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Metal Mixture Modeling Evaluation project: 2. Comparison of four modeling approaches

As part of the Metal Mixture Modeling Evaluation (MMME) project, models were developed by the National Institute of Advanced Industrial Science and Technology (Japan), the U.S. Geological Survey (USA), HDR⎪HydroQual, Inc. (USA), and the Centre for Ecology and Hydrology (UK) to address the effects of metal mixtures on biological responses of aquatic organisms. A comparison of the 4 models, as they were presented at the MMME Workshop in Brussels, Belgium (May 2012), is provided herein. Overall, the models were found to be similar in structure (free ion activities computed by WHAM; specific or non-specific binding of metals/cations in or on the organism; specification of metal potency factors and/or toxicity response functions to relate metal accumulation to biological response). Major differences in modeling approaches are attributed to various modeling assumptions (e.g., single versus multiple types of binding site on the organism) and specific calibration strategies that affected the selection of model parameters. The models provided a reasonable description of additive (or nearly additive) toxicity for a number of individual toxicity test results. Less-than-additive toxicity was more difficult to describe with the available models. Because of limitations in the available datasets and the strong inter-relationships among the model parameters (log KM values, potency factors, toxicity response parameters), further evaluation of specific model assumptions and calibration strategies is needed.

Environmental Toxicology and Chemistry

Bioavailability and toxicity models of copper to freshwater life: The state of regulatory science

Efforts to incorporate bioavailability adjustments into regulatory water quality criteria in the United States have included four major procedures: hardness-based single-linear regression equations, water-effect ratios (WERs), biotic ligand models (BLMs), and multiple-linear regression models (MLRs) that use dissolved organic carbon, hardness, and pH. The performance of each with copper (Cu) is evaluated, emphasizing the relative performance of hardness-based versus MLR-based criteria equations. The WER approach was shown to be inherently highly biased. The hardness-based model is in widest use, and the MLR approach is the US Environmental Protection Agency's (USEPA's) present recommended approach for developing aquatic life criteria for metals. The performance of criteria versions was evaluated with numerous toxicity datasets that were independent of those used to develop the MLR models, including olfactory and behavioral toxicity, and field and ecosystem studies. Within the range of water conditions used to develop the Cu MLR criteria equations, the MLR performed well in terms of predicting toxicity and protecting sensitive species and ecosystems. In soft waters, the MLR outperformed both the BLM and hardness models. In atypical waters with pH <5.5 or >9, neither the MLR nor BLM predictions were reliable, suggesting that site-specific testing would be needed to determine reliable Cu criteria for such settings. The hardness-based criteria performed poorly with all toxicity datasets, showing no or weak ability to predict observed toxicity. In natural waters, MLR and BLM criteria versions were strongly correlated. In contrast, the hardness-criteria version was often out of phase with the MLR and, depending on waterbody and season, could be either strongly overprotective or underprotective. The MLR-based USEPA-style chronic criterion appears to be more generally protective of ecosystems than other models.

Environmental Toxicology and Chemistry

Toxicological responses to sublethal anticoagulant rodenticide exposure in free-flying hawks

An important component of assessing the hazards of anticoagulant rodenticides to non-target wildlife is observations in exposed free-ranging individuals. The objective of this study was to determine whether environmentally realistic, sublethal first-generation anticoagulant rodenticide (FGAR) exposures via prey can result in direct or indirect adverse effects to free-flying raptors. We offered black-tailed prairie dogs ( Cynomys ludovicianus ) that had fed on Rozol® Prairie Dog Bait (Rozol, 0.005% active ingredient chlorophacinone, CPN) to six wild-caught red-tailed hawks (RTHA, Buteo jamaicensis ), and also offered black-tailed prairie dogs that were not exposed to Rozol to another two wild-caught RTHAs for 7 days. On day 6, blood was collected to determine CPN’s effects on blood clotting time. On day 7, seven of the eight RTHAs were fitted with VHF radio telemetry transmitters and the RTHAs were released the following day and were monitored for 33 days. Prothrombin time (PT) and Russell’s viper venom time confirmed that the CPN-exposed RTHAs were exposed to and were adversely affected by CPN. Four of the six CPN-exposed RTHAs exhibited ptiloerection, an indication of thermoregulatory dysfunction due to CPN toxicity, but no signs of intoxication were observed in the reference hawk or the remaining two CPN-exposed RTHAs. Of note is that PT values were associated with ptiloerection duration and frequency; therefore, sublethal CPN exposure can directly or indirectly evoke adverse effects in wild birds. Although our sample sizes were small, this study is a first to relate coagulation times to adverse clinical signs in free-ranging birds.

Colorado

Avian mercury exposure and toxicological risk across western North America: A synthesis

Methylmercury contamination of the environment is an important issue globally, and birds are useful bioindicators for mercury monitoring programs. The available data on mercury contamination of birds in western North America were synthesized. Original data from multiple databases were obtained and a literature review was conducted to obtain additional mercury concentrations. In total, 29219 original bird mercury concentrations from 225 species were compiled, and an additional 1712 mean mercury concentrations, representing 19998 individuals and 176 species, from 200 publications were obtained. To make mercury data comparable across bird tissues, published equations of tissue mercury correlations were used to convert all mercury concentrations into blood-equivalent mercury concentrations. Blood-equivalent mercury concentrations differed among species, foraging guilds, habitat types, locations, and ecoregions. Piscivores and carnivores exhibited the greatest mercury concentrations, whereas herbivores and granivores exhibited the lowest mercury concentrations. Bird mercury concentrations were greatest in ocean and salt marsh habitats and lowest in terrestrial habitats. Bird mercury concentrations were above toxicity benchmarks in many areas throughout western North America, and multiple hotspots were identified. Additionally, published toxicity benchmarks established in multiple tissues were summarized and translated into a common blood-equivalent mercury concentration. Overall, 66% of birds sampled in western North American exceeded a blood-equivalent mercury concentration of 0.2 &mu;g/g wet weight (ww; above background levels), which is the lowest-observed effect level, 28% exceeded 1.0 &mu;g/g ww (moderate risk), 8% exceeded 3.0 &mu;g/g ww (high risk), and 4% exceeded 4.0 &mu;g/g ww (severe risk). Mercury monitoring programs should sample bird tissues, such as adult blood and eggs, that are most-easily translated into tissues with well-developed toxicity benchmarks and that are directly relevant to bird reproduction. Results indicate that mercury contamination of birds is prevalent in many areas throughout western North America, and large-scale ecological attributes are important factors influencing bird mercury concentrations.

Science of the Total Environment

The silence of the clams: Forestry registered pesticides as multiple stressors on soft-shell clams

Contaminants are ubiquitous in the environment, often reaching aquatic systems. Combinations of forestry use pesticides have been detected in both water and aquatic organism tissue samples in coastal systems. Yet, most toxicological studies focus on the effects of these pesticides individually, at high doses, and over acute time periods, which, while key for establishing toxicity and safe limits, are rarely environmentally realistic. We examined chronic (90 days) exposure by the soft-shell clam, Mya arenaria , to environmentally relevant concentrations of four pesticides registered for use in forestry (atrazine, 5 μg/L; hexazinone, 0.3 μg/L; indaziflam, 5 μg/L; and bifenthrin, 1.5 μg/g organic carbon (OC)). Pesticides were tested individually and in combination, except bifenthrin, which was tested only in combination with the other three. We measured shell growth and condition index every 30 days, as well as feeding rates, mortality, and chemical concentrations in tissue from a subset of clams at the end of the experiment to measure contaminant uptake. Indaziflam caused a high mortality rate (max. 36%), followed by atrazine (max. 27%), both individually as well as in combination with other pesticides. Additionally, indaziflam concentrations in tissue (61.70–152.56 ng/g) were higher than those of atrazine (26.48–48.56 ng/g), despite equal dosing concentrations, indicating higher tissue accumulation. Furthermore, clams exposed to indaziflam and hexazinone experienced reduced condition index and clearance rates individually and in combination with other compounds; however, the two combined did not result in significant mortality. These two compounds, even at environmentally relevant concentrations, affected a non-target organism and, in the case of the herbicide indaziflam, accumulated in clam tissue and appeared more toxic than other tested pesticides. These findings underscore the need for more comprehensive studies combining multiple compounds at relevant concentrations to understand their impacts on aquatic ecosystems.

Science of the Total Environment

Bird mercury concentrations change rapidly as chicks age: Toxicological risk is highest at hatching and fledging

Toxicological risk of methylmercury exposure to juvenile birds is complex due to the highly transient nature of mercury concentrations as chicks age. We examined total mercury and methylmercury concentrations in blood, liver, kidney, muscle, and feathers of 111 Forster's tern (Sterna forsteri), 69 black-necked stilt (Himantopus mexicanus), and 43 American avocet (Recurvirostra americana) chicks as they aged from hatching through postfledging at wetlands that had either low or high mercury contamination in San Francisco Bay, California. For each waterbird species, internal tissue, and wetland, total mercury and methylmercury concentrations changed rapidly as chicks aged and exhibited a quadratic, U-shaped pattern from hatching through postfledging. Mercury concentrations were highest immediately after hatching, due to maternally deposited mercury in eggs, then rapidly declined as chicks aged and diluted their mercury body burden through growth in size and mercury depuration into growing feathers. Mercury concentrations then increased during fledging when mass gain and feather growth slowed, while chicks continued to acquire dietary mercury. In contrast to mercury in internal tissues, mercury concentrations in chick feathers were highly variable and declined linearly with age. For 58 recaptured Forster's tern chicks, the proportional change in blood mercury concentration was negatively related to the proportional change in body mass, but not to the amount of feathers or wing length. Thus, mercury concentrations declined more in chicks that gained more mass between sampling events. The U-shaped pattern of mercury concentrations from hatching to fledging indicates that juvenile birds may be at highest risk to methylmercury toxicity shortly after hatching when maternally deposited mercury concentrations are still high and again after fledging when opportunities for mass dilution and mercury excretion into feathers are limited.

Environmental Science & Technology

Mortality and cholinesterase inhibition in butterflies following aerial naled applications for mosquito control on the National Key Deer Refuge

Natural resource managers are concerned about the impacts of aerial ultra-low volume spray (ULV) of insecticides for mosquito control (i.e., mosquito adulticides) and seek science-driven management recommendations that reduce risk but allow vector control for nearby human populations. Managers at the National Key Deer Refuge (Florida Keys, FL) are concerned for ULV effects upon conservation efforts for imperiled butterflies (Florida leafwing [ Anaea troglodyta floridalis ] and Bartram’s hairstreak [ Strymon acis bartrami ] butterflies). No-spray zones were designated for protection of those butterflies, but their effectiveness for mitigation is unclear. To address this uncertainty, cholinesterase activity (ChE) and mortality were monitored for caged butterflies gulf fritillary [ Agraulis vanilla ] and great southern white [ Ascia monuste ]) deployed on the Refuge during three aerial ULV applications of the insecticide naled. Residue samplers also were deployed to estimate butterfly exposure. Spray efficacy against mosquitoes was assessed by deploying caged mosquitoes at the same locations as the butterflies. Average naled residue levels on filter paper samplers in the target area (1882–2898 µg/m 2 ) was significantly greater than in the no-spray zone (9–1562 µg/m 2 ). Differences between the no-spray zone and target area for butterfly mortality and ChE were inconsistent. Average mortality was significantly lower, and average ChE was significantly higher in the no-spray zone for larvae of one species but not for larvae of the other species. Mosquito mortality did not differ significantly between the two areas. Data from the present study reflect the inconsistent effectiveness of no-spray zones on the Refuge using standard methods employed at the time by the vector control agency in the Florida Keys and possibly by other vector control agencies in similar coastal environments. Furthermore, these findings helped to guide the design and to improve the conservation value of future no-spray zone delineations while allowing for treatment in areas where mosquito control is necessary for vector-borne disease reduction.

Florida