Paul L. Pennington

Transfer of gold nanoparticles from the water column to the estuarine food web.

Within the next five years the manufacture of large quantities of nanomaterials may lead to unintended contamination of terrestrial and aquatic ecosystems. The unique physical, chemical and electronic properties of nanomaterials allow new modes of interaction with environmental systems that can have unexpected impacts. Here, we show that gold nanorods can readily pass from the water column to the marine food web in three laboratory-constructed estuarine mesocosms containing sea water, sediment, sea grass, microbes, biofilms, snails, clams, shrimp and fish. A single dose of gold nanorods (65 nm length x 15 nm diameter) was added to each mesocosm and their distribution in the aqueous and sediment phases monitored over 12 days. Nanorods partitioned between biofilms, sediments, plants, animals and sea water with a recovery of 84.4%. Clams and biofilms accumulated the most nanoparticles on a per mass basis, suggesting that gold nanorods can readily pass from the water column to the marine food web.

Pilot estuarine mesocosm study on the environmental fate of Silver nanomaterials leached from consumer products.

Although nanosilver consumer products (CPs) enjoy widespread availability, the environmental fate, leaching, and bioaccumulation behaviors of silver nanoparticles (AgNPs) from these products are not well understood. In this work, three nanosilver CPs, two AgNP standards, and an ionic silver (Ag(+)) standard were studied in estuarine mesocosms. The CPs exhibited long-term release of significant amounts of silver over a 60d residence time in the mesocosms, and ultimately released 82 - 99% of their total silver loads. Measurements of total silver as a function of time, by inductively coupled plasma mass spectrometry (ICP-MS), indicated that the silver was transferred from the water column and accumulated in the estuarine biota, including hard clams, grass shrimp, mud snails, cordgrass stalks and leaves, biofilms, intertidal sediment, and sand. The ICP-MS results and calculations of bioconcentration and trophic transfer factors indicated that significant amounts of silver were taken up by the organisms through trophic transfer. Silver was also adsorbed from the seawater into the biofilms, sediment, and sand, and from the sand into the clams.

Analysis of pesticide runoff from mid-Texas estuaries and risk assessment implications for marine phytoplankton

During 1993, estuarine surface water samples were collected from the mid-Texas coast (Corpus Christi to Port Lavaca, TX). Agricultural watershed areas as well as tidal creeks immediately downstream were chosen as sampling sites along with adjoining bay sampling stations. Collections were made throughout the growing season (February to October 1993) before and after periods of significant (>1.25 cm) rainfall. All samples were initially screened for the presence of pesticides using enzyme-linked immunosorbent assay (ELISA) test kits (EnviroGard™) for triazine herbicides and carbamate insecticides. All samples were extracted and then analyzed using gas chromatography (GC) for quantification of atrazine. Only samples testing positive for carbamate insecticides via ELISA were further extracted for GC analysis to quantify aldicarb and carbofuran. Additionally, laboratory toxicity tests using phytoplankton were examined from published, peer-reviewed literature and compared with the atrazine field levels found in Texas. Results of ELISA screening indicated the presence of triazine herbicides in nearly all samples (>93%). GC analysis further confirmed the presence of atrazine concentrations ranging from <0.01–62.5 μg/L. Screening tests also found detectable levels of carbamate insecticides (aldicarb and carbofuran) that were also confirmed and quantified by GC. Comparison of measured concentrations of atrazine compared with published toxicity tests results indicated that there was a potential environmental risk for marine/estuarine phytoplankton in surface waters of Texas estuaries, particularly when the chronic nature of atrazine exposure is considered.

Fluoxetine effects on sheepshead minnow (Cyprinodon variegatus) locomotor activity

Fluoxetine (FLX), a selective serotonin reuptake inhibitor, is among the top 100 drugs prescribed annually in the United States and the United Kingdom and is one of many pharmaceutical products that have been detected in global surface waters. Our study used sublethal concentrations to assess the impact of FLX exposure on sheepshead minnow (Cyprinodon variegatus) locomotor behavior. Exposures lasted for 56 hours, and fish were recorded for locomotor behavior assessment at six timepoints between 1–56 h post-dose. Behavior was recorded to quantify locomotor activity using line crossing counts. Animals treated with 300 μg L−1 FLX exhibited reduced locomotor activity at 1, 25, 32, 49 and 56 h post-dose. An EC25 value of 2 μg L−1 (lower and upper 95 % confidence limits at 1.3, 43 μg L−1, respectively) was determined for locomotor activity at 32 h of exposure. Changes in locomotor activity due to FLX exposure may have implications for the ecological response of populations to other natural and anthropogenic stressors.

Lethal and sublethal effects of simvastatin, irgarol, and PBDE-47 on the estuarine fish, Fundulus heteroclitus

This study investigated the effects of simvastatin, a lipid-regulating drug; irgarol, an antifouling biocide; and PBDE-47, a brominated flame retardant, on the estuarine fish, Fundulus heteroclitus. Sublethal effects (changes in glutathione (GSH), lipid peroxidation (LPx), acetylcholinesterase (AChE), and cholesterol (CHL) levels) and lethal effects (survival) were determined after individual exposure to the three compounds. There were no significant differences in GSH or CHL levels in fish exposed to any of the test compounds. LPx levels significantly decreased with increasing irgarol concentrations. AChE levels were significantly lower in fish exposed to simvastatin at the 1.25 mg/L concentration and significantly higher at the PBDE-47 concentration of 0.0125 mg/L. The LC50 values were 2.68, 3.22, and > 0.1 mg/L for simvastatin, irgarol and PBDE-47, respectively.

Surface Charge Controls the Fate of Au Nanorods in Saline Estuaries

This work reports the distribution of negatively charged, gold core nanoparticles in a model marine estuary as a function of time. A single dose of purified polystyrene sulfonate (PSS)-coated gold nanorods was added to a series of three replicate estuarine mesocosms to emulate an abrupt nanoparticle release event to a tidal creek of a Spartina -dominated estuary. The mesocosms contained several phases that were monitored: seawater, natural sediments, mature cordgrass, juvenile northern quahog clam, mud snails, and grass shrimp. Aqueous nanorod concentrations rose rapidly upon initial dosing and then fell to stable levels over the course of approximately 50 h, after which they remained stable for the remainder of the experiment (41 days total). The concentration of nanorods rose in all other phases during the initial phase of the experiment; however, some organisms demonstrated depuration over extended periods of time (100+ h) before removal from the dosed tanks. Clams and biofilm samples were also removed from the contaminated tanks post-exposure to monitor their depuration in pristine seawater. The highest net uptake of gold (mass normalized) occurred in the biofilm phase during the first 24 h, after which it was stable (to the 95% level of confidence) throughout the remainder of the exposure experiment. The results are compared against a previous study of positively charged nanoparticles of the same size to parameterize the role of surface charge in determining nanoparticle fate in complex aquatic environments.

Fate and transport of Irgarol 1051 in a modular estuarine mesocosm

Fate and transport of Irgarol 1051 were assessed using a modular estuarine mesocosm containing natural seawater, saltmarsh sediments, marsh grass, shrimp, clams, snails, and naturally derived planktonic and benthic microorganisms. The mesocosms were enclosed in a greenhouse under near ambient conditions, and included a saltwater sump and a simulated tidal flux. The exposure was comprised of four replicate treatments of 0, 100, 1,000 and 10,000 ng/L Irgarol. Solid-phase extraction (SPE) was used to extract Irgarol and its major metabolite M1 (aka GS26575) from water samples. Sediment samples were extracted using Accelerated Solvent Extraction (ASE) with 100% dichloromethane. Irgarol and M1 were separated and quantified utilizing Liquid Chromatography Tandem Mass Spectrometry (LC-MS-MS) with ElectroSpray Ionization in Multiple Reaction Monitoring mode. Aqueous concentrations of Irgarol declined rapidly (average 93% loss) over the course of the 35 day experiment while Irgarol was accumulated in the sediments (average mass balance of 75 +/- 5%). Loss of aqueous Irgarol occurred in two distinct phases, a relatively rapid phase up to 96 hours post-dose, and a slower phase following 96 hours. The rate constants of the initial rapid degradation phase (k(1)) for treatments 100 and 1,000 ng/L Irgarol were 2-3 times higher than the rate constants of the subsequent slow degradation phase (k(2)) for these treatments. The average half-life of Irgarol in water was 7 +/- 3 days. The aqueous concentration of Irgarols metabolite, M1 increased over the course of the experiment. By 35 days post-dose, M1 concentrations in water averaged about 3% of the parent compound. M1 also accumulated in mesocosm sediments (average 16.7 +/- 2.5% of total Irgarol dose). Mass balance calculations showed that by 35 days, Irgarol and M1 amounts in mesocosm water and sediments were close to 100% of the initial Irgarol dose. Average partition coefficient normalized for organic carbon (log K(oc)) calculated for Irgarol was 3.2 +/- 0.1 for 35 days post-dose. Accumulation of Irgarol and M1 in mesocosm sediments may warrant further study to assess toxicity for benthic communities.

Toxicity of synthetic pyrethroid insecticides to the grass shrimp, Palaemonetes pugio, parasitized with the bopyrid isopod, Probopyrus pandalicola

The grass shrimp, Palaemonetes pugio, plays a large role in the marine ecosystem, serving as a vital link in the food web between many other species. Marine parasites such as the bopyrid isopod, Probopyrus pandalicola, reduce shrimp growth and reproductive output and may also cause P. pugio to be more vulnerable to the lethal effects of contaminants. The purpose of this study was to determine the toxicity of resmethrin and bifenthrin on the grass shrimp, P. pugio, infected with the bopyrid isopod, Probopyrus pandalicola. A 96-h static renewal test was conducted to determine the toxicity of the pyrethroid insecticides resmethrin and bifenthrin to grass shrimp, Palaemonetes pugio, parasitized with the bopyrid isopod, Probopyrus pandalicola. The results were then compared to similar tests utilizing unparasitized P. pugio. Parasitized P. pugio had lower 24-h LC50 (1.08 μg/L) and 96-h LC50 (0.43 μg/L) values for resmethrin than unparasitized P. pugio. However, LC50 ratio tests found that there was no significant difference between parasitized and unparasitized shrimp when affected by resmethrin (p = 0.1751 and 0.1108, respectively). In contrast, an LC10 ratio test indicated that there was a significant difference between parasitized and unparasitized P. pugio after 96 h (p < 0.0001). When subjected to bifenthrin, parasitized P. pugio had a higher 24-h LC50 (0.049 μg/L6) than unparasitized P. pugio. The LC50 ratio test established that the effects of bifenthrin on parasitized P. pugio when compared to unparasitized P. pugio were significantly different at 24 h (p = 0.0065). However, there were no significant differences between parasitized and unparasitized after 96 h (p = 0.4229). In conclusion, both resmethrin and bifenthrin are toxic to the grass shrimp, P. pugio, regardless of parasite presence, and parasitized shrimp may be more susceptible to lower doses of resmethrin (when exposed in the field).

Baseline monitoring of organic sunscreen compounds along South Carolina's coastal marine environment

Organic ultraviolet filters (UV-F) are increasingly being used in personal care products to protect skin and other products from the damaging effects of UV radiation. In this study, marine water was collected monthly for approximately one year from six coastal South Carolina, USA sites and analyzed for the occurrence of seven organic chemicals used as UV filters (avobenzone, dioxybenzone, octocrylene, octinoxate, oxybenzone, padimate-o and sulisobenzone). The results were used to examine the relationship between beach use and the distribution of UV-F compounds along coastal South Carolina, USA. Five of the seven target analytes were detected in seawater along coastal South Carolina during this study. Dioxybenzone and sulisobenzone were not detected. The highest concentrations measured were >3700 ng octocrylene/L and ~2200 ng oxybenzone/L and beach use was greatest at this site; a local beach front park. Patterns in concentrations were assessed based on season and a measure of beach use.

Environmental effects and fate of the insecticide bifenthrin in a salt-marsh mesocosm.

Bifenthrin is a widely used synthetic pyrethroid insecticide that is often applied to crops, turf, and residential structures for the control of insects. Like other insecticides, bifenthrin has the potential to contaminate bodies of water that are adjacent to the application site via spray drift and runoff during storm events. The objective of this study was to examine the lethal and sublethal effects of bifenthrin on grass shrimp, Palaemonetes pugio, and sheepshead minnow, Cyprinodon variegatus in a 28 d mesocosm experiment under estuarine conditions. Endpoints included mortality and growth and the oxidative stress biomarkers of lipid peroxidation, glutathione, and catalase. In the mesocosm experiment, 24 h and 96 h caged shrimp LC50s were 0.061 and 0.051 μg L(-1), respectively. The uncaged grass shrimp 28 d LC50 was 0.062 μg L(-1). Fifty percent mortality was not reached in the uncaged sheepshead minnow. Bifenthrin did not have a significant effect on the growth of the shrimp, but there was an increasing impact on fish growth. However, it is uncertain as to whether this pattern is a direct effect of the chemical or if it is due to increased food availability resulting from mortality in prey species. The oxidative stress assays were largely inconclusive. Bifenthrin was eliminated rapidly from the water column and readily partitioned to sediments. The LC50s for adult and larval P. pugio were below published Estimated Environmental Concentration (EEC) values and were within the range of bifenthrin concentrations that have been measured in rivers, channels, and creeks.