Spatio-temporal bioaccumulation and trophic transfer of ionizable pharmaceuticals in a semi-arid urban river influenced by snowmelt.

Bioaccumulation of pharmaceuticals in aquatic organisms is increasingly reported in the peer-reviewed literature. However, seasonal instream dynamics including occurrence and bioaccumulation across trophic positions are rarely studied, particularly in semiarid streams with flows influenced by seasonal snowmelt and municipal effluent discharges. Thus, we selected East Canyon Creek in Park City, Utah, USA to examine spatio-temporal bioaccumulation of select ionizable pharmaceuticals across trophic positions using trophic magnification factors calculated at incremental distances (0.15, 1.4, 13 miles) downstream from a municipal effluent discharge during spring (May), Summer (August), and fall (October). Nine target analytes were detected in all species during all sampling events. Trophic dilution was consistently observed for amitriptyline, caffeine, diphenhydramine, diltiazem, fluoxetine, and sertraline, regardless of seasonal instream flows or distance from effluent discharge. Calculated TMFs ranged from 0.01-0.71 with negative slopes observed for all regressions of chemical residue in tissue and trophic position. We further presents the first empirical investigation of normalizing pharmaceutical concentrations to lipid, phospholipid or protein fractions using pair matched fish samples. Empirical results identify that normalization of ionizable pharmaceutical residues in aquatic tissues to neutral lipids, polar lipids, or the total protein fraction is inappropriate, though bioaccumulation studies examining influences of internal partitioning (e.g., plasma proteins) are needed.

N-P Fertilization Stimulates Anaerobic Selenium Reduction in an End-Pit Lake.

Selenium (Se), an essential micro nutrient, is toxic to aquatic life at slightly higher water concentrations. Watersheds receiving leachate from selenium rich sources require large-scale, long-term treatment to mitigate Se toxicity. We applied the principles of anaerobic bacterial bioreactors, previously successful in small scale Se mitigation, to a whole end-pit lake ecosystem. Fertilization of the lake with N and P increased primary production, creating a meromictic, anoxic layer, and enhanced the habitat for locally present, anaerobic, Se and sulfur reducing bacteria. Within two years, Se concentrations were reduced ten-fold, reaching water-quality guideline values. The successful experiment demonstrated a novel treatment of large volumes of Se-contaminated water, and introduced an inexpensive method to mitigate a persistent aquatic pollutant of global concern.

Oil sands process-affected water impairs feeding by Daphnia magna.

Growth in extraction of bitumen from oil sands has raised concerns about influences of this industry on surrounding environments. Water clearance rate (a surrogate of feeding rate by Daphnia magna) in water containing D. magna exposed to oil sands process-affected water (OSPW) and its principal components, dissolved component (DC) and suspended particulate matter (SPM), was reduced to 72, 29, and 59% of controls, respectively. This study also examined several possible mechanisms for the observed changes algal cell density (i.e., feeding rate). There was no change in the digestive enzymes trypsin or amylase when D. magna were exposed to DC or SPM; however, exposure to total OSPW reduced trypsin activity. Mandible rolling or post-abdominal rejections, which are indicators of feeding and palatability of food, were not affected by any exposures to OSPW. Beating of thoracic limbs, which provides water flow toward the feeding groove, was reduced by exposure to SPM or total OSPW. Peristaltic activity was reduced by exposure to DC, which then might result in reduced digestion time in D. magna exposed to DC, SPM or whole OSPW. All treatments caused an increase in numbers of intact algae cells in the hindgut and excreted material. These results suggest that both DC and SPM affect feeding of D. magna by impairing actions of the digestive system, but most probably not by reducing rates of ingestion.

Chemical, Physical, and Biological Factors Shape Littoral Invertebrate Community Structure in Coal-Mining End-Pit Lakes.

Aquatic invertebrates form the base of the consumer food web in lakes. In coal-mining end-pit lakes, invertebrates are exposed to an environment with potentially challenging physical and chemical features. We hypothesized that the physical and chemical features of end-pit lakes reduce critical littoral habitat and thus reduce invertebrate diversity, thereby limiting the potential for these lakes to be naturalized. We used a multivariate approach using principle component analysis and redundancy analysis to study relationships between invertebrate community structure, habitat features, and water quality in five end-pit lakes and five natural lakes in the Rocky Mountain foothills of west-central Alberta, Canada. Results show a significantly different invertebrate community structure was present in end-pit lakes as compared with reference lakes in the same region, which could be accounted for by water hardness, conductivity, slope of the littoral zone, and phosphorus concentrations. Habitat diversity in end-pit lakes was also limited, cover provided by macrophytes was scarce, and basin slopes were significantly steeper in pit lakes. Although water chemistry is currently the strongest influencing factor on the invertebrate community, physical challenges of habitat homogeneity and steep slopes in the littoral zones were identified as major drivers of invertebrate community structure. The addition of floating wetlands to the littoral zone of existing pit lakes can add habitat complexity without the need for large-scale alterations to basing morphology, while impermeable capping of waste-rock and the inclusion of littoral habitat in the planning process of new pit lakes can improve the success of integrating new pit lakes into the landscape.

Bioaccumulation of human pharmaceuticals in fish across habitats of a tidally influenced urban bayou.

Though pharmaceuticals and other contaminants of emerging concern are increasingly observed in inland water bodies, the occurrence and bioaccumulation of pharmaceuticals in estuaries and coastal ecosystems are poorly understood. In the present study, bioaccumulation of select pharmaceuticals and other contaminants of emerging concern was examined in fish from Buffalo Bayou, a tidally influenced urban ecosystem that receives effluent from a major (∼200 million gallons per day) municipal wastewater treatment plant in Houston, Texas, USA. Using isotope dilution liquid chromatography-tandem mass spectrometry, various target analytes were observed in effluent, surface water, and multiple fish species. The trophic position of each species was determined using stable isotope analysis. Fish tissue levels of diphenhydramine, which represented the only pharmaceutical detected in all fish species, did not significantly differ between freshwater and marine fish predominantly inhabiting benthic habitats; however, saltwater fish with pelagic habitat preferences significantly accumulated diphenhydramine to the highest levels observed in the present study. Consistent with previous observations from an effluent-dependent freshwater river, diphenhydramine did not display trophic magnification, which suggests site-specific, pH-influenced inhalational uptake to a greater extent than dietary exposure in this tidally influenced urban ecosystem. The findings highlight the importance of understanding differential bioaccumulation and risks of ionizable contaminants of emerging concern in habitats of urbanizing coastal systems.

Surface coal mining influences on macroinvertebrate assemblages in streams of the Canadian Rocky Mountains.

To determine the region-specific impacts of surface coal mines on macroinvertebrate community health, chemical and physical stream characteristics and macroinvertebrate family and community metrics were measured in surface coal mine-affected and reference streams in the Canadian Rocky Mountains. Water chemistry was significantly altered in mine-affected streams, which had elevated conductivity, alkalinity, and selenium and ion concentrations compared with reference conditions. Multivariate redundancy analysis (RDA) indicated alterations in macroinvertebrate communities downstream of mine sites. In RDA ordination, Ephemeroptera family densities, family richness, Ephemeroptera, Plecoptera, Trichoptera (EPT) richness, and % Ephemeroptera declined, whereas densities of Capniidae stoneflies increased along environmental gradients defined by variables associated with mine influence including waterborne Se concentration, alkalinity, substrate embeddedness, and interstitial material size. Shifts in macroinvertebrate assemblages may have been the result of multiple region-specific stressors related to mining influences including selenium toxicity, ionic toxicity, or stream substrate modifications.

Bioaccumulation and trophic dilution of human pharmaceuticals across trophic positions of an effluent-dependent wadeable stream.

Though pharmaceuticals are increasingly observed in a variety of organisms from coastal and inland aquatic systems, trophic transfer of pharmaceuticals in aquatic food webs have not been reported. In this study, bioaccumulation of select pharmaceuticals was investigated in a lower order effluent-dependent stream in central Texas, USA, using isotope dilution liquid chromatography-tandem mass spectrometry (MS). A fish plasma model, initially developed from laboratory studies, was tested to examine observed versus predicted internal dose of select pharmaceuticals. Pharmaceuticals accumulated to higher concentrations in invertebrates relative to fish; elevated concentrations of the antidepressant sertraline and its primary metabolite desmethylsertraline were observed in the Asian clam, Corbicula fluminea, and two unionid mussel species. Trophic positions were determined from stable isotopes (δ(15)N and δ(13)C) collected by isotope ratio-MS; a Bayesian mixing model was then used to estimate diet contributions towards top fish predators. Because diphenhydramine and carbamazepine were the only target compounds detected in all species examined, trophic magnification factors (TMFs) were derived to evaluate potential trophic transfer of both compounds. TMFs for diphenhydramine (0.38) and carbamazepine (1.17) indicated neither compound experienced trophic magnification, which suggests that inhalational and not dietary exposure represented the primary route of uptake by fish in this effluent-dependent stream.

Development and evaluation of a regression-based model to predict cesium concentration ratios for freshwater fish.

Data from published studies and World Wide Web sources were combined to produce and test a regression model to predict Cs concentration ratios for freshwater fish species. The accuracies of predicted concentration ratios, which were computed using 1) species trophic levels obtained from random resampling of known food items and 2) K concentrations in the water for 207 fish from 44 species and 43 locations, were tested against independent observations of ratios for 57 fish from 17 species from 25 locations. Accuracy was assessed as the percent of observed to predicted ratios within factors of 2 or 3. Conservatism, expressed as the lack of under prediction, was assessed as the percent of observed to predicted ratios that were less than 2 or less than 3. The model's median observed to predicted ratio was 1.26, which was not significantly different from 1, and 50% of the ratios were between 0.73 and 1.85. The percentages of ratios within factors of 2 or 3 were 67 and 82%, respectively. The percentages of ratios that were <2 or <3 were 79 and 88%, respectively. An example for Perca fluviatilis demonstrated that increased prediction accuracy could be obtained when more detailed knowledge of diet was available to estimate trophic level.

Aquatic and terrestrial organic matter in the diet of stream consumers: implications for mercury bioaccumulation.

The relative contribution of aquatic vs. terrestrial organic matter to the diet of consumers in fluvial environments and its effects on bioaccumulation of contaminants such as mercury (Hg) remain poorly understood. We used stable isotopes of carbon and nitrogen in a gradient approach (consumer isotope ratio vs. periphyton isotope ratio) across temperate streams that range in their pH to assess consumer reliance on aquatic (periphyton) vs. terrestrial (riparian vegetation) organic matter, and whether Hg concentrations in fish and their prey were related to these energy sources. Taxa varied in their use of the two sources, with grazing mayflies (Heptageniidae), predatory stoneflies (Perlidae), one species of water strider (Metrobates hesperius), and the fish blacknose dace (Rhinichthys atratulus) showing strong connections to aquatic sources, while Aquarius remigis water striders and brook trout (Salvelinus fontinalis) showed a weak link to in-stream production. The aquatic food source for consumers, periphyton, had higher Hg concentrations in low-pH waters, and pH was a much better predictor of Hg in predatory invertebrates that relied mainly on this food source vs. those that used terrestrial C. These findings suggest that stream biota relying mainly on dietary inputs from the riparian zone will be partially insulated from the effects of water chemistry on Hg availability. This has implications for the development of a whole-system understanding of nutrient and material cycling in streams, the choice of taxa in contaminant monitoring studies, and in understanding the fate of Hg in stream food webs.

Estimating terrestrial contribution to stream invertebrates and periphyton using a gradient-based mixing model for delta13C.

1. This paper outlines a gradient-based model that can be used for isotopic signature source partitioning, even if source signatures are not distinct, as long as their spatial gradients differ. A model of this type is applied to the partitioning of autochthonous vs. allochthonous contribution to stream invertebrate delta(13)C signatures, which has often been confounded by overlap in source signatures. 2. delta(13)C signatures of inorganic carbon and most autochthonous production exhibit pronounced gradients along rivers, being depleted relative to terrestrial signatures in upstream reaches, and enriched downstream. Terrestrial detritus, by contrast, exhibits no gradient. Thus terrestrial food consumption reduces downstream signature slopes in proportion to the amount of terrestrial food consumed. 3. The gradient-based mixing model produces estimates of the proportion of terrestrial consumption (p(T)) from signature slopes of consumers; p(T) estimates for invertebrate primary consumers were: herbivore/grazers (0.15) 1, indicating selective assimilation of the autochthonous component from the biofilms.

Estimating the scale of fish feeding movements in rivers using delta(13)C signature gradients.

1. Isotopic signatures of consumers provide a time integration of their feeding history, and as a result of movements, are often out of line with signatures of their local resources. Such disequilibrium can be useful for inferring the spatial scale of consumer movement. 2. delta(13)C signatures of dissolved inorganic carbon as well as periphyton and invertebrates, exhibit pronounced gradients along rivers. We outline an analytical framework to estimate the spatial scale of movement of riverine fish by comparing the slopes of their delta(13)C signature gradients to that of the stream invertebrates they consume. For free-ranging juvenile Atlantic salmon (Salmo salar L.), unconstrained by barriers, delta(13)C signatures departed considerably from invertebrate signatures, and along-stream slopes were as little as half those recorded for stream invertebrates. Movement estimates for these fish, based on their signature slopes, are approximately 20 km. 3. By contrast, stream resident salmonids (whose movements are constrained by physical barriers) and sedentary taxa such as sculpins and sticklebacks, have carbon signatures much closer to invertebrate signatures where they were collected. For these groups, our method yields negligible estimates of movement, similar to those of invertebrates. 4. Although this method cannot provide precise estimates of how much individual organisms move, or reveal details of movement history, it may provide an effective complement to telemetric and other methods of studying movement.

Does life-history variability in salmonids affect habitat use by juveniles? A comparison among streams open and closed to anadromy.

1. Migratory and resident forms of salmonids coexist in many river systems. Although such coexistence is widespread, little is known about its ecological basis and no studies have compared the habitat use of premigratory juveniles and residents. 2. We employed a comparative approach to explore the differential habitat use of juvenile anadromous and resident brook trout. This required the investigation of habitat use in streams closed to anadromy, containing only resident brook trout Salvelinus fontinalis ('resident-only' streams) and streams open to anadromy, containing coexisting Atlantic salmon Salmo salar and anadromous and resident brook trout ('migrant-resident' streams). 3. We demonstrate that fast habitats (riffles) are occupied more frequently in streams with migratory brook trout relative to riffle habitats of streams with only resident brook trout. In contrast, occupation of slow current velocities (pools) was observed in both migrant-resident and resident-only streams as both stream types contain resident brook trout. The net effect is a wider distribution of occupied habitats (pool and riffles) in migrant-resident streams relative to resident-only streams, resulting in few, if any, unused habitats. 4. These results are consistent with previously reported bioenergetic, morphological and stable isotope differences observed between anadromous and resident brook trout. 5. Our findings suggest that a link exists between juvenile habitat use, metabolic costs and life-history strategies.

Patterns of Food Chain Length in Lakes: A Stable Isotope Study.

Food web structure is paramount in regulating a variety of ecologic patterns and processes, although food web studies are limited by poor empirical descriptions of inherently complex systems. In this study, stable isotope ratios (δ15N and δ13C) were used to quantify trophic relationships and food chain length (measured as a continuous variable) in 14 Ontario and Quebec lakes. All lakes contained lake trout as the top predator, although lakes differed in the presumed number of trophic levels leading to this species. The presumed number of trophic levels was correlated with food chain length and explained 40% of the among-lake variation. Food chain length was most closely related to fish species richness ([Formula: see text]) and lake area ([Formula: see text]). However, the two largest study lakes had shorter food chains than lakes of intermediate size and species richness, producing hump-shaped relationships with food chain length. Lake productivity was not a powerful predictor of food chain length ([Formula: see text]), and we argue that productive space (productivity multiplied by area) is a more accurate measure of available energy. This study addresses the need for improved food web descriptions that incorporate information about energy flow and the relative importance of trophic pathways.