David M. Costello

Acute toxic effects of ionic liquids on zebra mussel (Dreissena polymorpha) survival and feeding

Ionic liquids (ILs) are being designed as green alternatives to volatile organic solvents that are currently used in a wide range of industrial processes. While knowledge about the toxicity of various ILs to aquatic organisms has expanded in recent years, toxicity data remains limited to a few animal taxa. Furthermore, few studies have examined the non-lethal effects of ILs on aquatic organisms. We investigated how ILs affect mortality and feeding of the zebra mussel (Dreissena polymorpha), a sessile bivalve that is invasive in North America and much of Europe. Lethal effects of six ILs (butyl-, hexyl-, or octyl-chains on either a methylpyridinium or methylimidazolium cationic base) were studied with 96 h acute bioassays. Filtering behavior was examined in 2 h feeding trials of individual mussels fed Chlamydomonas reinhardtii and exposed to sublethal concentrations of the three imidazolium-based ILs. The ILs tested caused acute mortality over a wide range of concentrations (LC50 = 21.4 to 1290 mg L−1), ILs with longer alkyl chains were more toxic, and pyridinium- and imidazolium-based ILs had similar toxicities. When comparing toxicity to the same IL across organisms, zebra mussels exhibit some of the highest LC50 values and would be among the most resistant aquatic organisms in the event of an IL release. Short-term exposure to any IL reduced zebra mussel feeding. For butyl- and hexyl-chain ILs, feeding was significantly reduced at the acute LC50, whereas the octyl-chain IL reduced feeding at the acute LC5. Reduced survival and feeding by zebra mussels in the presence of ILs could have substantial effects on other trophic levels, which could lead to changes to affected ecosystems that would not have been predicted solely from standard mortality bioassays. Based on our mortality data, ILs are no worse than currently used industrial solvents; however, results from our feeding experiments demonstrate the potential for significant effects at sublethal concentrations. Consequently, we suggest that more ecologically relevant endpoints should be incorporated into a thorough hazard assessment of ILs.

Nickel phase partitioning and toxicity in field-deployed sediments.

The pool of bioavailable metal in sediments can be much smaller than total metal concentration due to complexation and precipitation with ligands. Metal bioavailability and toxicity in sediment is often predicted from models of simultaneous extracted metal and acid volatile sulfide (SEM-AVS); however, studies of the applicability of these models for Ni-contaminated sediments have been conducted primarily in laboratory settings. We investigated the utility of the SEM-AVS models under field conditions: Five lotic sediments with a range of sulfide and organic carbon contents were amended with four concentrations of Ni, deployed in streams for eight weeks, and examined for colonizing macroinvertebrates. After four weeks, colonizing macroinvertebrates showed a strong negative response to the Ni-treated sediments and SEM-AVS models of bioavailability differentiated between toxic and nontoxic conditions. By Week 8, relationships deteriorated between colonizing macroinvertebrates and SEM-AVS model predictions. Total Ni in the sediment did not change through time; however, Ni partitioning shifted from being dominated by organic cabon at deployment to associations with Fe and Mn. Combined geochemical and toxicity results suggest that Fe and Mn oxides in surface sediments resulted in Ni being less available to biota. This implies that current SEM-AVS models may overestimate bioavailable Ni in sediments with oxic surface layers and sufficient Fe and Mn.

Evaluating the Performance of Diffusive Gradients in Thin Films for Predicting Ni Sediment Toxicity

Diffusive gradients in thin films (DGTs) rapidly measure labile fractions of metal and are promoted as an assessment tool for bioavailability. Using macroinvertebrate community composition as a response, this study compared the predictive ability of DGT-measured Ni with acid volatile sulfide (AVS) and organic carbon (OC) corrected Ni [(SEM(Ni)-AVS)/f(OC)] and total Ni concentrations. In two experiments, sediments were amended with Ni and placed within either a streamside mesocosm or deployed in situ. DGT-measured Ni concentrations (C(DGT)) increased with increasing total Ni, were greater at depth, and decreased over time. Relationships between Ni C(DGT) and sediment geochemistry indicated a shift in Ni partitioning from AVS-bound to Fe- and Mn-associated Ni. In both experiments, DGT-measured Ni poorly predicted the invertebrate response to metal, whereas models that included total Ni or (SEM(Ni)-AVS)/f(OC) effectively predicted the invertebrate response for the streamside mesocosm and in situ experiments, respectively. C(DGT) overestimated the available Ni fraction, possibly due to sampling either nonbioavailable solid-phase Ni or Ni irrespective of cations competing at the biotic ligand. We suggest that C(DGT) cannot replace (SEM(Ni)-AVS)/f(OC) for predicting invertebrate response to sediment Ni, and greater understanding of metal species lability to DGTs is needed before assuming equivalence between bioavailable and DGT-labile metals in sediments.

Predator-induced defenses in tadpoles confound body stoichiometry predictions of the general stress paradigm

Predation is known to have both direct and indirect effects on nutrient cycling in terrestrial and aquatic ecosystems, and the general stress paradigm (GSP) has been promoted as a theory for describing predator-mediated indirect effects on nutrient cycling. The GSP predicts that prey exposed to predators will produce glucocorticosteroids, which have a host of physiological effects including gluconeogenesis, increased respiration, excretion of N and P, and increases in body C:N. We tested the nutrient predictions of the GSP using anuran larvae, which exhibit morphological defenses in addition to behavioral defenses for which the GSP was conceived. Genetically similar Hyla versicolor tadpoles were placed in mesocosms either in the presence or absence of a fed predator (Dytiscus verticalis), and after two weeks, tadpoles exposed to predators exhibited strong induced defenses with large, tubular bodies, larger tails, and reduced activity. Tadpole body %C and N:P increased with no change in C:N, which is contrary to expectations from the GSP. Statistical models suggested that changes in body morphology (e.g., tail muscle width) rather than behavioral defenses (i.e., reduced activity) were most likely responsible for predator-mediated differences in body stoichiometry. This study suggests that strong morphological defenses may overwhelm or counteract the nutrient predictions of the GSP.

Copper Sediment Toxicity and Partitioning during Oxidation in a Flow-Through Flume

The bioavailability of transition metals in sediments often depends on redox conditions in the sediment. We explored how the physicochemistry and toxicity of anoxic Cu-amended sediments changed as they aged (i.e., naturally oxidized) in a flow-through flume. We amended two sediments (Dow and Ocoee) with Cu, incubated the sediments in a flow-through flume, and measured sediment physicochemistry and toxicity over 213 days. As sediments aged, oxygen penetrated sediment to a greater depth, the relative abundance of Fe oxides increased in surface and deep sediments, and the concentration of acid volatile sulfide declined in Ocoee surface sediments. The total pool of Cu in sediments did not change during aging, but porewater Cu, and Cu bound to amorphous Fe oxides decreased while Cu associated with crystalline Fe oxides increased. The dose-response of the epibenthic amphipod Hyalella azteca to sediment total Cu changed over time, with older sediments being less toxic than freshly spiked sediments. We observed a strong dose-response relationship between porewater Cu and H. azteca growth across all sampling periods, and measurable declines in relative growth rates were observed at concentrations below interstitial water criteria established by the U.S. EPA. Further, solid-phase bioavailability models based on AVS and organic carbon were overprotective and poorly predicted toxicity in aged sediments. We suggest that sediment quality criteria for Cu is best established from measurement of Cu in pore water rather than estimating bioavailable Cu from the various solid-phase ligands, which vary temporally and spatially.

Deforestation and cultivation mobilize mercury from topsoil

Terrestrial biomass and soils are a primary global reservoir of mercury (Hg) derived from natural and anthropogenic sources; however, relatively little is known about the fate and stability of Hg in the surface soil reservoir and its susceptibility to change as a result of deforestation and cultivation. In southwest Ohio, we measured Hg concentrations in soils of deciduous old- and new-growth forests, as well as fallow grassland and agricultural soils that had once been forested to examine how, over decadal to century time scales, man-made deforestation and cultivation influence Hg mobility from temperate surface soils. Mercury concentrations in surficial soils were significantly greater in the old-growth than new-growth forest, and both forest soils had greater Hg concentrations than cultivated and fallow fields. Differences in Hg:lead ratios between old-growth forest and agricultural topsoils suggest that about half of the Hg lost from deforested and cultivated Ohio soils may have been volatilized and the other half eroded. The estimated mobilization potential of Hg as a result of deforestation was 4.1 mg m(-2), which was proportional to mobilization potentials measured at multiple locations in the Amazon relative to concentrations in forested surface soils. Based on this relationship and an estimate of the global average of Hg concentrations in forested soils, we approximate that about 550 M mol of Hg has been mobilized globally from soil as a result of deforestation during the past two centuries. This estimate is comparable to, if not greater than, the amount of anthropogenic Hg hypothesized by others to have been sequestered by the soil reservoir since Industrialization. Our results suggest that deforestation and soil cultivation are significant anthropogenic processes that exacerbate Hg mobilization from soil and its cycling in the environment.

Slipping through the Cracks: Why is the U.S. Environmental Protection Agency Not Funding Extramural Research on Chemicals in Our Environment?

Protection Agency Not Funding Extramural Research on Chemicals in Our Environment? G. Allen Burton, Jr.,*,† Richard Di Giulio,‡ David Costello, and Jason R. Rohr †University of Michigan, School of Natural Resources & Environment, 440 Church St., Ann Arbor, Michigan 48109, United States ‡Duke University, Nicholas School of Environment, Durham, North Carolina 27708, United States Kent State University, Department of Biological Sciences, 1275 University Esplanade, Kent, Ohio 44242, United States University of South Florida, Department of Integrative Biology, 4202 East Fowler Ave., Tampa, Florida 33620, United States

Copper and nickel partitioning with nanoscale goethite under variable aquatic conditions

Metal contaminated sediments can be toxic to aquatic organisms and are common in human-dominated ecosystems, which results in metals being a leading cause of ecosystem impairment. Bioavailability of metals is influenced by their affinity for dissolved and solid-phase ligands, including iron (Fe) oxyhydroxides, which have been hypothesized to reduce metal toxicity in sediments. The authors examined the adsorption kinetics of copper (Cu) and nickel (Ni) with goethite (α-FeOOH) and characterized the influences of solute metal concentration, pH, ionic strength, and humate concentration on steady-state partitioning of the metals with goethite under conditions representative of natural aquatic environments. Copper and Ni readily adsorbed to goethite, and steady-state partitioning was achieved within 2 h. Although ionic strength had no effect on metal partitioning, adsorption of Cu and Ni to goethite was enhanced by alkaline pH and reduced by competition with humate. Because distribution coefficient (KD ) values for Cu and Ni from the present study are comparable to values measured in natural systems, the authors hypothesize that goethite may contribute significantly to the adsorption of both Ni and Cu to particles in the environment. The authors suggest that incorporating binding by Fe oxides in metal bioavailability models should be a priority for improving risk assessment of metal-contaminated oxic sediments.

Interactive effects of phosphorus and copper on Hyalella azteca via periphyton in aquatic ecosystems.

This research examined the interaction between dissolved copper and phosphorus, with respect to their effects on the freshwater amphipod Hyalella azteca feeding on periphyton. Field-collected periphyton communities were exposed to different nutrient and metal conditions in indoor recirculating streams. H. azteca were then exposed to water and periphyton from these streams. There was rapid Cu accumulation by periphyton but the total Cu concentration of periphyton was not directly related to dissolved P. In terms of H. azteca growth, an interactive effect was found between Cu and P as growth was reduced more than expected in the low Cu-high P treatment. Our data suggest that eutrophic conditions result in greater Cu toxicity to benthic macroinvertebrates at lower metal concentrations, likely due to higher assimilation efficiency of dietary Cu from periphyton incubated under eutrophic conditions. These results imply that non-additive interactions between multiple stressors may cause ecosystem effects as detected in standard laboratory bioassays conducted under controlled conditions.

Net methylmercury production in 2 contrasting stream sediments and associated accumulation and toxicity to periphyton.

Periphyton uptake of bioaccumulative methylmercury (MeHg) may be an important entryway into the food web of many stream ecosystems where periphyton can be dominant primary producers. The net production of MeHg in stream sediment, its bioaccumulation in periphyton, and the potential toxicity of divalent Hg (Hg[II]) and MeHg in sediment to periphyton were investigated with a 67-d in situ incubation experiment using chemical exposure substrates containing either a fine-grained, organic-rich or a sandy, low-organic sediment, each amended with varying concentrations of mercuric chloride. Methylmercury was produced in sediment, and concentrations increased with greater amounts of added Hg(II); however, the net production of MeHg was inhibited in the highest Hg(II) treatments of both sediments. The range of total Hg concentrations that inhibited MeHg production was between approximately 80 000 ng Hg and 350 000 ng Hg per gram of organic matter for both sediments. Periphyton colonizing substrates accumulated MeHg in proportion to the concentration in sediment, but periphyton exposed to the sandy sediment accumulated approximately 20-fold more than those exposed to the organic-rich sediment relative to sediment MeHg concentrations. Toxicity of either Hg(II) or MeHg to periphyton was not observed with either periphyton organic content, net primary production, or respiration as endpoints. These results suggest that in situ production and bioaccumulation of MeHg in stream ecosystems can vary as a function of sediment characteristics and Hg(II) loadings to the sediment. Environ Toxicol Chem 2016;35:1759-1765.