Positive feedbacks and alternative stable states in forest leaf types.

The emergence of alternative stable states in forest systems has significant implications for the functioning and structure of the terrestrial biosphere, yet empirical evidence remains scarce. Here, we combine global forest biodiversity observations and simulations to test for alternative stable states in the presence of evergreen and deciduous forest types. We reveal a bimodal distribution of forest leaf types across temperate regions of the Northern Hemisphere that cannot be explained by the environment alone, suggesting signatures of alternative forest states. Moreover, we empirically demonstrate the existence of positive feedbacks in tree growth, recruitment and mortality, with trees having 4-43% higher growth rates, 14-17% higher survival rates and 4-7 times higher recruitment rates when they are surrounded by trees of their own leaf type. Simulations show that the observed positive feedbacks are necessary and sufficient to generate alternative forest states, which also lead to dependency on history (hysteresis) during ecosystem transition from evergreen to deciduous forests and vice versa. We identify hotspots of bistable forest types in evergreen-deciduous ecotones, which are likely driven by soil-related positive feedbacks. These findings are integral to predicting the distribution of forest biomes, and aid to our understanding of biodiversity, carbon turnover, and terrestrial climate feedbacks.

Assessment of Graphite, Graphene, and Hydrophilic-Treated Graphene Electrodes to Improve Power Generation and Wastewater Treatment in Microbial Fuel Cells.

In this study, graphite, graphene, and hydrophilic-treated graphene electrodes were evaluated in a dual-chamber microbial fuel cell (DC-MFC). Free-oxygen conditions were promoted in anodic and cathodic chambers. Hydrochloric acid at 0.1 M and pH 1.1 was used as a catholyte, in addition to deionized water in the cathodic chamber. Domestic wastewater was used as a substrate, and a DuPontTM Nafion 117 membrane was used as a proton exchange membrane. The maximum power density of 32.07 mW·m-2 was obtained using hydrophilic-treated graphene electrodes and hydrochloric acid as catholyte. This power density was 1.4-fold and 32-fold greater than that of graphene (22.15 mW·m-2) and graphite (1.02 mW·m-2), respectively, under the same operational conditions. In addition, the maximum organic matter removal efficiencies of 69.8% and 75.5% were obtained using hydrophilic-treated graphene electrodes, for hydrochloric acid catholyte and deionized water, respectively. Therefore, the results suggest that the use of hydrophilic-treated graphene functioning as electrodes in DC-MFCs, and hydrochloric acid as a catholyte, favored power density when domestic wastewater is degraded. This opens up new possibilities for improving DC-MFC performance through the selection of suitable new electrode materials and catholytes.

Contribution of configurations, electrode and membrane materials, electron transfer mechanisms, and cost of components on the current and future development of microbial fuel cells.

Microbial fuel cells (MFCs) are a technology that can be applied to both the wastewater treatment and bioenergy generation. This work discusses the contribution of improvements regarding the configurations, electrode materials, membrane materials, electron transfer mechanisms, and materials cost on the current and future development of MFCs. Analysis of the most recent scientific publications on the field denotes that dual-chamber MFCs configuration offers the greatest potential due to the excellent ability to be adapted to different operating environments. Carbon-based materials show the best performance, biocompatibility of carbon-brush anode favors the formation of the biofilm in a mixed consortium and in wastewater as a substrate resembles the conditions of real scenarios. Carbon-cloth cathode modified with nanotechnology favors the conductive properties of the electrode. Ceramic clay membranes emerge as an interesting low-cost membrane with a proton conductivity of 0.0817 S cm-1, close to that obtained with the Nafion membrane. The use of nanotechnology in the electrodes also enhances electron transfer in MFCs. It increases the active sites at the anode and improves the interface with microorganisms. At the cathode, it favors its catalytic properties and the oxygen reduction reaction. These features together favor MFCs performance through energy production and substrate degradation with values above 2.0 W m-2 and 90% respectively. All the recent advances in MFCs are gradually contributing to enable technological alternatives that, in addition to wastewater treatment, generate energy in a sustainable manner. It is important to continue the research efforts worldwide to make MFCs an available and affordable technology for industry and society.

Pharmaceuticals Market, Consumption Trends and Disease Incidence Are Not Driving the Pharmaceutical Research on Water and Wastewater.

Pharmaceuticals enhance our quality of life; consequently, their consumption is growing as a result of the need to treat ageing-related and chronic diseases and changes in the clinical practice. The market revenues also show an historic growth worldwide motivated by the increase on the drug demand. However, this positivism on the market is fogged because the discharge of pharmaceuticals and their metabolites into the environment, including water, also increases due to their inappropriate management, treatment and disposal; now, worldwide, this fact is recognized as an environmental concern and human health risk. Intriguingly, researchers have studied the most effective methods for pharmaceutical removal in wastewater; however, the types of pharmaceuticals investigated in most of these studies do not reflect the most produced and consumed pharmaceuticals on the market. Hence, an attempt was done to analyze the pharmaceutical market, drugs consumption trends and the pharmaceutical research interests worldwide. Notwithstanding, the intensive research work done in different pharmaceutical research fronts such as disposal and fate, environmental impacts and concerns, human health risks, removal, degradation and development of treatment technologies, found that such research is not totally aligned with the market trends and consumption patterns. There are other drivers and interests that promote the pharmaceutical research. Thus, this review is an important contribution to those that are interested not only on the pharmaceutical market and drugs consumption, but also on the links, the drivers and interests that motivate and determine the research work on certain groups of pharmaceuticals on water and wastewater.

Electrochemical oxidation of acetaminophen and its transformation products in surface water: effect of pH and current density.

Several studies have been conducted worldwide to develop effective and affordable methods to degrade pharmaceuticals and their metabolites/intermediates/oxidation products found in surface water, wastewater and drinking water. In this work, acetaminophen and its transformation products were successfully degraded in surface water by electrochemical oxidation using stainless steel electrodes. The effect of pH and current density on the oxidation process was assessed and the oxidation kinetics and mechanisms involved were described. Additionally, the results were compared with those obtained in acetaminophen synthetic solutions. It was found that conducting the electrochemical oxidation at 16.3 mA/cm2 and pH 5, good performance of the process was achieved and not only acetaminophen, but also its transformation products were totally degraded in only 7.5 min; furthermore, small number of transformation products were generated. On the other hand, degradation rates of acetaminophen and its transformation products in surface water were much faster (more than 2.5 times) and the reaction times much shorter (more than 4.0 times) than in synthetic solutions at all current densities and pH values evaluated. At pH 3 and pH 5, greater soluble chlorine formation due to the higher HCl amount used to acidify the surface water solutions could enhance the degradation rates of acetaminophen and its transformation products. However, constituents of surface water (ions and solids) could also have an important role on the oxidation process because at pH 9 (non-acidified solutions) the degradation rates were also much greater and the reaction times were much shorter in surface water than in acetaminophen synthetic solutions.

Degradation of Paracetamol and Its Oxidation Products in Surface Water by Electrochemical Oxidation.

Paracetamol and its toxic transformation products have been found in surface water, wastewater, and drinking water. Effective methods to degrade these products must be found to reduce their detrimental effects on microorganisms in aquatic systems and minimize the concern on human health. Thus, this study looked into the electrochemical oxidation of paracetamol and its oxidation products on surface water, and results were compared with those of paracetamol synthetic solution oxidation. Degradation of paracetamol was conducted using a stainless steel electrode cell, a pH of 3, and direct current densities of 5.7 mA/cm2 (6 V) and 7.6 mA/cm2 (12 V). For both current densities applied, the pharmaceutical and its oxidation products observed by high-performance liquid chromatography with diode-array detection (HPLC-DAD) at 254 nm were totally degraded. Faster degradation of paracetamol was observed at a higher current density. Indeed, 95% of paracetamol was oxidized in only 15 min at the 7.6 mA/cm2 current density. In comparison to the paracetamol synthetic solution's oxidation, degradation of paracetamol was faster in the surface water than the synthetic solution, at 5.7 mA/cm2. Nevertheless, at 7.6 mA/cm2, total degradation of paracetamol in surface water was delayed up to 40 min, versus 7.5 min in the synthetic solution. Three oxidation products, observed by HPLC-DAD at 254 nm, were fully oxidized. In comparison with the paracetamol synthetic solution, degradation of the oxidation products in surface water was faster than in synthetic solutions for both current densities. Furthermore, the 7.6 mA/cm2 current density resulted in faster degradation of oxidation products. Results obtained from this work are promising for practical applications because short reaction times and low current densities are needed for degradation of paracetamol and its oxidation products. These densities can be potentially supplied by photovoltaic cells.

Synthesis of stable TiO2 nanotubes: effect of hydrothermal treatment, acid washing and annealing temperature.

Effect of hydrothermal treatment, acid washing and annealing temperature on the structure and morphology of TiO2 nanotubes during the formation process was assessed. X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy analysis were conducted to describe the formation and characterization of the structure and morphology of nanotubes. Hydrothermal treatment of TiO2 precursor nanoparticles and acid washing are fundamental to form and define the nanotubes structure. Hydrothermal treatment causes a change in the crystallinity of the precursor nanoparticles from anatase phase to a monoclinic phase, which characterizes the TiO2 nanosheets structure. The acid washing promotes the formation of high purity nanotubes due to Na+ is exchanged from the titanate structure to the hydrochloric acid (HCl) solution. The annealing temperature affects the dimensions, structure and the morphology of the nanotubes. Annealing temperatures in the range of 400 °C and 600 °C are optimum to maintain a highly stable tubular morphology of nanotubes. Additionally, nanotubes conserve the physicochemical properties of the precursor Degussa P25 nanoparticles. Temperatures greater than 600 °C alter the morphology of nanotubes from tubular to an irregular structure of nanoparticles, which are bigger than those of the precursor material, i.e., the crystallinity turn from anatase phase to rutile phase inducing the collapse of the nanotubes.

Simultaneous extraction and determination of four different groups of pharmaceuticals in compost using optimized ultrasonic extraction and ultrahigh pressure liquid chromatography-mass spectrometry.

An analytical method for the simultaneous extraction and determination of four different groups of pharmaceuticals in compost from the biodegradation of biological infectious hazardous wastes (BIHW) was developed and successfully validated. Compost samples were spiked with known concentrations of the pharmaceuticals of interest. Ultrasonic extraction with an ethyl acetate and methanol solution (1:1) resulted to be effective for the extraction of eight target compounds. All the compounds were separated in a single gradient run by UHPLC using a Zorbax SB C18 Agilent (2.1×50mm, 1.8µm) column. Analytes were detected and quantified via multiple reaction monitoring (MRM) using an AB SCIEX API-5000TM triple quadrupole with electrospray ionization (ESI) in positive mode. The optimum mobile phase consisted of ammonium formate (2mM, pH 3): MeOH (50:50). Recovery values of the ultrasonic extraction for all compounds were on the order of 87% to 113% with absolute deviations lower than 11%. The limits of detection and quantification for the eight pharmaceuticals were on the order of 0.66ngg(-1) and 2ngg(-1) respectively for all the pharmaceuticals analyzed. These values are lower than those values reported in the literature. Suitable level of linearity, acceptable limits of detection and quantification, good repeatability and inter-day precision, non-ion interference, and low matrix effect resulted from the validation of the analytical method. Implementation of the analytical procedure proposed in this research will contribute in having shorter analysis time and lower costs when working with complex matrices such as compost.

Relaxant effect of xanthomicrol and 3alpha-angeloyloxy-2alpha-hydroxy-13,14z-dehydrocativic acid from Brickellia paniculata on rat uterus.

Brickellia paniculata has been used as spasmolytic in Mexican traditional medicine. Xanthomicrol and 3alpha-angeloyloxy-2alpha-hydroxy-13,14Z-dehydrocativic acid (AAHDD) are two of the main leaf components with antispasmodic activity. However, their mechanism of action remains unknown. An in vitro comparative study between xanthomicrol and AAHDD on rat uterus precontracted by either KCl (60 mM) or oxytocin (10 mIU/ml) was carried out to investigate the mechanism of action of these compounds on smooth muscle. Relaxant effect was measured as median inhibitory concentration (IC(50)) and maximal effect as maximal relaxant response (R(max)). Xanthomicrol was significantly more potent than AAHDD in inhibiting contractions induced by KCl 60 mM, whereas AAHDD was more potent than xanthomicrol in inhibiting contractions induced by oxytocin 10 mIU/ml. These results suggest that xanthomicrol induces a greater blocking effect on voltage-operated calcium channels than on receptor-operated gates.

Transformation and characterisation of dissolved organic matter during the thermophilic aerobic biodegradation of faeces.

We conducted a comparison of the characteristics of dissolved organic matter (DOM) taken from the bio-toilet and other sources. A characterisation of DOM was carried out to assess the stability of the compost generated during the thermophilic and aerobic biodegradation of faeces. In addition, levels of soluble microbial products generated in the bio-toilet composting reactor were compared with those taken from other sources. The results showed that (i) the main component of DOM from the bio-toilet are solutes with molecular weight (MW)>30,000 Da (40%), whereas micromolecules (MW< 1000 Da) constituted more than 60% of the DOM from other solid samples, while liquid samples reached even more than 90%; (ii) the DOM stabilisation level in the composting reactor of the bio-toilet system was greater than that shown by DOM from other sources; (iii) stabilisation of DOM in the bio-toilet system was characterised by an increasing amount of macromolecules (MW>30,000 Da) after a decreasing trend was observed in the early stages of the biodegradation process; and (iv) net production of lipopolysaccharide (LPS) in wastewater treatment plants is greater than in the bio-toilet.

Temperature effect on aerobic biodegradation of feces using sawdust as a matrix.

Temperature is one of the most important factors affecting microbial growth and biological reactions. In this study, the effect of temperature on aerobic biodegradation of feces is described through the comparison and analysis of experimental oxygen utilization rates (OUR) profiles obtained from batch tests conducted at several temperatures covering mainly mesophilic and thermophilic ranges. Additionally, the temperature effect was incorporated into the bio-kinetic model introduced by Lopez Zavala et al. (Water Res 38(5) (2004) 1327) and simulation of experimental OUR profiles was conducted. Results show that mesophilic and thermophilic microorganisms behaved differently to temperature; additionally, results suggest that the optimum temperature from the viewpoint of feces biodegradability is within the thermophilic range, nearly 60 degrees C. The enzymatic activity of microorganisms at 70 degrees C was remarkably diminished. For better predictions in the mesophilic range, two fractions of slowly biodegradable organic matter were identified, easily hydrolyzable organic matter (X(Se)) and slowly hydrolyzable organic matter (X(Ss)).

Modeling of aerobic biodegradation of feces using sawdust as a matrix.

Composting in the bio-toilet system is a continuous thermophilic-aerobic biodegradation process. Unlike to the traditional composting systems, biodegradation rates of organic matter are very important because feces are daily added into the composting reactor of the bio-toilet and an accelerated decomposition is aimed. The models developed for conventional composting processes include simple formulations of biodegradation kinetics and deal mainly with energy and water balances. Therefore, formulation of kinetics that can reasonably describe the biodegradation process in the bio-toilet system is required for better modeling predictions. In this work, a bio-kinetic model was introduced to describe the aerobic biodegradation of feces in the bio-toilet system. This model includes three processes for carbonaceous material degradation and is prepared by using the activated sludge modeling techniques and formulations. Stoichiometric parameters were adopted from literature on activated sludge processes. Kinetic parameters were estimated by conducting batch tests for several organic loadings and by using respirometry, curve-fitting techniques, and sensitivity analysis. Feasibility and applicability of these parameters were assessed by conducting feces intermittent-feeding tests and by simulating the experimental respiration rates. Model, stoichiometric and kinetic parameters proved to be affordable for describing the biodegradation of feces in the bio-toilet system.