Somatic Growth Dilution of a toxicant in a predator-prey model under stoichiometric constraints.

The development of aquatic food chain models that incorporate both the effects of nutrient availability, as well as, track toxicants through trophic levels will shed light on ecotoxicological processes and ultimately help improve risk assessment efforts. Here we develop a stoichiometric aquatic food chain model of two trophic levels that investigates concurrent nutrient and toxic stressors in order to improve our understanding of the processes governing the trophic transfer for nutrients, energy, and toxicants. Analytical analysis of positive invariance, local stability of boundary equilibria, numerical simulations, and bifurcation analysis are presented. The model captures and explores a phenomenon called the Somatic Growth Dilution (SGD) effect recently observed empirically, where organisms experience a greater than proportional gain in biomass relative to toxicant concentrations when consuming food with high nutritional content vs. low quality food.

Calcium uptake in aquatic insects: influences of phylogeny and metals (Cd and Zn).

Calcium sequestration in the hypo-osmotic freshwater environment is imperative in maintaining calcium homeostasis in freshwater aquatic organisms. This uptake process is reported to have the unintended consequence of potentially toxic heavy metal (Cd, Zn) uptake in a variety of aquatic species. However, calcium uptake remains poorly understood in aquatic insects, the dominant invertebrate faunal group in most freshwater ecosystems. Here, we examined Ca uptake and interactions with heavy metals (Cd, Zn) at low ambient Ca levels (12.5 µmol l(-1)) in 12 aquatic insect species within Ephemerellidae (mayfly) and Hydropsychidae (caddisfly), two families differentially responsive to trace metal pollution. We found Ca uptake varied 70-fold across the 12 species studied. Body mass and clade (family) were found to significantly influence both Ca uptake and adsorption (P≤0.05). Zn and Cd uptake rate constants (ku) exhibited a strong correlation (r=0.96, P<0.0001), suggesting a shared transport system. Ca uptake failed to significantly correlate with either Zn or Cd ku values. Further, neither Zn nor Cd exhibited inhibitory effects toward Ca uptake. In fact, we saw evidence of modest stimulation of Ca uptake rates in some metal treatments. This work suggests that insects generally differ from other freshwater taxa in that aqueous Ca uptake does not appear to be compromised by Cd or Zn exposure. It is important to understand the trace metal and major ion physiology of aquatic insects because of their ecological importance and widespread use as ecological indicators.

Phylogeny and size differentially influence dissolved Cd and Zn bioaccumulation parameters among closely related aquatic insects.

Evolutionarily distinct lineages can vary markedly in their accumulation of, and sensitivity to, contaminants. However, less is known about variability among closely related species. Here, we compared dissolved Cd and Zn bioaccumulation in 19 species spanning two species-rich aquatic insect families: Ephemerellidae (order Ephemeroptera (mayflies)), generalized to be metal sensitive, and Hydropsychidae (order Trichoptera (caddisflies)), generalized to be metal tolerant. Across all species, Zn and Cd uptake rate constants (k(u)s), efflux rate constants (k(e)s) and bioconcentration factors (BCFs) strongly covaried, suggesting that these metals share transport pathways in these distinct lineages. K(u)s and BCFs were substantially larger in Ephemerellidae than in Hydropsychidae, whereas k(e)s did not dramatically differ between the two families. Body size played an important role in driving ku differences among species, but had no influence on k(e)s. While familial differences in metal bioconcentration were striking, each family exhibited tremendous variability in all bioaccumulation parameters. At finer levels of taxonomic resolution (within families), phylogeny did not account for differences in metal bioaccumulation. These findings suggest that intrafamily variability can be profound and have important practical implications in that we need to better understand how well "surrogate species" represent their fellow congeners and family members.

Evolutionary patterns in trace metal (cd and zn) efflux capacity in aquatic organisms.

The ability to eliminate (efflux) metals is a physiological trait that acts as a major driver of bioaccumulation differences among species. This species-specific trait plays a large role in determining the metal loads that species will need to detoxify to persist in chronically contaminated environments and, therefore, contributes significantly to differences in environmental sensitivity among species. To develop a better understanding of how efflux varies within and among taxonomic groupings, we compared Cd and Zn efflux rate constants (ke values) among members of two species-rich aquatic insect families, Ephemerellidae and Hydropsychidae, and discovered that ke values strongly covaried across species. This relationship allowed us to successfully predict Zn efflux from Cd data gathered from aquatic species belonging to other insect orders and families. We then performed a broader, comparative analysis of Cd and Zn ke values from existing data for arthropods, mollusks, annelids, and chordates (77 species total) and found significant phylogenetic patterns. Taxonomic groups exhibited marked variability in ke magnitudes and ranges, suggesting that some groups are more constrained than others in their abilities to eliminate metals. Understanding broader patterns of variability can lead to more rational extrapolations across species and improved protectiveness in water-quality criteria and ecological assessment.

Divalent metal (Ca, Cd, Mn, Zn) uptake and interactions in the aquatic insect Hydropsyche sparna.

Despite their ecological importance and prevalent use as ecological indicators, the trace element physiology of aquatic insects remains poorly studied. Understanding divalent metal transport processes at the water-insect interface is important because these metals may be essential (e.g. Ca), essential and potentially toxic (e.g. Zn) or non-essential and toxic (e.g. Cd). We measured accumulation kinetics of Zn and Cd across dissolved concentrations ranging 4 orders of magnitude and examined interactions with Ca and Mn in the caddisfly Hydropsyche sparna. Here, we provide evidence for at least two transport systems for both Zn and Cd, the first of which operates at concentrations below 0.8 µmol l(-1) (and is fully saturable for Zn). We observed no signs of saturation of a second lower affinity transport system at concentrations up to 8.9 µmol l(-1) Cd and 15.3 µmol l(-1) Zn. In competition studies at 0.6 µmol l(-1) Zn and Cd, the presence of Cd slowed Zn accumulation by 35% while Cd was unaffected by Zn. At extreme concentrations (listed above), Cd accumulation was unaffected by the presence of Zn whereas Zn accumulation rates were reduced by 58%. Increasing Ca from 31.1 µmol l(-1) to 1.35 mmol l(-1) resulted in only modest decreases in Cd and Zn uptake. Mn decreased adsorption of Cd and Zn to the integument but not internalization. The L-type Ca(2+) channel blockers verapamil and nifedipine and the plasma membrane Ca(2+)-ATPase inhibitor carboxyeosin had no influence on Ca, Cd or Zn accumulation rates, while Ruthenium Red, a Ca(2+)-ATPase inhibitor, significantly decreased the accumulation of all three in a concentration-dependent manner.

Absolute quantification of free glutathione and cysteine in aquatic insects using isotope dilution and selected reaction monitoring.

A simple and robust isotope dilution mass spectrometry-based assay was developed for the determination of free cysteine and glutathione (GSH) in aquatic insects. Several experimental parameters were evaluated and optimized to provide specific and sensitive detection of both compounds by in situ derivatization with N-ethylmaleimide followed by acid alkylation quenching and reverse-phased liquid chromatography coupled with selected reaction monitoring. For both targets, the assay was evaluated over a concentration range of 0.313 to 320 µM and was demonstrated to have a quantitative dynamic range spanning nearly three orders of magnitude, with lower limits of quantification being 0.330 µM for GSH and 0.370 µM for cysteine. Additionally, measurements were observed to be highly reproducible over the course of several days. When applied to the analysis of four different species of insects, large biological variation between and within species was observed. Different feeding regimens were also tested within two species of insects but statistical comparisons revealed no significant difference in the levels of either compound.