Current water quality guidelines across North America and Europe do not protect lakes from salinization.

Human-induced salinization caused by the use of road deicing salts, agricultural practices, mining operations, and climate change is a major threat to the biodiversity and functioning of freshwater ecosystems. Yet, it is unclear if freshwater ecosystems are protected from salinization by current water quality guidelines. Leveraging an experimental network of land-based and in-lake mesocosms across North America and Europe, we tested how salinization-indicated as elevated chloride (Cl-) concentration-will affect lake food webs and if two of the lowest Cl- thresholds found globally are sufficient to protect these food webs. Our results indicated that salinization will cause substantial zooplankton mortality at the lowest Cl- thresholds established in Canada (120 mg Cl-/L) and the United States (230 mg Cl-/L) and throughout Europe where Cl- thresholds are generally higher. For instance, at 73% of our study sites, Cl- concentrations that caused a ≥50% reduction in cladoceran abundance were at or below Cl- thresholds in Canada, in the United States, and throughout Europe. Similar trends occurred for copepod and rotifer zooplankton. The loss of zooplankton triggered a cascading effect causing an increase in phytoplankton biomass at 47% of study sites. Such changes in lake food webs could alter nutrient cycling and water clarity and trigger declines in fish production. Current Cl- thresholds across North America and Europe clearly do not adequately protect lake food webs. Water quality guidelines should be developed where they do not exist, and there is an urgent need to reassess existing guidelines to protect lake ecosystems from human-induced salinization.

Changes in water quality related to permafrost thaw may significantly impact zooplankton in small Arctic lakes.

Rising temperatures are leading to permafrost thaw over vast areas of the northern hemisphere. In the Canadian Arctic, permafrost degradation is causing significant changes in surface water quality due to the release of solutes that can alter conductivity, water clarity, and nutrient levels. For this study, we examined how changes in water quality associated with permafrost thaw might impact zooplankton, a group of organisms that play an important role in the food web of Arctic lakes. We conducted a biological and water quality survey of 37 lakes in the Mackenzie Delta region of Canada's Northwest Territories. We then used this data set to develop models linking variation in the abundance, diversity, and evenness of zooplankton communities to physicochemical, biological, and spatial variables. Subsequently, we used these models to predict how zooplankton communities might respond as water quality is altered by permafrost thaw. Our models explained 47%, 68%, and 69% of the variation in zooplankton abundance, diversity, and evenness, respectively. Importantly, the most parsimonious models always included variables affected by permafrost thaw, such as calcium and conductivity. Predictions based on our models suggest significant increases in zooplankton abundance (1.6-3.6 fold) and decreases in diversity (1.2-1.7 fold) and evenness (1.1-1.4 fold) in response to water quality changes associated with permafrost thaw. These changes are in line with those described for significant perturbations such as eutrophication, acidification, and the introduction of exotic species such as the spiny water flea (Bythotrephes). Given their important role in aquatic food webs, we expect these changes in zooplankton communities will have ramifications for organisms at higher (fish) and lower (phytoplankton) trophic positions in Arctic lakes.

Surface Charge Influence on the Phase Separation and Viscosity of Cellulose Nanocrystals.

A series of four cellulose nanocrystal (CNC) suspensions were prepared from bleached softwood kraft pulp using different conditions of sulfuric acid hydrolysis. The CNCs were identical in size (95 nm in length × 5 nm in width) but had different surface charges corresponding to the harshness of the hydrolysis conditions. Consequently, it was possible to isolate the effects of surface charge on the self-assembly and viscosity of the CNC suspensions across surface charges ranging from 0.27%S to 0.89%S. The four suspensions (never-dried, free of added electrolyte) all underwent liquid crystalline phase separation, but the concentration onset for the emergence of the chiral nematic phase shifted to higher values with increasing surface charge. Similarly, suspension viscosity was also influenced by surface charge, with suspensions of lower surface charge CNCs more viscous and tending to gel at lower concentrations. The properties of the suspensions were interpreted in terms of the increase in effective diameter of the nanocrystals due to the surface electrostatic repulsion of the negative sulfate half-esters, as modified by the screening effects of the H+ counterions in the suspensions. The results suggest that there is a threshold surface charge density (∼0.3%S) above which effective volume considerations are dominant across the concentration range relevant to liquid crystalline phase formation. Above this threshold value, phase separation occurs at the same effective volume fraction of CNCs (∼10 vol %), with a corresponding increase in critical concentration due to the decrease in effective diameter that occurs with increasing surface charge. Below or near this threshold value, the formation of end-to-end aggregates may favor gelation and interfere with ordered phase formation.

Order and gelation of cellulose nanocrystal suspensions: an overview of some issues.

Cellulose nanocrystals (CNCs) are polydisperse rod-shaped particles of crystalline cellulose I, typically prepared by sulfuric acid hydrolysis of natural cellulose fibres to give aqueous colloidal suspensions stabilized by sulfate half-ester groups. Sufficiently dilute suspensions are isotropic fluids, but as the concentration of CNC in water is increased, a critical concentration is reached where a spontaneously ordered phase is observed. The (equilibrium) phase separation of the ordered chiral nematic phase is in competition with a tendency of the CNC suspension to form a gel. Qualitatively, factors that reduce the stability of the CNC suspension favour the onset of gelation. The chiral nematic structure is preserved, at least partially, when the suspension dries. Solid chiral nematic films of cellulose are of interest for their optical and templating properties, but the preparation of the films requires improvement. The processes that govern the formation of solid chiral nematic films from CNC suspensions include phase separation, gelation and also the effects of shear on CNC orientation during evaporation. Some insight into these processes is provided by polarized light microscopy, which indicates that the relaxation of shear-induced orientation to give a chiral nematic structure may occur via an intermediate twist-bend state.This article is part of a discussion meeting issue 'New horizons for cellulose nanotechnology'.

Formation of chiral nematic films from cellulose nanocrystal suspensions is a two-stage process.

The evaporation of aqueous suspensions of cellulose nanocrystals (CNCs) gives iridescent chiral nematic films with reflection colors at visible wavelengths. A key problem is controlling the chiral nematic pitch, P, and hence the reflection colors of CNC films. By adding D-(+)-glucose to the suspension, we show that the change in P during evaporation occurs in two distinct stages. The first stage is the decrease in P as the concentration of CNC in the chiral nematic suspension increases due to evaporation; the addition of glucose causes a decrease in P at this stage. In a second stage, a concentration of CNC is reached where the formation of ordered gels and glasses prevents further major changes in P. The addition of glucose lowers the CNC concentration at which this occurs, leading to an increase in P and hence an overall shift to the red end of the spectrum in the final film.

A(3)-Coupling catalyzed by robust Au nanoparticles covalently bonded to HS-functionalized cellulose nanocrystalline films.

We decorated HS-functionalized cellulose nanocrystallite (CNC) films with monodisperse Au nanoparticles (AuNPs) to form a novel nanocomposite catalyst AuNPs@HS-CNC. The uniform, fine AuNPs were made by the reduction of HAuCl4 solution with thiol (HS-) group-functionalized CNC films. The AuNPs@HS-CNC nanocomposites were examined by X-ray photoelectron spectroscopy (XPS), TEM, ATR-IR and solid-state NMR. Characterizations suggested that the size of the AuNPs was about 2-3 nm and they were evenly distributed onto the surface of CNC films. Furthermore, the unique nanocomposite Au@HS-CNC catalyst displayed high catalytic efficiency in promoting three-component coupling of an aldehyde, an alkyne, and an amine (A(3)-coupling) either in water or without solvent. Most importantly, the catalyst could be used repetitively more than 11 times without significant deactivation. Our strategy also promotes the use of naturally renewable cellulose to prepare reusable nanocomposite catalysts for organic synthesis.

Does dispersal limitation impact the recovery of zooplankton communities damaged by a regional stressor?

The acidification and ongoing pH recovery of lakes in Killarney Provincial Park, Canada, provide a unique opportunity to increase our understanding of the role of dispersal as communities respond to environmental change. Time lags in community recovery following pH increases in acidified lakes have typically been attributed to local factors; however, no studies have been conducted to determine if colonist availability could also play a role. Moreover, the rates and mechanisms of dispersal to recovering lakes are poorly understood. In this study, we sought to determine if dispersal limitation could impede the recovery of zooplankton communities affected by a regional stressor. To achieve this objective, we used a combination of empirical data collection along with spatial modeling and variation partitioning techniques. Data were collected by measuring dispersal to four recovering lakes in Killarney Park. Dispersal traps were placed next to lakes to measure immigration overland, drift nets were used to measure immigration via streams, and in situ emergence traps were used to quantify immigration from historically deposited resting eggs. Documented dispersal levels were then compared with the theoretical critical density required for reproduction (N(c)) to determine if adequate numbers were dispersing to establish populations of acid-sensitive species in recovering lakes. Spatial modeling and variation partitioning were conducted using community and physical/chemical data for 45 park lakes that were collected in 1972-1973, 1990, and 2005. Field data demonstrated that a variety of zooplankton species were dispersing to recovering lakes through streams and the egg bank, but few individuals were collected dispersing overland. Although we identified 24 species of zooplankton dispersing, only six species absent from the communities of our study lakes were identified from our traps, and two of these species did not disperse in high enough numbers to surpass N(c). Local environmental variables explained the largest proportion of the variation in zooplankton communities (18-37%); however, spatial variables were also important (7-18%). The significant spatial patterns we found in the park's zooplankton communities, combined with the low overland dispersal levels we documented, suggest that dispersal limitation may be a more important impediment to recovery than was previously thought.

The interplay between environmental conditions and allee effects during the recovery of stressed zooplankton communities.

Many important ecological phenomena depend on the success or failure of small introduced populations. Several factors are thought to influence the fate of small populations, including resource and habitat availability, dispersal levels, interspecific interactions, mate limitation, and demographic stochasticity. Recent field studies suggest that Allee effects resulting from mate limitation can prevent the reestablishment of sexual zooplankton species following a disturbance. In this study, we explore the interplay between Allee effects and local environmental conditions in determining the population growth and establishment of two acid-sensitive zooplankton species that have been impacted by regional anthropogenic acidification. We conducted a factorial design field experiment to test the impact of pH and initial organism densities on the per capita population growth (r) of the sexual copepod Epischura lacustris and the seasonally parthenogenetic cladoceran Daphnia mendotae. In addition, we conducted computer simulations using r values obtained from our experiments to determine the probability of extinction for small populations of acid-sensitive colonists that are in the process of colonizing recovering lakes. The results of our field experiment demonstrated that local environmental conditions can moderate the impacts of Allee effects for E. lacustris: Populations introduced at low densities had a significantly lower r at pH 6 than at pH 7. In contrast, r did not differ between pH 6 and 7 environments when E. lacustris populations were introduced at high densities. D. mendotae was affected by pH levels, but not by initial organism densities. Results from our population growth simulations indicated that E. lacustris populations introduced at low densities to pH 6 conditions had a higher probability of extinction than those introduced at low densities to a pH 7 environment. Our study indicates that environmental conditions and mate limitation can interact to determine the fate of small populations of sexually reproducing zooplankton species. If a more rapid recovery of acid-damaged zooplankton communities is desired, augmentation of dispersal levels may be needed during the early phases of pH recovery in order to increase the probability of establishment for mate-limited zooplankton species.

Bactericidal paper impregnated with silver nanoparticles for point-of-use water treatment.

There is an urgent need for cheap point-of-use methods to purify drinking water. We describe a method to deactivate pathogenic bacteria by percolation through a paper sheet containing silver nanoparticles. The silver nanoparticles are deposited by the in situ reduction of silver nitrate on the cellulose fibers of an absorbent blotting paper sheet. The aim is to achieve inactivation of bacteria during percolation through the sheet, rather than removal of bacteria from the effluent by filtration. The silver-nanoparticle containing (AgNP) papers were tested for performance in the laboratory with respect to bacteria inactivation and silver leaching as suspensions of bacteria percolated through the paper. The AgNP sheets exhibited antibacterial properties toward suspensions of Escherichia coli and Enterococcus faecalis, with log reduction values in the effluent of over log 6 and log 3, respectively. The silver loss from the AgNP sheets was minimal, with values under 0.1 ppm (the current US EPA and WHO limit for silver in drinking water). These results show promise that percolation of bacterially contaminated water through paper embedded with silver nanoparticles could be an effective emergency water treatment.

Nanocelluloses: a new family of nature-based materials.

Cellulose fibrils with widths in the nanometer range are nature-based materials with unique and potentially useful features. Most importantly, these novel nanocelluloses open up the strongly expanding fields of sustainable materials and nanocomposites, as well as medical and life-science devices, to the natural polymer cellulose. The nanodimensions of the structural elements result in a high surface area and hence the powerful interaction of these celluloses with surrounding species, such as water, organic and polymeric compounds, nanoparticles, and living cells. This Review assembles the current knowledge on the isolation of microfibrillated cellulose from wood and its application in nanocomposites; the preparation of nanocrystalline cellulose and its use as a reinforcing agent; and the biofabrication of bacterial nanocellulose, as well as its evaluation as a biomaterial for medical implants.

Once Upon A Time In Visualization: Understanding the Use of Textual Narratives for Causality.

Causality visualization can help people understand temporal chains of events, such as messages sent in a distributed system, cause and effect in a historical conflict, or the interplay between political actors over time. However, as the scale and complexity of these event sequences grows, even these visualizations can become overwhelming to use. In this paper, we propose the use of textual narratives as a data-driven storytelling method to augment causality visualization. We first propose a design space for how textual narratives can be used to describe causal data. We then present results from a crowdsourced user study where participants were asked to recover causality information from two causality visualizations-causal graphs and Hasse diagrams-with and without an associated textual narrative. Finally, we describe Causeworks, a causality visualization system for understanding how specific interventions influence a causal model. The system incorporates an automatic textual narrative mechanism based on our design space. We validate Causeworks through interviews with experts who used the system for understanding complex events.

Protein alignment using cellulose nanocrystals: practical considerations and range of application.

Cellulose nanocrystals (CNCs) form liquid crystals in aqueous solution that confer alignment to macromolecules and permit the measurement of residual dipolar couplings. CNCs possess many attractive features as an alignment medium. They are inexpensive, non-toxic, chemically inert, and robust to denaturants and temperature. Despite these advantages, CNCs are seldom employed as an alignment medium and the range of their applicability has not yet been explored. We have re-examined the use of CNCs in biomolecular NMR by analyzing the effects concentration, ionic strength, and temperature on molecular alignment. Stable alignment was obtained over wide ranges of temperature (10-70 degrees C) and pH (2.5-8.0), which makes CNCs potentially very useful in studies of thermophilic proteins and acid-stabilized molecules. Notably, we find that CNC suspensions are very sensitive to the concentrations of biological buffers, which must be taken into account when they are used in NMR analyses. These results have led us to develop a general procedure for preparing aligned samples with CNCs. Using the SH3 domain from the Fyn tyrosine kinase as a model system, we find that CNCs produce an alignment frame collinear with that of the commonly used Pf1 bacteriophage alignment medium, but of opposite magnitude.

Surface grafting of cellulose nanocrystals with poly(ethylene oxide) in aqueous media.

Aqueous suspensions of poly(ethylene oxide)-grafted nanocrystalline cellulose (PEO-grafted NCC) were prepared in order to achieve steric instead of electrostatic stabilization. A two-step process was employed: in the first step NCC suspensions prepared by sulfuric acid hydrolysis were desulfated with sodium hydroxide, and in the second step the surfaces of the crystals were functionalized with epoxy-terminated poly(ethylene oxide) (PEO epoxide) under alkaline conditions. The PEO-grafted samples were analyzed by conductometric titration, ATR-IR, solid-state NMR, MALDI-TOF MS, SEC MALLS, and AFM. The covalent nature of the linkage was confirmed by weight increase and MALDI-TOF analysis. The PEO-grafted cellulose nanocrystals (CNCs) formed a stable colloidal suspension that remained well dispersed, while the desulfated nanoparticles aggregated and precipitated. Upon concentration of the PEO-grafted aqueous NCC suspension, a chiral nematic phase was observed.

Direct surface force measurements of polyelectrolyte multilayer films containing nanocrystalline cellulose.

Polyelectrolyte multilayer films containing nanocrystalline cellulose (NCC) and poly(allylamine hydrochloride) (PAH) make up a new class of nanostructured composite with applications ranging from coatings to biomedical devices. Moreover, these materials are amenable to surface force studies using colloid-probe atomic force microscopy (CP-AFM). For electrostatically assembled films with either NCC or PAH as the outermost layer, surface morphology was investigated by AFM and wettability was examined by contact angle measurements. By varying the surrounding ionic strength and pH, the relative contributions from electrostatic, van der Waals, steric, and polymer bridging interactions were evaluated. The ionic cross-linking in these films rendered them stable under all solution conditions studied although swelling at low pH and high ionic strength was inferred. The underlying polymer layer in the multilayered film was found to dictate the dominant surface forces when polymer migration and chain extension were facilitated. The precontact normal forces between a silica probe and an NCC-capped multilayer film were monotonically repulsive at pH values where the material surfaces were similarly and fully charged. In contrast, at pH 3.5, the anionic surfaces were weakly charged but the underlying layer of cationic PAH was fully charged and attractive forces dominated due to polymer bridging from extended PAH chains. The interaction with an anionic carboxylic acid probe showed similar behavior to the silica probe; however, for a cationic amine probe with an anionic NCC-capped film, electrostatic double-layer attraction at low pH, and electrostatic double-layer repulsion at high pH, were observed. Finally, the effect of the capping layer was studied with an anionic probe, which indicated that NCC-capped films exhibited purely repulsive forces which were larger in magnitude than the combination of electrostatic double-layer attraction and steric repulsion, measured for PAH-capped films. Wherever possible, DLVO theory was used to fit the measured surface forces and apparent surface potentials and surface charge densities were calculated.

Cellulose nanocrystal research; A personal perspective.

This contribution to the special issue of Carbohydrate Polymers commemorating the 100th Anniversary of the Cellulose and Renewable Materials Division of the American Chemical Society is a personal account, from a research chemist's point of view, of some aspects of the discovery, development and utilization of nanocellulosic materials. The main focus is on cellulose nanocrystals stabilized by sulfate half-ester surface charges.

A database of chlorophyll and water chemistry in freshwater lakes.

Measures of chlorophyll represent the algal biomass in freshwater lakes that is often used by managers as a proxy for water quality and lake productivity. However, chlorophyll concentrations in lakes are dependent on many interacting factors, including nutrient inputs, mixing regime, lake depth, climate, and anthropogenic activities within the watershed. Therefore, integrating a broad scale dataset of lake physical, chemical, and biological characteristics can help elucidate the response of freshwater ecosystems to global change. We synthesized a database of measured chlorophyll a (chla) values, associated water chemistry variables, and lake morphometric characteristics for 11,959 freshwater lakes distributed across 72 countries. Data were collected based on a systematic review examining 3322 published manuscripts that measured lake chla, and we supplemented these data with online repositories such as The Knowledge Network for Biocomplexity, Dryad, and Pangaea. This publicly available database can be used to improve our understanding of how chlorophyll levels respond to global environmental change and provide baseline comparisons for environmental managers responsible for maintaining water quality in lakes.

Identifying the source of species invasions: sampling intensity vs. genetic diversity.

Population geneticists and community ecologists have long recognized the importance of sampling design for uncovering patterns of diversity within and among populations and in communities. Invasion ecologists increasingly have utilized phylogeographical patterns of mitochondrial or chloroplast DNA sequence variation to link introduced populations with putative source populations. However, many studies have ignored lessons from population genetics and community ecology and are vulnerable to sampling errors owing to insufficient field collections. A review of published invasion studies that utilized mitochondrial or chloroplast DNA markers reveals that insufficient sampling could strongly influence results and interpretations. Sixty per cent of studies sampled an average of less than six individuals per source population, vs. only 45% for introduced populations. Typically, far fewer introduced than source populations were surveyed, although they were sampled more intensively. Simulations based on published data forming a comprehensive mtDNA haplotype data set highlight and quantify the impact of the number of individuals surveyed per source population and number of putative source populations surveyed for accurate assignment of introduced individuals. Errors associated with sampling a low number of individuals are most acute when rare source haplotypes are dominant or fixed in the introduced population. Accuracy of assignment of introduced individuals is also directly related to the number of source populations surveyed and to the degree of genetic differentiation among them (F(ST)). Incorrect interpretations resulting from sampling errors can be avoided if sampling design is considered before field collections are made.

A meta-analysis of the impact of the two-layer method of preservation on human pancreatic islet transplantation.

There are conflicting reports about the effectiveness of perfluorocarbons used in the two-layer method (TLM) of pancreas preservation for human islet transplantation. The mechanism of action is unclear and the optimal role of this method uncertain. The study design was a meta-analysis of the evidence that TLM improves islet isolation outcomes. Pubmed, CENTRAL, EMBASE, Science Citation Index, and BIOSIS were searched electronically in January 2008. After selecting the relevant human trials for meta-analysis data relating to donor variables, study design, primary and secondary islet isolation outcomes were extracted. Electronic searches identified eight unique citations, describing 11 human studies that were eligible for the meta-analysis. When comparing TLM with preservation in University of Wisconsin (UW) solution, there was a statistically significant higher islet yield [WMD 711.55, 95% confidence interval (CI) 140.03-1283.07] in the TLM group. The proportion of transplantable preparations obtained was not significantly different (OR 1.30, 95% CI 0.89-1.88) between the two groups. The rate of successful islet isolations for marginal organs was higher in the TLM group (OR 6.69, 95% CI 1.80-24.87). Improved oxygenation and preservation of cellular bioengertics is thought to be the main underlying mechanism, although no single mechanism has yet been confirmed. There is currently no clear evidence that the TLM is beneficial in human islet transplantation. It may improve the preservation of marginal organs.

In Situ Preparation of Silver Nanoparticles in Paper by Reduction with Alkaline Glucose Solutions.

Percolation of contaminated water through paper sheets containing silver nanoparticles is a promising way to provide emergency drinking water. The silver nanoparticles are deposited by the in situ reduction of silver nitrate on the cellulose fibers of an absorbent blotting paper sheet. Sodium borohydride has been used as the reductant but is toxic and expensive. Glucose is a benign alternative but is much less reactive. In this note, we demonstrate an improved way to produce silver nanoparticles in paper sheets by adding sodium hydroxide to the glucose reductant. The silver content of the sheets, measured by diffuse reflectance spectroscopy, was around 2-3 mg of silver per gram of dry paper. This was sufficient to reduce the concentration of a model Escherichia coli suspension after percolation through the sheet.

Characterisation of collagen VI within the islet-exocrine interface of the human pancreas: implications for clinical islet isolation?

BACKGROUND: To optimize the methods used for human islet isolation for transplantation, it is important to improve our understanding of the structure of the islet-exocrine interface. In this study, the composition of collagen subtypes in the interface have been characterized and quantified in human pancreas. METHODS: Human adult pancreases were retrieved from older (mean age 55.7+/-3.0 yrs) and young donors (mean age 21.8+/-3.2 yrs). Tissue from the body of each pancreas was examined by quantitative immunohistochemistry. Collagen within the islet-exocrine interface was identified by immunolabeling for collagen I, IV, V or VI and islets identified either morphologically or by immunolabeling for insulin. Collagen subtypes were quantified and data expressed as collagen area at the interface relative to the islet area. Statistical analysis was by ANOVA or Mann Whitney U test. RESULTS: In older pancreases, collagen IV, V and VI were present throughout the islet-exocrine interface, whereas collagen I was more variable. The mean peri-islet collagen VI proportion was significantly greater than that of collagen I or IV. Mean islet area and the proportional collagen VI content in specimens from younger subjects were not significantly different to those in older subjects. CONCLUSIONS: Collagen VI is a major component of the islet-exocrine interface of the adult pancreas, the content being more than double that of collagen I or IV. However, the proportional collagen VI content was not dependent on the age of the donor. These data may facilitate the design of new collagenases, targeting major substrates such as collagen VI in order to improve clinical islet isolation.