A Multifunctional Zwitterion Electrolyte Additive for Highly Reversible Zinc Metal Anode.

Although zinc metal anode is promising for zinc-ion batteries (ZIBs) owing to high energy density, its reversibility is significantly obstructed by uncontrolled dendrite growth and parasitic reactions. Optimizing electrolytes is a facile yet effective method to simultaneously address these issues. Herein, 2-(N-morpholino)ethanesulfonic acid (MES), a pH buffer as novel additive, is initially introduced into conventional ZnSO4 electrolyte to ensure a dendrite-free zinc anode surface, enabling a stable Zn/electrolyte interface, which is achieved by controlling the solvated sheath through H2O poor electric double layer (EDL) derived from zwitterionic groups. Moreover, this zwitterionic additive can balance localized H+ concentration of the electrolyte system, thus preventing parasitic reactions in damaging electrodes. DFT calculation proves that the MES additive has a strong affinity with Zn2+ and induces uniform deposition along (002) orientation. As a result, the Zn anode in MES-based electrolyte exhibits exceptional plating/stripping lifespan with 1600 h at 0.5 mA cm-2 (0.5 mAh cm-2) and 430 h at 5.0 mA cm-2 (5.0 mAh cm-2) while it maintains high coulombic efficiency of 99.8%. This work proposes an effective and facile approach for designing dendrite-free anode for future aqueous Zn-based storage devices.

Highly Reversible Zinc Metal Anode in a Dilute Aqueous Electrolyte Enabled by a pH Buffer Additive.

Aqueous zinc-ion batteries have drawn increasing attention due to the intrinsic safety, cost-effectiveness and high energy density. However, parasitic reactions and non-uniform dendrite growth on the Zn anode side impede their application. Herein, a multifunctional additive, ammonium dihydrogen phosphate (NHP), is introduced to regulate uniform zinc deposition and to suppress side reactions. The results show that the NH4 + tends to be preferably absorbed on the Zn surface to form a "shielding effect" and blocks the direct contact of water with Zn. Moreover, NH4 + and (H2 PO4 )- jointly maintain pH values of the electrode-electrolyte interface. Consequently, the NHP additive enables highly reversible Zn plating/stripping behaviors in Zn//Zn and Zn//Cu cells. Furthermore, the electrochemical performances of Zn//MnO2 full cells and Zn//active carbon (AC) capacitors are improved. This work provides an efficient and general strategy for modifying Zn plating/stripping behaviors and suppressing side reactions in mild aqueous electrolyte.

Organic pH Buffer for Dendrite-Free and Shuttle-Free Zn-I2 Batteries.

Aqueous Zn-Iodine (I2 ) batteries are attractive for large-scale energy storage. However, drawbacks include, Zn dendrites, hydrogen evolution reaction (HER), corrosion and, cathode "shuttle" of polyiodines. Here we report a class of N-containing heterocyclic compounds as organic pH buffers to obviate these. We evidence that addition of pyridine /imidazole regulates electrolyte pH, and inhibits HER and anode corrosion. In addition, pyridine and imidazole preferentially absorb on Zn metal, regulating non-dendritic Zn plating /stripping, and achieving a high Coulombic efficiency of 99.6 % and long-term cycling stability of 3200 h at 2 mA cm-2 , 2 mAh cm-2 . It is also confirmed that pyridine inhibits polyiodines shuttling and boosts conversion kinetics for I- /I2 . As a result, the Zn-I2 full battery exhibits long cycle stability of >25 000 cycles and high specific capacity of 105.5 mAh g-1 at 10 A g-1 . We conclude organic pH buffer engineering is practical for dendrite-free and shuttle-free Zn-I2 batteries.

Synergistic Modulation of In-Situ Hybrid Interface Construction and pH Buffering Enabled Ultra-Stable Zinc Anode at High Current Density and Areal Capacity.

In aqueous electrolytes, the uncontrollable interfacial evolution caused by a series of factors such as pH variation and unregulated Zn2+ diffusion would usually result in the rapid failure of metallic Zn anode. Considering the high correlation among various triggers that induce the anode deterioration, a synergistic modulation strategy based on electrolyte modification is developed. Benefitting from the unique pH buffer mechanism of the electrolyte additive and its capability to in situ construct a zincophilic solid interface, this synergistic effect can comprehensively manage the thermodynamic and kinetic properties of Zn anode by inhibiting the pH variation and parasitic side reactions, accelerating de-solvation of hydrated Zn2+ , and regulating the diffusion behavior of Zn2+ to realize uniform Zn deposition. Thus, the modified Zn anode can achieve an impressive lifespan at ultra-high current density and areal capacity, operating stably for 609 and 209 hours at 20 mA cm-2 , 20 mAh cm-2 and 40 mA cm-2 , 20 mAh cm-2 , respectively. Based on this exceptional performance, high loading Zn||NH4 V4 O10 batteries can achieve excellent cycle stability and rate performance. Compared with those previously reported single pH buffer strategies, the synergistic modulation concept is expected to provide a new approach for highly stable Zn anode in aqueous zinc-ion batteries.

Calcium Carbonate Dissolution from the Laboratory to the Ocean: Kinetics and Mechanism.

The ultimate fate, over the course of millennia, of nearly all of the carbon dioxide formed by humankind is for it to react with calcium carbonate in the world's oceans. Although, this reaction is of global relevance, aspects of the calcite dissolution reaction remain poorly described with apparent contradictions present throughout the expansive literature. In this perspective we aim to evidence how a lack of appreciation of the role of mass-transport may have hampered developments in this area. These insights have important implications for both idealised experiments performed under laboratory conditions and for the measurement and modelling of oceanic calcite sediment dissolution.

The function of geophagy in Nepal gray langurs: Sodium acquisition rather than detoxification or prevention of acidosis.

OBJECTIVES: Geophagy has several hypothesized functions, among them (1) detoxification of plant secondary compounds, for example, tannins, (2) buffering stomach pH to alleviate acidosis caused by high sugar intake, and (3) supplementing the diet with mineral nutrients. We tested these hypotheses in Nepal gray langurs (Semnopithecus schistaceus), a foregut fermenter for which fruits and leaves dominate the diet at different times of the year. MATERIALS AND METHODS: We collected data on feeding time per food item for 21 unprovisioned adult langurs at Ramnagar, Nepal, for 1 year using instantaneous sampling (773 observation hours). We combined these data with relative sugar and tannin content of food items to estimate diet content. We collected rainfall data to distinguish the wet season (May-September) from the dry season (October-April). We collected soil samples from consumption and control sites to test for pH and sodium, potassium, magnesium, and calcium concentrations. RESULTS: Langurs consumed soil from two sources: termite structures (in almost all months) and river banks and beds (mainly in the dry season). Soil feeding was not positively correlated with dietary tannin or sugar content (GLMM). Soil pH was not high enough to buffer stomach contents. Only sodium was significantly higher in consumed soil. DISCUSSION: The most likely function of geophagy was the acquisition of sodium. This conclusion is consistent with reports for other animals. Buffering stomach pH, an often-suggested function for animals with ruminant-like digestion, was not supported. Detoxification, often proposed for animals with a diet high in secondary compounds, was also not supported.

Influence of Buffers of Different pH and Composition on the Murine Skin Barrier, Epidermal Proliferation, Differentiation, and Inflammation.

The pH of the skin is tightly regulated by endogenous buffering systems. We examined the influence of buffers of different pH and composition on skin barrier repair, pH, inflammation, and epidermal thickness/proliferation/differentiation. After tape-stripping in hairless mice buffers with pH 4-7 were applied in patch test chambers. After removal of the chambers, skin pH and transepidermal water loss (TEWL) were monitored for 24 h, and biopsies were taken for histology/immunohistology. Hairless mice showed a basal skin pH of about 5.8. Following barrier disruption and application of water, the pH increased by 0.6 units; increase in pH was reduced by the pH 4 glycolate buffer, unchanged by pH 4 citrate and pH 5.5 buffers, and even increased by the pH 7 buffer. pH 5.5, pH 4 citrate, and pH 4 glycolate buffers led to a slight, while the pH 7 buffer led to a significant increase in TEWL after barrier disruption compared to water. The pH 7 buffers led to a significant increase in epidermal thickness/proliferation/differentiation and inflammation after barrier disruption, whereas buffers with pH 4 and 5.5 caused a slight increase. In conclusion, only the pH 4 glycolate buffer significantly reduced the skin barrier disruption-related increase in skin pH. This was accompanied by only slight increase in epidermal thickness and inflammation compared to water. Application of the pH 7 buffer led to a significant increase in the skin pH, TEWL, epidermal thickness, and inflammation. The results are important for the formulation of topical products for effective acidification in pathological skin conditions.

Reversible Deposition/Dissolution of Double Hydroxides to Modulate Electrolyte pH Enabling High-Performance Aqueous Zinc-Ion Batteries.

Vanadium oxide has been extensively studied as a host of zinc ion intercalation but still suffers from low conductivity, dissolution, and byproduct accumulation during cycling. Here, we hydrothermally synthesize the VO2@MXene Ti3C2 (MV) composite and find that in the MV//3 M Zn(CF3SO3)2//Zn system, the double hydroxide Zn12(CF3SO3)9(OH)15·nH2O (ZCOH) uniformly covers VO2 during the charging process and dissolves reversibly during the discharge process. In situ X-ray diffraction of the MV combined with in situ pH measurements reveals that ZCOH acts as a pH buffer during cycling, which is beneficial to the cycling stability of batteries. And the theoretical calculation indicates that the decomposition energy required by ZCOH on the MV surface is lower than that on pure VO2, which is more conducive to ZCOH dissolution. The coin battery exhibits high-rate performance of 65.1% capacity retention at a current density of 15 A g-1 (compared to 0.6 A g-1) and a long cycling life of 20,000 cycles with a capacity retention of 80.7%. For a 22.4 mA h soft-packaged battery, its capacity remains at 72.1% after 2000 cycles. This work demonstrates the active role of ZCOH in the electrochemical process of VO2 and provides a new perspective for exploiting this mechanism to develop high-performance aqueous zinc-ion battery vanadium oxide cathode materials.

Selective separation of hemicellulose from poplar by hydrothermal pretreatment with ferric chloride and pH buffer.

As an environmentally friendly lignocellulosic biomass separation technology, hydrothermal pretreatment (HP) has a strong application prospect. However, the low separation efficiency is a main factor limiting its application. In this study, the poplar components were separated using HP with ferric chloride and pH buffer (HFB). The optimal conditions were ferric chloride concentration of 0.10 M, reaction temperature of 150 °C, reaction time of 15 min and pH 1.9. The separation of hemicellulose was increased 34.03 % to 77.02 %. The pH buffering resulted in the highest cellulose and lignin retention yields compared to ferric chloride pretreatment (FC). The high efficiency separation of hemicellulose via HFB pretreatment inhibited the degradation of xylose. The hydrolysate was effectively reused for five times. The fiber crystallinity index reached 60.05 %, and the highest C/O ratio was obtained. The results provide theoretical support for improving the efficiency of HP and promoting its application.

Composite carrier enhanced bacterial adhesion and nitrogen removal in partial nitrification/anammox process.

The rapid start-up and stable operation of one-stage (Partial nitrification/anammox) PN/A process for low-ammonium wastewater are difficult to be achieved, and many carriers are designed to solve this problem. Here, a composite carrier was developed, in which sepiolite and non-woven fabrics were assembled in polypropylene spherical shells. At the start-up phase, PA reactor using the composite carriers reached a higher nitrogen removal rate of 134.50 ± 19.60 mg·N·L-1d-1, in contrast to that of 48.85 ± 19.64 mg·N·L-1d-1 in the PB reactor without sepiolite carriers. When the final influent ammonium concentration of PN/A process is 100 mg/L, the total nitrogen removal efficiency can reach 72 ± 0.03 %. High biomass immobilization ability of composite carrier was evidenced by the greater adsorption trend between sludge and sepiolite than that between sludge and non-woven fabrics, where hydrophobic interaction and Van der Waals interaction played a major role. Extracellular protein (PN) content and the ratio of PN and extracellular polysaccharide of samples in PA were significantly higher than those in PB, verifying higher biofilm formation ability on the composite carrier. The composite carrier also increased the abundance of dominant bacteria in PN/A process, especially AOB, the relative abundance of which reached 46.11 %. And it increased the abundance of essential functional genes for nitrogen conversion as their perfect acid neutralizing effects. This study is of great significance in improving the start-up speed and stable operation of this process.

Intense pH Sensitivity Modulation in Carbon Nanotube-Based Field-Effect Transistor by Non-Covalent Polyfluorene Functionalization.

We compare the pH sensing performance of non-functionalized carbon nanotubes (CNT) field-effect transistors (p-CNTFET) and CNTFET functionalized with a conjugated polyfluorene polymer (labeled FF-UR) bearing urea-based moieties (f-CNTFET). The devices are electrolyte-gated, PMMA-passivated, 5 µm-channel FETs with unsorted, inkjet-printed single-walled CNT. In phosphate (PBS) and borate (BBS) buffer solutions, the p-CNTFETs exhibit a p-type operation while f-CNTFETs exhibit p-type behavior in BBS and ambipolarity in PBS. The sensitivity to pH is evaluated by measuring the drain current at a gate and drain voltage of -0.8 V. In PBS, p-CNTFETs show a linear, reversible pH response between pH 3 and pH 9 with a sensitivity of 26 ± 2.2%/pH unit; while f-CNTFETs have a much stronger, reversible pH response (373%/pH unit), but only over the range of pH 7 to pH 9. In BBS, both p-CNTFET and f-CNTFET show a linear pH response between pH 5 and 9, with sensitivities of 56%/pH and 96%/pH, respectively. Analysis of the I-V curves as a function of pH suggests that the increased pH sensitivity of f-CNTFET is consistent with interactions of FF-UR with phosphate ions in PBS and boric acid in BBS, with the ratio and charge of the complexed species depending on pH. The complexation affects the efficiency of electrolyte gating and the surface charge around the CNT, both of which modify the I-V response of the CNTFET, leading to the observed current sensitivity as a function of pH. The performances of p-CNTFET in PBS are comparable to the best results in the literature, while the performances of the f-CNTFET far exceed the current state-of-the-art by a factor of four in BBS and more than 10 over a limited range of pH in BBS. This is the first time that a functionalization other than carboxylate moieties has significantly improved the state-of-the-art of pH sensing with CNTFET or CNT chemistors. On the other hand, this study also highlights the challenge of transferring this performance to a real water matrix, where many different species may compete for interactions with FF-UR.

Extraction of niclosamide from commercial approved tablets into aqueous buffered solution creates potentially approvable oral and nasal sprays against COVID-19 and other respiratory infections.

Motivation: The low solubility, weak acid drug, niclosamide is a host cell modulator with broad-spectrum anti-viral cell-activity against many viruses, including stopping the SARS-CoV-2 virus from infecting cells in cell culture. As a result, a simple universal nasal spray preventative was proposed and investigated in earlier work regarding the dissolution of niclosamide into simple buffers. However, starting with pharmaceutical grade, niclosamide represents a new 505(b)(2) application. The motivation for this second paper in the series was therefore to explore if and to what extent niclosamide could be extracted from commercially available and regulatory-approved niclosamide oral tablets that could serve as a preventative nasal spray and an early treatment oral/throat spray, with possibly more expeditious testing and regulatory approval. Experimental: Measurements of supernatant niclosamide concentrations were made by calibrated UV-Vis for the dissolution of niclosamide from commercially available Yomesan crushed into a powder for dissolution into Tris Buffer (TB) solutions. Parameters tested were as follows: time (0-2 days), concentration (300 µM to -1 mM), pH (7.41 to 9.35), and anhydrous/hydrated state. Optical microscopy was used to view the morphologies of the initial crushed powder, and the dissolving and equilibrating undissolved excess particles to detect morphologic changes that might occur. Results: Concentration dependence: Niclosamide was readily extracted from powdered Yomesan at pH 9.34 TB at starting Yomesan niclosamide equivalents concentrations of 300 µM, 600 µM, and 1 mM. Peak dissolved niclosamide supernatant concentrations of 264 µM, 216 µM, and 172 µM were achieved in 1 h, 1 h, and 3 h respectively. These peaks though were followed by a reduction in supernatant concentration to an average of 112.3 µM ± 28.4 µM after overnight stir on day 2. pH dependence: For nominal pHs of 7.41, 8.35, 8.85, and 9.35, peak niclosamide concentrations were 4 µM, 22.4 µM, 96.2 µM, and 215.8 µM, respectively. Similarly, the day 2 values all reduced to 3 µM, 12.9 µM, 35.1 µM, and 112.3 µM. A heat-treatment to 200 °C dehydrated the niclosamide and showed a high 3 h concentration (262 µM) and the least day-2 reduction (to 229 µM). This indicated that the presence, or formation during exposure to buffer, of lower solubility polymorphs was responsible for the reductions in total solubilities. These morphologic changes were confirmed by optical microscopy that showed initially featureless particulate-aggregates of niclosamide could grow multiple needle-shaped crystals and form needle masses, especially in the presence of Tris-buffered sodium chloride, where new red needles were rapidly made. Scale up: A scaled-up 1 L solution of niclosamide was made achieving 165 µM supernatant niclosamide in 3 h by dissolution of just one fifth (100 mg niclosamide) of a Yomesan tablet. Conclusion: These comprehensive results provide a guide as to how to utilize commercially available and approved tablets of niclosamide to generate aqueous niclosamide solutions from a simple dissolution protocol. As shown here, just one 4-tablet pack of Yomesan could readily make 165 L of a 20 µM niclosamide solution giving 16,500 10 mL bottles. One million bottles, from just 60 packs of Yomesan, would provide 100 million single spray doses for distribution to mitigate a host of respiratory infections as a universal preventative-nasal and early treatment oral/throat sprays throughout the world. Graphical Abstract: pH dependence of niclosamide extraction from crushed Yomesan tablet material into Tris buffer (yellow-green in vial) and Tris-buffered saline solution (orange-red in vial). Initial anhydrous dissolution concentration is reduced by overnight stirring to likely monohydrate niclosamide; and is even lower if in TBSS forming new niclosamide sodium needle crystals grown from the original particles. Supplementary Information: The online version contains supplementary material available at 10.1186/s41120-023-00072-x.

Disagreements Between Calorimetric and Van't Hoff Enthalpies of Adsorption II: Effect of pH and pH Buffers on Phenobarbital Adsorption to Activated Carbon.

The reported inconsistencies between the van't Hoff equation and calorimetry hinder the utility of thermodynamics in biochemical and pharmaceutical research. A novel thermodynamic approach is developed herein for ligand adsorption with a focus on the interpretation of calorimetric data in the presence of concurrent proton exchange reactions. Such exchange reactions typically result in a pH-dependence of calorimetric measurements that obscures intrinsic binding enthalpies. It is shown that for the adsorption of phenobarbital to activated carbon, the measured calorimetric enthalpy is a result of three linked acid/base equilibria. A model was established to predict the intrinsic binding enthalpy using 1) the adsorbate's pKa and 2) the adsorbate's enthalpy of protonation. The observed calorimetric enthalpy of binding exhibited both pH and buffer-dependence and was between -5 and -42 kJ/mol. Meanwhile, the predicted intrinsic enthalpy (-25.1 kJ/mol) of binding was in excellent agreement with the measured intrinsic enthalpy (-25.6 kJ/mol). Corrections to the observed calorimetric enthalpies allowed comparisons with enthalpies obtained from the van't Hoff method. It is shown that the predicted intrinsic calorimetric enthalpy agrees well with the van't Hoff enthalpies in instances where observed enthalpies significantly deviated. This treatment is general and is not specific to phenobarbital or activated carbon.

Effect of lime on selected soil chemical properties, maize (Zea mays L.) yield and determination of rate and method of its application in Northwestern Ethiopia.

Soil acidity is the major soil chemical constraint that limits agricultural productivity in the highlands of Ethiopia receiving high rainfall. This study was conducted to evaluate the effect of different lime rates determined through different lime rate determination methods on selected soil chemical properties and yield of maize (Zea mays L.) on acidic Nitisols of Mecha district, Amhara Region, Ethiopia. The experiment had 10 treatments (0, 0.06, 0.12, 0.18, 1, 2, 3.5, 4, 7 and 14 tons ha-1 lime) that were calculated by three lime rate determination methods and applied through three lime application methods (spot, drill and broadcast). The experiment was arranged in randomized complete block design (RCBD) with four replications. N at the rate of 180 kg ha-1 and P at the rate of138 P2O5 kg ha-1 were applied to all plots. A full dose of P and lime as a treatment were applied at planting; whereas N was applied in split, 1/2 at planting and 1/2 at knee height stage. One composite soil sample before planting from experimental site and again one composite sample from each experimental unit were taken after harvest to analyze soil chemical parameters following appropriate laboratory procedure. Liming showed a positive significant difference on pH-H2O, pH-buffer, cation exchange capacity (CEC) and exchangeable bases but it had an inverse and significant effect on exchangeable acidity (EA). However, it didn't show any significant difference on soil C and N. Grain and above-ground biomass of maize yields had significant differences among treatments. The highest grain and biomass yields (7719 and 18180.6 kg ha-1, respectively) were obtained from application of broad cast method while the lowest (6479 and 15004.6 kg ha-1, respectively) were obtained from control treatment. Drill lime application method provided better efficiency with over 200% cost reduction advantage compared to the broadcast method to ameliorate the same level of acidity. Application of 3.5 tons ha-1 lime in the drilling method is recommendable to ameliorate soil acidity. However, from an economic point of view, application of 0.12 tons ha-1 lime applied in the micro-dosing method is more profitable due to low variable cost.

Alkaline Salt Inhibits Seed Germination and Seedling Growth of Canola More Than Neutral Salt.

Salinity is a major constraint to crop growth and productivity, limiting sustainable agriculture production. Planting canola (Brassica napus L.) variety with salinity-alkalinity tolerance as a green manure on the large area of salinity-affected land in Xinjiang could alleviate feed shortage. To investigate the differential effects of neutral and alkaline salt stress on seed germination and seedling growth of canola, we used two salts at varying concentrations, i.e., NaCl (neutral salt at 100, 150, and 200 mM) and Na2CO3 (alkaline salt at 20, 30, and 40 mM). To further explore the effects of Na+ and pH on seed germination, we included combined of NaCl (0, 100, 150, and 200 mM) and pH (7.1, 8.0, 9.0, 10.0, and 11.0). Shoot growth was promoted by low concentrations of NaCl and Na2CO3 but inhibited at high salt concentrations. Given the same Na+ concentration, Na2CO3 inhibited seed germination and seedling growth more than NaCl. The results showed that the main factor affecting seed germination and seedling growth is not pH alone, but the interaction between pH and salt ions. Under NaCl stress, canola increased the absorption of K+, Ca2+, and Mg2+ in roots and K+ in leaves. However, under Na2CO3 stress, canola maintained a high K+ concentration and K+/Na+ ratio in leaves and increased Ca2+ and Mg2+ in roots. Our study showed that alkaline salts inhibit canola seed germination and seedling growth more significantly than neutral salts and salt species, salt concentration, and pH significantly affected on seed germination and seedling growth. However, pH affected seed germination and seedling growth mainly through an interaction with salt ions.

Effect of pH Buffer and Carbon Metabolism on the Yield and Mechanical Properties of Bacterial Cellulose Produced by Komagataeibacter hansenii ATCC 53582.

Bacterial cellulose (BC) is widely used in the food industry for products such as nata de coco. The mechanical properties of BC hydrogels, including stiffness and viscoelasticity, are determined by the hydrated fibril network. Generally, Komagataeibacter bacteria produce gluconic acids in a glucose medium, which may affect the pH, structure and mechanical properties of BC. In this work, the effect of pH buffer on the yields of Komagataeibacter hansenii strain ATCC 53582 was studied. The bacterium in a phosphate and phthalate buffer with low ionic strength produced a good BC yield (5.16 and 4.63 g/l respectively), but there was a substantial reduction in pH due to the accumulation of gluconic acid. However, the addition of gluconic acid enhanced the polymer density and mechanical properties of BC hydrogels. The effect was similar to that of the bacteria using glycerol in another carbon metabolism circuit, which provided good pH stability and a higher conversion rate of carbon. This study may broaden the understanding of how carbon sources affect BC biosynthesis.

Syngas biomethanation: effect of biomass-gas ratio, syngas composition and pH buffer.

The concept of syngas biomethanation is attractive, however, it still needs improvement in optimizing the operational conditions. In the present study, syngas fermentations under different carbon monoxide (CO), carbon dioxide (CO2) and hydrogen (H2) compositions were conducted under two different biomass-gas ratio (BGR) systems. The results showed that high BGR enhanced the CO consumption rate, achieving a 60% enhancement with CO as the sole substrate. Stoichiometric H2 addition could successfully convert all the CO and CO2 to pure methane, however, higher H2 partial pressure might decline the CO consumption due to pH inhibition from consumption of bicarbonate. Microbial analysis showed different syngas composition could affect the bacteria community, while, archaea community was only slightly affected with Methanothermobacter as the dominant methanogen. This study provided strategy for efficient syngas biomethanation and deeper insight into effect of H2 addition on CO conversion under different BGR systems.

Nano zero-valent iron: A pH buffer, electron donor and activator for chain elongation.

Chain elongation produce medium chain carboxylates, which are important precursors to many pharmaceuticals, antimicrobials and biofuels. Results in the presented investigations show that the supply of nano zero-valent iron (NZVI) can enhance caproate production. The highest caproate concentration achieved amounted to 27.2 mmol/L when 5 g/L NZVI were added, which was about 100% higher than the control. The study also showed increase of ethanol oxidation and decrease of butyrate and butanol with NZVI addition. Mechanism study showed NZVI can stimulate caproate production by preventing pH to fall below 5.4 through displacement reaction. Electron balance analysis displayed that NZVI provides extra electron by promoting ethanol oxidation and its dissolution. H2 was the potential electron shuttle between NZVI and chain elongators; High throughput sequencing showed function of NZVI on reshaping of microbial communities, especially enriching Oscillibacter Marseille-P3260, a kind of chain elongator and Corynebacterium which possesses fatty acid biosynthesis and iron utilization.

An innovative nutritional slow-release packing material with functional microorganisms for biofiltration: Characterization and performance evaluation.

The type of packing material for biofiltration has a great impact on microbial growth and pollutant removal. This study evaluated the feasibility of a nutritional slow-release packing material with functional microorganisms (NSRP-FM) in a biofilter for the removal of gaseous n-butyl acetate. Through the emulsification-cross linked process and microbial immobilization, an innovative packing material was obtained, with a specific surface area of 2.45 m2 g-1 and a bulk density of 40.75 kg m-3. The cumulative release rates of total phosphorus and total nitrogen were 90.6% and 75.6%, respectively, as measured while continuously spraying deionized water. To evaluate the performance of biofiltration, NSRP-FM was compared with the commercial polyurethane foam (PU-foam), in two identical biotrickling filters (BTFs). The BTF packed with the prepared NSRP-FM maintained a consistent removal efficiency (over 95%) without nutrients addition and pH adjustment. The other BTF had poor removal performance, and the removal efficiency declined to 65% when there was no pH adjustment. Energy dispersive X-ray spectroscopy (EDS) analysis of NSRP-FM showed that inorganic elements were released during the operation of BTF. The abundance of functional microorganisms suggested that the prepared NSRP-FM provided a better environment for microbial growth, despite changes in the operating conditions.

Transport and release of electron donors and alkalinity during reductive dechlorination by combined emulsified vegetable oil and colloidal Mg(OH)2: Laboratory sand column and microcosm tests.

Emulsified vegetable oil combined with colloidal Mg(OH)2 (EVO-CM) can slowly release electron donors and OH- into groundwater and is therefore regarded as a promising amendment for enhanced in situ treatment of chlorinated solvents, such as tetrachloroethene (PCE) and trichloroethene (TCE). However, its migration ability in different porous media and the simultaneous release of electron donor and pH buffer during enhanced reductive dechlorination (ERD) have never been evaluated in detail. In this study, EVO-CM with uniform drop size and desirable stability was prepared. Laboratory-scale column tests were conducted to investigate the transport and spatial distribution of the EVO-CM in different porous media. Batch microcosm experiments were carried out to study the dechlorination efficiency under different EVO:Mg(OH)2 ratios. Experimental results indicate that prepared EVO-CM emulsions can be transported effectively through different porous media with grain size ranging from 0.1-1.0 mm. The emulsified vegetable oil (EVO) and colloidal Mg(OH)2 showed synchronous movement through the porous media column systems, providing both electron donor and alkalinity at the same location. The retention degree of EVO-CM is greater in the finer grained media and decreases with increasing distance from the inlet. The injection of EVO-CM lead to a significant mobilization of TCE in the column. The reductive dechlorination of TCE in the microcosms was remarkably enhanced in the presence of EVO-CM. The coaddition of sufficient colloidal Mg(OH)2 effectively limits the deleterious pH decline caused by acid release. The microcosm achieves an optimum dechlorination efficiency when the EVO:Mg(OH)2 ratio is 1:1.