% in all experiments. We observed extensive dilution of runoff water in the wetland subsurface indicating mixing with pre-event ground water in the wetland. The results indicated that intermittent inputs of NO3- and PO4(-3) could be successfully attenuated in the wetland on the time scale of natural storm events.

Mechanisms of nutrient attenuation in a subsurface flow riparian wetland.

Riparian wetlands are transition zones between terrestrial and aquatic environments that have the potential to serve as nutrient filters for surface and ground water due to their topographic location. We investigated a riparian wetland that had been receiving intermittent inputs of NO3- and PO4(3-) during storm runoff events to determine the mechanisms of nutrient attenuation in the wetland soils. Few studies have shown whether infrequent pulses of NO3- are sufficient to maintain substantial denitrifying communities. Denitrification rates were highest at the upstream side of the wetland where nutrient-rich runoff first enters the wetland (17-58 microg N2O-N kg soil(-1) h(-1)) and decreased further into the wetland. Carbon limitation for denitrification was minor in the wetland soils. Samples not amended with dextrose had 75% of the denitrification rate of samples with excess dextrose C. Phosphate sorption isotherms suggested that the wetland soils had a high capacity for P retention. The calculated soil PO4(3-) concentration that would yield an equilibrium aqueous P04(3-) concentration of 0.05 mg P L(-1) was found to be 100 times greater than the soil PO4(3-) concentration at the time of sampling. This indicated that the wetland could retain a large additional mass of PO4(3-) without increasing the dissolved P04(3-) concentrations above USEPA recommended levels for lentic waters. These results demonstrated that denitrification can be substantial in systems receiving pulsed NO3- inputs and that sorption could account for extensive PO4(3-) attenuation observed at this site.

Effect of pulse frequency and interval on the toxicity of chlorpyrifos to Daphnia magna.

Due to the episodic nature in which organisms are exposed to non-point source pollutants, it is necessary to understand how they are affected by pulsed concentrations of contaminants. This is essential, as standard toxicity tests may not adequately simulate exposure scenarios for short-lived hydrophobic compounds, such as chlorpyrifos (CPF), a broad-spectrum organophosphate insecticide. Studies were conducted with 7-day old Daphnia magna for 7 days to evaluate the effect of pulse frequency and interval among multiple CPF exposures. Daphnids were exposed to a total exposure of either 12 h at 0.5 microg/l or 6 h at 1.0 microg/l nominal CPF, respectively, in all studies. For interval studies, D. magna were exposed to two pulses of CPF at each concentration, with 0-96-h intervals between pulses. For frequency studies, D. magna were exposed to each CPF concentration altering the pulse scheme by decreasing the exposure duration but increasing the number of pulses, keeping the total exposure time the same. The pulse interval between multiple pulses in these experiments was 24 h. Our results suggest that D. magna can withstand an acutely lethal CPF exposure provided that there is adequate time for recovery between exposures.

Metalaxyl toxicity, uptake, and distribution in several ornamental plant species.

Phytoremediation depends on the ability of plants to tolerate and assimilate contaminants. This research characterized the interaction between several ornamental plant species and the fungicidal active ingredient, metalaxyl [N-(2,6-dimethylphenyl)-N-(methoxyacetyl)alanine methyl ester]. Species evaluated included sweetflag (Acorus gramineus Sol. ex Aiton), canna (Canna hybrida L. 'Yellow King Humbert'), parrotfeather [Myriophyllum aquaticum (Vell.) Verdc.], and pickerelweed (Pontederia cordata L.). Metalaxyl tolerance levels for each species were determined by exposing plants for 7 d to solutions containing 0, 5, 10, 25, 50, 75, or 100 mg metalaxyl L-1 aqueous nutrient media. Response endpoints included fresh mass production after 7 d exposure and 7 d post-exposure and quantum efficiency using dark-adapted (Fv/Fm) and light-adapted (fluorescence yields) plants. Metalaxyl uptake and distribution within the plant was determined by growing plants in aqueous nutrient media containing 1.18 x 10(6) Bq L-1 [14C]metalaxyl (0.909 mg L-1) for 1, 3, 5, or 7 d. Plant tissues were combusted and analyzed by liquid scintillation counting. Metalaxyl had no effects on the endpoints measured, except for fresh mass production of sweetflag at the 75 and 100 mg L-1 treatment levels. However, leaf necrosis was apparent in most species after 5 d exposure to concentrations greater than 25 mg L-1. Metalaxyl removal from the spiked nutrient media ranged from 15 to 60% during the 7-d exposure period. The majority of metalaxyl removed from the solution was detected within individual plants. In nearly all cases, activity from the radiolabeled pesticide accumulated in the leaves. Uptake of metalaxyl was correlated with water uptake throughout the 7 d. These results suggest that all species examined may be good candidates for incorporation into a phytoremediation scheme for metalaxyl.

Further considerations of the skeletal system as a biomarker of episodic chlorpyrifos exposure.

The mummichog, Fundulus heteroclitus, is a common inhabitant of eastern seaboard estuaries. As such, it can be affected by coastal agricultural and other nonpoint source runoff. We examined the effects of short-term episodic exposures to an agricultural pesticide, chlorpyrifos, on brain acetylcholinesterase (AChE) activity and vertebral yield strength in lab-reared and wild-caught fish. Brain AChE activity was chosen as an indicator because it is the target system for organophosphate action. Vertebral yield strength was chosen as an indicator because previous research warranted further investigation (Karen et al., 1998). Four daily or weekly 6 h exposures (2.5, 5.0, and 10.0 microg/l chlorpyrifos) in decreased salinity seawater (5 g/kg) significantly reduced brain AChE activity. The lowest concentration was within the range of reported environmental chlorpyrifos concentrations; thus inhibition of brain AChE from environmental chlorpyrifos exposures may pose a hazard to estuarine organisms. Yield strength measured in lab-reared fish appeared to be more sensitive to episodic chlorpyrifos exposures, because chlorpyrifos was a significant factor in 75% (3 out of 4) of tests performed with lab-reared fish. Chlorpyrifos exposure was a significant factor in only 25% (1 out of 4) tests performed with wild fish. These results suggested that changes in the responses of bone to load testing, following several short exposures to an organophosphate, could be sensitive indicators in lab-reared organisms.

Metalaxyl and simazine toxicity to and uptake by Typha latifolia.

This research focused on the potential use of common cattails (Typha latifolia) for removing metalaxyl and simazine residues from contaminated water. Specifically, it established toxicity thresholds to the herbicide simazine and characterized the uptake and distribution of simazine and metalaxyl by the plants. Simazine tolerance levels were determined by exposing plants to a series of six concentrations (0-3.0 mg L(-1)) in aqueous nutrient media for 7 days. Metalaxyl toxicity was not evaluated because other studies indicated it was relatively nontoxic to plants. Toxicity endpoints measured included fresh mass production after 7 days of exposure and 7 days postexposure. Pesticide uptake and distribution were determined by growing plants in nutrient media amended with (14)C-ring-labeled metalaxyl (0.909 mg L(-1)) or simazine (0.242 mg L(-1)) for 1, 3, 5, or 7 days. Plants were dissected, and tissues were combusted and analyzed by liquid scintillation spectroscopy. Cattail fresh mass production was reduced 84 and 117% at 1.0 and 3.0 mg L(-1) simazine, respectively, after 7 days of exposure. Metalaxyl and simazine activity in solution was reduced 34 and 65%, respectively, after 7 days. By day 7, activity from both pesticides was detected predominantly in the leaves. Uptake of each pesticide was correlated with water uptake throughout the 7 days. These results suggest that the common cattail may be a good candidate for incorporation into a phytoremediation scheme for metalaxyl and simazine.