A steady-state pH-control model for the biological production of elemental sulfur from sulfate in mining-influenced water.

We developed a model to predict pH, alkalinity, and the Langelier Saturation Index (LSI) in coupled systems of hydrogen-based autotrophic sulfate reduction and aerobic oxidation of sulfide to elemental sulfur. To neutralize the biologically generated base, the model allows for the addition of CO2 as part of the gas mixture, the independent addition of HCl or CO2, or a combination of the alternatives. The model was evaluated against the results from a laboratory system for the production of elemental sulfur from sulfate present in mine-tailings water, which is characterized by the presence of elevated sulfate and calcium concentrations. Model results were consistent with measurements of pH, alkalinity, and LSI. The model showed how the acid demands of the coupled reactors vary with pH, being approximately equivalent at pH over 8, when ionized sulfide predominates. Also, while the sulfidogenic reactor was well buffered due to the production of ionized sulfide, the sulfidotrophic reactor in the absence of sulfide and carbonate alkalinity was prone to pH declines. Considering that both reactors operated in the positive range of LSI, the model also indicated that addition of CO2 should be minimized due to increase in the bicarbonate concentration and its effect on increasing the LSI. Furthermore, the model also showed that exclusive reliance on HCl for pH control can be incompatible with Cl- effluent standards, which means that a compromise must be reached between CO2 and HCl additions.

Optimization of the chemolithotrophic denitrification of ion exchange concentrate using hydrogen-based membrane biofilm reactors.

A H2-based membrane biofilm reactor (MBfR) was used to remove nitrate from a synthetic ion-exchange brine made up of 23.8 g L-1 NaCl. To aid the selection of the best nitrate management strategy, our research was based on the integrated analysis of ionic exchange and MBfR processes, including a detailed cost analysis. The nitrate removal flux was not affected if key nutrients were present in the feed solution including potassium and sodium bicarbonate. Operating pH was maintained between 7 and 8. By using a H2 pressure of 15 psi, a hydraulic retention time (HRT) of 4 h, and a surface loading rate of 13.6 ± 0.2 g N m-2 d-1, the average nitrate removal flux was 3.3 ± 0.6 g N m-2 d-1. At HRTs of up to 24 h, the system was able to maintain a removal flux of 1.6 ± 0.2 g N m-2 d-1. Microbial diversity analysis showed that the consortium was dominated by the genera Sulfurimonas and Marinobacter. The estimated cost for a 200 m3/h capacity, coupled ion exchange (IX) + MBfR treatment plant is 0.43 USD/m3. This is a sustainable and competitive alternative to an IX-only plant for the same flowrate. The proposed treatment option allows for brine recycling and reduces costs by 55% by avoiding brine disposal expenses.

A large-scale neurocomputational model of spatial cognition integrating memory with vision.

We introduce a large-scale neurocomputational model of spatial cognition called 'Spacecog', which integrates recent findings from mechanistic models of visual and spatial perception. As a high-level cognitive ability, spatial cognition requires the processing of behaviourally relevant features in complex environments and, importantly, the updating of this information during processes of eye and body movement. The Spacecog model achieves this by interfacing spatial memory and imagery with mechanisms of object localisation, saccade execution, and attention through coordinate transformations in parietal areas of the brain. We evaluate the model in a realistic virtual environment where our neurocognitive model steers an agent to perform complex visuospatial tasks. Our modelling approach opens up new possibilities in the assessment of neuropsychological data and human spatial cognition.

Binding of Pentagalloyl Glucose to Aortic Wall Proteins: Insights from Peptide Mapping and Simulated Docking Studies.

Pentagalloyl glucose (PGG) is currently being investigated as a non-surgical treatment for abdominal aortic aneurysms (AAAs); however, the molecular mechanisms of action of PGG on the AAA matrix components and the intra-luminal thrombus (ILT) still need to be better understood. To assess these interactions, we utilized peptide fingerprinting and molecular docking simulations to predict the binding of PGG to vascular proteins in normal and aneurysmal aorta, including matrix metalloproteinases (MMPs), cytokines, and fibrin. We performed PGG diffusion studies in pure fibrin gels and human ILT samples. PGG was predicted to bind with high affinity to most vascular proteins, the active sites of MMPs, and several cytokines known to be present in AAAs. Finally, despite potential binding to fibrin, PGG was shown to diffuse readily through thrombus at physiologic pressures. In conclusion, PGG can bind to all the normal and aneurysmal aorta protein components with high affinity, potentially protecting the tissue from degradation and exerting anti-inflammatory activities. Diffusion studies showed that thrombus presence in AAAs is not a barrier to endovascular treatment. Together, these results provide a deeper understanding of the clinical potential of PGG as a non-surgical treatment of AAAs.

High-Rate Sulfate Removal Coupled to Elemental Sulfur Production in Mining Process Waters Based on Membrane-Biofilm Technology.

It is anticipated that copper mining output will significantly increase over the next 20 years because of the more intensive use of copper in electricity-related technologies such as for transport and clean power generation, leading to a significant increase in the impacts on water resources if stricter regulations and as a result cleaner mining and processing technologies are not implemented. A key concern of discarded copper production process water is sulfate. In this study we aim to transform sulfate into sulfur in real mining process water. For that, we operate a sequential 2-step membrane biofilm reactor (MBfR) system. We coupled a hydrogenotrophic MBfR (H2-MBfR) for sulfate reduction to an oxidizing MBfR (O2-MBfR) for oxidation of sulfide to elemental sulfur. A key process improvement of the H2-MBfR was online pH control, which led to stable high-rate sulfate removal not limited by biomass accumulation and with H2 supply that was on demand. The H2-MBfR easily adapted to increasing sulfate loads, but the O2-MBfR was difficult to adjust to the varying H2-MBfR outputs, requiring better coupling control. The H2-MBfR achieved high average volumetric sulfate reduction performances of 1.7-3.74 g S/m3-d at 92-97% efficiencies, comparable to current high-rate technologies, but without requiring gas recycling and recompression and by minimizing the H2 off-gassing risk. On the other hand, the O2-MBfR reached average volumetric sulfur production rates of 0.7-2.66 g S/m3-d at efficiencies of 48-78%. The O2-MBfR needs further optimization by automatizing the gas feed, evaluating the controlled removal of excess biomass and S0 particles accumulating in the biofilm, and achieving better coupling control between both reactors. Finally, an economic/sustainability evaluation shows that MBfR technology can benefit from the green production of H2 and O2 at operating costs which compare favorably with membrane filtration, without generating residual streams, and with the recovery of valuable elemental sulfur.

Evaluation of percrystallization coupled with electrodialysis for zero liquid discharge in the pulping industry.

We evaluated percrystallization at laboratory scale to determine its suitability as core technology for achieving Zero Liquid Discharge (ZLD) in a Kraft effluent desalination process. Compared with conventional evaporation/crystallization techniques, percrystallization allows to operate at room temperature and with barely pressurized fluids, using relatively unexpensive membranes and vacuum to allow evaporation of aqueous brine solutions. For further comprehension of the technology before experimentation, a computational fluid dynamics model was developed, showing how temperature affects the performance of percrystallization in terms of transmembrane flux. Additionally, we performed experiments with single and double salt solutions (NaCl and NaCl/Na2SO4) and concentrated industrial effluent from a Kraft pulp mill (brine from the effluent desalination with electrodialysis). Percrystallization of the concentrated industrial effluent was successfully achieved at laboratory scale, showing no signs of fouling on the membrane surface. However, high energy consumptions (above 3000 kWh/ton of evaporated water) were measured. Theoretical power consumptions of an optimized industrial percrystallization system were therefore computed. Percrystallization showed a more efficient performance compared with similar membrane systems, such as vacuum membrane distillation, but higher energy consumptions than conventional ZLD technologies (mechanical vapor compression), having an estimated energy consumption of around 110-150 kWh/ton of removed water, depending on the feed fluid temperature. Nevertheless, percrystallization could be suitable for ZLD applications where low-cost heating (e.g., solar) is available, since the vacuum energy demand is only 32-140 kWh/ton. Alternatively, it could be applied to low scale processes where the temperature of the solution must remain low (e.g., less than 40 °C).

Optimal attention tuning in a neuro-computational model of the visual cortex-basal ganglia-prefrontal cortex loop.

Visual attention is widely considered a vital factor in the perception and analysis of a visual scene. Several studies explored the effects and mechanisms of top-down attention, but the mechanisms that determine the attentional signal are less explored. By developing a neuro-computational model of visual attention including the visual cortex-basal ganglia loop, we demonstrate how attentional alignment can evolve based on dopaminergic reward during a visual search task. Unlike most previous modeling studies of feature-based attention, we do not implement a manually predefined attention template. Dopamine-modulated covariance learning enable the basal ganglia to learn rewarded associations between the visual input and the attentional gain represented in the PFC of the model. Hence, the model shows human-like performance on a visual search task by optimally tuning the attention signal. In particular, similar as in humans, this reward-based tuning in the model leads to an attentional template that is not centered on the target feature, but a relevant feature deviating away from the target due to the presence of highly similar distractors. Further analyses of the model shows, attention is mainly guided by the signal-to-noise ratio between target and distractors.

Long-term operation of a permeable reactive barrier with diffusive exchange.

In this study, we evaluate the long term operation of a bench-scale reactor which simulates a permeable reactive barrier with sulfidic diffusive exchange (SDES PRB) to treat acid mine drainage (AMD), considering that treatment costs are very sensitive to the useful life for passive reactors. Its functioning was evaluated for a much longer period of 591 days compared to previous SDES PRB studies, with two influents simulating moderately and highly acid groundwater contaminated by AMD. First, we fed water amended with 200 mg/L Zn2+ and 3300 mg/L SO42- at pH 4.9; and after, water with 450 mg/L Fe2+, 100 mg/L Zn2+, 10 mg/L Ni2+, 5 mg/L Cu2+ and 3600 mg/L SO42- at pH 2.5. Biologically produced sulfide and alkalinity were enough to remove both metals and acidity (~99%) from the moderately acidic water, while with the highly acidic water, they resulted in significant removal of the metals reaching up to 87% and 79% of total Fe and Zn, respectively. Furthermore, no inhibitory effect was apparent, as the sulfate reduction rates in the two experiments did not vary significantly (averages close to 0.2 mol/m3-d), despite the much higher acidity and metal load in the second case. Hence, the SDES PRB protected the microbial consortium from metal toxicity and acidity in the long-term, and thus is suitable for remediation of AMD contaminated groundwater with high concentrations of metals, extending the operational range of conventional biological PRBs. Furthermore, an economic evaluation shows that SDES costs can be competitive with the costs of conventional chemical precipitation if the enhanced reactivity that SDES technology offers is realized.

High frequency pulsed electrodialysis of acidic filtrate in kraft pulping.

We introduce high frequency pulsed electrodialysis (hf-pED) to process the acidic filtrate of a Kraft pulp bleaching stage, tested in a pilot trial. Compared with conventional electrodialysis, hf-pED at 2,000 Hz allows a reduction in operational cost by 12%, estimated as 0.54 USD/m3 of acidic filtrate, while simultaneously preventing membrane fouling. The proposed sectorial stream treatment is demonstrated to significantly improve the quality of the final effluent, according to mass balances, making it more suitable for irrigation applications, considering requirements of irrigation norms. Thus, we estimate a reduction of 59, 21, and 20% in the concentration of chloride, sodium, and sulfate, respectively, in the final effluent of a conventional Kraft pulping mill. This strategy is presented as a sustainable and economic solution compared with the desalinization of the whole final effluent.

A membrane-biofilm system for sulfate conversion to elemental sulfur in mining-influenced waters.

A system of two membrane biofilm reactors (MBfRs) was tested for the conversion of sulfate (1.5 g/L) in mining-process water into elemental sulfur (S0) particles. Initially, a H2-based MBfR reduced sulfate to sulfide, and an O2-based MBfR then oxidized sulfide to S0. Later, the two MBfRs were coupled by a recirculation flow. Surface loading, reactor-coupling configuration, and substrate-gas pressure exerted important controls over performance of each MBfR and the coupled system. Continuously recirculating the liquid between the H2-based MBfR and the O2-based MBfR, compared to series operation, avoided the buildup of sulfide and gave overall greater sulfate removal (99% vs 62%) and production of S0 (61% vs 54%). The trade-off was that recirculation coupling demanded greater delivery of H2 and O2 (in air) due to the establishment of a sulfur cycle catalyzed by Sulfurospirillum spp., which had an average abundance of 46% in the H2-based MBfR fibers and 62% in the O2-based MBfR fibers at the end of the experiments. Sulfate-reducing bacteria (Desulfovibrio and Desulfomicrobium) and sulfur-oxidizing bacteria (Thiofaba, Thiomonas, Acidithiobacillus and Sulfuricurvum) averaged only 22% and 11% in the H2-based MBfR and O2-based MBfR fibers, respectively. Evidence suggests that the undesired Sulfurospirillum species, which reduce S0 to sulfide, can be suppressed by increasing sulfate-surface loading and H2 pressure.

Acidiferrimicrobium australe gen. nov., sp. nov., an acidophilic and obligately heterotrophic, member of the Actinobacteria that catalyses dissimilatory oxido-reduction of iron isolated from metal-rich acidic water in Chile.

A novel acidophilic member of the phylum Actinobacteria was isolated from an acidic, metal-contaminated stream draining from an abandoned underground coal mine (Trongol mine), situated close to Curanilahue, Biobío Region, Chile. The isolate (USS-CCA1T) was demonstrated to be a heterotroph that catalysed under aerobic conditions the oxidation of ferrous iron and the reduction of ferric iron under anaerobic conditions, but not the oxidation of sulfur nor hydrogen. USS-CCA1T is a Gram-positive, motile, short rod-shaped, mesophilic bacterium with a temperature growth optimum at 30 °C (range 20-39 °C). It was categorized as an extreme acidophile growing between 1.7 and 4.5 and optimally at pH 3.0. The G+C content of the chromosomal DNA of the isolate was 74.1 mol%, which is highly related to Aciditerrimonas ferrireducens IC-180T , (the most closely related genus; 94.4 % 16S rRNA gene identity), and higher than other acidophilic actinobacteria. The isolate (USS-CCA1T) was shown to form a distinct 16S rRNA clade from characterized acidophilic actinobacteria, well separated from the genera Acidimicrobium, Ferrimicrobium, Ferrithrix, 'Acidithrix' and Aciditerrimonas. Genomic indexes (ANIb, DDH, AAI, POCP) derived from the USS-CCA1T draft genome sequence (deposited at DDBJ/ENA/GenBank under the accession WJHE00000000) support assignment of the isolate to a new species and a new genus within the Acidimicrobiaceae family. Isolate USS-CCA1T is the designated type strain of the novel species Acidiferrimicrobium australe (=DSM 106828T,=RGM 2506T).

Influence of operating conditions on sulfate reduction from real mining process water by membrane biofilm reactors.

Two H2-based membrane biofilm reactor (H2-MBfR) systems, differing in membrane type, were tested for sulfate reduction from a real mining-process water having low alkalinity and high concentrations of dissolved sulfate and calcium. Maximum sulfate reductions were 99%, with an optimum pH range between 8 and 8.5, which minimized any toxic effect of unionized hydrogen sulfide (H2S) on sulfate-reducing bacteria (SRB) and calcite scaling on the fibers and in the biofilm. Although several strategies for control of pH and gas back-diffusion were applied, it was not possible to sustain a high degree of sulfate reduction over the long-term. The most likely cause was precipitation of calcite inside the biofilm and on the surface of fibers, which was shown by scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS) analysis. Another possible cause was a decline in pH, leading to inhibition by H2S. A H2/CO2 mixture in the gas supply was able to temporarily recover the effectiveness of the reactors and stabilize the pH. Biomolecular analysis showed that the biofilm was comprised of 15-20% SRB, but a great variety of autotrophic and heterotrophic genera, including sulfur-oxidizing bacteria, were present. Results also suggest that the MBfR system can be optimized by improving H2 mass transfer using fibers of higher gas permeability and by feeding a H2/CO2 mixture that is automatically adjusted for pH control.

Evaluation of the bio-protection mechanism in diffusive exchange permeable reactive barriers for the treatment of acid mine drainage.

This research studied the bio-protection mechanism based on chemical gradients in diffusive exchange permeable reactive barriers, evaluating the thickness of the reactive layers in the treatment of concentrated acid mine drainage (AMD). Six bench-scale reactors were constructed with reactive layer thicknesses of 2.5, 5, and 7.5 cm in duplicate. The reactors were first fed a sulfated solution for 55 days, followed by concentrated AMD for 166 days. The change of feed to AMD mainly affected the reactors with thinner 2.5 cm layers in comparison to the reactors with 5 and 7.5 cm layers. Cu and Zn removal efficiency was practically 100% in all the reactors; however, in the thinner layer reactors, metal breakthrough occurred towards the end of the experiment concurrently with inhibitory metal concentrations in the reactive layers. On the contrary, the reactors with layer thicknesses of 5 and 7.5 cm evaluated did not present toxic concentrations of these metals at any of the monitoring points. The bio-protection criterion qD correctly predicted that the thin-layer reactor would be the most affected by the toxicity of AMD. The criterion also indicated that all the reactors should fail. Nevertheless, the fault in the thinner layer reactor registered in the effluent after >150 days; therefore, the possibility of failure in the 5 and 7.5 cm thickness reactors is not rejected, as it could have occurred if the experiment had continued.

Performance of two differently designed permeable reactive barriers with sulfate and zinc solutions.

For the first time, this laboratory-scale study evaluates the feasibility of incorporating diffusive exchange in permeable reactive barriers. In order to do this, the performance of two permeable reactive barriers (PRB) with different internal substrate arrangements were compared during the administration of a sulfate solution without metals (for 163 days) and with metals (for 60 days), simulating groundwater contaminated with acid mine drainage (AMD). In order to simulate a traditional PRB, a homogeneous distribution was implemented in the first reactor and the other PRB reactor utilized diffusion-active technology (DAPRB). In the DAPRB, the distribution of the reactive material was interspersed with the conductive material. The measurements in the internal ports showed that transverse gradients of sulfide formed in the DAPRB, causing the diffusion of sulfide from the substrate toward the layer interface, which is where the sulfide reacts by forming complexes with the metal. The DAPRB prevents the microorganisms from direct contact with AMD. This protection caused greater activity (sulfide production).

Pharmacokinetics and Safety of Risperidone Subcutaneous Implants in Stable Patients With Schizophrenia.

A subcutaneous risperidone implant (RI) formulation was developed to improve medication adherence in schizophrenia. Two phase 1 studies were conducted to evaluate the pharmacokinetics of RI in adult patients with schizophrenia. In study 1, all subjects were stable on 4 mg oral risperidone; subsequently, the first subject received 375 mg RI for 1 month, and the remaining subjects received 375 mg RI for 3 months. In study 2, all subjects were stable on oral risperidone 4 mg, 6 mg, or 8 mg and subsequently received RI 480 mg, 720 mg, or 960 mg, respectively, for 6 months. Blood samples were collected at prespecified time points. Various pharmacokinetic parameters were determined in both studies. In both studies risperidone total active moiety plasma concentrations following RI increased slowly, reached therapeutic levels within approximately 2 days, and remained relatively stable. In study 1, the average concentration for RI was 81.3% of the oral trough concentration and 27.5% of the oral peak concentration. In study 2, the steady-state concentration for RI was comparable to the oral trough concentration of the corresponding dose. Patient disease status remained stable with no major safety issues. RI may represent an alternative formulation for schizophrenia treatment with a lower peak-to-trough plasma drug ratio than oral risperidone.

Do subtoxic levels of chlorate influence the desiccation tolerance of Egeria densa?

Among the different factors hypothesized to be responsible for the virtual disappearance of Egeria densa, once a dominant aquatic macrophyte in a southern Chile wetland ecosystem, are the negative effects of certain chemical compounds (mainly chlorate) and harsh environmental conditions (desiccation caused by prolonged atmospheric exposure). The authors performed an integrated experiment in which E. densa plants were first exposed for four weeks inside a mesocosm system to levels of chlorate that existed in the wetland at the time of the plant's demise and then exposed to desiccation conditions that also resembled those that the system had experienced. Hence, the authors tested the hypothesis that E. densa plants exposed to sublethal levels of chlorate are more susceptible to the deleterious effect of desiccation compared with plants that had not been exposed to chlorate. This hypothesis was tested by means of quantifying physiologically related parameters in plants right after the four weeks under water and then after the desiccation period of 6 h. Their results rejected this hypothesis, because all plants, regardless of their history, are equally affected by desiccation.

Chlorate reduction capacity and characterisation of chlorate reducing bacteria communities in sediments of the rio Cruces wetland in southern Chile.

This study investigated chlorate reduction kinetics in multiple samples of sediments from a longitudinal profile of a wetland located downstream of the effluent discharge of a cellulose plant, including characterisation of the bacterial communities involved. The sediments were exposed to different initial chlorate concentrations in microcosm tests, with and without the addition of acetate as an external electron donor, and in a matrix of natural water or a defined medium. At a high initial chlorate concentration of 100 mg/L, in the absence of an external electron source, the degradation curves presented first-order kinetics, influenced by electron donor availability. The first-order kinetic constant varied between 0.05 and 0.17 day(-1). Subsequently, when the initial chlorate concentration was reduced to 7 mg/L, a zero-order kinetic was obtained, with the kinetic constant presenting values between 1.1 and 1.3 mg/L-day. No correlation was observed between chlorate degradation kinetics and the location of the sampling points or the previous history of exposure to chlorate. Other factors evaluated, such as the availability of organic matter or the chlorate reducing bacteria count, also proved not to have any incidence on the results. The richness of chlorate reducing bacteria species in the different samples analysed were also similar, with the greatest similarity being found between cld genes in the samples from the upstream or downstream sampling points. Additionally, cld genes most similar to those present in PCRB like Dechlorospirillum sp., Alicycliphilus denitrificans, Dechloromonas agitata, Dechloromonas sp. LT1 and Ideonella dechloratans were detected. This study showed that the anaerobic sediments of the Cruces river wetland present a high potential for chlorate natural attenuation, regardless of the previous history of exposure to chlorate. This capacity is associated with the presence of a diverse community of chlorate reducing bacteria.

Three-electrode self-actuating self-sensing quartz cantilever: design, analysis, and experimental verification.

We present a novel quartz cantilever for frequency-modulation atomic force microscopy (FM-AFM) which has three electrodes: an actuating electrode, a sensing electrode, and a ground electrode. By applying an ac signal on the actuating electrode, the cantilever is set to vibrate. If the frequency of actuation voltage closely matches one of the characteristic frequencies of the cantilever, a sharp resonance should be observed. The vibration of the cantilever in turn generates a current on the sensing electrode. The arrangement of the electrodes is such that the cross-talk capacitance between the actuating electrode and the sensing electrode is less than 10(-16) F, thus the direct coupling is negligible. To verify the principle, a number of samples were made. Direct measurements with a Nanosurf easyPPL controller and detector showed that for each cantilever, one or more vibrational modes can be excited and detected. Using classical theory of elasticity, it is shown that such novel cantilevers with proper dimensions can provide optimized performance and sensitivity in FM-AFM with very simple electronics.