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Industrial productivity is often judged solely by the primary product's marketability, while opportunities for secondary products derived from process by-products are often overlooked. In paper mills, large volumes of moisture-rich paper mill residuals (cellulose sludge) are produced, for which commercial use is currently difficult. Port Hawkesbury Paper LP, Port Hawkesbury, Nova Scotia, produces over 7 t/hr of waste sludge with a seasonally-dependent dryness ranging from 25 to 38% (w/w). Various chemical or mechanical dewatering options exist; however, knowledge of the unique sludge composition and properties is essential to predicting how the product will react under each method. Sonication, Fournier rotary press technology, freeze/thaw cycling, and gravity drying were among the dewatering opportunities briefly explored outside of the chosen method, acidification. Notably, many industries utilizing dewatering technologies may not be producing value-added by-products, while geographic and climatic placement may limit processes which are possible for others. In the present study examining enhanced end-use value, further dewatering occurred through a comparative in situ experiment contrasting sulfuric acid and ferric sulfate acidification (direct acid injection into sludge). While both proton donors acidified the sludge and decreased moisture content, sulfuric acid was the more cost-effective option, yielding an ∼4% increase in dryness, with commensurate economic and environmental benefits. [ABSTRACT FROM AUTHOR]

Abstract: A new thin film microextraction (TFME) configuration based on C18 thin film was optimized to improve solid phase microextraction (SPME) sensitivity and extraction kinetics for in vivo determinations of trace pharmaceuticals in fish tissue. Optimization of SPME involved increasing sampler surface area and volume of extraction phase to improve performance within in vitro applications such as agarose gel matrix and spiked fish tissue, as well as in vivo determinations of pharmaceuticals in fish exposed to municipal wastewater. Rainbow trout (Oncorhynchus mykiss) were exposed for 4d to effluents from a municipal wastewater plant that was treated under three different configurations of a pilot plant. Fathead minnow (Pimephales promelas) were caged for 14d upstream and downstream of municipal wastewater effluent discharges along Grand River at near Kitchener, ON. TFME and regular C18 fibers were inserted into the dorsal-epaxial muscle of rainbow trout and fathead minnow, respectively, for 30min sampling intervals. Sample extracts obtained from fibers were desorbed in methanol:water (3:2) for 90min under 1500rpm agitation and analyzed using liquid chromatography coupled with tandem mass spectrometry (LC/MS–MS) to determine pharmaceutical bioconcentration. Most target pharmaceuticals were detected in the wastewater with the exception of norfluoxetine and paroxetine. C18 TFME phase successfully quantified fluoxetine, venlafaxine, sertraline, paroxetine, and carbamazapine in muscle of living fish at concentrations ranging from 1.7 to 259ng/g. Reproducibility of the method in spiked fish muscle was 9–18% RSD with limits of detection and quantification ranging from 0.08 to 0.21ng/g and 0.09 to 0.64ng/g (respectively) for the analytes examined. Ibuprofen and gemfibrozil were not detected in fish tissues, likely due to rapid excretion leading to low rates of bioconcentration. This study demonstrates improved in vivo SPME sensitivity (recovery) and extraction rates during pre-equilibrium sampling of target pharmaceuticals in fish tissue due to the improved C18 extraction phase geometry. [Copyright &y& Elsevier]

The parallel in vivo measurement of chemicals at various locations in living tissues is an important approach furthering our understanding of biological uptake, transportation, and transformation dynamics. However, from a technical perspective, such measurements are difficult to perform with traditional in vivo sampling techniques, especially in freely moving organisms such as fish. These technical challenges can be well addressed by the proposed depth-profiling solid-phase microextraction (DP-SPME) technique, which utilizes a single soft, flexible fiber with high spatial resolution. The analytical accuracy and depth-profiling capability of DP-SPME was established in vitro within a multilayer gel system and an onion artificially contaminated with pharmaceuticals. In vivo efficacy was demonstrated by monitoring pharmaceutical distribution and accumulation in fish muscle tissue. The DP-SPME method was validated against pre-equilibrium SPME (using multiple small fibers), equilibrium SPME, and liquid extraction methods; results indicated DP-SPME significantly improved precision and data quality due to decreased intersample variation. No significant adverse effects or increases in mortality were observed in comparisons of fish sampled by DP-SPME relative to comparable fish not sampled by this method. Consequently, the simplicity, effectiveness, and improved precision of the technique suggest the potential for widespread application of DP-SPME in the sampling of heterogeneous biotic and abiotic systems. [ABSTRACT FROM AUTHOR]

Abstract: Sub-chronic exposure to municipal wastewater effluent (MWWE) in situ was recently shown to impact the acute response to a secondary stressor in rainbow trout (Oncorhynchus mykiss). However, little is known about whether MWWE exposure in itself is stressful to the animal. To address this, we carried out a laboratory study to examine the organismal and cellular stress responses and tissue-specific metabolic capacity in trout exposed to MWWE. Juvenile rainbow trout were exposed to 0, 20 and 90% MWWE (from a tertiary wastewater treatment plant), that was replenished every 2d, for 14d. Fish were sampled 2, 8 or 14d post-exposure. Plasma cortisol, glucose and lactate levels were measured as indicators of organismal stress response, while inducible heat shock protein 70 (hsp70), constitutive heat shock protein 70 (hsc70) and hsp90 expression in the liver were used as markers of cellular stress response. Impact of MWWE on cortisol signaling was ascertained by determining glucocorticoid receptor protein (GR) expression in the liver, brain and, heart, and metabolic capacity was evaluated by measuring liver glycogen content and tissue-specific activities of key enzymes in intermediary metabolism. Plasma glucose and lactate levels were unaffected by exposure to MWWEs, whereas cortisol showed a transient increase in the 20% group at 8d. Liver hsc70 and hsp90, but not hsp70 expression, were higher in the 90% MWWE group after 8d. There was a temporal change in GR expression in the liver and heart, but not brain of trout exposed to MWWE. Liver glycogen content and activities liver gluconeogenic enzyme phosphoenolpyruvate carboxykinase (PEPCK), and alanine aminotransferase (AlaAT) were significantly affected by MWWE exposure. The glycolytic enzymes pyruvate kinase (PK) and hexokinase (HK) activities were significantly higher temporally by MWWE exposure in the gill and heart, but not in the liver and brain. Overall, a 14d exposure to MWWE evokes a cellular stress response and perturbs the cortisol stress response in rainbow trout. The tissue-specific temporal changes in the metabolic capacity suggest enhanced energy demand in fish exposed to MWWE, which may eventually lead to reduced fitness. [Copyright &y& Elsevier]

The present study investigates possible uptake and bioconcentration of different classes of pharmaceuticals residues (organic contaminants) in fish bile using a simplified analytical methodology based on solid phase microextration (SPME). The use of solid phase microextraction (SPME), as a simple analytical tool, to screen for target pharmaceuticals in fish bile samples was validated in rainbow trout (Oncorhynchus mykiss) following short-term laboratory exposures to carbamazepine and fluoxetine. While fish bioconcentrated both fluoxetine and carbamazepine from exposure water, fluoxetine accumulated to a greater degree in bile than carbamazepine. Good agreement was obtained for both analytes in bile samples between SPME and traditional liquid (solvent) extraction approaches (R² > 0.99). The field application of SPME sampling was further demonstrated in fathead minnow (Pimephales promelas), a small-bodied fish caged upstream and downstream of a local wastewater treatment plant where fluoxetine, atorvastatin, and sertraline were detected in fish bile at the downstream location. SPME is a promising analytical tool for investigating the bioconcentration of trace contaminants in fish bile, facilitating detection of trace environmental contaminants otherwise undetectable due to low concentrations in the environment and biological tissues as well as the complexity of the sample matrices. [ABSTRACT FROM AUTHOR]

Abstract: Accumulation, fate and tissue distribution of environmental pharmaceuticals and personal-care products in exposed fish is an emerging area of research that has benefitted from recent advances in in vivo sampling, such as solid-phase microextraction (SPME). This review summarizes recent challenges and solutions associated with the application of in vivo SPME in freely moving fish, including questions of invasiveness, sequential sampling of individual fish, calibration methods, and interpretation of data and their ecotoxicological relevance. We also examine spatial and temporal resolution and associated technical parameters, such as sampling time and dimensions of the SPME probe. Relative to other in vivo sampling techniques, such as microdialysis, in vivo tissue collection or biosensors, SPME has distinct advantages in its simplicity and its ability to sample simultaneously various tissues and locations in a single fish in a relatively non-invasive, timely and cost-effective manner. Finally, we identify the challenges and the opportunities for in vivo monitoring of endogenous compounds by SPME, which could enable this approach to make a significant contribution to the burgeoning field of metabolomics. [Copyright &y& Elsevier]

Abstract: A variety of emerging chemicals of concern are released continuously to surface water through the municipal wastewater effluent discharges. The ability to rapidly determine bioaccumulation of these contaminants in exposed fish without sacrificing the animal (i.e. in vivo) would be of significant advantage to facilitate research, assessment and monitoring of their risk to the environment. In this study, an in vivo solid phase micro-extraction (SPME) approach was developed and applied to the measurement of a variety of emerging contaminants (carbamazepine, naproxen, diclofenac, gemfibrozil, bisphenol A, fluoxetine, ibuprofen and atrazine) in fish. Our results indicated in vivo SPME was a potential alternative extraction technique for quantitative determination of contaminants in lab exposures and as well after exposure to two municipal wastewater effluents (MWWE), with a major advantage over conventional techniques due to its ability to non-lethally sample tissues of living organisms. [Copyright &y& Elsevier]

Solid-phase microextraction (SPME) is a promising technique for determining organic contaminants within biotic systems. Existing in vivo SPME-kinetic calibration (SPME-KC) approaches are unwieldy due to the necessity of predetermining a distribution coefficient for the analyte of interest in the tissue and the preloading of a calibrating compound to the fiber. In this study, a rapid and convenient SPME alternative calibration method for in vivo analysis, termed SPME-sampling rate (SPME-SR) calibration, was developed and validated under both laboratory and field conditions to eliminate such presampling requirements. Briefly, the SPME probe is inserted into tissue, in this study fish dorsal-epaxial muscle, for 20 min allowing the concentrations of target analytes in the fish muscle to be determined by the extracted amount of analyte and the predetermined sampling rates. Atrazine, carbamazepine, and fluoxetine were detected nonlethally in the low ppb levels within fish muscle, with both laboratory and field-derived results obtained by in vivo SPME-KC comparable (within a factor of 1.27) to those obtained by lethal sampling followed by tissue liquid extraction. The technique described in this study represents an important advance which broadens the application of SPME in vivo sampling technology. [ABSTRACT FROM AUTHOR]

Solid-phase microextraction (SPME) coupled to liquid chromatography with electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) has been widely used to analyze biological fluids, tissues, and environmental matrixes for a variety of organic compounds including pharmaceuticals. However, effects of the sample matrix coextracted by SPME on tandem mass spectrometry analysis have not been systematically investigated. In this study, we characterized the complexity of matrix effects (ME) by analyzing SPME extracts of fish muscle and brain tissue, blood, and bile, as well as tap water, surface water, and the influent and effluent from a wastewater treatment plant. Significant enhancement or suppression of ionization (>15%) was observed with all biological and environmental samples. Intrasample ME variability was assessed through comparison of multiple samples from the same sample matrix, while intersample variability between different experimental subjects or varying sample treatment, storage, and sampling conditions were evaluated. To correct for ME, an isotopic internal standard (IIS) method was developed, with the strengths and limitations of the approach discussed. This study provides a framework for applying SPME within complex sample systems where the influences of ME are inevitable, thus ensuring more accurate quantitation of analytes during biological and environmental analysis. [ABSTRACT FROM AUTHOR]

Rate and equilibrium constants of weak noncovalent molecular interactions are extremely difficult to measure. Here, we introduced a homogeneous approach called equilibrium Pre-equilibrium solid-phase microextraction (PE-SPME) has attracted considerable research attention due to shorter sampling times and better temporal resolution than afforded by equilibrium SPME (E-SPME). However, the calibration of PE-SPME is often time-consuming and requires deuterated calibrants, which if available, are often expensive. To address these challenges, we propose a simple but versatile kinetic calibration method, in which nonisotopic (label-free) compounds of interest can supplant the use of deuterated analogues, and the need to determine partitioning coefficients inherent to earlier procedures has been eliminated. Using this approach, both free and total concentrations of analytes can be simultaneously measured within complex sample systems with high accuracy and precision. This calibration method was validated against established E-SPME and solid-phase extraction techniques through the measurement of selected pharmaceuticals in progressively complex matrixes including inorganic buffers, fish blood, and municipal wastewater effluents. This calibration approach may significantly improve time and cost-effectiveness, while improving the application of the SPME approach within highly dynamic systems. [ABSTRACT FROM AUTHOR]

To address the challenge of measuring real-time analyte concentrations within dynamic systems, the temporal resolution of the solid-phase microextraclion (SPME) approach has been investigated. A mass-uptake model for SPME within a dynamic system was developed and validated, with experimental factors affecting the temporal resolution (sampling time, agitation, SPME fiber dimensions, sample concentration and change rate, and instrument sensitivity) characterized. Calibration methods for time-resolved sampling in a dynamic system were compared. To demonstrate the efficacy of time-resolved SPME, this approach was successfully applied to investigate the binding kinetics between plasma proteins and pharmaceuticals, which verified a decrease in free pharmaceutical concentrations over time in the presence of bovine serum albumin. The current study provides the theoretical and logistical framework for applying SPME to the real-lime measurement of dynamic systems, facilitating future SPME applications such as in vivo metabolomic studies. [ABSTRACT FROM AUTHOR]

Abstract: On August 2, 2005, Air France Flight 358 descended on Lester B. Pearson International Airport (Toronto, ON, Canada) during adverse weather conditions and overran the runway, leading to an onboard fire which destroyed the aircraft. Large quantities (48000L) of aqueous film-forming foam (AFFF) were applied to the burning fuselage within meters of Etobicoke Creek. Local authorities could not confirm the identity of the AFFF formulation applied, but chemical analyses of fish livers collected 9 days post-AFFF application indicated that no perfluorinated acids (PFAs) were elevated at the site of application or downstream. This, and higher concentrations of a fluorotelomer sulfonate in fish liver collected downstream, suggests that an AFFF containing telomerized polyfluorinated material was likely used. However, as an urbanized stream within a heavily developed commercial, industrial, and residential watershed, background levels of perfluorinated compounds in Etobicoke Creek were considerable at all sites. Enlarged fish livers adjacent the AFFF-application site, commensurate with depressed peroxisomal β-oxidation and hepatic oxidative stress, demonstrate some short-term impact of the AFFF on exposed fish within 9 days of its release. Most fish biochemical responses had recovered to normal values by 120 days, although there was some indication that AFFF-associated contamination shifted further downstream over this interval. This study suggests contemporary AFFFs exert relatively low toxicity on fish communities under realistic exposure scenarios. [Copyright &y& Elsevier]

The space-resolved solid-phase microextraction (SR-SPME) technique was employed to study the tissue-specific bioconcentration of pharmaceuticals in live fish. The segmented design of the SPME fibers allowed for the simultaneous determination of pharmaceutical residues in fish dorsal-epaxial muscle and adipose tissue with a single SPME fiber. The miniaturized fiber endowed the technique with high spatial resolution allowing for quantification of analytes within adjacent, relatively small tissues of immature rainbow trout. The pre-equilibrium sampling and kinetic calibration approach yielded efficient and accurate quantitation of pharmaceuticals in fish tissue. The ability of the SPME method to repeatedly sample the same fish circumvents problems arising from interanimal variation, thus improving the precision of generated bioconcentration kinetic profiles. In vivo monitoring with SR-SPME was validated with in vitro liquid extraction of tissue samples using methanol. Of the nine compounds evaluated, five (atrazine, gemfibrozil, carbamazepine, ibuprofen, and fluoxetine) bioconcentrated in adipose and muscle tissue over the eight exposure days. Although the accumulation of analytes in both tissues was positively correlated, each compound partitioned with differing affinities as modified by their hydrophobicity and unique molecular structure. Water samples analyzed using the SPME technique yielded results similar to those determined by solid-phase extraction (SPE); however, SPME was more rapid and operationally much simpler. This study illustrates the application conditions for in situ SR-SPME while demonstrating the potential of these miniaturized SPME fibers for simultaneous in vivo repeated sampling of multiple tissues. [ABSTRACT FROM AUTHOR]

Previous field studies utilizing solid-phase microextraction (SPME) predominantly focused on volatile and semivolatile compounds in air or water. Earlier in vivo sampling studies utilizing SPME were limited to the liquid matrix (blood). The present study has expanded the SPME technique to semisolid tissues under laboratory and field conditions through the investigation of both theoretical and applied experimental approaches. Pre-equilibrium extraction and desorption were performed in vivo in two separate animals. Excellent linearity was found between the amounts extracted by SPME from the muscle of living fish and the waterborne concentrations of pharmaceuticals. A simple SPME method is also described to simultaneously determine free and total analyte concentrations in living tissue. The utility of in vivo SPME sampling was evaluated in wild fish collected from a number of different river locations undervarying degrees of influence from municipal wastewater effluents. Diphenhydramine and diltiazem were detected in the muscle of fish downstream of a local wastewater treatment plant Based on this study, SPME demonstrated several important advantages such as simplicity, sensitivity, and robustness under laboratory and in vivo field sampling conditions. [ABSTRACT FROM AUTHOR]

This study investigates the relationship between oxidative stress and reproductive dysfunction in wild white sucker (Catostomus commersoni) with short-term exposures to pulp-mill effluent. Hepatic oxidative damage, as quantified using 2-thiobarbituric acid-reactive substances UBARS). was often increased with effluent exposure within 4–8 d, but responses varied by species, sex, and effluent. Fatty acyl-coenzyme A (CoA) oxidase (FAO) and ethoxyresorufin O-deethylase (EROD) activities were also significantly induced between 4 and S d of exposure. There were marked species differences in oxidative stress, as TSARS, MO, and EROD responses in white sucker differed dramatically from those of longnose sucker (Catostonius catostomus) exposed under identical conditions. Exposure for 8 d to pulp-mill effluent delayed ovulation in white sucker, and these delays were independent of changes in circulating testosterone and 17α,20β-dihydroxy-4-pregnen-3-one titers. Evaluations of the effects of pulp mill effluent on in vivo plasma steroid levels and in vitro steroidogenic capacities were compromised due to caging stress. In vivo preexposure to pulp-mill effluent did not reduce in vitro ovarian follicle steroidogenic capacities when exposed to additional reactive oxygen species (ROS) generators. Endocrine and oxidative stress parameters may be interrelated, as the in vivo administration ferric nitrilotriacetate (Fe3+ NTA) significantly reduced circulating sex steroids. Administration a superactive GnRH analog containing a dopamine inhibitor significantly increased TBARS within 24 h. indicating endocrine status is capable of modifying oxidative stress responses. study provides new knowledge regarding the onset of oxidative stress and changes in reproductive endpoints in fish following pulp-mill effluent exposure. [ABSTRACT FROM AUTHOR]

This study investigates reproductive impairment and biochemical changes in fathead minnow (Pimephales promelas) exposed for 39 d to varying concentrations of perfluorooctanoic acid (PFOA) under microcosm conditions. While the concentrations tested in this study were much higher than those normally found in the environment, no mortality was associated with PFOA exposure. Only modest changes were observed in condition factor and in relative liver and gonad size. Significant declines in circulating plasma steroids were observed, but these were accompanied by only limited increases in time to first oviposition and decreases in overall egg production. Peroxisome proliferation, as quantified by fatty acyl-CoA oxidase (FAO) activity, was elevated with low PFOA concentrations but attenuated with exposure to higher PFOA doses. Little evidence was seen of differential induction of peroxisome-associated enzyme activity with sex. Oxidative stress, as quantified by the 2-thiobarbituric acid reactive substances (TBARS) assay, was only modestly influenced by PFOA exposure and is not a significant consequence of FAO activity in fathead minnow. Perfluorooctanoic acid appears to be relatively nontoxic at environmentally relevant concentrations but may impact biochemical and reproductive endpoints under conditions associated with environmental spills. [ABSTRACT FROM AUTHOR]

While recent evidence indicates that the generation of reactive oxygen species (ROS) and associated oxidative damage are frequently observed in fish populations with exposure to pulp and paper mill effluents, the potential for ROS generation from municipal sewage effluents has not been addressed. This study investigates the utility of measures of oxidative stress in delineating the effects of both pulp and paper mill and municipal sewage discharges. Longnose sucker (Catostomus catostomus) were collected below three pulp and paper mill and two municipal sewage effluent discharges over a 3-year period within the Wapiti and Athabasca River systems in northern Alberta. Biochemical responses in longnose sucker varied between the two rivers systems, with more pronounced changes occurring within the Wapiti River. Of the suite of biochemical parameters examined, fatty acyl-CoA oxidase (FAO) activity was the most sensitive indicator of pulp and paper mill exposure, but was only infrequently induced with exposure to municipal sewage effluent. Hepatic and gonadal 2-thiobarbituric acid reactive substances, lipid hydroperoxides, and hepatic free iron were less consistently elevated with exposure to pulp and paper mill effluent than FAO activity, and were also only infrequently altered with sewage effluent exposure. Hepatic ascorbic acid, liver somatic index, and condition factor were consistently altered with exposure to both sewage and pulp and paper mill effluents. While specific biochemical and organismal responses varied with effluents and time, the collective suite of oxidative stress endpoints proved to be useful tools in identifying relative influences of municipal sewage and pulp and paper mill effluent on fish populations in adjacent receiving waters. [Copyright &y& Elsevier]

Recent evidence indicates that contaminant-stimulated free radical production and resulting oxidative damage may be an important mechanism of toxicity in organisms exposed to water-borne contaminants. This study tested the hypothesis that increases in oxidative stress and associated biochemical alterations would be present in white sucker (Catostomus commersoni) living in an environment receiving pulp mill effluent. Consistent increases in liver TBARS and frequent increases in gonadal TBARS were observed immediately downstream of the pulp mill effluent discharge; observable effects were attenuated with distance until they were not significantly different from reference values. Increases detected with the TBARS assay were commensurate with increases detected using the lipid hydroperoxides assay, a mechanistically independent technique. Fish exposed to pulp mill effluent also exhibited significant increases in hepatic free iron and ascorbic acid and a reduced free radical scavenging capacity in the livers of fish downstream of the effluent discharge relative to reference fish. Increases in oxidative stress are not necessarily dependent on increases in lipid substrate or related to reductions in ascorbic acid. TBARS values similar to those observed in fish resident below pulp mill effluent discharges were observed in white sucker 2 h after intraperitoneal injection using 15 mg/kg body weight ferric nitrilotriacetate (Fe3+ NTA) as a positive control. This study indicates oxidative stress could be a mechanism of toxicity in fish exposed to pulp mill effluent and demonstrates the utility of TBARS in delineating zones of exposure to pulp mill effluent. [Copyright &y& Elsevier]

The accurate measurement of free analyte concentrations within complex sample matrixes by pre-equilibrium solid-phase microextraction (SPME) has proven challenging due to variations in mass uptake kinetics. For the first time, the effects of the sample binding matrix and tortuosity on the kinetics of analyte extraction (from the sample to the SPME fiber) are demonstrated to be quantitatively symmetrical with those of the desorption of preloaded deuterated standards (from the fiber to the sample matrix). Consequently, kinetic calibration methods can be employed to correct for variation in SPME sampling kinetics, facilitating the application of pre-equilibrium SPME within complex sample systems. This approach was applied ex vivo to measure pharmaceuticals in fish muscle tissues, with results consistent with those obtained from equilibrium SPME and micro dialysis. The developed method has the inherent advantages of being more accurate, precise, and reproducible, thus providing the framework for applications where rapid measurement of free analyte concentrations (within complicated sample matrixes such as biological tissues, sediment, and surface water) are required. [ABSTRACT FROM AUTHOR]

Large terrestrial consumers have direct and indirect effects on forest ecosystem function, but few studies have investigated the impacts of terrestrial consumers on freshwater ecosystems. In the Cape Breton Highlands of Nova Scotia, browsing by hyper‐abundant moose following a spruce budworm outbreak has transformed boreal forest into grasslands. We conducted a field study to investigate the potential for cross‐ecosystem effects of hyper‐abundant moose following budworm outbreak on small boreal stream ecosystem structure and function. With our field study, we tested the prediction that watersheds with higher levels of moose‐mediated grasslands in their sub‐basin would have higher stream temperatures, total nitrogen, electrical conductivity, periphyton biomass and macroinvertebrate abundances. While our data supported several of our predictions pertaining to moose impacts on the abiotic variables (i.e. temperature range, total nitrogen, electrical conductivity) we found evidence of variable moose impacts on the benthic community. Specifically, we observed lower relative abundance of predatory invertebrates in streams with high moose impacts compared to streams with low moose impacts in their watersheds but no evidence of moose impacts on the relative abundance of shredders, filterers, gatherers, and grazers. This empirical study fills a key gap in our understanding of spatial ecosystem ecology by providing insight into the effects of large terrestrial consumers across ecosystem boundaries with potential implications for landscape‐scale management of hyper‐abundant ungulates. Given the broad availability and improvement in remote sensing technology, the novel integration of remote sensing and field studies employed here may provide a roadmap for future studies of meta‐ecosystem dynamics. [ABSTRACT FROM AUTHOR]

This study investigates the temporal onset of reactive oxygen species (ROS) damage and changes in circulating sex steroids in immature rainbow trout exposed over 21 d to two pulp-mill effluents. Exposure to effluent from a bleached sulfite mill produced increases in 2-thiobarbituric acid reactive substances (TBARS), ethoxyresorufin O-deethylase (EROD) activity, hepatic free iron, and significant depressions in hepatic ascorbic acid. Impairments in pregnenolone production relative to cholesterol availability suggest an effect of sulfite-mill effluent early in the steroidogenic pathway. Induction of vitellogenin in immature fish exposed to effluent from this mill, relative to waterborne 17 β-estradiol treatments, indicated sulfite-mill effluent contained constituents capable of binding the estrogen receptor. Exposure to a kraft-mill effluent also elevated hepatic TBARS, tissue normalized fatty acyl-coenzyme A oxidase (FAO) activity, and hepatic free iron while producing commensurate declines in hepatic ascorbic acid. Plasma testosterone, 11-ketotestosterone, and 17 β-estradiol were elevated with kraft-mill effluent exposure, but no changes in vitellogenin induction were observed. In summary, effluent from bleached sulfite and bleached kraft mills yielded similar oxidative stress responses, but marked differences were observed in the endocrine-disrupting potential of each effluent. [ABSTRACT FROM AUTHOR]

This study investigated the effects of exposure to waterborne perfluorooctane sulfonate (PFOS) on oxidative stress and reproductive endpoints in fish. Exposures utilized species commonly used in toxicological testing, including the fathead minnow (Pimephales promelas) and rainbow trout (Oncorhynchus mykiss), as well as relatively insensitive taxa such as creek chub (Semotilus atromaculatus), spottail shiner (Notropis hudsonius), and white sucker (Catostomus commersoni). In all fish species, short-term (14-28 d) exposure to PFOS produced only modest mortality at concentrations consistent with environmental spill scenarios. However, PFOS consistently increased hepatic fatty acyl--CoA oxidase activity and increased oxidative damage, as quantified using the 2-thiobarbituric acid--reactive substances assay. Plasma testosterone, 11-ketotestosterone, and 17ß-estradiol titers were often elevated with PFOS exposure. Vitellogenin, the egg yolk precursor protein, was occasionally altered in the plasma with PFOS exposure, but responses varied with maturity. Oviposition frequency and egg deposition in fathead minnow were not significantly impaired with PFOS exposure, despite a trend toward progressive impairment with increasing exposure concentrations. Although short-term PFOS exposure produced significant impacts on biochemical and reproductive endpoints in fish at concentrations consistent with environmental spills, the impact of long-term exposure to environmentally relevant concentrations of PFOS is unclear. [ABSTRACT FROM AUTHOR]

[Display omitted] • Electrochemical techniques for uranium extraction from water were reviewed. • The strengths, limitations, applicability of each method were evaluated. • The fouling of membranes and electrodes is a main challenge. • Environmental and economic considerations are discussed. Electrochemical removal of uranium from water is an emerging topic that addresses the treatment of drinking water, remediation of contaminated sites, and mining from seawater. Electrochemical strategies compare favorably to conventional processes, such as adsorption and coagulation/flocculation, with advantages in speed and efficiency, materials regeneration, uranium recovery, and recycling. This review assesses all published work on electrochemical techniques for uranium extraction from water, including capacitive deionization (electrosorption), electrodeposition, electrodialysis, and electrocoagulation. This work compares these approaches with conventional techniques and discusses their applicability in different use cases. Environmental and economic considerations are discussed, as well as the current outlook and opportunities for engagement in this emerging field. [ABSTRACT FROM AUTHOR]

The use of solid-phase microextraction ( SPME) as a nonlethal technique for in vivo sampling of pharmaceutical residue in fish tissue has been documented in the literature. However, there is need to improve its simplicity and robustness for wider applications in the laboratory and field. The objective of this research is to develop and improve the SPME device for sampling of pharmaceuticals in fish tissue. The practical application of the new device was demonstrated in the field where some wild fish ( Esox masquinongy) were caught in the river and sampled by the device. The samples were analyzed using LC coupled with MS/ MS ( LC- MS/ MS). The new in vivo SPME device with a PDMS extraction phase (sorbent) was demonstrated to a robust tool by both experts and nonexpert of the method and it is simpler than the traditional device. The detection limit of the method in gel and fish tissue was 0.01-0.26 ng/g. The interday reproducibility in gel and fish homogenized fish tissue was 8-16% RSD. This study demonstrates that the new device will provide a platform or opportunity for rapid sampling of carbamazepine, diazepam, and nordiazepam in fish muscle with acceptable precision. [ABSTRACT FROM AUTHOR]

Abstract: The detection of trace levels of pharmaceuticals in environmental matrices requires an analyte pre-concentration procedure to obtain the required sensitivity for quantitative determination. This research aims to develop a simple automated analytical method based on C18 thin film solid phase microextraction (TF-SPME) for the simultaneous extraction of pharmaceutical compounds detected in surface waters. As a sample preparation method, solid phase microextraction, is a rapid, environmentally friendly, and a sensitive analytical technique which isolates and pre-concentrates trace organic pollutants from environmental water samples in a single step. High throughput analysis was achieved with the use of a robotic auto sampler which enabled parallel analyte extraction in a 96-well plate format. Application of the method was demonstrated using wastewater from pilot-scale municipal treatment plants and environmental water samples from wastewater-dominated reaches of the Grand River (adjacent Waterloo, ON) which were analysed using a liquid chromatography–mass spectrometry (LC–ESI–MS/MS) technique. The proposed method successfully determined concentrations of carbamazepine, fluoxetine, sertraline, and paroxetine in treated effluent at concentrations ranging from 240 to 3820ng/L with a method detection limit of 2–13ng/L with a relative standard deviation of less than 16%. Matrix effect was not observed with this method; therefore internal standards are not necessary for quantification of target compounds. The results suggest that this method is capable of detecting and quantifying many compounds present in both wastewater and wastewater-influenced surface water from multiple municipal sources. In this study, automated TF-SPME system is demonstrated as a simple and fast alternative method for high throughput analysis of pharmaceutical contaminants in environmental matrices. [Copyright &y& Elsevier]

Abstract: Highly entangled TiO2 nanowires were directly synthesized by hydrothermal growth on Ti substrates at 180°C utilizing various organic solvents to oxidize Ti. The growth mechanism, microstructure and phase transition of TiO2 nanowire membranes were investigated in detail. TiO2 nanowires, with diameters of 10–20nm and lengths up to 100μm, show a phase transition from Type-B to anatase by annealing at 700°C. Robust, free standing TiO2 nanowire membranes with millimeter level thickness can be cleaved from Ti substrates or directly prepared from thin Ti foils. These porous TiO2 membranes, while effective for mechanical microfiltration, can also photocatalytically degrade pharmaceuticals such as trimethoprim under UV irradiation. [Copyright &y& Elsevier]

Abstract: Large volumes of fluid tailings are generated during the extraction of bitumen from oil sands. As part of their reclamation plan, oil sands operators in Alberta propose to transfer these fluid tailings to end pit lakes and, over time, these are expected to develop lake habitats with productive capabilities comparable to natural lakes in the region. This study evaluates the potential impact of various oil sands process-affected waters (OSPW) on the reproduction of adult fathead minnow (Pimephales promelas) under laboratory conditions. Two separate assays with aged OPSW (>15 years) from the experimental ponds at Syncrude Canada Ltd. showed that water containing high concentrations of naphthenic acids (NAs; >25mg/l) and elevated conductivity (>2000μS/cm) completely inhibited spawning of fathead minnows and reduced male secondary sexual characteristics. Measurement of plasma sex steroid levels showed that male fathead minnows had lower concentrations of testosterone and 11-ketotestosterone whereas females had lower concentrations of 17β-estradiol. In a third assay, fathead minnows were first acclimated to the higher salinity conditions typical of OSPW for several weeks and then exposed to aged OSPW from Suncor Energy Inc. (NAs ∼40mg/l and conductivity ∼2000μS/cm). Spawning was significantly reduced in fathead minnows held in this effluent and male fathead minnows had lower concentrations of testosterone and 11-ketotestosterone. Collectively, these studies demonstrate that aged OSPW has the potential to negatively affect the reproductive physiology of fathead minnows and suggest that aquatic habitats with high NAs concentrations (>25mg/l) and conductivities (>2000μS/cm) would not be conducive for successful fish reproduction. [ABSTRACT FROM AUTHOR]

To facilitate rapid in situ analyte monitoring within heterogeneous samples, a space-resolved solid phase microextraction (SR-SPME) technique was developed that utilized miniaturized segmented fibers. Initially, a multi-layered agarose gel was used to determine the effects of diffusion-based mass transfer and fiber dimension on the space-resolving capability of SPME. For diazepam within agarose gel, the SR-SPME limit of detection was 2.5 ng/ ml, with a linear dynamic range up to 500 ng/mL The efficacy of the SR-SPME technique was further evaluated within diverse biological matrices (onion bulb, fish muscle, and adipose tissues) containing stratified pharmaceutical analytes. Empirically, the results agreed well with established techniques such as microdialysis and liquid extraction, but SR-SPME was simpler to implement, displayed higher spatial resolution, and was more cost-effective than traditional approaches. Additionally, the segmented design of the SPME fibers and stepwise desorption protocols offer potential advantages within high throughput applications. [ABSTRACT FROM AUTHOR]

[Display omitted] • Graphene quantum dots enhance the photocatalytic activity of black TiO 2 nanofibers. • Graphene quantum dots enhance charge carrier separation and photodegradation. • Increased surface adsorption has negligible contribution to photodegradation. • Superoxide radical anions are the main reactive oxygen species generated. The photocatalytic activity of black titanium dioxide nanofibers (bTiO 2 NFs) can be enhanced through composition with carbon nanomaterials. However, it is unclear whether enhanced charge separation or increased surface adsorption of organic pollutants to the nanocomposite surfaces is the dominant contributor. This knowledge gap was filled when we sought to enhance the surface contact of carbon with the bTiO 2 NFs by using graphene quantum dots (GQDs) hypothesizing that this would further enhance photocatalytic activity. The results showed a similar Rhodamine B (RhB) photodegradation rate between the optimal loadings of GQDs and RGO we reported previously. This allowed for further elucidation of the enhancement mechanism, where charge carrier separation enhancement at the photocatalyst surface is the dominant effect, whereas RhB adsorption does not make significant contribution. This significant insight enhances our understanding towards engineering highly efficient composite photocatalysts for organic pollutant removal in water. [ABSTRACT FROM AUTHOR]

Conventionally, both a working and counter electrode are housed in a single cell to form an electrochemical device for quantification of various analytes. For reductive sensing of hydrogen peroxide, however, analyte losses due to oxidation and catalytic decomposition on the counter electrode are significant, rendering such devices unsuitable for continuous monitoring of analyte concentration changes over time. Further, only chemically inert materials such as platinum can be used to construct the counter electrode, where their high cost limits potential applications. To circumvent such issues, an anion-exchange membrane was employed to fabricate a two-chamber device housing each electrode in each individual chamber, to physically prevent the counter electrode from interfering with working electrode analysis. Such a design enables the use of sacrificial anodes as the counter electrodes, thereby significantly expanding the linear range of detection, improving sensitivity, and reducing device cost. [ABSTRACT FROM AUTHOR]

Layered double hydroxide nanoparticles (LDH NPs) have attracted interest as an effective gene delivery vehicle in biomedicine. Recent advances in clinic trials have demonstrated the efficacy of Mg/Fe LDHs for hyperphosphatemia treatment, but their feasibility for gene delivery has not been systematically evaluated. As a starting point, we aimed to study the interaction between oligo-DNA and Mg/Fe LDH NPs. Our investigation revealed the chemisorption mechanism of DNA on Mg/Fe LDH surfaces, wherein the phosphate backbone of the DNA polymer coordinates with the metal cations of the LDH lattice via the ligand-exchange process. This mechanistic insight may facilitate future gene delivery applications using Mg/Fe LDH NPs. [ABSTRACT FROM AUTHOR]

A highly selective, ultrasensitive (visual and instrumental detection limits of 40 nM and 0.1 nM, respectively), environmentally-friendly, simple and rapid colorimetric sensor was developed for the detection of copper(ii) in water. This sensor is based on a novel signal-amplification mechanism involving reactive halide species (RHSs) including chlorides or bromides, which accelerate copper Fenton reactions oxidizing the chromogenic substrate to develop colour. The results of this study expand our understanding of copper-based Fenton chemistry. [ABSTRACT FROM AUTHOR]

A highly regenerative multifunctional nanobot system, using Fe3O4@SiO2@MgFe-LDH nanoparticles, is developed for efficient removal of waterborne azo dyes and pharmaceuticals. Efficient capture of pollutants, powerful Fenton degradation, and superior materials regeneration lead to a simple and cost-effective wastewater remediation solution. [ABSTRACT FROM AUTHOR]

The variability and extent of the intersex condition (oocytes in testes, or testis-ova) was documented in fish along an urban gradient in the Grand River, Ontario, Canada, that included major wastewater treatment plant outfalls. A method for rapid enumeration of testis-ova was developed and applied that increased the capacity to quantify intersex prevalence and severity. Male rainbow darters ( Etheostoma caeruleum) sampled downstream of the first major wastewater outfall (Waterloo) had a significant increase, relative to 4 upstream reference sites, in the mean proportion of fish with at least 1 testis-oocyte per lobe of testes (9-20% proportion with ≤ 1 testis-oocyte/lobe vs 32-53% and >1.4 testis-oocyte/lobe). A much higher mean incidence of intersex proportion and degree was observed immediately downstream of the second wastewater outfall (Kitchener; 73-100% and 8-70 testis-oocyte/lobe); but only 6.3 km downstream of the Kitchener outfall, the occurrence of intersex dropped to those of the reference sites. In contrast, downstream of a tertiary treated wastewater outfall on a small tributary, intersex was similar to reference sites. Estrogenicity, measured using a yeast estrogen screen, followed a similar pattern, increasing from 0.81 ± 0.02 ng/L 17b-estradiol equivalents (EEq) (Guelph), to 4.32 ± 0.07 ng/L (Waterloo), and 16.99 ± 0.40 ng/L (Kitchener). Female rainbow darter downstream of the Kitchener outfall showed significant decreases in gonadosomatic index and liver somatic index, and increases in condition factor (k) relative to corresponding reference sites. The prevalence of intersex and alterations in somatic indices suggest that exposure to municipal wastewater effluent discharges can impact endocrine function, energy use, and energy storage in wild fish. Environ Toxicol Chem. 2013;32:1981-1991. © 2013 SETAC [ABSTRACT FROM AUTHOR]

Abstract: Urine-derived human genomic DNA (gDNA) has wide application in a variety of disciplines including clinical medicine, sports, and forensic science. We describe a novel method for gDNA extraction from urine samples using carboxylated magnetic nanoparticles (CMNPs) as solid-phase adsorbents. Sedimentation associated with freezing of urine samples significantly reduces cell capture by CMNPs. However, the addition of 10mM EDTA and subsequent pH modification (pH 6.0–7.1) can re-dissolve urine sediments. Purified gDNA ranged from around 0.1kb to more than 23kb. PCR using specific primers targeting K-ras, GAPDH, CYP3A4 and GDF5 amplified 100% of varying sized gene fragments, verifying the high quality of the isolated DNA. Successful PCR amplifications using DNA isolated from urine samples as small as 50μl were demonstrated. Enrichment of urine cells and subsequent adsorption of DNA can be achieved with the same CMNPs, greatly simplifying extraction procedures. The CMNP gDNA extraction technique proved to be simple, rapid, sensitive and environmentally friendly, with application for routine laboratory use and potentially within automated urine extraction platforms. [Copyright &y& Elsevier]

Antidepressants are a widely prescribed group of pharmaceuticals that can be biotransformed in humans to biologically active metabolites. In the present study, the distribution of six antidepressants (venlafaxine, bupropion, fluoxetine, sertraline, citalopram, and paroxetine) and five of their metabolites was determined in a municipal wastewater treatment plant (WWTP) and at sites downstream of two WWTPs in the Grand River watershed in southern Ontario, Canada. Fathead minnows (Pimephales promelas) caged in the Grand River downstream of a WWTP were also evaluated for accumulated antidepressants. Finally, drinking water was analyzed from a treatment plant that takes its water from the Grand River 17 km downstream of a WWTP. In municipal wastewater, the antidepressant compounds present in the highest concentrations (i.e., >0.5 µg/L) were venlafaxine and its two demethylation products, O- and N-desmethyl venlafaxine. Removal rates of the target analytes in a WWTP were approximately 40%. These compounds persisted in river water samples collected at sites up to several kilometers downstream of discharges from WWTPs. Venlafaxine, citalopram, and sertraline, and demethylated metabolites were detected in fathead minnows caged 10 m below the discharge from a WWTP, but concentrations were all <7 µg/kg wet weight. Venlafaxine and bupropion were detected at very low (<0.005 µg/L) concentrations in untreated drinking water, but these compounds were not detected in treated drinking water. The present study illustrates that data are needed on the distribution in the aquatic environment of both the parent compound and the biologically active metabolites of pharmaceuticals. Environ. Toxicol. Chem. 2010;29:79–89. © 2009 SETAC [ABSTRACT FROM AUTHOR]

[Display omitted] • Black TiO 2 can utilize abundant visible–NIR for photocatalysis. • Reduced graphene oxide (RGO) enhances charge separation and photo-efficiency. • Black TiO 2 /RGO is kinetically superior for broad spectrum photocatalysis. • Superoxide radicals are the primary ROS in black TiO 2 /RGO catalysis. Black titanium dioxide (bTiO 2) is a new narrow bandgap photocatalyst that exploits the full solar spectrum with applications in sustainable environmental remediation and energy harvesting. Composition of bTiO 2 with 5 wt% of reduced graphene oxide (RGO) increases the Rhodamine B photodegradation rate by 3.2 and 12.2-fold relative to bTiO 2 alone and anatase, respectively, under simulated sunlight. Broad spectrum utilization and charge carrier separation enabled by bTiO 2 and RGO, respectively, resulted in rapid generation of superoxide radial anions that, though less energetic than hydroxyl radicals generated by UV-excited anatase, are sufficient for degrading all but the most recalcitrant contaminants. The kinetic advantages of RGO/bTiO 2 composites enable highly efficient removal of organic pollutants by exploiting the less energetic, but abundant, Vis-NIR spectrum. [ABSTRACT FROM AUTHOR]

Abstract: Carboxyl group-functionalized magnetic nanoparticles were used to develop an RNase-free method for plasmid DNA (pDNA) purification directly from RNA-containing crude Escherichia coli lysates. This method takes advantage of differing adsorption behaviors of pDNA and RNA onto magnetic nanoparticle surfaces at different temperatures. Pure pDNA can be isolated between 70 and 80°C without sacrificing DNA quality and quantity, as evidenced by comparison with that obtained using organic solvents or commercial kits. This RNase-free method is rapid, simple, cost-effective, and environmentally friendly, and it can be easily scaled up for the production of pharmacological-grade pDNA. [Copyright &y& Elsevier]

Abstract: A multifunctional magnetic nanoparticle (MNP)-assisted bioseparation method was developed to isolate plasmid DNA (pDNA) from Escherichia coli culture. Using the pH-sensitive carboxyl-modified magnetic nanoparticles, both cell capture and the subsequent removal of genomic DNA/protein complex after lysis can be achieved simply by magnetic separation. Furthermore, the yield and purity of pDNA extracted by MNPs are comparable to those obtained using organic solvents or commercial kits. This time- and cost-effective protocol does not require centrifugation or precipitation steps and has the potential for automated DNA extraction, especially within miniaturized lab chip applications. [Copyright &y& Elsevier]