Electrocatalytic Upcycling of Nitrate Wastewater into an Ammonia Fertilizer via an Electrified Membrane.

Electrochemically upcycling wastewater nitrogen such as nitrate (NO3-) and nitrite (NO2-) into an ammonia fertilizer is a promising yet challenging research topic in resource recovery and wastewater treatment. This study presents an electrified membrane made of a CuO@Cu foam and a polytetrafluoroethylene (PTFE) membrane for reducing NO3- to ammonia (NH3) and upcycling NH3 into (NH4)2SO4, a liquid fertilizer for ready-use. A paired electrolysis process without external acid/base consumption was achieved under a partial current density of 63.8 ± 4.4 mA·cm-2 on the cathodic membrane, which removed 99.9% NO3- in the feed (150 mM NO3-) after a 5 h operation with an NH3 recovery rate of 99.5%. A recovery rate and energy consumption of 3100 ± 91 g-(NH4)2SO4·m-2·d-1 and 21.8 ± 3.8 kWh·kg-1-(NH4)2SO4, respectively, almost outcompete the industrial ammonia production cost in the Haber-Bosch process. Density functional theory (DFT) calculations unraveled that the in situ electrochemical conversion of Cu2+ into Cu1+ provides highly dynamic active species for NO3- reduction to NH3. This electrified membrane process was demonstrated to achieve synergistic nitrate decontamination and nutrient recovery with durable catalytic activity and stability.

Probing Internal Pressures and Long-Term Stability of Nanobubbles in Water.

Nanobubbles (NBs) in liquid exhibit many intriguing properties such as low buoyancy and high mass transfer efficiency and reactivity as compared to large bulk bubbles. However, it remains elusive why or how bulk NBs are stabilized in water, and particularly, the states of internal pressures of NBs are difficult to measure due to the lack of proper methodologies or instruments. This study employed the injection of high-pressure gases through a hydrophobized ceramic membrane to produce different gaseous NBs (e.g., N2, O2, H2, and CO2) in water, which is different from cavitation bubbles with potential internal low pressure and noncondensed gases. The results indicate that increasing the injection gas pressure (60-80 psi) and solution temperatures (6-40 °C) both reduced bubble sizes from approximately 400 to 200 nm, which are validated by two independent models developed from the Young-Laplace equation and contact mechanics. Particularly, the colloidal force model can explain the effects of surface tension and surface charge repulsion on bubble sizes and internal pressures. The contact mechanics model incorporates the measurement of the tip-bubble interaction forces by atomic force microscopy to determine the internal pressures and the hardness of NBs (e.g., Young's modulus). Both the colloidal force balance model and our contact mechanics model yielded consistent predictions of the internal pressures of various NBs (120-240 psi). The developed methods and model framework will be useful to unravel properties of NBs and support engineering applications of NBs (e.g., aeration or ozonation). Finally, the bulk NBs under sealed storage could be stable for around a week and progressively reduce in concentrations over the next 30-60 days.

Autohydrogenotrophic Denitrification Using the Membrane Biofilm Reactor for Removing Nitrate from High Sulfate Concentration of Water.

This study investigated the performance of an autohydrogenotrophic membrane biofilm reactor (MBfR) to remove nitrate from water with high sulfate concentrations. The results of simulated running showed that TN removal could be over than 98.8% with the maximum denitrification rate of 134.6 g N/m3 d under the conditions of the influent sulfate concentrations of 300 mg SO42-/l. The distribution ratio of H2 electron donor for nitrate and sulfate was 70.0 : 26.9 at the high influent loading ratio of sulfate/nitrate of 853.3 g SO42-/m3 d : 140.5 g N/m3 d, which indicated that denitrification bacteria (DB) were normally dominated to complete H2 electron with sulfate bacteria (SRB). The results of molecular microbiology analysis showed that the dominated DB were Rhodocyclus and Hydrogenophaga, and the dominated SRB was Desulfohalobium, under the high influent sulfate concentrations.

Coagulation behavior and floc characteristics of a novel composite poly-ferric aluminum chloride-polydimethyl diallylammonium chloride coagulant with different OH/(Fe3+ + Al3+) molar ratios.

In this paper, flocculating performance and mechanisms of a new composite coagulant, poly-ferric aluminum chloride-polydimethyl diallylammonium chloride (PFAC-PD) with different OH-/(Fe3+ + Al3+) molar ratios, were investigated for humic acid (HA)-kaolin synthetic wastewater treatment. The impact of OH-/(Fe3+ + Al3+) molar ratios on the removal efficiencies of turbidity and dissolved organic carbon, specific UV absorbance, coagulation mechanisms and dynamics was explored during the coagulation process using composite coagulants. The coagulation experimental results revealed that the composite coagulants with lower OH-/(Fe3+ + Al3+) molar ratio exhibited better coagulation efficiency. When OH-/(Fe3+ + Al3+) molar ratio of the composite coagulant was 1.5, adsorption-bridging played a dominant role in coagulating HA-kaolin synthetic wastewater. The floc growth rate and floc size, increased with increasing OH-/(Fe3+ + Al3+) molar ratio and the highest peak height of the size distribution was obtained by PFAC-PD with OH-/(Fe3+ + Al3+) = 1.5. Also, the composite coagulants with higher OH-/(Fe3+ + Al3+) molar ratio formed more compact flocs, as reflected by the higher fractal dimension value. The flocs coagulated by PFAC-PD with basicity value of 1.0 gave strong strength and good recoverability.

Nanobubble-enabled foam fractionation to remove algogenic odorous micropollutants.

Due to climate change and environmental pollution, natural lakes and reservoir water suffer increasingly serious algal blooms and associated water quality problems due to the presence of algal or algogenic organic matter (AOM) such as algal odour and toxins. Effective removal of these micropollutants, especially in the event of algal blooms, is critical to aesthetic values of water bodies, drinking water security and human health. The study investigated the removal efficiency of two common odorous compounds, trans-1,10-dimethyl-trans-9-decalol (geosmin) and 2-Methylisoborneol (2-MIB), using foam fractionation enabled by air nanobubbles with addition of two common cationic and anionic surfactants, sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB), to enhance foaming ability and stability. The results showed that the cationic surfactant (i.e., CTAB), a low pH, and high ionic strength significantly promoted the removal of geosmin and 2-MIB. For example, the removal tests using the synthetic water determined that the conditions of pH = 7, [CTAB] = 20 mg·L-1 and IS = 10 mM as NaCl resulted in both the highest geosmin removal rate of 91.81% and highest 2-MIB removal rate of 85.0%. The removal of two odorous compounds in real lake water was evaluated, which yielded removal rates of 83.2% for geosmin and 48.1% for 2-MIB, highlighting the minor inhibition from water matrixes on the removal performances. Compared to microbubbles, nanobubbles enabled greater surface areas of foam and higher removal efficiencies. The study provided new insights into the use of foam fractionation with air nanobubbles to enhance the removal of odorous compounds from impaired water and mitigate the negative environmental and health impacts of harmful algal blooms (HABs).

Unveiling the potential of nanobubbles in water: Impacts on tomato's early growth and soil properties.

Nanobubbles (NBs) in water have been proven to improve plant growth and seed germination, potentially reducing both water and fertilizer consumption. To unravel the promotion mechanism of NBs on plant growth, this study investigated the characteristics of NBs in tap water and their impacts on tomato's early growth, soil chemical properties, enzymatic activity and electrochemical properties of plant roots. Oxygen NBs (ONBs) were found to increase the seed germination by 10 % and plant growth by 30 %-50 % (e.g., stem and diameter), whereas nitrogen NBs (NNBs) only had a significant promotion (7 %-34 %) on plant height. Additionally, compared to control group, irrigation with ONBs increased the peroxidase activities by 500 %-1000 % in tomato leaves, which may increase the expression of genes for peroxidase and promote cell proliferation and plant growth. Moreover, electrical impedance spectroscopy (EIS) revealed that the ONBs could reduce the interfacial impedance due to the increased active surface area and electrical conductivity of root.

Aeration and dissolution behavior of oxygen nanobubbles in water.

HYPOTHESIS: Nanobubbles (NBs) in water elicit unique physicochemical and colloidal properties (e.g., high stability and longevity). Aeration kinetics and dissolution behavior of oxygen (O2) NBs are assumed to be bubble size dependent. EXPERIMENTS: As an indicator for aeration efficiency, volumetric mass transfer coefficient (KL·a) was assessed by measuring the dissolved oxygen (DO) levels during aeration using O2 NBs with different sizes. Mass transfer coefficient (KL) was estimated by correlation analysis. Moreover, a modified Epstein-Plesset (EP) model was developed to predict the dissolution behavior by monitoring the DO and size changes during the dissolution of O2 NBs in water. FINDINGS: A higher rate of DO increase and a higher equilibrium DO level were both observed after aeration with NBs that present higher surface areas for the mass transfer of O2 and a higher vapor pressure of O2 to drive the partitioning equilibrium. Dissolution kinetics of O2 NBs were highly dependent on the initial bubble size as indicated by the changes of bubble size and DO. Smaller NBs raised up DO faster, whereas larger NBs could lead to higher equilibrium DO levels. Moreover, the rate of DO decline and the quasi-steady DO levels both decreased when the dilution ratio increased, confirming that O2 NBs dictates the DO level in water. Finally, the dissolving NBs may either swell or shrink according to the model prediction.

Probing Surface Electrochemical Activity of Nanomaterials using a Hybrid Atomic Force Microscope-Scanning Electrochemical Microscope (AFM-SECM).

Scanning electrochemical microscopy (SECM) is used to measure the local electrochemical behavior of liquid/solid, liquid/gas and liquid/liquid interfaces. Atomic force microscopy (AFM) is a versatile tool to characterize micro- and nanostructure in terms of topography and mechanical properties. However, conventional SECM or AFM provides limited laterally resolved information on electrical or electrochemical properties at nanoscale. For instance, the activity of a nanomaterial surface at crystal facet levels is difficult to resolve by conventional electrochemistry methods. This paper reports the application of a combination of AFM and SECM, namely, AFM-SECM, to probe nanoscale surface electrochemical activity while acquiring high-resolution topographical data. Such measurements are critical to understanding the relationship between nanostructure and reaction activity, which is relevant to a wide range of applications in material science, life science and chemical processes. The versatility of the combined AFM-SECM is demonstrated by mapping topographical and electrochemical properties of faceted nanoparticles (NPs) and nanobubbles (NBs), respectively. Compared to previously reported SECM imaging of nanostructures, this AFM-SECM enables quantitative assessment of local surface activity or reactivity with higher resolution of surface mapping.

Generation of nanobubbles by ceramic membrane filters: The dependence of bubble size and zeta potential on surface coating, pore size and injected gas pressure.

Generation of gaseous nanobubbles (NBs) by simple, efficient, and scalable methods is critical for industrialization and applications of nanobubbles. Traditional generation methods mainly rely on hydrodynamic, acoustic, particle, and optical cavitation. These generation processes render issues such as high energy consumption, non-flexibility, and complexity. This research investigated the use of tubular ceramic nanofiltration membranes to generate NBs in water with air, nitrogen and oxygen gases. This system injects pressurized gases through a tubular ceramic membrane with nanopores to create NBs. The effects of membrane pores size, surface energy, and the injected gas pressures on the bubble size and zeta potential were examined. The results show that the gas injection pressure had considerable effects on the bubble size, zeta potential, pH, and dissolved oxygen of the produced NBs. For example, increasing the injection air pressure from 69 kPa to 414 kPa, the air bubble size was reduced from 600 to 340 nm respectively. Membrane pores size and surface energy also had significant effects on sizes and zeta potentials of NBs. The results presented here aim to fill out the gaps of fundamental knowledge about NBs and development of efficient generation methods.

Influences of Air, Oxygen, Nitrogen, and Carbon Dioxide Nanobubbles on Seed Germination and Plant Growth.

Nanobubbles (NBs) hold promise in green and sustainable engineering applications in diverse fields (e.g., water/wastewater treatment, food processing, medical applications, and agriculture). This study investigated the effects of four types of NBs on seed germination and plant growth. Air, oxygen, nitrogen, and carbon dioxide NBs were generated and dispersed in tap water. Different plants, including lettuce, carrot, fava bean, and tomato, were used in germination and growth tests. The seeds in water-containing NBs exhibited 6-25% higher germination rates. Especially, nitrogen NBs exhibited considerable effects in the seed germination, whereas air and carbon dioxide NBs did not significantly promote germination. The growth of stem length and diameter, leave number, and leave width were promoted by NBs (except air). Furthermore, the promotion effect was primarily ascribed to the generation of exogenous reactive oxygen species by NBs and higher efficiency of nutrient fixation or utilization.

Biosorption of Cu2+, Cd2+, Pb2+, and Zn2+ using dried marine green macroalga Caulerpa lentillifera.

The sorption of Cu2+, Cd2+, Pb2+, and Zn2+ by a dried green macroalga Caulerpa lentillifera was investigated. The removal efficiency increased with pH. The analysis with FT-IR indicated that possible functional groups involved in metal sorption by this alga were O-H bending, N-H bending, N-H stretching, C-N stretching, C-O, SO stretching, and S-O stretching. The sorption of all metal ions rapidly reached equilibrium within 20min. The sorption kinetics of these metals were governed by external mass transfer and intraparticle diffusion processes. The sorption isotherm followed the Langmuir isotherm where the maximum sorption capacities was Pb2+>Cu2+>Cd2+>Zn2+.

FTIR evaluation of functional groups involved in the formation of haloacetic acids during the chlorination of raw water.

This work investigated the formation potential of haloacetic acid (HAA) compounds in the raw water for the Bangkhen water treatment plant (Bangkok, Thailand). The resin adsorption technique (with three different types of resins, i.e. DAX-8, AG-MP-50 and WA-10) was employed to characterize the organic content in the raw water into six fractions, i.e. hydrophobic neutral (HPON), hydrophobic acid (HPOA), hydrophobic base (HPOB), hydrophilic neutral (HPIN), hydrophilic acid (HPIA) and hydrophilic base (HPIB). Hydrophilic species appeared to be the predominant organic species in this water source (approximately 60%) with the neutral fraction being the most abundant (approximately 40%). Hydrophobic species, on the other hand, played the most important role in the formation of haloacetic acids as they contributed to as much as approximately 56% of total HAA formation potential. Among the three hydrophobic species, the hydrophobic base exhibited the highest specific HAA formation with 208mugHAAs/mg of dissolved organic carbon (DOC). Each organic fraction was examined for its associated functional groups by Fourier transform infrared (FTIR). The investigation of the formation of HAAs was achieved by tracking the changes in the FTIR results of the same water sample before and after the chlorination reaction. Based on the results obtained from this study, carboxylic acids, ketone, amide, amino acids and aromatic characteristic organics seemed to be the main precursors to HAA formation.

Trihalomethanes formation potential of shrimp farm effluents.

Shrimp farm effluents along the Bangpakong River in the Chachoengsao Province of Thailand were evaluated for their trihalomethane formation potential (THMFP) and related parameters. The dissolved organic carbon (DOC), salinity and bromide ion concentrations of shrimp farm effluents were in the ranges of 12-14 mg/L, 0.1-14.5 ppt, and 0-14 mg/L, respectively. The dissolved organic matter was fractionated into hydrophobic and hydrophilic fractions having a range concentration of 3-5 and 8-10mg/L, respectively. The THMFP for all shrimp farm effluents analyzed was in the range of 810-3100 microg/L. The hydrophilic organic fraction was found to be a more active precursor of trihalomethanes (THMs) with 700-966 microg/L THMFP obtained from this fraction, while only 111-363 microg/L THMFP was derived from the hydrophobic fraction. The experimental results showed that salinity and bromide played crucial roles in the formation of THMs. At low salinity and bromide levels, chloroform was the dominant THM species, whereas at high salinity and bromide levels, bromoform became the dominant species. A Fourier Transform Infrared (FTIR) spectrum analysis of the samples before and after chlorination illustrated that the functional groups involved in the THM formation reaction were phenolic compounds, amines, aromatic hydrocarbons, aliphatic bromo-compounds, and aliphatic chloro-compounds.

Ceramic membrane defouling (cleaning) by air Nano Bubbles.

Ceramic membranes are among the most promising technologies for membrane applications, owing to their excellent resistance to mechanical, chemical, and thermal stresses. However, membrane fouling is still an issue that hampers the applications at large scales. Air Nano Bubbles (NBs), due to high mass transfer efficiency, could potentially prevent fouling of ceramic membrane filtration processes. In this study, bench and pilot scale ceramic membrane filtration was performed with air NBs to resist fouling. To simulate fouling, humic acid, as an organic foulant, was applied to the membrane flat sheet surface. Complete membrane clogging was achieved in less than 6 h. Membrane defouling (cleaning) was performed by directly feeding of air NBs to the membrane cells. The surface of the ceramic membrane was superbly cleaned by air NBs, as revealed by atomic force microscope (AFM) images before and after the treatment. The permeate flux recovered to its initial level (e.g., 26.7 × 10(-9) m(3)/m(2)/s at applied pressure of 275.8 kPa), which indicated that NBs successfully unclogged the pores of the membrane. The integrated ceramic membrane and air NBs system holds potential as an innovative sustainable technology.

A SEM and X-ray study for investigation of solidified/stabilized arsenic-iron hydroxide sludge.

Despite the fact that the solidification/stabilization of arsenic containing wastes with Portland cement and lime has an extensively documented history of use, the physical and chemical phenomena as a result of the interaction between arsenic and cement components have not been fully characterized. The study investigates the behavior of synthesized arsenic-iron hydroxide sludge, the by-product of arsenic removal by coagulation with ferric chloride, in solidified/stabilized matrices as well as its binding mechanisms by exploring the cementitious matrices in the micro-scale by scanning electron microscopy equipped with energy dispersive X-ray spectrometer (SEM-EDS). It was revealed that arsenic can be chemically fixed into cementitious environment of the solidified/stabilized matrices by three important immobilization mechanisms; sorption onto C-S-H surface, replacing SO4(2-) of ettringite, and reaction with cement components to form calcium-arsenic compounds, the solubility limiting phases.

Reduction of organic matter and trihalomethane formation potential in reclaimed water from treated industrial estate wastewater by coagulation.

Raw water from treated industrial estate wastewater in northern Thailand was used in jar-test coagulation experiments with variations of separate alum and ferric chloride dosages from 10 to 80 mg/L at pH conditions ranging from 5 to 6.5. Natural organic matter (NOM) surrogates and trihalomethane formation potential (THMFP) were determined to study their reduction. The obtained results showed that total organic carbon (TOC) were gradually reduced from the average value of about 6.1 mg/L to a level of about 4.0 mg/L by alum and ferric chloride dosages of approximately 40 mg/L. Moreover, dissolved organic carbon (DOC) were reduced from an average value of 5.1 mg/L to a level of about 4.0 mg/L by alum and ferric chloride dosages of approximately 40 mg/L. Specific ultraviolet absorption (SUVA) were decreased from an average value of approximately 4.7 L/mgm to a level of about 2 L/mgm by alum and ferric chloride dosages of approximately 20 mg/L. In addition, chlorine demands at 1 day reaction were the same as those of 7-day demands with a correlation coefficient of 0.98 (n = 10, correlation significant at the 0.01 level). Interestingly, chloroform of approximately 65 and 60% of total THMFP was found as the predominant THMFP species in treated industrial estate wastewater and reclaimed water, respectively, in comparison with other THM species. Maximum THMFP percentage removal of 25 and 28 by using alum and ferric chloride dosages of about 80 mg/L at pH 5.5 and 5 were obtained, respectively, at the examined conditions.

Reduction of organic matter and trihalomethane formation potential in reclaimed water from treated industrial estate wastewater by coagulation.

Raw water from treated industrial estate wastewater in northern Thailand was used in jar-test coagulation experiments with variations of separate alum and ferric chloride dosages from 10 to 80 mg/L at pH conditions ranging from 5 to 6.5. Natural organic matter (NOM) surrogates and trihalomethane formation potential (THMFP) were determined to study their reduction. The obtained results showed that total organic carbon (TOC) were gradually reduced from the average value of about 6.1 mg/L to a level of about 4.0 mg/L by alum and ferric chloride dosages of approximately 40 mg/L. Moreover, dissolved organic carbon (DOC) were reduced from an average value of 5.1 mg/L to a level of about 4.0 mg/L by alum and ferric chloride dosages of approximately 40 mg/L. Specific ultraviolet absorption (SUVA) were decreased from an average value of approximately 4.7 L/mg-m to a level of about 2 L/mg-m by alum and ferric chloride dosages of approximately 20 mg/L. In addition, chlorine demands at 1-day reaction were the same as those of 7-day demands with a correlation coefficient of 0.98 (n = 10, correlation significant at the 0.01 level). Interestingly, chloroform of approximately 65 and 60% of total THMFP was found as the predominant THMFP species in treated industrial estate wastewater and reclaimed water, respectively, in comparison with other THM species. Maximum THMFP percentage removal of 25 and 28 by using alum and ferric chloride dosages of about 80 mg/L at pH 5.5 and 5 were obtained, respectively, at the examined conditions.

Characterization of precursors to trihalomethanes formation in Bangkok source water.

Resin adsorption techniques using three types of resin (DAX-8, AG-MP-50, and WA-10) were employed to characterize the raw water (RW) from the major 3 million m3/day (793 million gal/day) drinking water treatment plant in Bangkok, Thailand. The dissolved organic carbon (DOC) mass distribution sequences of the six organic fractions in raw water, from high to low, were hydrophilic neutral (HPIN), hydrophobic acid (HPOA), hydrophilic acid (HPIA), hydrophobic neutral (HPON), hydrophilic base (HPIB), and hydrophobic base (HPOB). HPIN and HPOA were the two main precursors for trihalomethanes formation (THMFP) in this water source following chlorination. The chlorination of HPON and HPIN fractions only led to the formation of mostly chloroform, while other organic fractions formed both chloroform and bromodichloromethane. The linear dependency between each organic fraction concentration and THMFP indicated that the reactions of each organic fraction with chlorine were first-order.

Predicting organic loading in natural water using spectral fluorescent signatures.

Spectral fluorescent signature (SFS) is a rapid, reagent free and inexpensive technique, which has great potential for environmental monitoring of aqueous systems, especially for predicting dissolved organic carbon (DOC) along natural waters. This technical note aimed to examine the possibility to use SFS associated with partial least squares regression (PLS) to assess the organic loading in natural water. A model was built using samples of water collected between October 1999 and February 2002 on the Passaic River at Little Falls, NJ, USA. A correlation was established between measured DOC, SFS, and the corresponding daily registered flow from United States Geological Survey (USGS) New Jersey's streamflow database. The methodology presented herein looks promising in making use of the significant organic characteristics information contained in a SFS for application and use in spatial and temporal water quality management and treatment.

Comparison of spectral fluorescent signatures-based models to characterize DOM in treated water samples.

Statistical procedures enable a multivariate analysis of the measurements to identify specific characteristics of the dissolved organic matter (DOM) fractions in raw natural water, including the concentrations. In this work, three already established models were used to predict the concentrations of fractions of DOM from spectral fluorescent signatures (SFSs): a general linear regression (GLR), loadings and scores of a principal components analysis (PCA), and a partial least squares regression (PLS). Details about the method undertaken to prepare the fractions were given. Water samples from surface water treatment plants in New Jersey were used for the testing. In all cases, PLS have shown much better biases and accuracies than GLR and PCA models. Hydrophilic neutral, however, showed poor performances (bias 33%) due to the isolation technique used. Recommendations were provided in order to improve the DOM characterization through SFS, which linked to PLS make a powerful and cost-effective surrogate parameter to characterize DOM.