Mercury and Selenium Accumulation in the Tissues of Stranded Bottlenose Dolphins (Tursiops truncatus) in Northeast Florida, 2013-2021.

Bottlenose dolphins (Tursiops truncatus) are long-lived marine mammals, upper-level predators, and they inhabit near-shore environments, which increases their exposure to pollution. Mercury is a ubiquitous and persistent metal pollutant that can bioaccumulate and biomagnify up the food chain. Dolphins are known to accumulate mercury, and limited research has shown that mercury exposure can weaken the immune system of dolphins. The objectives of this study were to assess the mercury concentrations in the tissues (muscle, small intestine, liver) of stranded bottlenose dolphins and to compare the tissue mercury levels in dolphins that were stranded during the 2013-2015 morbillivirus Unusual Mortality Event (UME; immunosuppressed individuals) with the levels of those that were stranded at a normal rate (2016-2021). Selenium has been shown to reduce mercury toxicity in many animals; therefore, tissue selenium concentration and the molar ratio of selenium to mercury were also assessed. The tissue mercury (muscle, liver) and selenium (liver) concentrations increased with the age of the dolphins, with the liver accumulating the highest concentrations. No sex differences were observed in the mercury and selenium concentrations. While differences in tissue mercury concentrations were not observed due to the UME, the selenium accumulation profiles were significantly different between the two time periods. These results suggest that selenium may not have been as protective against mercury toxicity in the bottlenose dolphins that were stranded during the UME, possibly due to infection with morbillivirus.

A Quantitative Analysis of Microplastics in the Gastrointestinal Tracts of Odontocetes in the Southeast Region of the United States.

Microplastics (<5 mm in diameter) are ubiquitous in the oceanic environment, yet microplastic accumulation in marine mammals is vastly understudied. In recent years, efforts have been made to document microplastic profiles in odontocetes. The objective of the present study was to describe and quantify microplastics in the gastrointestinal (GI) tracts of deceased odontocetes that stranded in the southeastern United States. Our study included 24 bottlenose dolphins (Tursiops truncatus), two pygmy sperm whales (Kogia breviceps), one pantropical spotted dolphin (Stenella attenuata), one short-snouted spinner dolphin (Stenella clymene), one Risso's dolphin (Grampus griseus), and one dwarf sperm whale (Kogia sima) obtained from stranding networks in Texas, Alabama, Florida, and Puerto Rico. Contents found in the GI tracts, namely, the stomach and portions of the intestinal tract, were subjected to a laboratory procedure to isolate microplastics. The physical characteristics of microparticles were analyzed with a stereomicroscope, and microplastics were classified by polymer type via Fourier-transform infrared spectroscopy. There was an average of 47.6 ± 41.4 microparticles, ranging from 1 to 193 items per stomach. More specifically, there was an average of 5.6 ± 4.7 microplastics per stomach. The predominant morphologies, colors, and polymer types were fibers, white-colored items, and polyester, respectively. This research contributes to the current knowledge of microplastic exposure in top marine mammal predators and sets the stage for further exploration into the associated risks of microplastics in odontocetes within the United States and worldwide. Environ Toxicol Chem 2024;43:1260-1273. © 2024 SETAC.

Tissue metal concentrations and antioxidant enzyme activity in western north Atlantic white sharks (Carcharodon carcharias).

Anthropogenic practices have increased metal contamination in marine ecosystems. Most sharks have long lifespans, occupy an important ecological position at the top of marine food webs, and can accumulate metals. However, reference levels of metal contaminants in the tissues of sharks, particularly, apex predators such as the white shark (Carcharodon carcharias), are lacking. In this study, concentrations of copper (Cu), cadmium (Cd), nickel (Ni), lead (Pb), silver (Ag), and zinc (Zn) were measured in the muscle tissue of white (n = 42) and tiger (Galeocerdo cuvier; n = 3) sharks. Metal exposure in various species, including sharks, has been correlated with increased oxidative stress. Therefore, the main objectives of this study were to assess metal accumulation and antioxidant enzyme activity (superoxide dismutase (SOD), catalase (CAT), and glutathione peroxidase (GPx)) in the muscle tissue of the population of white sharks and tiger sharks inhabiting the Western North Atlantic. The measured parameters were qualitatively compared between species. The small sample size of tiger sharks (collected from only one site) limited statistical analyses, therefore, white sharks were the primary focus of this study. Differences in tissue metal (Cu, Cd, Ni, and Zn) concentrations and antioxidant enzyme activities were detected based on collection site, with significant positive correlations between Cd and enzymes, SOD and CAT, and Zn and enzymes, SOD and GPx in C. carcharias. Differences in Ni concentration were detected based on sex, with females having higher Ni levels. Additionally, plasma osmolality was not correlated with tissue metal concentrations; however, osmolality decreased with increasing length in C. carcharias. This study is the first to report baseline levels of Cu, Zn, Cd, Ni, Ag, and Pb in muscle of North Atlantic white sharks and provides new insights into oxidative stress responses of these sensitive species to metal contaminants.

Comparative metal analysis in a species assemblage of mammals from the Southeastern United States.

Metal pollution commonly occurs in many terrestrial environments and may pose a threat for the animals inhabiting such areas. Here, we present concentrations of six metals (cadmium [Cd], copper [Cu], nickel [Ni], lead [Pb], selenium [Se], and zinc [Zn]) in the liver tissues of seven species of mammals obtained from a study that examined the impact of mesopredator removal on northern bobwhite (Colinus virginianus) populations. A total of 1326 samples were collected from 2003 to 2006 at four sites in southwest Georgia and north Florida from nine-banded armadillos (Dasypus novemcinctus), bobcats (Lynx rufus), feral cats (Felis catus), coyotes (Canis latrans), grey foxes (Urocyon cinereoargenteus), opossums (Didelphis virginiana), and raccoons (Procyon lotor). Data from armadillos, bobcats, opossums, and raccoons were published previously to examine age, sex, spatial (between sites), and temporal (between years) variation. In this paper, we present similar comparisons for the remaining three species as well as comparisons of metal concentrations among all seven species. Concentrations of Cu and Pb exhibited strong negative relationships with body weight in coyotes, while Ni was positively correlated with weight in feral cats. Concentrations of these metals, as well as the other two tested (Cd and Zn), were not significantly correlated with one another in any of the three species. The only sex difference in liver metal concentrations was observed in female feral cats, which had higher levels of Pb than did males. Coyotes exhibited significant differences in Cu concentrations between sites and between years (2005 versus 2006). We also found significant differences between sites in Pb concentrations for both feral cats and grey foxes. There were significant differences in metal concentrations among all seven species for all metals except Cd. With the exception of Cd and Se (tested only in bobcats and opossums), a three-way ANOVA with species, year, and site as the three factors revealed significant differences among species for every metal but only a single main effect of year for Cu, and no main effects of site. In sum, our results provide an extensive survey of metal concentrations in a diverse assemblage of mammals and suggest that metal accumulation may be heavily influenced by species identity, which in turn may reflect ecological lifestyle.

The influence of salinity and water chemistry on acute toxicity of cadmium to two euryhaline fish species.

The euryhaline killifishes, Fundulus heteroclitus and Kryptolebias marmoratus inhabit estuaries that rapidly change salinity. Although cadmium (Cd) toxicity has been well characterized in fish inhabiting freshwaters, fewer studies have examined the toxic effects of Cd in estuarine and saltwater environments. Additionally, current environmental regulations do not account for organism physiology in different salinity waters even though metal sensitivity is likely to change in these environments. In this study, we investigated effects of changing salinity on acute Cd toxicity to larval (7-9 d old) F. heteroclitus and K. marmoratus. Median 96-h lethal concentrations (LC50) for Cd were calculated for both fish species at six different salinities. As salinity increased, metal toxicity decreased in both fish species up to 18 ppt salinity; and F. heteroclitus were more sensitive than K. marmoratus at salinities above 12 ppt. To determine which components of saltwater were protective against Cd toxicity, we investigated the influence of CaSO4 (100 and 200 mg/L), CaCl2 (200 mg/L), and MgSO4 (300 mg/L) on Cd toxicity to K. marmoratus. The results demonstrated that both competition with calcium and complexation with chloride reduced the toxic effects of Cd to K. marmoratus. These findings could be used to improve marine/estuarine biotic ligand models for the determination of site-specific water quality criteria for Cd.

Physiological responses of corals to ocean acidification and copper exposure.

Acidification and land-based sources of pollution have been linked to widespread declines of coral cover in coastal reef ecosystems. In this study, two coral species, Acropora cervicornis and Pocillopora damicornis were exposed to increased copper at two CO2 levels for 96 h. Copper accumulation and anti-oxidant enzyme activities were measured. Copper accumulation only increased in A. cervicornis zooxanthellae and corresponded with photosynthetic toxicity. Enzyme activities in both coral species were affected; however, A. cervicornis was more sensitive than P. damicornis, and zooxanthellae were more affected than animal fractions of holobionts. Generally, activities of all anti-oxidant enzymes increased, with copper exposure in corals; whereas, activities of glutathione reductase and to some degree glutathione peroxidase were observed due to increasing CO2 exposure alone. Exposure to copper in combination with higher CO2 resulted in a synergistic response in some cases. These results provide insight into mechanisms of copper and CO2 impacts in corals.

The Alapahoochee watershed microgeographic structure and its potential influence on metal concentrations and genetic structure in the Florida cottonmouth, Agkistrodon piscivorus conanti, within the watershed.

This study examines the microgeographic structure of the Alapahoochee watershed, part of the Suwannee River basin, south-central GA, USA, and relates it to variations in liver metal concentrations and genetic structure of the Florida cottonmouth, Agkistrodon piscivorus conanti. One objective was to determine if liver metal concentrations in A. piscivorus differ between Grand Bay and Mud creeks, which form the watershed's upper portion. Grand Bay Creek is relatively pristine, whereas Mud Creek is polluted with various metals. Genetic analyses were used to assess possible migration patterns between the creeks indicating whether the basin possesses a single population or two populations. Collections occurred in 2008 and 2009. Specimens were captured, euthanized, or collected as road kills, and liver metal concentrations were analyzed and DNA extracted. No differences in metal concentrations were detected between the creeks, except for nickel in females. Metal concentrations in A. piscivorus were not significantly different between males and females nor show a relationship to body size. Genetic analyses were limited to three primer sets, which amplified informative loci. Locus, CH4B, was highly divergent between the putative populations and particularly informative. Genetic structure indicates potential population isolation within the two creeks. Results suggest that two distinct A. piscivorus populations were present and those populations did not differ in their liver metal concentrations (exception being nickel), despite the differences in environmental metal concentrations in the areas. These findings provide new insight into metal accumulation and detoxification in these animals.

Photosynthetic efficiency predicts toxic effects of metal nanomaterials in phytoplankton.

High Throughput Screening (HTS) using in vitro assessments at the subcellular level has great promise for screening new chemicals and emerging contaminants to identify high-risk candidates, but their linkage to ecological impacts has seldom been evaluated. We tested whether a battery of subcellular HTS tests could be used to accurately predict population-level effects of engineered metal nanoparticles (ENPs) on marine phytoplankton, important primary producers that support oceanic food webs. To overcome well-known difficulties of estimating ecologically meaningful toxicity parameters, we used novel Dynamic Energy Budget and Toxicodynamic (DEBtox) modeling techniques to evaluate impacts of ENPs on population growth rates. Our results show that population growth was negatively impacted by all four ENPs tested, but the HTS tests assessing many cell/physiological functions lacked predictive power at the population level. However, declining photosynthetic efficiency, a traditional physiological endpoint for photoautotrophs, was a good predictor of population level effects in phytoplankton. DEBtox techniques provided robust estimates of EC10 for population growth rates in exponentially growing batch cultures of phytoplankton, and should be widely useful for ecotoxicological testing. Adoption of HTS approaches for ecotoxicological assessment should carefully evaluate the predictive power of specific assays to minimize the risk that effects at higher levels of biological organization may go undetected.

Assessment of metal contamination in the biota of four rivers experiencing varying degrees of human impact.

Urbanization, agriculture, and other land transformations can affect water quality, decrease species biodiversity, and increase metal and nutrient concentrations in aquatic systems. Metal pollution, in particular, is a reported consequence of elevated anthropogenic inputs, especially from urbanized areas. The objectives of this study were to quantify metal (Cu, Al, Cd, Ni, and Pb) concentrations in the waters and biota of four streams in South Georgia, USA, and relate metal concentrations to land use and abiotic and biotic stream processes. Additionally, macrophytes, invertebrates, and fish were identified to assess biodiversity at each site. Metal concentrations in the three trophic levels differed among sites and species, correlating to differences in land use surrounding the rivers. The highest metal concentrations (except Al) were found in the streams most impacted by urbanization and development. Al concentrations were highest in streams surrounded by land dominated by forested areas. Metal content in macrophytes reflected metal concentrations in the water and was at least three orders of magnitude higher than any other trophic level. Despite metal concentration differences, all four streams contained similar water quality and were healthy based on macroinvertebrate community structure. This study provides insight into the impact of urbanization and the fate and effects of metals in river ecosystems with varying degrees of anthropogenic impact.

Responses of the sea anemone, Exaiptasia pallida, to ocean acidification conditions and zinc or nickel exposure.

Ocean acidification, caused by increasing atmospheric carbon dioxide (CO2), is a growing concern in marine environments. Land-based sources of pollution, such as metals, have also been a noted problem; however, little research has addressed the combined exposure of both pollutants to coral reef organisms. In this study we examined tissue metal accumulation and physiological effects (activity of anti-oxidant enzymes, catalase and glutathione reductase) in the sea anemone, Exaiptasia pallida after exposure to increased CO2, as well as zinc (Zn) or nickel (Ni). After exposure to four concentrations (nominal values=control, 10, 50, 100µg/L) of Zn or Ni over 7days, both metals accumulated in the tissues of E. pallida in a concentration-dependent manner. Anemones exposed to elevated CO2 (1000ppm) accumulated significant tissue burdens of Zn or Ni faster (by 48h) than those exposed to the same metal concentrations at ambient CO2. No differences were observed in catalase activity due to Zn exposure; however, 50µg/L Ni caused a significant increase in catalase activity at ambient CO2. No significant effect on catalase activity from CO2 exposure alone was observed. Glutathione reductase activity was affected by increased Zn or Ni exposure and those effects were influenced by increased CO2. Results of this study provide insight into the toxic mechanisms and environmental implications of CO2 and Zn or Ni exposure to the cnidarian E. pallida.

Metal accumulation in bobcats in the Southeastern USA.

Bobcats (Lynx rufus) are wide-ranging mammals found throughout the continental USA. As carnivores near the top of their food chain, bobcats would seem to be a useful bioindicator of metal pollution in terrestrial environments. However, there is very limited research on bobcats in toxicology studies. Here, we offer the first analysis of metal (copper, selenium, silver, and zinc) contaminants in the livers of wild bobcats. Liver tissues from 120 adult bobcats (i.e., estimated to be ≥1 year old) were collected from 2003 to 2006 at four sites in Georgia and Florida, USA that experienced relatively similar levels of human disturbance. We found no differences in metal concentrations between males and females. At two of the sites sampled over three consecutive years, there was substantial year-to-year variation in the concentrations of Cu, Se, and Zn. We also documented some variation between sites, but only between sites sampled in different years, which may reflect additional temporal, rather than spatial, variation. Concentrations of Cu and Ag were significantly positively correlated with one another, as were concentrations of Se and Zn. Contrary to expectation, there were no significant relationships between body weight and metal concentrations. Finally, comparison with results from previous metal toxicology studies of nine-banded armadillos (Dasypus novemcinctus) and Virginia opossums (Didelphis virgianus), collected from the same sites during the same years, showed differential patterns of accumulation across species, suggesting that ecological lifestyle is an important influence on metal accumulation. This study provides reference levels of metal contaminants in the liver of bobcats as well as insight into metal accumulation in a top level carnivore.

Metal accumulation in wild-caught opossum.

The Virginia opossum (Didelphis virginiana) is widespread in the USA, ranging south through Latin America. The ecology of opossums is such that they are in frequent contact with soils, suggesting that they may function as a valuable bioindicator for chemical contamination in terrestrial environments. Surprisingly, there have been virtually no toxicology studies on opossums. Here, we provide the first analysis of metal contaminants in opossum liver tissues. Liver samples were obtained from 471 opossums, collected from 2003 to 2006, at four sites in North Florida and South Georgia, USA, and concentrations of copper, lead, nickel, selenium, and zinc were measured. We found little evidence of age differences in the concentration of any of the metals. However, there were at least some significant differences between years, males and females, and between sites for each metal, although the pattern of these differences was not always consistent across metals. Concentrations of metals in liver tissue were positively correlated with one another, primarily of each metal (except Pb) with zinc. Reference levels of metal contaminants are not available for opossums, but concentrations of Cu, Ni, Pb, and Zn in our samples were for the most part significantly higher than those reported from liver tissues of nine-banded armadillos (Dasypus novemcinctus) collected at the same sites and in the same years. Data from other small mammals studied elsewhere further indicate that metal concentrations in opossums were high, but at this time, it is not possible to determine if these elevated levels generated toxicity. The substantial temporal and spatial variation we found in metal concentrations suggests that determination of baseline levels for opossums may not be straightforward. Nonetheless, this is the first study quantifying metal accumulation in the livers of Didelphis virginiana and, as such, provides an important starting point for future research.

Responses of the sea anemone, Exaiptasia pallida, to ocean acidification conditions and copper exposure.

Ocean acidification (OA) is a growing concern due to its deleterious effects on aquatic organisms. Additionally, the combined effects of OA and other local stressors like metal pollution are largely unknown. In this study, we examined physiological effects in the sea anemone, Exaiptasia pallida after exposure to the global stressor carbon dioxide (CO2), as well as the local stressor copper (Cu) over 7 days. Cu accumulated in the tissues of E. pallida in a concentration-dependent manner. At some time points, sea anemones exposed to 1000 ppm CO2 had higher tissue Cu concentrations than those exposed to 400 ppm CO2 at the same Cu exposure concentrations. In general, the activities of all anti-oxidant enzymes measured (catalase, CAT; glutathione peroxidase, GPx, glutathione reductase, GR) increased with exposure to increasing Cu concentrations. Significant differences in GR, CAT and to some degree GPx activity, were observed due to increasing CO2 exposure in control treatments. Sea anemones exposed to Cu in combination with higher CO2 generally had higher anti-oxidant enzyme activities than those exposed to the same concentration of Cu and lower CO2. Activity of the enzyme, carbonic anhydrase (CA), involved in acid-base balance, was significantly decreased with increasing Cu exposure. At the two lowest Cu concentrations, the extent of CA inhibition was lessened with increasing CO2 concentration. These results provide insight into toxic mechanisms of both Cu and CO2 exposure to the sensitive cnidarian E. pallida and have implications for environmental exposure of multiple contaminants.

Dietary metal toxicity to the marine sea hare, Aplysia californica.

Metal pollution from anthropogenic inputs is a concern in many marine environments. Metals accumulate in tissue and in excess cause toxicity in marine organisms. This study investigated the accumulation and effects of dietary metals in a macroinvertebrate. The green seaweed, Ulva lactuca and the red seaweed, Agardhiella subulata were each concurrently exposed to two concentrations (100 or 1000 µg/L) of five metals (Cu, Ni, Pb, Cd, and Zn). Additionally, U. lactuca was exposed to 10 µg/L of the metal mixture as well as 10 or 100 µg/L of each metal individually for 48 h. The seaweeds were then used as food for the sea hare, Aplysia californica for two to three weeks depending on the exposure concentration. Body mass of A. californica was measured weekly, and at the end of the exposure duration, metal concentrations were quantified in dissected organs (mouth, esophagus, crop, gizzard, ovotestis, heart, hepatopancreas, gill, and the carcass). Metal distribution and accumulation in the organs of A. californica varied with the metal. A. californica fed the metal-exposed diets had significantly reduced body weight by the end of the exposure periods, as compared to controls; however, differences were observed in the extent of growth reductions, dependent on exposure concentration, duration, and exposure regime (metal mixture versus individual metal-exposed diet). Metal mixture diets decreased A. californica growth more so than comparable individual metal diets, despite more metal accumulating in the individual metal diets. Additionally, Zn- and Cu-contaminated algal diets decreased control-normalized growth of A. californica significantly more than comparable Cd-, Pb-, or Ni-contaminated diets. The seaweed diets in this study contained environmentally relevant tissue metal burdens. Therefore, these results have implications for metals in marine systems.

Accumulation and effects of metal mixtures in two seaweed species.

Metal pollution, due to various anthropogenic sources, may pose a threat to marine ecosystems. Metals can be introduced into food chains via bioaccumulation in primary producers, and may potentially lead to toxic effects. Macroalgae are used as food by a wide variety of organisms, and are therefore extremely important in aquatic systems. This study investigated the accumulation and effects of metals in two macroalgae species. The green seaweed, Ulva lactuca and the red seaweed, Agardhiella subulata were each concurrently exposed to five metals (Cu, Ni, Pb, Cd, and Zn) and U. lactuca was also exposed to each metal individually for 48 h. Metal accumulation in the seaweed was measured, and various photosynthetic parameters were assessed, using imaging pulse amplitude modulated (PAM) fluorometry. Increased metal accumulation occurred in both seaweed species after 48 h exposure to metal mixtures and each metal individually. The distribution of metals in both seaweed species changed with increasing metal exposure concentrations, resulting in higher proportions of Cu and Zn in the metal-exposed groups, as compared to respective controls. Further, U. lactuca accumulated higher concentrations of metals when exposed to each metal individually rather than in metal mixtures, suggesting interactions among metals for uptake and/or bioaccumulation. Significant impairment of photosynthetic parameters in U. lactuca was observed after exposure to 100 and 1000 µg/L metal mixtures, as well as 100 µg/L of either Cd or Cu. These results demonstrate metal bioaccumulation and toxic effects in important primary producers, and may have implications for higher trophic levels.

Comparative effects of dissolved copper and copper oxide nanoparticle exposure to the sea anemone, Exaiptasia pallida.

Increasing use of metal oxide nanoparticles (NP) by various industries has resulted in substantial output of these NP into aquatic systems. At elevated concentrations, NP may interact with and potentially affect aquatic organisms. Environmental implications of increased NP use are largely unknown, particularly in marine systems. This research investigated and compared the effects of copper oxide (CuO) NP and dissolved copper, as copper chloride (CuCl2), on the sea anemone, Exaiptasia pallida. Sea anemones were collected over 21 days and tissue copper accumulation and activities of the enzymes: catalase, glutathione peroxidase, glutathione reductase, and carbonic anhydrase were quantified. The size and shape of CuO NP were observed using a ecanning electron microscope (SEM) and the presence of copper was confirmed by using Oxford energy dispersive spectroscopy systems (EDS/EDX). E. pallida accumulated copper in their tissues in a concentration- and time-dependent manner, with the animals exposed to CuCl2 accumulating higher tissue copper burdens than those exposed to CuO NP. As a consequence of increased copper exposure, as CuO NP or CuCl2, anemones increased activities of all of the antioxidant enzymes measured to some degree, and decreased the activity of carbonic anhydrase. Anemones exposed to CuO NP generally had higher anti-oxidant enzyme activities than those exposed to the same concentrations of CuCl2. This study is useful in discerning differences between CuO NP and dissolved copper exposure and the findings have implications for exposure of aquatic organisms to NP in the environment.

The influence of salinity and copper exposure on copper accumulation and physiological impairment in the sea anemone, Exaiptasia pallida.

Copper is a common pollutant in many aquatic environments, particularly those surrounding densely populated areas with substantial anthropogenic inputs. These same areas may also experience changes in salinity due to freshwater discharge and tidal influence. Biota that inhabit near-shore coastal environments may be susceptible to both stressors. Although copper is a noted concern in marine environments, effects of copper and varying salinity on symbiotic cnidarians are only scarcely studied. The sea anemone, Exaiptasia pallida, was used to investigate effects of copper on physiological impairment (i.e. activities of anti-oxidant enzymes) at two different salinities (20 and 25ppt). E. pallida was exposed to a control and three elevated copper concentrations for up to 21d, and copper accumulation and activity of the enzymes: catalase, glutathione reductase, glutathione peroxidase, and carbonic anhydrase were measured in the anemones. Photosynthetic parameters in E. pallida's symbiotic dinoflagellate algae were also quantified. Over the course of the exposure, E. pallida accumulated copper in a concentration-dependent manner. Higher tissue copper concentrations were observed in anemones exposed to the lower salinity water (20ppt), and physiological impairment was observed as a consequence of both increased copper exposure and decreased salinity; however, changes in salinity caused a greater response than copper exposure, at the levels tested. In general, antioxidant enzyme activity increased as a consequence of decreased salinity and/or increased copper exposure. These results clearly demonstrated the influence of two local stressors, at environmentally realistic concentrations, on a sensitive cnidarian, and highlight the importance of characterizing combined exposure scenarios.

Cellular partitioning of nanoparticulate versus dissolved metals in marine phytoplankton.

Discharges of metal oxide nanoparticles into aquatic environments are increasing with their use in society, thereby increasing exposure risk for aquatic organisms. Separating the impacts of nanoparticle from dissolved metal pollution is critical for assessing the environmental risks of the rapidly growing nanomaterial industry, especially in terms of ecosystem effects. Metal oxides negatively affect several species of marine phytoplankton, which are responsible for most marine primary production. Whether such toxicity is generally due to nanoparticles or exposure to dissolved metals liberated from particles is uncertain. The type and severity of toxicity depends in part on whether phytoplankton cells take up and accumulate primarily nanoparticles or dissolved metal ions. We compared the responses of the marine diatom, Thalassiosira weissflogii, exposed to ZnO, AgO, and CuO nanoparticles with the responses of T. weissflogii cells exposed to the dissolved metals ZnCl2, AgNO3, and CuCl2 for 7 d. Cellular metal accumulation, metal distribution, and algal population growth were measured to elucidate differences in exposure to the different forms of metal. Concentration-dependent metal accumulation and reduced population growth were observed in T. weissflogii exposed to nanometal oxides, as well as dissolved metals. Significant effects on population growth were observed at the lowest concentrations tested for all metals, with similar toxicity for both dissolved and nanoparticulate metals. Cellular metal distribution, however, markedly differed between T. weissflogii exposed to nanometal oxides versus those exposed to dissolved metals. Metal concentrations were highest in the algal cell wall when cells were exposed to metal oxide nanoparticles, whereas algae exposed to dissolved metals had higher proportions of metal in the organelle and endoplasmic reticulum fractions. These results have implications for marine plankton communities as well as higher trophic levels, since metal may be transferred from phytoplankton through food webs vis à vis grazing by zooplankton or other pathways.