Aggregation behaviour of engineered nanoparticles in natural waters: characterising aggregate structure using on-line laser light scattering.

Adsorption of natural organic matter, aggregation and disaggregation have been identified as three of the main processes affecting the fate and behaviour of engineered nanoparticles (ENPs) in aquatic environments. However, although several methods have been developed to study the aggregation behaviour of ENPs in natural waters, there are only a few studies focusing on the fate of such aggregates and their potential disaggregation behaviour. In this study, we proposed and demonstrated a simple method for characterising the aggregation behaviour and aggregate structure of ENPs in different natural waters. Both the aggregate size of ENPs and their adsorption capacity for dissolved organic matter (DOM) were strongly related (R(2)>0.97, p<.05) to the combined effect of initial concentration of dissolved organic matter (DOM) and the ionic strength of the natural waters. The structure of the formed aggregates was strongly correlated (R(2)>0.95, p<.05) to the amount of DOM adsorbed by the ENPs during the aggregation process. Under high ionic strength conditions, aggregation is mainly governed by diffusion and the aggregates formed under these conditions showed the lowest stability and fractal dimension, forming linear, chain-like aggregates. In contrast, under low ionic strength conditions, the aggregate structure was more compact, most likely due to strong chemical binding with DOM and bridging mechanisms involving divalent cations formed during reaction-limited aggregation.

Comparison of a novel polytitanium chloride coagulant with polyaluminium chloride: coagulation performance and floc characteristics.

Polymerized inorganic coagulants are increasingly being used in the water supply and wastewater treatment process, yet there is limited research on the development of polytitanium coagulants. The aim of this study is to synthesize polytitanium chloride (PTC) coagulants and investigate their coagulation behavior and floc characteristics for humic acid removal in comparison to polyaluminum chloride (PAC). The PTC samples with different B (molar ratios of OH/Ti) values were prepared using an instantaneous base-feeding method, employing sodium carbonate as the basification agent. The coagulation efficiency was significantly influenced by different B values. The results suggest that the humic acid removal increased with the increasing B value for PAC, while the inverse trend was observed for PTC. The optimum B value was chosen at 1.0 and 2.0 for PTC and PAC, respectively. Under the optimum coagulant dose and initial solution pH conditions, the PTC coagulant performed better than the PAC coagulant and the floc properties were significantly improved in terms of floc growth rate and floc size. However, the PAC coagulants produced flocs with better floc recoverability than the PTC coagulants.

Stability of Fe-oxide nanoparticles coated with natural organic matter under relevant environmental conditions.

Manufactured nanoparticles (MNPs) are increasingly released into the environment and thus research on their fate and behaviour in complex environmental samples is urgently needed. The fate of MNPs in the aquatic environment will mainly depend on the physico-chemical characteristics of the medium. The presence and concentration of natural organic matter (NOM) will play a significant role on the stability of MNPs by either decreasing or exacerbating the aggregation phenomenon. In this study, we firstly investigated the effect of NOM concentration on the aggregation behaviour of manufactured Fe-oxide nanoparticles. Then, the stability of the coated nanoparticles was assessed under relevant environmental conditions. Flow field-flow fractionation, an emerging method which is gaining popularity in the field of nanotechnology, has been employed and results have been compared to another size-measurement technique to provide increased confidence in the outcomes. Results showed enhanced stability when the nanoparticles are coated with NOM, which was due to electrosteric stabilisation. However, the presence of divalent cations, even at low concentration (i.e. less than 1 mM) was found to induce aggregation of NOM-coated nanoparticles via bridging mechanisms between NOM and Ca(2+).

Forward osmosis for the treatment of reverse osmosis concentrate from water reclamation: process performance and fouling control.

While high quality water reuse based on dual membrane filtration (membrane filtration or ultrafiltration, followed by reverse osmosis) is expected to be progressively applied, treatment and sustainable management of the produced reverse osmosis concentrate (ROC) are still important issues. Forward osmosis (FO) is a promising technology for maximising water recovery and further dewatering ROC so that zero liquid discharge is produced. Elevated concentrations of organic and inorganic compounds may act as potential foulants of the concentrate desalting system, in that they consist of, for example, FO and a subsequent crystallizer. The present study investigated conditions under which the FO system can serve as concentration phase with the focus on its fouling propensity using model foulants and real ROC. Bulk organics from ROC consisted mainly of humic acids (HA) and building blocks since wastewater-derived biopolymers were retained by membrane filtration or ultrafiltration. Organic fouling of the FO system by ROC-derived bulk organics was low. HA was only adsorbed moderately at about 7% of the initial concentration, causing a minor flux decline of about 2-4%. However, scaling was a major impediment to this process if not properly controlled, for instance by pH adjustment or softening.

Removal of natural organic matter by titanium tetrachloride: The effect of total hardness and ionic strength.

This study is the first attempt to investigate the effect of total hardness and ionic strength on coagulation performance and the floc characteristics of titanium tetrachloride (TiCl4). Membrane fouling under different total hardness and ionic strength conditions was also evaluated during a coagulation-ultrafiltration (C-UF) hybrid process. Coagulation experiments were performed with two simulated waters, using humic acid (HA, high molecular weight) and fulvic acid (FA, relatively low molecular weight), respectively, as model natural organic matter (NOM). Results show that both particle and organic matter removal can be enhanced by increasing total hardness and ionic strength. Floc characteristics were significantly influenced by total hardness and ionic strength and were improved in terms of floc size, growth rate, strength, recoverability and compactness. The results of the UF tests show that the pre-coagulation with TiCl4 significantly improves the membrane permeate fluxes. Under different total hardness and ionic strength conditions, the membrane permeate flux varied according to both NOM and floc characteristics. The increase in total hardness and ionic strength improved the membrane permeate flux in the case of HA simulated water treatment.

Preparation and characterization of novel polytitanium tetrachloride coagulant for water purification.

Polymeric metal coagulants are increasingly being used to improve coagulation efficiency, yet the research on the development of titanium and particularly polytitanium salts remains limited. This study is the first attempt in the synthesis, characterization, and application of polytitanium salts as coagulants. Polytitanium tetrachloride (PTC) solutions with different basicity values B (OH/Ti molar ratio) were prepared using a slow alkaline titration method. Jar tests were conducted to assess coagulation performance using both synthetic and real raw water samples, and the floc characteristics were monitored online using a laser diffraction particle size analyzer. Electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) was utilized to identify various Ti species, with the results providing strong evidence of the presence of various hydrolyzed Ti species in the titanium aqueous phase. Compared to titanium tetrachloride (TiCl4), higher or comparable turbidity and organic matter removal efficiency could be achieved by PTC with improved floc characteristics in terms of size, growth rate, and structure. Besides, the water pH after PTC coagulation was significantly improved toward neutral pH. This study indicates that PTC is an effective and promising coagulant for water purification. Besides, the PTC flocculated sludge was able to recycle and produce functional TiO2 photocatalyst.

Cationic polyacrylamide as coagulant aid with titanium tetrachloride for low molecule organic matter removal.

This is the first attempt to use cationic polyacrylamide (PAM) as coagulant aid with titanium tetrachloride (TiCl4) to improve the coagulation performance and floc properties. Coagulation-flocculation treatment was applied to simulated water (with fulvic acid (FA) as model organic matter) for both coagulation behavior investigation and floc characterization. The effect of PAM on floc reformation properties after cyclic breakage/regrowth was also investigated. Ultrafiltration experiments were performed to investigate the influence of PAM aided TiCl4 coagulation on the membrane fouling. The results showed that organic removal was enhanced by PAM addition at low TiCl4 doses. Floc growth rate and floc size were significantly affected by dosing sequence. TiCl4-PAM significantly improved the floc strength factors (Sf) and recovery factors (Rf). The dosing sequence of TiCl4 and PAM significantly influenced the floc structure. Characterization of the flocculated sludge indicated that TiO2 with anatase structure and high photocatalytic activity could be obtained from the TiCl4-PAM flocculated sludge.

Preparation of titanium dioxide nanoparticles from electrocoagulated sludge using sacrificial titanium electrodes.

A comprehensive investigation of electrocoagulation using sacrificial titanium (Ti) electrodes in wastewater was carried out. The effects of specific process variables, such as initial pH, mixing, current density, initial organic loading, and ionic/electrolyte strength were first optimized to produce recyclable Ti-based sludge. The sludge was incinerated at 600 degrees C to produce functional TiO(2) photocatalyst. X-ray diffraction analysis revealed that TiO(2) produced at optimum electrocoagulation conditions was mostly anatase structure. The specific surface area of the synthesized TiO(2) photocatalyst was higher than that of the commercially available and widely used Degussa P-25 TiO(2). Furthermore, energy dispersive X-ray and X-ray photoelectron spectroscopy analyses showed that in additional to titanium and oxygen, this photocatalyst is also composed of carbon and phosphorus. These elements were mainly doped as a substitute site for the oxygen atom. Transmission electron microscopy images exhibited sharply edged nanorods, round nanoparticles, and nanotubes with nonuniform shapes showing some structural defects. Photodecomposition of gaseous acetaldehyde by this photocatalyst was also conducted under UV and visible light irradiation to study the photocatalytic properties of the doped TiO(2) photocatalyst. While no photocatalytic activity was observed under visible light irradiation, this doped TiO(2) photocatalyst exhibited high photocatalytic activity under UV light.