Quantifying fish otolith mineralogy for trace-element chemistry studies.

Otoliths are frequently used to infer environmental conditions or fish life history events based on trace-element concentrations. However, otoliths can be comprised of any one or combination of the three most common polymorphs of calcium carbonate-aragonite, calcite, and vaterite-which can affect the ecological interpretation of otolith trace-element results. Previous studies have reported heterogeneous calcium carbonate compositions between left and right otoliths but did not provide quantitative assessments of polymorph abundances. In this study, neutron diffraction and Raman spectroscopy were used to identify and quantify mineralogical compositions of Chinook salmon Oncorhynchus tshawytscha otolith pairs. We found mineralogical compositions frequently differed between otoliths in a pair and accurate calcium carbonate polymorph identification was rarely possible by visual inspection alone. The prevalence of multiple polymorphs in otoliths is not well-understood, and future research should focus on identifying otolith compositions and investigate how variations in mineralogy affect trace-element incorporation and potentially bias environmental interpretations.

Influence of ontogenetic development, temperature, and pCO2 on otolith calcium carbonate polymorph composition in sturgeons.

Changes to calcium carbonate (CaCO3) biomineralization in aquatic organisms is among the many predicted effects of climate change. Because otolith (hearing/orientation structures in fish) CaCO3 precipitation and polymorph composition are controlled by genetic and environmental factors, climate change may be predicted to affect the phenotypic plasticity of otoliths. We examined precipitation of otolith polymorphs (aragonite, vaterite, calcite) during early life history in two species of sturgeon, Lake Sturgeon, (Acipenser fulvescens) and White Sturgeon (A. transmontanus), using quantitative X-ray microdiffraction. Both species showed similar fluctuations in otolith polymorphs with a significant shift in the proportions of vaterite and aragonite in sagittal otoliths coinciding with the transition to fully exogenous feeding. We also examined the effect of the environment on otolith morphology and polymorph composition during early life history in Lake Sturgeon larvae reared in varying temperature (16/22 °C) and pCO2 (1000/2500 µatm) environments for 5 months. Fish raised in elevated temperature had significantly increased otolith size and precipitation of large single calcite crystals. Interestingly, pCO2 had no statistically significant effect on size or polymorph composition of otoliths despite blood pH exhibiting a mild alkalosis, which is contrary to what has been observed in several studies on marine fishes. These results suggest climate change may influence otolith polymorph composition during early life history in Lake Sturgeon.

Morphology and composition of Goldeye (Hiodontidae; Hiodon alosoides) otoliths.

We provide up-to-date morphological and compositional data on otoliths of the osteoglossomorph Goldeye (Hiodon alosoides). Using computed tomography (CT) X-ray, we documented the location of each of the three pairs of otoliths (lapilli, sagittae, and asterisci) in relation to the swim bladder, which extended forward in close proximity to the sagittae and asterisci. The lappili were the largest otoliths in terms of surface area and volume, but the sagittae were highly modified, appearing spiral in shape when viewed dorsally, with a surface area to volume ratio more than double that of the lapilli. Using scanning electron microscopy, the surface of each otolith was viewable in great detail, and small otoconia (~10.5 µm diameter) were observed on each, but were most numerous on the sagittae. On scanning electron micrographs, the sagittae appeared to be bi-lobed, with asymmetrical lobes each oriented in the same general direction. Using neutron and X-ray diffraction methods, we found three polymorphs of calcium carbonate crystals (aragonite, vaterite, and calcite), sometimes all within the same otolith. However, in general, lapilli and sagittae were composed predominately of aragonite whereas asterisci were composed chiefly of vaterite. With these results, we provide information on a unique species, whose inclusion in future studies would benefit our understanding of fish hearing, fish evolution, and fisheries ecology.

Texture Analysis of Polycrystalline Vaterite Spherulites from Lake Sturgeon Otoliths.

Fish otoliths, or ear bones, are comprised of the CaCO3 polymorphs (aragonite, calcite and vaterite), which can occur either alone or in combination. The polymorph phase abundance in an otolith depends on, as yet, unexplained genetic and environmental factors. Most fish otoliths are comprised of the densest CaCO3 polymorph, aragonite. Sturgeon otoliths, on the other hand, contain significant amounts of the rare and the structurally enigmatic polymorph, vaterite. Sturgeon otoliths are frequently comprised of agglomerations of small microcrystalline vaterite spherulites (<300 µm in diameter), that range in shape from nearly perfect spheres to oblate spheroids. These spherulites are similar to the synthetic vaterite microspheres employed in laser trapping applications. Vaterite spherulites from both hatchery-reared (juvenile) and wild (adult) Lake Sturgeon exhibit extreme crystallographic texture as evidenced by X-ray diffraction patterns and their reconstructed pole-figures determined here. The vaterite crystallites making up the spherulites have excellent registry in both the axial and equatorial directions. Whether synthesized or natural, the texture manifested in these spherulites suggests that vaterite nucleates and grows similarly in vivo otolith formation as well as from laboratory synthesis. The uniaxial optical character of the vaterite spherulites, confirmed by these diffraction experiments and combined with their large birefringence, makes them well suited for laser trapping applications.

Otoliths of sub-adult Lake Sturgeon Acipenser fulvescens contain aragonite and vaterite calcium carbonate polymorphs.

In this study we quantified the percent CaCO3 polymorph composition in otoliths of larval and juvenile Lake Sturgeon Acipenser fulvescens via X-ray microdiffraction. Sagittal otoliths of sub-adults were primarily composed of aragonite (> 90%) while the lapilli otoliths were 100% vaterite. This is the first time the presence of aragonite in otoliths has been reported in an acipenseriform and is surprising given that the ability to form aragonite otoliths was not thought to have evolved until the separation of teleost and holostean species from other Actinopterygian fishes (e.g., sturgeon, paddlefish, gar).

Empirically testing vaterite structural models using neutron diffraction and thermal analysis.

Otoliths, calcium carbonate (CaCO3) ear bones, are among the most commonly used age and growth structures of fishes. Most fish otoliths are comprised of the most dense CaCO3 polymorph, aragonite. Sturgeon otoliths, in contrast, have been characterized as the rare and structurally enigmatic polymorph, vaterite-a metastable polymorph of CaCO3. Vaterite is an important material ranging from biomedical to personal care applications although its crystal structure is highly debated. We characterized the structure of Lake Sturgeon otoliths using thermal analysis and neutron powder diffraction, which is used non-destructively. We confirmed that while Lake Sturgeon otoliths are primarily composed of vaterite, they also contain the denser CaCO3 polymorph, calcite. For the vaterite fraction, neutron diffraction data provide enhanced discrimination of the carbonate group compared to x-ray diffraction data, owing to the different relative neutron scattering lengths, and thus offer the opportunity to uniquely test the more than one dozen crystal structural models that have been proposed for vaterite. Of those, space group P6522 model, a = 7.1443(4)Å, c = 25.350(4)Å, V = 1121.5(2)Å3 provides the best fit to the neutron powder diffraction data, and allows for a structure refinement using rigid carbonate groups.

Relating fish health and reproductive metrics to contaminant bioaccumulation at the Tennessee Valley Authority Kingston coal ash spill site.

A 4.1 million m(3) coal ash release into the Emory and Clinch rivers in December 2008 at the Tennessee Valley Authority's Kingston Fossil Plant in east Tennessee, USA, prompted a long-term, large-scale biological monitoring effort to determine if there are chronic effects of this spill on resident biota. Because of the magnitude of the ash spill and the potential for exposure to coal ash-associated contaminants [e.g., selenium (Se), arsenic (As), and mercury (Hg)] which are bioaccumulative and may present human and ecological risks, an integrative, bioindicator approach was used. Three species of fish were monitored-bluegill (Lepomis macrochirus), redear sunfish (L. microlophus), and largemouth bass (Micropterus salmoides)-at ash-affected and reference sites annually for 5 years following the spill. On the same individual fish, contaminant burdens were measured in various tissues, blood chemistry parameters as metrics of fish health, and various condition and reproduction indices. A multivariate statistical approach was then used to evaluate relationships between contaminant bioaccumulation and fish metrics to assess the chronic, sub-lethal effects of exposure to the complex mixture of coal ash-associated contaminants at and around the ash spill site. This study suggests that while fish tissue concentrations of some ash-associated contaminants are elevated at the spill site, there was no consistent evidence of compromised fish health linked with the spill. Further, although relationships between elevated fillet burdens of ash-associated contaminants and some fish metrics were found, these relationships were not indicative of exposure to coal ash or spill sites. The present study adds to the weight of evidence from prior studies suggesting that fish populations have not incurred significant biological effects from spilled ash at this site: findings that are relevant to the current national discussions on the safe disposal of coal ash waste.

Threats and opportunities for freshwater conservation under future land use change scenarios in the United States.

Freshwater ecosystems provide vital resources for humans and support high levels of biodiversity, yet are severely threatened throughout the world. The expansion of human land uses, such as urban and crop cover, typically degrades water quality and reduces freshwater biodiversity, thereby jeopardizing both biodiversity and ecosystem services. Identifying and mitigating future threats to freshwater ecosystems requires forecasting where land use changes are most likely. Our goal was to evaluate the potential consequences of future land use on freshwater ecosystems in the coterminous United States by comparing alternative scenarios of land use change (2001-2051) with current patterns of freshwater biodiversity and water quality risk. Using an econometric model, each of our land use scenarios projected greater changes in watersheds of the eastern half of the country, where freshwater ecosystems already experience higher stress from human activities. Future urban expansion emerged as a major threat in regions with high freshwater biodiversity (e.g., the Southeast) or severe water quality problems (e.g., the Midwest). Our scenarios reflecting environmentally oriented policies had some positive effects. Subsidizing afforestation for carbon sequestration reduced crop cover and increased natural vegetation in areas that are currently stressed by low water quality, while discouraging urban sprawl diminished urban expansion in areas of high biodiversity. On the other hand, we found that increases in crop commodity prices could lead to increased agricultural threats in areas of high freshwater biodiversity. Our analyses illustrate the potential for policy changes and market factors to influence future land use trends in certain regions of the country, with important consequences for freshwater ecosystems. Successful conservation of aquatic biodiversity and ecosystem services in the United States into the future will require attending to the potential threats and opportunities arising from policies and market changes affecting land use.

Distribution of selenium, mercury, and methylmercury in surficial Missouri River sediments.

Sediment deposition into Lewis and Clark Lake, an impoundment of the Missouri River, has caused substantial storage capacity reductions. Current proposals to hydrologically flush sediment would disturb river and reservoir sediment that may contain heavy metals. We quantified existing concentrations of selenium (Se), mercury (Hg), and methylmercury (MeHg) in surficial sediments upstream of and in Lewis and Clark Lake. We found elevated levels of Se (range 0.12-9.62 microg/g) and Hg (range 0.021.55 microg/g) at several sites throughout the study area; however, few sites contained levels of MeHg above detection limits. Sites with highest MeHg concentrations were found in Lewis and Clark Lake and ranged from below detection limit to 0.79 ng/g. We conclude that further investigation of sediment-sequestered contaminants in Lewis and Clark Lake should be conducted.

Chronology and development of juvenile bluegill parasite communities.

This study describes the parasite communities of juvenile bluegill and examines the development of parasite communities in juvenile bluegill from 2 Michigan lakes. Parasitological examination of 510 juvenile bluegill from 2 Michigan lakes (Three Lakes II [TL] and Gull Lake [GL]) demonstrated that TL bluegill harbored 19 parasite species and GL bluegill harbored 16 parasite species. Parasite communities of juvenile bluegill from both lakes were dominated by larval parasites, particularly larval trematodes. A nonmetric multidimensional scaling analysis showed bluegill of similar lengths to have similar parasite communities. Relative influences of species richness on parasite infracommunities of juvenile bluegill suggest similar patterns of parasite community structure between TL and GL. Patterns in parasite colonization evident in both lakes suggest that the smallest juvenile bluegill are primarily vulnerable to colonization by parasites acquired through direct contact, particularly larval trematodes, while the majority of parasites acquired through ingestion are not acquired until juvenile bluegill are larger and less-gape limited.