Severe cyanobacterial blooms in an Australian lake; causes and factors controlling succession patterns.

Cyanobacterial blooms have major impacts on the ecological integrity and anthropogenic value of freshwater systems. Chrysosporum ovalisporum, a potentially toxic cyanobacteria has been rare in Australian waters until recently when is has bloomed in a number of lake and river systems. The aim of this study was to determine drivers of its growth and growing dominance. We performed regular monitoring of Mannus Lake, a small freshwater reservoir in South-Eastern Australia that has recently undergone extremely dense bloom events. Blooms of the diazotrophic Chrysosporum ovalisporum occurred in both summers of the 19 month study during periods of persistent thermal stratification. Following the C. ovalisporum blooms, non-diazotrophic taxa (Microcystis aeruginosa and Woronichinia sp.) dominated the phytoplankton community under less stratified conditions. Thermal stratification and nitrogen availability appeared to be the primary drivers of changes in cyanobacterial community structure. We propose that the observed transition from C. ovalisporum to M. aeruginosa and/or Woronichinia sp. may be a result of nitrogen limitation in early summer, which combined with persistent thermal stratification led to an ecological advantage for the nitrogen-fixing C. ovalisporum. Mixing events caused the senescence of the C. ovalisporum bloom, likely supplementing the nutrient budget of the lake with atmospherically derived N and alleviating N limitation to non-diazotrophic taxa. Non-diazotrophic cyanobacterial growth then increased, albeit at much lower biovolumes compared to the initial bloom. Overall, the results demonstrate the role of thermal stratification and nutrient cycling in structuring the cyanobacterial community and provide insights into the environmental factors driving the proliferation of the relatively new, potentially toxic cyanobacterium C. ovalisporum in Australian waters.

Controlling adsorption density of polymer-stabilised metal nanoparticles at the oil-water interface.

Emulsion droplets offer an alternative to solid supports as templates for the deposition of metallic nanoparticles. An emulsion interface provides the opportunity to exploit both sides of the nanoparticles and to utilise the liquid core as a microreactor in addition to forming a scaffold for encapsulation. However, despite the extensive literature studying a very broad range of factors influencing the characteristics of particle-stabilised (Pickering) emulsions, most reports focus on particles of diameters >100 nm and a very small proportions consider particles of diameters <10 nm. For catalytic purposes of course, the latter species are of utmost interest. Here, we report the synthesis of poly(vinyl pyrrolidone) (PVP) stabilised platinum nanoparticles, where the platinum core ranges between 3 and 5 nm in diameter and their subsequent use as emulsifiers for the oil-water interface where they form a densely packed layer. The nanoparticle density at the interface is quantified by both measuring the remaining concentration of nanoparticles in the aqueous phase after adsorption and also directly at the oil-water interface via cryo-TEM. The effect of electrolyte concentration and of addition of excess PVP in the bulk aqueous nanoparticle dispersion prior to emulsification on the resulting nanoparticle density at the oil-water interface is also determined.

Microplastics can alter phytoplankton community composition.

Microplastic pollution is a growing concern globally due to the risks they may pose to ecological communities. Phytoplankton are key ecological community in aquatic ecosystems providing both energy to food webs and have critical roles in ecosystem functions such as carbon cycling. To date studies on how microplastics effect phytoplankton have largely been limited to laboratory exposure studies using monocultures of algae. It remains unknown how the structure of phytoplankton communities will be influenced by growing microplastic pollution. The aim of this study was to determine how different concentrations microplastic fibers influence phytoplankton community structure. Two six-day microcosm studies were conducted testing the response of the phytoplankton community to low, medium, and high microplastics concentrations on the Georges River, Australia. The results showed the highest concentrations of microplastics significantly altered the structure phytoplankton community. These differences were largely driven by increased abundances of cyanobacteria taxa Aphanocapsa and Pseudanabaena, and to a lesser extent reduced abundances of taxa including Crucigenia and Chlamydmonas. There were no significant differences between controls and the low and medium treatments in either experiment. The high concentrations used in this experiment whilst likely rare in the environment are environmentally relevant and equivalent to some of more polluted ecosystems. The results highlight the potential risk to food webs and ecosystem functioning through altering the dynamics of primary production and provide evidence for further study examining the response of ecological communities to microplastics in the environment.

Storm events as key moments of microplastic contamination in aquatic ecosystems.

Microplastic (MP) pollution is an emerging issue in aquatic sciences. Rain and storm events are responsible for the mobilization and transport of a range of pollutants in aquatic systems, yet to date no study has examined how microplastic abundance changes in waterways during such events. The aim of this study was to determine how microplastic concentrations changed over the course of the storm event in an urban estuary. Sampling was conducted at high frequency before, during, and after a storm event that caused flooding in the Cooks River estuary, Australia. Microplastic abundance increased during two days of heavy rain from 400 particles m3 before storm event to up to 17,383 particles m3 after the event. Variation in microplastic abundance was positively related to five-day average antecedent rainfall. The results highlight the importance of rain and storm events as key moments of microplastic contamination in aquatic systems. The results have implications for considering the maximum number of microplastics that aquatic life may be exposed to and the importance of strategies to manage stormwater to minimize the input of microplastics to aquatic ecosystems.

Metal-shell nanocapsules for the delivery of cancer drugs.

Cytotoxic drugs tend to have substantial side effects on healthy tissues leading to systemic toxicity, limited tolerated doses and reduced drug efficacy. A prominent research area focuses on encapsulating cytotoxic drugs for targeted delivery to cancer tissues. However, existing carriers suffer from low drug loading levels and high drug leaching both when circulating systemically and when accumulating in non-target organs. These challenges mean that only few encapsulation technologies for delivery of cytotoxic drugs have been adopted for clinical use. Recently, we have demonstrated efficient manufacture of impermeable metal-shell/liquid core microcapsules that permit localised delivery by triggering release with ultrasound. This method has the potential to improve on existing methods for localised drug delivery because it:We demonstrate here the further miniaturization of both the emulsion droplet template and the thickness of the surrounding metal shell to the nanoscale in an attempt to take advantage of the EPR effect and the excretion of nanoparticles by the hepatobiliary system.

Ultrasound-triggered release from metal shell microcapsules.

Metal shell microcapsules have been shown to completely retain their core until its release is triggered, making them a promising candidate for use as a controllable drug delivery vehicle due to their superior retention properties as compared to polymer shell microcapsules. Focused ultrasound (FUS) has been successfully utilised to trigger release of lipophilic drugs from polymer microcapsules, and in this work the response of gold shell microcapsules with and without an inner polymeric shell, to FUS and standard ultrasound is explored. The results show that gold shell microcapsules with an inner polymer shell rupture when exposed to standard ultrasound and that there is a linear correlation between the gold shell thickness and the extent of shell rupture. When FUS is applied to these microcapsules, powers as low as 0.16 W delivered in bursts of 10 ms/s over a period of 120 s are sufficient to cause rupture of 53 nm gold shell microcapsules. Additional findings suggest that gold shell microcapsules without the polymer layer dispersed in a hydrogel matrix, as opposed to aqueous media, rupture more efficiently when exposed to FUS, and that thicker gold shells are more responsive to ultrasound-triggered rupture regardless of the external environment. Release of dye from all successfully ruptured capsules was sustained over a period of between 7 and 35 days. These findings suggest that emulsion-templated gold shell microcapsules embedded in a hydrogel matrix would be suitable for use as an implantable drug delivery vehicle with FUS used to externally trigger release.

Encapsulation of Emulsion Droplets with Metal Shells for Subsequent Remote, Triggered Release.

A two-step method to encapsulate an oil core with an impermeable shell has been developed. A thin metallic shell is deposited on the surface of emulsion droplets stabilized by metal nanoparticles. This thin shell is shown to prevent diffusion of the oil from within the core of the metal-shell microcapsules when placed in a continuous phase that fully dissolves the oil. The stabilizing nanoparticles are sterically stabilized by poly(vinyl pyrrolidone) chains and are here used as a catalyst/nucleation site at the oil-water interface to grow a secondary metal shell on the emulsion droplets via an electroless deposition process. This method provides the simplest scalable route yet to synthesize impermeable microcapsules with the added benefit that the final structure allows for drastically improving the overall volume of the encapsulated core to, in this case, >99% of the total volume. This method also allows for very good control over the microcapsule properties, and here we demonstrate our ability to tailor the final microcapsule density, capsule diameter, and secondary metal film thickness. Importantly, we also demonstrate that such impermeable microcapsule metal shells can be remotely fractured using ultrasound-based devices that are commensurate with technologies currently used in medical applications, which demonstrate the possibility to adapt these microcapsules for the delivery of cytotoxic drugs.

Microplastic pollution in estuaries across a gradient of human impact.

Microplastic (MP) pollution is an emerging issue in aquatic sciences. Little comparative information currently exists about the problem in coastal systems exposed to different levels of human impact. Here we report a year-long study on the abundance of MP in the water column of three estuaries on the east-coast of Australia. The estuaries are subject to different scales of human impact; the Clyde estuary has little human modification, the Bega estuary has a small township and single wastewater treatment works discharging to its waters, and the Hunter estuary which has multiple townships, multiple wastewater treatment plants, and heavy industry. MP abundance followed an expected pattern with the lowest abundance in the low-impact Clyde estuary (98 part. m3), moderate levels of MP in the moderately impacted Bega estuary (246 part. m3), and high MP abundance in the highly impacted Hunter estuary (1032 part. m3). The majority of particles were <200 µm and fragment-like rather than fiber-like. MP abundance was positively related to maximum antecedent rainfall in the Bega estuary, however there are no clear environmental factors that could explain MP variation in the other systems. MP were generally higher in summer and following freshwater inflow events. On the Hunter estuary MP abundance was at times as high as zooplankton abundance, and within the range of numbers reported in other highly impacted systems globally. The results confirm that higher levels of human impact lead to greater plastic pollution and highlight the need to examine aquatic ecosystems under a range of conditions in order to adequately characterize the extent of MP pollution in rivers and coastal systems.

Adsorption of Catalytic Nanoparticles onto Polymer Substrates for Controlled Deposition of Microcapsule Metal Shells.

Efficient encapsulation of small chemical molecules and their controlled targeted delivery provides a very important challenge to be overcome for a wide range of industrial applications. Typically rapid diffusion of these actives across capsule walls has so far prevented the development of a versatile widely applicable solution. In an earlier publication, we have shown that thin metal shells are able to permanently retain small molecules. The critical step in the microcapsule synthesis is the formation of a strongly adsorbed, dense monolayer of catalytic nanoparticles on the surface as this affects the secondary metal film quality. Control over Pt-nanoparticle adsorption density and a clear understanding of Pt-nanoparticle adsorption kinetics is therefore paramount. Maximising the density of heterogeneous catalysts on surfaces is generally of interest to a broad range of applications. In this work, transmission electron microscopy (TEM) and quartz crystal microbalance (QCM) are used to demonstrate that the concentration of nanoparticle polymer stabilizer used during particle synthesis and nanoparticle suspension concentration can be used to control nanoparticle surface adsorption density. We demonstrate that excess polymer, which is often used in nanoparticle synthesis but rarely discussed as an important parameter in the literature, can compete with and thus drastically affect the adsorption of the Pt-nanoparticles.

A two-step synthesis for preparing metal microcapsules with a biodegradable polymer substrate.

Metal microcapsules have recently received attention and are being developed as improved carrier materials when compared to polymer microcapsules. In this work we have developed a novel, simplified method by which polymeric microcapsules can be synthesised using a combination of poly(vinyl pyrrolidone)-stabilised platinum nanoparticles (PVP-Pt) and poly(vinyl pyrrolidone) (PVP) as stabilisers, to allow for a secondary metal shell to be grown. We investigate the relationship between the molar ratio of reducing agent to platinum salt and the size of the resulting NPs and seek to develop further fundamental understanding of the factors governing the secondary metal shell thickness and quality, to allow production of cost-effective metal microcapsules without sacrificing core retention efficiency. We found that the size of the nanoparticles had no significant effect on secondary shell thickness, but did affect the quality of the resulting gold shells. Gold salt concentration was found to be a limiting factor in the electroless deposition of the metal shell. In this work, we have successfully produced PLGA microcapsules with more cost-effective gold shells, as thin as 56 ± 13 nm and capable of complete core retention of volatile actives.

Understanding the Mechanisms of Gold Shell Growth onto Polymer Microcapsules to Control Shell Thickness.

Polymer microcapsules have been used commercially for decades, however they have an inherent flaw which renders them impractical as a carrier of small, volatile molecules. The porous nature of the polymer shell allows for diffusion of the encapsulated molecules into the bulk. The use of metal shells is an innovative way to prevent undesired loss of small molecules from the core of microcapsules, however it is important, particularly when using expensive metals to ensure that the resulting shell is as thin as possible. Here we investigate the fundamental mechanisms controlling the gold shell thickness when a fragrance oil is encapsulated in a poly(methyl methacrylate) shell. We consider the distribution of the nanoparticles on the capsule surface, and from quantification of the adsorbed nanoparticle (NP) density and resulting shell thickness, we propose mechanisms to describe the gold shell growth for systems with high and low NP surface coverage. We suggest from our observations that the gold grows to fill in the gaps between NPs. At low NP concentrations, thicker metal shells form. We postulate that this is due to the low NP density on the surface, forcing the gold clusters to grow larger before they meet the adjacent ones. Thus, to grow the thinnest possible shells a densely packed monolayer of platinum nanoparticles is required on the capsule surface.

The effect of surfactant chain length on the morphology of poly(methyl methacrylate) microcapsules for fragrance oil encapsulation.

The solvent evaporation method for producing microcapsules relies upon the correct wetting conditions between the three phases involved in the synthesis to allow core-shell morphologies to form. By measuring the interfacial tensions between the oil, polymer and aqueous phases, spreading coefficients can be calculated, allowing the capsule morphology to be predicted. In this work we explore the effect of surfactant chain length on capsule morphology using poly(methyl methacrylate) as the polymer and hexadecane as the core. We compared the predicted morphologies obtained using the polymer as a solid, and the polymer dissolved in dichloromethane to represent the point at which capsule formation begins. We found that using the polymer in its final, solid form gave predictions which were more consistent with our observations. The method was applied to successfully predict the capsule morphologies obtained when commercial fragrance oils were encapsulated.

Long-Term Retention of Small, Volatile Molecular Species within Metallic Microcapsules.

Encapsulation and full retention of small molecular weight active ingredients is a challenging task that remains unsolved by current technologies used in industry and academia. In particular, certain everyday product formulations provide difficult environments in which preventing active leakage through capsule walls is not feasible. For example, a continuous phase that can fully dissolve an encapsulated active will typically force full release over a fraction of the intended lifetime of a product. This is due to the inherent porosity of polymeric membranes typically used as capsule wall material in current technologies. In this study, we demonstrate a method for preventing undesired loss of encapsulated actives under these extreme conditions using a simple threestep process. Our developed methodology, which forms an impermeable metal film around polymer microcapsules, prevents loss of small, volatile oils within an ethanol continuous phase for at least 21 days while polymeric capsules lose their entire content in less than 30 min under the same conditions. Polymer shell-oil core microcapsules are produced using a well-known cosolvent extraction method to precipitate a polymeric shell around the oil core. Subsequently, metallic catalytic nanoparticles are physically adsorbed onto the microcapsule polymeric shells. Finally, this nanoparticle coating is used to catalyze the growth of a secondary metallic film. Specifically, this work shows that it is possible to coat polymeric microcapsules containing a model oil system or a typical fragrance oil with a continuous metal shell. It also shows that the coverage of nanoparticles on the capsule surface can be controlled, which is paramount for obtaining a continuous impermeable metal film. In addition, control over the metal shell thickness is demonstrated without altering the capability of the metal film to retain the encapsulated oils.

Comparison of hamstring and quadriceps femoris electromyographic activity between men and women during a single-limb squat on both a stable and labile surface.

The purpose of this study was to determine if women are quadriceps dominant and men are hamstring dominant during the performance of a partial single-leg squat (SLS) on both a stable and labile ground surface against body weight resistance. Thirty healthy participants (15 men and 15 women) performed an SLS on both a stable surface and a 6.4-cm-thick vinyl pad. Surface electromyographic (EMG) recordings were obtained from the quadriceps femoris and hamstring muscles during the extension phase of the SLS. Statistical analysis revealed that women produced 14% more EMG activity (p = 0.04) in their quadriceps than the men during the SLS on a stable surface, whereas the men generated 18% more EMG activity (p = 0.04) in their hamstrings than the women during the SLS on a labile surface. Additionally, we found a statistically significant sex effect (p = 0.048) for the hamstring/quadriceps (H/Q) EMG ratio, which was 2.25 and 0.62, respectively, for men and women on the stable surface and 2.52 and 0.71, respectively, on the labile surface. We concluded that women are quadriceps dominant and men are hamstring dominant during the performance of SLS against body weight resistance on either a stable or labile surface condition. During an SLS, men showed an H/Q ratio approximately 3.5 times larger than their female counterparts, suggesting that men activate their hamstrings more effectively than women during an SLS. According to our data, the SLS may not be an ideal exercise for activating the hamstring muscles in women without additional neuromuscular training techniques, because women are quadriceps dominant during the SLS.

Field efficacy of deltamethrin for rodent flea control in San Bernardino County, California, USA.

A study was conducted to determine the initial and residual activity of deltamethrin (0.05% dust) applied to rodent burrows (at approximately 14 g/burrow) against fleas in the Silverwood Lake area of San Bernardino County. In initial toxicity (2-d post-treatment), deltamethrin provided 97% flea control and in residual toxicity it resulted in 68% control of the rodent fleas at 15-d post-treatment. The flea fauna consisted of Oropsylla montana (89.9%) and Hoplopsylls anomalus (10.1%). All rodents captured in this study were California ground squirrels, Spermophilus beecheyi. In mark-release-recapture trials, using the microchip identification implant method at the treatment site, the recapture rate of rodents was 29% from 2- to 58-d post-treatment, declining to 21% after 98 d. In the tail-clip method at the treatment site, the recapture rate of 40% at 15-d post-treatment rose to 87% and 73% at 56- and 58-d post-treatment, respectively. At the control site, the recapture rate of 100% at 15-d post-post-treatment dropped to 20% after 98 d. In another trial at Camp Cedar Crest in the Running Springs area, deltamethrin applied to rodent burrows resulted in 70% control of fleas infesting S. beecheyi. Based on the two trials, deltamethrin showed a good initial control of rodent fleas in enzootic or epizootic plague control.