Emissions rate measurement with flow modelling to optimize landfill gas collection from horizontal collectors.

A two-dimensional landfill gas flow model using the FEFLOW numerical code was developed to assess the potential improvement in landfill gas (LFG) collection and the reduction in greenhouse gas emissions at a landfill due to increases in the vacuum of horizontal collectors and/or installation of additional LFG collection infrastructure. A key calibration input parameter for the model, the fugitive methane emission rate from the study area, was measured using the airborne matter mapping method. The measurement showed that, at the time, the methane collection efficiency for the study area was approximately 37 %. The model indicated that increasing the vacuum of the existing collection system by 0.75 kPa could result in an improvement in collection efficiency from 37 % to 49 % within the selected study area. A similar increase of collection efficiency could be obtained by either doubling the number of horizontal collectors on a platform or installing a layer of permeable demolition waste on that level, without an increase in collection system vacuum. Combining the addition of collection infrastructure with an increase in collection system vacuum by 1 kPa was predicted to improve the collection efficiency for the study area to about 74 %.

Field Evaluations of Three Botanically Inspired Repellents Against the Blacklegged Tick, Ixodes scapularis (Acari: Ixodidae).

Three compounds synthetically-derived from botanicals sources, ethyl perillyl carbonate, geranyl isovalerate, and citronellyl cyclobutane carboxylate, were tested for repellent activity against Ixodes scapularis Say in a field trial. Tick drags were treated with the compounds or with N, N-diethyl-m-toluamide (DEET) at high (0.25 mg/cm2) or low (0.16 mg/cm2) concentrations. Negative controls included untreated drags and drags treated with acetone, the carrier for all repellents. Freshly treated drags (within 20 min) were used to collect I. scapularis ticks at a county park in Wisconsin. To assess effectiveness, we measured tick encounter rates, detachment rate, and time to detachment. None of the repellent treatments, including DEET, resulted in significantly fewer encounters compared to both control treatments. However, the percentage of ticks that detached within 3 min was significantly higher on drags treated with repellents compared to controls. DEET was the most effective, repelling 69.7-87% of ticks by 3 min, but the effectiveness of the three test compounds was still high, with 42-87% of ticks detaching by 3 min. For time to detachment, there were no significant differences between DEET and the three test compounds. We conclude that these synthetically-derived repellents were effective against I. scapularis in a field trial and could be viable alternatives to DEET.

Three molecules found in rosemary or nutmeg essential oils repel ticks (Dermacentor variabilis) more effectively than DEET in a no-human assay.

BACKGROUND: Development of new personal repellents to prevent tick bites is progressing to keep up with the increasing threat of tick-borne diseases in humans. However, the market share of natural, plant-based repellents is still quite small. We tested all of the major (>1%) components found in the essential oils of rosemary (Spanish variety) and nutmeg. These were tested with Dermacentor variabilis ticks, a robust tick capable of vectoring human diseases, in a no-human horizontal Petri dish assay. For comparison, we also tested the active ingredients currently recommended by the CDC and EPA as personal repellents for use against ticks. RESULTS: Of the 16 oil components tested, three performed significantly better than N,N-diethyl-meta-toluamide (DEET) in our assay. These compounds were myristicin and safrole found in the nutmeg oil, and terpinolene found in nutmeg oil and as a minor (<1%) constituent of rosemary oil. The current market natural product, 2-undecanone, also performed strongly in our assay. CONCLUSIONS: Our assay focused on comparing active ingredients as potential repellents and found that many natural products can elicit a strong response from ticks. Terpinolene is the most promising active ingredient identified, owing to human health concerns regarding myristicin and safrole. Our results from examining individual terpenoids from two essential oils suggest that there remain unexploited natural compounds that could be further developed for new personal tick repellents. © 2020 Society of Chemical Industry.

Menthol acts as a positive allosteric modulator on nematode levamisole sensitive nicotinic acetylcholine receptors.

The ongoing and widespread emergence of resistance to the existing anti-nematodal pharmacopeia has made it imperative to develop new anthelminthic agents. Historically, plants have been important sources of therapeutic compounds and offer an alternative to synthetic drugs. Monoterpenoids are phytochemicals that have been shown to produce acute toxic effects in insects and nematodes. Previous studies have shown nicotinic acetylcholine receptors (nAChRs) to be possible targets for naturally occurring plant metabolites such as carvacrol and carveol. In this study we examined the effects of monoterpenoid compounds on a levamisole sensitive nAChR from Oesophagostomum dentatum and a nicotine sensitive nAChR from Ascaris suum. We expressed the receptors in Xenopus laevis oocytes and used two-electrode voltage-clamp to characterize the effect of various compounds on these cys-loop receptors. At 100 µM the majority of these compounds acted as antagonists. Interestingly, further experiments revealed that both 0.1 µM and 10 µM menthol potentiated acetylcholine and levamisole responses in the levamisole sensitive receptor but not the nicotine sensitive receptor. We also investigated the effects of 0.1 µM menthol on the contractility of A. suum somatic muscle strips. Menthol produced significant potentiation of peak contractions at each concentration of acetylcholine. The positive allosteric modulatory effects of menthol in both in vivo and in vitro experiments suggests menthol as a promising candidate for combination therapy with cholinergic anthelmintics.

Analysis of the number of flux chamber samples and study area size on the accuracy of emission rate measurements.

Monte Carlo simulations were conducted on a set of flux chamber measurements at a landfill to estimate the relationship between the number of flux chamber samples and study area size on the emission rate measurement accuracy. The spatial variability of flux was addressed in the study by utilizing an existing flux chamber measurement data set that is one of the most dense flux chamber sampling arrays published to date for a landfill. At a probability of 95%, the Monte Carlo simulations indicated that achieving an accuracy within 10% with the flux chamber method is highly unlikely. An accuracy within 20% was achieved for small areas of less than about 0.2 hectares using 220 flux chamber measurements, but achieving this level of accuracy for area emission sources, of similar or greater variability, that are larger than this is highly unlikely. An accuracy within 30% was achieved up to the Full Area of about 0.4 hectares if more than approximately 120 samples were obtained. Even for an accuracy within 50%, at least 40 flux chamber measurements were needed for the Full Area of about 0.4 hectares. Available methods of estimating the number of samples required were compared to the Monte Carlo simulation results. The Monte Carlo simulations indicate that, in general, more samples are required than determined from an existing statistical method, which is a function of the mean and standard deviation of the population. Specifying the number of samples based on a regulatory method results in very poor accuracy. A modification to the statistical method for estimating the number of samples, or for estimating an accuracy for a given probability and number of samples, is proposed. IMPLICATIONS: The flux chamber method is the most widely used method of measuring fugitive emission rates from area sources. However, extrapolation of a set of individual flux chamber samples to a larger area results in area flux measurement values of unknown accuracy. Quantification of the accuracy of the extrapolation of a set of flux chamber measurements would be beneficial for understanding the confidence that can be placed on the measurement results. Guidance as to the appropriate number of flux chamber measurements to achieve a desired level of accuracy would benefit flux chamber method practitioners.

Dissipation of double-stranded RNA in aquatic microcosms.

Silencing genes of a pest with double-stranded RNA (dsRNA) is a promising new pest management technology. As part of the environmental risk assessment for dsRNA-based products, the environmental fate and the potential for adverse effects to on-target organisms should be characterized. In the present study, a nonbioactive dsRNA was spiked into the water column of a water and sediment microcosm to mimic drift from a spray application run off of unbound dsRNA or transport of plant tissues. Dissipation of dsRNA in the water column and partitioning into sediment was determined. The dsRNA rapidly dissipated in the water column and was below the limit of detection after 96 h. The levels detected in the sediment were not significant and may indicate rapid degradation in the water column prior to partitioning to sediment. Environ Toxicol Chem 2017;36:1249-1253. © 2016 SETAC.

Microwave Exfoliation of Graphite Oxides in H2S Plasma for the Synthesis of Sulfur-Doped Graphenes as Oxygen Reduction Catalysts.

Tuning the electronic and chemical properties of graphene can be carried out through heteroatomic doping, enabling its use as an electrocatalyst. Sulfur-doped graphene has been suggested to be a viable alternative to traditional Pt-based catalysts for oxygen reduction under alkaline conditions. Herein we present a fast and efficient route to synthesize S-doped graphenes through the microwave-assisted exfoliation and reduction of three different graphite oxides in the presence of hydrogen sulfide. The materials obtained were characterized using scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, combustion elemental analysis, and voltammetry. These S-doped graphenes were found to have good electrochemical performance and were active in the catalysis of the oxygen reduction reaction.

Graphene and its electrochemistry - an update.

The electrochemistry of graphene and its derivatives has been extensively researched in recent years. In the aspect of graphene preparation methods, the efficiencies of the top-down electrochemical exfoliation of graphite, the electrochemical reduction of graphene oxide and the electrochemical delamination of CVD grown graphene, are currently on par with conventional procedures. Electrochemical analysis of graphene oxide has revealed an unexpected inherent redox activity with, in some cases, an astonishing chemical reversibility. Furthermore, graphene modified with p-block elements has shown impressive electrocatalytic performances in processes which have been historically dominated by metal-based catalysts. Further progress has also been achieved in the practical usage of graphene in sensing and biosensing applications. This review is an update of our previous article in Chem. Soc. Rev. 2010, 39, 4146-4157, with special focus on the developments over the past two years.

Geographical and geological origin of natural graphite heavily influence the electrical and electrochemical properties of chemically modified graphenes.

Natural graphite is an important precursor for the production of chemically modified graphenes in bulk quantities for electrochemical applications. These natural graphites have varying fundamental properties due to the different geological processes and environments at their points of origin, which are expected to affect their chemical reactivity and hence the properties of the derived graphene materials. Four different natural graphites with known geographical and geological origins were exposed to a modified Hummers oxidation method and the resulting graphite oxides were studied. The graphite oxides were shown to have different extents of oxidation and types of oxygen groups, which directly influenced their electrochemical properties. These differences were propagated further in the subsequent chemical reduction of the graphite oxides, and the reduced graphene oxides exhibited significantly different reduction efficiencies and electrical conductivities. These findings show that the choice of natural graphite of known origin is important to synthesize chemically modified graphenes with a desired set of properties.

Synthetic routes contaminate graphene materials with a whole spectrum of unanticipated metallic elements.

The synthesis of graphene materials is typically carried out by oxidizing graphite to graphite oxide followed by a reduction process. Numerous methods exist for both the oxidation and reduction steps, which causes unpredictable contamination from metallic impurities into the final material. These impurities are known to have considerable impact on the properties of graphene materials. We synthesized several reduced graphene oxides from extremely pure graphite using several popular oxidation and reduction methods and tracked the concentrations of metallic impurities at each stage of synthesis. We show that different combinations of oxidation and reduction introduce varying types as well as amounts of metallic elements into the graphene materials, and their origin can be traced to impurities within the chemical reagents used during synthesis. These metallic impurities are able to alter the graphene materials' electrochemical properties significantly and have wide-reaching implications on the potential applications of graphene materials.

The Rho GTPase Rac1 is required for recycling endosome-mediated secretion of TNF in macrophages.

Rho GTPases are required for many cellular events such as adhesion, motility, and membrane trafficking. Here we show that in macrophages, the Rho GTPases Rac1 and Cdc42 are involved in lamellipodia and filopodia formation, respectively, and that both of these Rho GTPases are essential for the efficient surface delivery of tumor necrosis factor (TNF) to the plasma membrane following TLR4 stimulation. We have previously demonstrated intracellular trafficking of TNF via recycling endosomes in lipopolysaccharide (LPS)-activated macrophages. Here, we further define a specific role for Rac1 in intracellular TNF trafficking, demonstrating impairment in TNF release following TLR4 stimulation in the presence of a Rac inhibitor, in cells expressing a dominant negative (DN) form of Rac1, and following small interfering RNA (siRNA) knockdown of Rac1. Rac1 activity was required for TNF trafficking but not for TLR4 signaling following LPS stimulation. Reduced TNF secretion was due to a defect in Rac1 activity, but not of the closely related Rho GTPase Rac2, demonstrated by the additional use of macrophages derived from Rac2-deficient mice. Labeling recycling endosomes by the uptake of fluorescent transferrin enabled us to show that Rac1 was required for the final stages of TNF trafficking and delivery from recycling endosomes to the plasma membrane. Thus, actin remodeling by the Rho GTPase Rac1 is required for TNF cell surface delivery and release from macrophages.

Calibration of a fugitive emission rate measurement of an area source.

A major challenge to measuring fugitive emission rates from large area sources, such as landfills or tailings ponds, has been the establishment of the accuracy of such methods, or of a particular measurement. When such measurements are carried out, they are invariably associated with a relatively high degree of uncertainty. The Airborne Matter Mapping (AMM) method is a new method of measuring fugitive emission rates that can be applied to large area sources. The method was applied to the measurement of methane emissions from a landfill to assess the potential accuracy of the method, and the measurement process was calibrated to increase confidence in the measured value. First, a measured rate of methane from a gas cylinder was released from near the center of the landfill and the AMM method was applied to measure the methane flow rate across a measurement surface. Then, the AMM method was performed a second time along the same measurement surface without the intentional release of methane. The difference of the flow rates across the measurement surface were then compared with the measured rate of methane released from the gas cylinder. The relatively small difference of -5.7% between the flow rates, relative to the methane release rate from the gas cylinder provides confidence in the accuracy of this AMM method measurement. An adjustment to the AMM method analysis was made such that the difference between the flow rates was negligible, which resulted in a calibrated measurement of the methane emission rate from the landfill of 0.87 g/sec.

Graphane and hydrogenated graphene.

Graphane, the fully hydrogenated analogue of graphene, and its partially hydrogenated counterparts are attracting increasing attention. We review here its structure and predicted material properties, as well as the current methods of preparation. Graphane and hydrogenated graphenes are far more complex materials than graphene, expected to have a tuneable band gap via the extent of hydrogenation, as well as exhibit ferromagnetism. The methods for hydrogenated graphene characterization are discussed. We show that hydrogenation methods based on low or high pressure gas hydrogenation lead to less hydrogen saturation than wet chemistry methods based on variations of Birch reduction. The special cases of patterning of hydrogenated graphene strips in a graphene lattice are discussed.

Unscrolling of multi-walled carbon nanotubes: towards micrometre-scale graphene oxide sheets.

Chemical routes toward obtaining graphene materials are commonly used in the field, and one such preparation method is the unzipping of carbon nanotubes into long, thin graphene nanoribbons. In this work, we show that oxidative permanganate treatment of Scroll type multi-walled carbon nanotubes can lead to large, stacked sheets instead of nanoribbons. This difference is suggested to arise from the type of nanotube used, such as the Russian Doll form or Scroll form causing a change in the initial oxidation site location and ultimately leading to an alternate nanotube opening process.

Rab6a/a' are important Golgi regulators of pro-inflammatory TNF secretion in macrophages.

Lipopolysaccharide (LPS)-activated macrophages secrete pro-inflammatory cytokines, including tumor necrosis factor (TNF) to elicit innate immune responses. Secretion of these cytokines is also a major contributing factor in chronic inflammatory disease. In previous studies we have begun to elucidate the pathways and molecules that mediate the intracellular trafficking and secretion of TNF. Rab6a and Rab6a' (collectively Rab6) are trans-Golgi-localized GTPases known for roles in maintaining Golgi structure and Golgi-associated trafficking. We found that induction of TNF secretion by LPS promoted the selective increase of Rab6 expression. Depletion of Rab6 (via siRNA and shRNA) resulted in reorganization of the Golgi ribbon into more compact structures that at the resolution of electron microcopy consisted of elongated Golgi stacks that likely arose from fusion of smaller Golgi elements. Concomitantly, the delivery of TNF to the cell surface and subsequent release into the media was reduced. Dominant negative mutants of Rab6 had similar effects in disrupting TNF secretion. In live cells, Rab6-GFP were localized on trans-Golgi network (TGN)-derived tubular carriers demarked by the golgin p230. Rab6 depletion and inactive mutants altered carrier egress and partially reduced p230 membrane association. Our results show that Rab6 acts on TNF trafficking at the level of TGN exit in tubular carriers and our findings suggest Rab6 may stabilize p230 on the tubules to facilitate TNF transport. Both Rab6 isoforms are needed in macrophages for Golgi stack organization and for the efficient post-Golgi transport of TNF. This work provides new insights into Rab6 function and into the role of the Golgi complex in cytokine secretion in inflammatory macrophages.

Thermally reduced graphenes exhibiting a close relationship to amorphous carbon.

Graphene is an important material for sensing and energy storage applications. Since the vast majority of sensing and energy storage chemical and electrochemical systems require bulk quantities of graphene, thermally reduced graphene oxide (TRGO) is commonly employed instead of pristine graphene. The sp(2) planar structure of TRGO is heavily damaged, consisting of a very short sp(2) crystallite size of nanometre length and with areas of sp(3) hybridized carbon. Such a structure of TRGO is reminiscent of the key characteristic of the structure of amorphous carbon, which is defined as a material without long-range crystalline order consisting of both sp(2) and sp(3) hybridized carbons. Herein, we describe the characterization of TRGO, its parent graphite material and carbon black (a form of amorphous carbon) via transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry experiments. We used the data obtained as well as consideration of practical factors to perform a comparative assessment of the relative electrochemical performances of TRGO against amorphous carbon. We found out that TRGO and amorphous carbon exhibit almost identical characteristics in terms of density of defects in the sp(2) lattice and a similar crystallite size as determined by Raman spectroscopy. These two materials also exhibit similar amounts of oxygen containing groups as determined by XPS and nearly indistinguishable cyclic voltammetric response providing almost identical heterogeneous electron transfer constants. This leads us to conclude that for some sensing and energy storage electrochemical applications, the use of amorphous carbon might be a much more economical solution than the one requiring digestion of highly crystalline graphite with strong oxidants to graphite oxide and then thermally exfoliating it to thermally reduced graphene oxide.

Synthesis and application of a recyclable ionic liquid-supported imidazolidinone catalyst in enantioselective 1,3-dipolar cycloaddition.

The synthesis of recyclable ionic liquid-supported imidazolidinone catalyst I and its application in 1,3-dipolar cycloaddition of nitrone with α,ß-unsaturated aldehyde with high performance were described. Most importantly, the catalyst I can be recovered and recycled for up to five runs without observing significant decrease in catalytic activity.

Extensively drug-resistant tuberculosis: New Zealand's first case and the challenges of management in a low-prevalence country.

In 2010, an immigrant from Burma was the first person to be diagnosed in New Zealand with extensively drug-resistant tuberculosis (XDR-TB). The strain of Mycobacterium tuberculosis is the most resistant reported to date in Australasia. Key difficulties of managing this disease in a low-prevalence country were delays from drug-susceptibility testing and in acquiring appropriate medicines, and a lack of evidence-based guidelines. Solutions are needed for New Zealand and the wider region as more cases of XDR-TB are likely to be encountered in the future.