probing-surface-electrochemical-activity-nanomaterials-using-hybrid

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. ...

New Jersey Institute of Technology

Spectro-fluorescence signature (SFS) of water samples contains information that may be used to quantify dissolved organic carbon (DOC) if combined with multivariate analyses. A model was built through SFS and partial least squared (PLS) regression. The SFSs of 219 samples of natural water along the Raritan River and Millstone River watersheds located in central New Jersey, and their corresponding DOC concentrations were used to build the model. Calibration, full cross-validation, and prediction performances of various models were statistically compared before optimal model selection. The final selected model, tested on the Passaic River watershed in northern New Jersey, provided a bias of 0.028 mg/l and a root mean squared error of prediction (RMSEP) of 0.35 mg/l. Linked to PLS, SFS can be a quality and cost effective method to perform on-line rapid DOC measurements.

Spectral fluorescence signatures and partial least squares regression: model to predict dissolved organic carbon in water.

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.

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

Chemical, biological and physical data monitored at 12 locations along the Passaic River, New Jersey, during the year 1998 are analyzed. Principal component analysis (PCA) was used: (i) to extract the factors associated with the hydrochemistry variability; (ii) to obtain the spatial and temporal changes in the water quality. Solute content, temperature, nutrients and organics were the main patterns extracted. The spatial analysis isolated two stations showing a possible point or non-point source of pollution. This study shows the importance of environmental monitoring associated with simple but powerful statistics to better understand a complex water system.

Using principal component analysis to monitor spatial and temporal changes in water quality.

A technique to fractionate dissolved organic materials (DOMs) from low DOM water (<5mg/l) was developed by using triple columns of DAX-8 adsorption resin, one column of AG-MP-50 cationic resin, and another column of WA 10 weak anionic resin in sequence. The procedure was then applied to fractionate water samples obtained at various sampling locations throughout two surface water treatment plants (WTPs) in central New Jersey to study its effectiveness, DOM occurrence, and variation along treatment units. The treatment plants utilize different treatment methods, hence producing variability in DOM fractions suitable for examining the procedure's effectiveness. This procedure was compared with current fractionation protocols and proved to be accurate in fractionation of low DOM water.

Modified dissolved organic matter fractionation technique for natural water.

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.

Predicting organic loading in natural water using spectral fluorescent signatures.

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.

Trihalomethanes formation potential of shrimp farm effluents.

The characterization of dissolved organic matter (DOM) in source water not only is central to the study of precursors to disinfection by-products (DBPs), but can also aid in controlling the discharge of potentially harmful organic chemicals in water bodies. Rapid determination of six DOM fraction concentrations provides an added advantage in understanding the organic character of water in comparison to the measure of dissolved organic carbon (DOC), which is an aggregate parameter typically used by water purveyors. The experimental procedure for DOM isolation and fractionation by ionic resins is lengthy and tedious. Many attempts have been made towards the development of faster and reliable techniques including statistical analysis applied to spectral fluorescent signature (SFS). Fluorescence is a very sensitive technique and works best only at certain wavelengths that are different for different materials. It is therefore difficult to quantify a material using fluorescence technique, especially when the entire fluorescence matrix is considered. To address this difficulty, an innovative two-stage processing technique is developed in this research in order to build an enhanced, more robust empirical model. At stage I, the dimensionality of the input data is reduced by focusing on specific portion of the entire matrix obtained by applying scatter removal, peak analysis, and coefficient of variation (CV) analysis. Then statistical analysis in the form of principal component regression (PCR) follows as stage II. In addition, the same technique is applied to predict trihalomethanes formation potential (THMFP). This model provides better sensitivity and accuracy, while maintaining the advantages of the SFS technique for rapid identification and quantification of DOM fractions.

Principal component regression model applied to dimensionally reduced spectral fluorescent signature for the determination of organic character and THM formation potential of source water.

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.

Ceramic membrane defouling (cleaning) by air Nano Bubbles.

In this paper, flocculating performance and mechanisms of a new composite coagulant, poly-ferric aluminum chloride-polydimethyl diallylammonium chloride (PFAC-PD) with different OH/(Fe + Al) molar ratios, were investigated for humic acid (HA)-kaolin synthetic wastewater treatment. The impact of OH/(Fe + Al) 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/(Fe + Al) molar ratio exhibited better coagulation efficiency. When OH/(Fe + Al) 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/(Fe + Al) molar ratio and the highest peak height of the size distribution was obtained by PFAC-PD with OH/(Fe + Al) = 1.5. Also, the composite coagulants with higher OH/(Fe + Al) 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.

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

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.

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

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.

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

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/m d under the conditions of the influent sulfate concentrations of 300 mg SO/l. The distribution ratio of H electron donor for nitrate and sulfate was 70.0 : 26.9 at the high influent loading ratio of sulfate/nitrate of 853.3 g SO/m d : 140.5 g N/m d, which indicated that denitrification bacteria (DB) were normally dominated to complete H electron with sulfate bacteria (SRB). The results of molecular microbiology analysis showed that the dominated DB were  and , and the dominated SRB was , under the high influent sulfate concentrations.

Autohydrogenotrophic Denitrification Using the Membrane Biofilm Reactor for Removing Nitrate from High Sulfate Concentration of 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., N, O, H, and CO) 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.

Article	Year
Spectral fluorescence signatures and partial least squares regression: model to predict dissolved organic carbon in water. Journal of hazardous materials\| PubMed ID: 12573831	2003
Comparison of spectral fluorescent signatures-based models to characterize DOM in treated water samples. Journal of hazardous materials\| PubMed ID: 12835017	2003
Using principal component analysis to monitor spatial and temporal changes in water quality. Journal of hazardous materials\| PubMed ID: 12835021	2003
Modified dissolved organic matter fractionation technique for natural water. Journal of hazardous materials\| PubMed ID: 12850319	2003
Predicting organic loading in natural water using spectral fluorescent signatures. Journal of hazardous materials\| PubMed ID: 15120874	2004
Trihalomethanes formation potential of shrimp farm effluents. Journal of hazardous materials\| PubMed ID: 16442713	2006
Principal component regression model applied to dimensionally reduced spectral fluorescent signature for the determination of organic character and THM formation potential of source water. Journal of hazardous materials\| PubMed ID: 19477070	2009
Ceramic membrane defouling (cleaning) by air Nano Bubbles. Chemosphere\| PubMed ID: 26741542	2016
Coagulation behavior and floc characteristics of a novel composite poly-ferric aluminum chloride-polydimethyl diallylammonium chloride coagulant with different OH/(Fe + Al) molar ratios. Water science and technology : a journal of the International Association on Water Pollution Research\| PubMed ID: 27763344	2016
Generation of nanobubbles by ceramic membrane filters: The dependence of bubble size and zeta potential on surface coating, pore size and injected gas pressure. Chemosphere\| PubMed ID: 29626810	2018
Influences of Air, Oxygen, Nitrogen, and Carbon Dioxide Nanobubbles on Seed Germination and Plant Growth. Journal of agricultural and food chemistry\| PubMed ID: 29722967	2018
Autohydrogenotrophic Denitrification Using the Membrane Biofilm Reactor for Removing Nitrate from High Sulfate Concentration of Water. Archaea (Vancouver, B.C.)\| PubMed ID: 30174556	2018
Probing Internal Pressures and Long-Term Stability of Nanobubbles in Water. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 33538170	2021

Taha Marhaba

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