Performance of titanium salts compared to conventional FeCl3 for the removal of algal organic matter (AOM) in synthetic seawater: Coagulation performance, organic fraction removal and floc characteristics.

During algal bloom periods, operation of seawater reverse osmosis (SWRO) pretreatment processes (e.g. ultrafiltration (UF)) has been hindered due to the high concentration of algal cells and algal organic matter (AOM). The present study evaluated for the first time the performance of titanium salts (i.e. titanium tetrachloride (TiCl4) and polytitanium tetrachloride (PTC)) for the removal of AOM in seawater and results were compared with the conventional FeCl3 coagulant. Previous studies already demonstrated that titanium salts not only provide a cost-effective alternative to conventional coagulants by producing a valuable by-product but also minimise the environmental impact of sludge production. Results from this study showed that both TiCl4 and PTC achieved better performance than FeCl3 in terms of turbidity, UV254 and dissolved organic carbon (DOC) removal at similar coagulant dose. Liquid chromatography - organic carbon detection (LC-OCD) was used to determine the removal of AOM compounds based on their molecular weight (MW). This investigation revealed that both humic substances and low MW organics were preferentially removed (i.e. up to 93% removal) while all three coagulants showed poorer performance for the removal of high MW biopolymers (i.e. less than 50% removal). The detailed characterization of flocs indicated that both titanium coagulants can grow faster, reach larger size and present a more compact structure, which is highly advantageous for the design of smaller and more compact mixing and sedimentation tanks. Both titanium coagulants also presented a higher ability to withstand shear force, which was related to the higher amount of DOC adsorbed with the aggregated flocs. Finally, TiCl4 had a better recovery after breakage suggesting that charge neutralization may be the dominant mechanism for this coagulant, while the lower recovery of both PTC and FeCl3 indicated that sweep flocculation is also a contributing mechanism for the coagulation of AOM.

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.

Agglomeration behaviour of titanium dioxide nanoparticles in river waters: A multi-method approach combining light scattering and field-flow fractionation techniques.

Titanium dioxide nanoparticles (TiO2 NPs) are currently one of the most prolifically used nanomaterials, resulting in an increasing likelihood of release to the environment. This is of concern as the potential toxicity of TiO2 NPs has been investigated in several recent studies. Research into their fate and behaviour once entering the environment is urgently needed to support risk assessment and policy development. In this study, we used a multi-method approach combining light scattering and field-flow fractionation techniques to assess both the aggregation behaviour and aggregate structure of TiO2 NPs in different river waters. Results showed that both the aggregate size and surface-adsorbed dissolved organic matter (DOM) were strongly related to the initial DOM concentration of the tested waters (i.e. R(2) > 0.90) suggesting that aggregation of TiO2 NPs is controlled by the presence and concentration of DOM. The conformation of the formed aggregates was also found to be strongly related to the surface-adsorbed DOM (i.e. R(2) > 0.95) with increasing surface-adsorbed DOM leading to more compact structures. Finally, the concentration of TiO2 NPs remaining in the supernatant after sedimentation of the larger aggregates was found to decrease proportionally with both increasing IS and decreasing DOM concentration, resulting in more than 95% sedimentation in the highest IS sample.

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.

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.

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.

How to optimize hollow-fiber submerged membrane bioreactors.

Membrane fouling is linked to reversible or irreversible accumulation of macromolecules and solids on membrane surfaces and to the irreversible adsorption inside pores. If reversible accumulation can be controlled by filtering in subcritical conditions, then adsorption could also be minimized by reducing the soluble organic matter [extracellular polymeric substances, soluble microbial products (SMP)]. This research shows how the choice of operating parameters related to biological reaction (solid retention time and the organic loading rate) can influence the process rate and the by-product (SMP) production. It also illustrates how suspension characteristics and membrane aeration can influence membrane fouling control according to the hollow fiber configuration and to the different scales of observation. The investigations were based on the definition of different fouling level and fine-tuning of a model to better understand the effects of operating parameters on membrane bioreactor filtration.

Preparation and characterisation of TiO2 nanoparticle and titanate nanotube obtained from Ti-salt flocculated sludge with drinking water and seawater.

This study aimed to prepare and characterise titanium dioxide (TiO2) nanoparticles and titanate nanotubes produced from Ti-sat flocculated sludge with drinking water (DW) and seawater (SW). The Ti-salt flocculated sludge from DW and SW was incinerated at 600 degrees C to produce TiO2 nanoparticles. XRD results showed that the anatase TiO2 structure was predominant for TiO2 from DW (TiO2-DW) and TiO2 from SW (TiO2-SW), which were mainly doped with carbon atoms. Titanate nanotubes (tiNT) were obtained when TiO2-DW and TiO2-SW were hydrothermally treated with NaOH solution. Structure phase, shape, crystallisation and photocatalytic activity of tiNT were affected by the incineration temperature and the amount of sodium present in different tiNT. The tiNT doped with thiourea incinerated at 600 degrees C presented anatase phase, showing a high increase of the degree of crystallisation with nanotube-like structures. The photocatalytic activity of these photocatalysts was evaluated using photooxidation of gaseous acetaldehyde. Thiourea doped tiNT-DW and tiNT-SW showed similar photocatalytic activity compared to commercially available TiO2-P25 under UV light and indicated a photocatalytic activity under visible light.

Sustainable engineering of sewers and sewage treatment plants for scenarios with urine diversion.

Urine diversion (UD) has been studied for decades as a way to enable distributed sanitation and to recycle nutrients onto land to fuel circular economies. No study to date has attempted a quantitative technical and economic analysis of the downstream effects of UD on sewage transport and treatment. This work used the SeweX model to reveal for the first time that through UD, hydrogen sulfide concentration in sewer headspaces can be reduced, and consequently sewer corrosion can be reduced. For a long rising main of 5 km, sewer headspace H2S can be reduced from 280 ppm to 200 ppm by diverting 75% of the urine. The same scenario enables the reduction of sewer corrosion from 12 to 10 mm/yr. Modeling sewage treatment plants with BioWin showed that sewage treatment responds to UD with a sharp reduction of the anoxic volume and a decrease of energy requirement by up to 50% at 75% UD. An upgrade of bioreactors to increase capacity by 20% can be completely avoided if 7% of the catchment's urine is diverted. Reductions in upgrade expenditure by up to 75% can provide the economic incentive for the uptake of UD.

Analysis of first flush to improve the water quality in rainwater tanks.

Although most Australians receive their domestic supply from reticulated mains or town water, there are vast areas with very low population densities and few reticulated supplies. In many of these areas rainwater collected in tanks is the primary source of drinking water. Heavy metals have recently become a concern as their concentration in rain water tanks was found to exceed recommended levels suitable for human consumption. Rainwater storage tanks also accumulate contaminants and sediments that settle to the bottom. Although not widely acknowledged, small amounts of contaminants such as lead found in rain water (used as drinking water) may have a cumulative and poisonous effect on human health over a life time. This is true for certain factors that underlie many of the chronic illnesses that are becoming increasingly common in contemporary society. The paper reports on a study which is part of a project that aims to develop a cost effective in-line filtration system to improve water quality in rainwater tanks. To enable this, the characteristics of rainwater need to be known. One component of this characterization is to observe the effects of the first flush on a rainwater tank. Samples of the roof runoff collected from an urban residential roof located in the Sydney Metropolitan Area in the initial first few millimetres of rain were analysed. The results show that bypassing the first 2 mm of rainfall gives water with most water quality parameters compliant with the Australian Drinking Water Guidelines (ADWG) standards. The parameters that did not comply were lead and turbidity, which required bypassing approximately the first 5 mm of rainfall to meet ADWG standards. Molecular weight distribution (MWD) analysis showed that the concentration of rainwater organic matter (RWOM) decreased with increasing amount of roof runoff.

Water quality characterisation of rainwater in tanks at different times and locations.

Rainwater collected from ten domestic roofs in Sydney and from one in Wollongong, a town south of Sydney, Australia was analysed to determine the water quality and to compare against the Australian Drinking Water Guidelines (ADWG) to determine its suitability as a potable water supply. The pollutants analysed were 13 heavy metals, 8 salts & minerals, pH, ammonia, orthophosphate, conductivity, water hardness, turbidity, total suspended solids, Total dissolved salts & Bicarbonate. The results indicate that the rainwater tested complied to most of the parameters specified in the ADWG. Molecular weight distribution of organic matter from one of the domestic rainwater tanks was analysed in terms of the effects of aging and roof contact. Molecular weight distribution of organic matter in rainwater showed prominent peaks at 37,500 daltons may be due to biopolymers, 850 Da to humic substances, 500 Da to building blocks, 220 Da to low MW acids, and less than 220 Da to amphiphilics. The findings also indicate that the first flush volumes that by-passed the tank can have a significant influence on the water quality in the rainwater tank.

Characterisation of titanium tetrachloride and titanium sulfate flocculation in wastewater treatment.

Flocculation with titanium tetrachloride (TiCl(4)) and titanium sulfate (Ti(SO(4))(2)) was investigated in terms of different coagulant doses, pH, turbidity, dissolved organic carbon (DOC), UV-254, colour, zeta potential, particle size and molecular weight distribution. The two coagulants were compared with the commonly used coagulants such as ferric chloride (FeCl(3)) and aluminium sulfate (Al(2)(SO(4))(3)). Titanium tetrachloride showed the highest turbidity removal, while titanium sulfate showed the highest reduction of UV-254 and colour at all pH values. The four coagulants were found to have similar organic removal up to 60-67% and resulted in similar organic removal in terms of various MW ranges. The decantability of the settled flocs was very high for titanium tetrachloride, titanium sulfate and ferric chloride compared with aluminium sulfate. The dominating coagulation mechanisms for titanium tetrachloride and titanium sulfate are still to be studied, since different precipitation reactions might take place at different pH even without flocculant addition. Titanium tetrachloride and titanium sulfate were found as effective new coagulants in wastewater treatment not only in terms of organic matter removal, but also in sludge reduction through the production of titanium dioxide.

Membrane fouling propensity after adsorption as pretreatment in rainwater: a detailed organic characterisation.

Organic characterisation in rainwater was investigated in terms of dissolved organic carbon (DOC) and molecular weight distribution (MWD) after powdered activated carbon (PAC) adsorption. PAC adsorption was used as pretreatment to membrane filtration to reduce membrane fouling. The MW of organic matter in rainwater used in this study was in the range of 43,000 Da to 30 Da. Each peak of organic matter consisted of biopolymers (polysaccharides and proteins), humic and fulvic acids, building blocks, low MW acids (hydrolysates of humic substances), low MW neutrals and amphiphilics. Rainwater contained the majority of hydrophilic compounds up to 72%. PAC adsorption removed 33% of total DOC. The removal efficiencies of the hydrophobic and hydrophilic fractions after PAC adsorption were 50% and 27%, respectively. PAC adsorption was found to preferentially remove the hydrophobic fraction. The majority of the smaller MW of 1,100 Da, 820 Da, 550 Da, 90 Da and 30 Da was removed after PAC adsorption. The MFI values decreased from 1,436 s/L2 to 147 s/L2 after PAC adsorption. It was concluded that PAC adsorption can be used as a pretreatment to membrane filtration with rainwater.

Evaluating the mobility of polymer-stabilised zero-valent iron nanoparticles and their potential to co-transport contaminants in intact soil cores.

The use of zero-valent iron nanoparticles (nZVI) has been advocated for the remediation of both soils and groundwater. A key parameter affecting nZVI remediation efficacy is the mobility of the particles as this influences the reaction zone where remediation can occur. However, by engineering nZVI particles with increased stability and mobility we may also inadvertently facilitate nZVI-mediated contaminant transport away from the zone of treatment. Previous nZVI mobility studies have often been limited to model systems as the presence of background Fe makes detection and tracking of nZVI in real systems difficult. We overcame this problem by synthesising Fe-59 radiolabelled nZVI. This enabled us to detect and quantify the leaching of nZVI-derived Fe-59 in intact soil cores, including a soil contaminated by Chromated-Copper-Arsenate. Mobility of a commercially available nZVI was also tested. The results showed limited mobility of both nanomaterials; <1% of the injected mass was eluted from the columns and most of the radiolabelled nZVI remained in the surface soil layers (the primary treatment zone in this contaminated soil). Nevertheless, the observed breakthrough of contaminants and nZVI occurred simultaneously, indicating that although the quantity transported was low in this case, nZVI does have the potential to co-transport contaminants. These results show that direct injection of nZVI into the surface layers of contaminated soils may be a viable remediation option for soils such as this one, in which the mobility of nZVI below the injection/remediation zone was very limited. This Fe-59 experimental approach can be further extended to test nZVI transport in a wider range of contaminated soil types and textures and using different application methods and rates. The resulting database could then be used to develop and validate modelling of nZVI-facilitated contaminant transport on an individual soil basis suitable for site specific risk assessment prior to nZVI remediation.

Analytical characterisation of nanoscale zero-valent iron: A methodological review.

Zero-valent iron nanoparticles (nZVI) have been widely tested as they are showing significant promise for environmental remediation. However, many recent studies have demonstrated that their mobility and reactivity in subsurface environments are significantly affected by their tendency to aggregate. Both the mobility and reactivity of nZVI mainly depends on properties such as particle size, surface chemistry and bulk composition. In order to ensure efficient remediation, it is crucial to accurately assess and understand the implications of these properties before deploying these materials into contaminated environments. Many analytical techniques are now available to determine these parameters and this paper provides a critical review of their usefulness and limitations for nZVI characterisation. These analytical techniques include microscopy and light scattering techniques for the determination of particle size, size distribution and aggregation state, and X-ray techniques for the characterisation of surface chemistry and bulk composition. Example characterisation data derived from commercial nZVI materials is used to further illustrate method strengths and limitations. Finally, some important challenges with respect to the characterisation of nZVI in groundwater samples are discussed.

Chemical coupling of photocatalysis with flocculation and adsorption in the removal of organic matter.

An experimental investigation was made to study the effects of chemical coupling of flocculation and adsorption with photocatalysis in treating persistent organic pollutants in wastewater. The photocatalysis alone showed initial reverse reaction when titanium oxide (TiO(2)) was used in catalysis. The effect of the pretreatment of adsorption with powdered activated carbon (PAC) on photocatalysis was studied. The results showed that PAC adsorption followed by photocatalysis was not effective in alleviating reverse reaction. On the other hand, when PAC and TiO(2) were added simultaneously, the reverse reaction was eliminated. Further, the organic removal was also improved by simultaneous PAC and TiO(2) additions. When flocculation with ferric chloride (FeCl(3)) was used as pretreatment, the organic removal efficiency was superior. The initial reverse reaction was also eliminated/minimized. However, inadequate doses of FeCl(3) (less than 30 mgl(-1)) resulted in initial reverse reaction and inferior DOC removal.

Is semi-flocculation effective as pretreatment to ultrafiltration in wastewater treatment?

In this study, ferric chloride (FeCl(3)) flocculation was used as a pretreatment to ultrafiltration (UF) in treating synthetic wastewater containing synthetic organic matter (SOM). The effect of flocculant dose was studied in terms of organic removal and membrane flux decline. The UF with optimum dose of FeCl(3) (68 mg L(-1)) did not experience any flux decline during the whole operation of 6 h. The preflocculation with a smaller dose of 20 mg L(-1) of FeCl(3) led to a severe flux decline in the UF (more than 65% in 6 h). To understand the phenomenon of the flux decline of UF, the MW ranges of SOM removed by different doses of FeCl(3) and by the post treatment of UF were studied. Flocculation with at least 50 mg L(-1) of FeCl(3) dose was found to be necessary to avoid any significant flux decline and to obtain superior DOC removal.

Foulant characterization of the NF membranes with and without pretreatment of biologically treated wastewater.

In this study, different pretreatment methods such as ferric chloride (FeCl3) flocculation and powdered activated carbon (PAC) adsorption were evaluated in terms of their capability in removing effluent organic matter (EfOM) and the characteristics of the foulants on the NF membranes. A detailed experiment was conducted with two NF membranes (NTR 729HF with MWCO 700 daltons and LF 10 with MWCO 200 daltons). With pretreatment, the concentration of organic matter on the membranes decreased to 5.671 x 10(-3) (NTR 729HF) and 4.940 x 10(-3) (LF 10) mg EfOM/cm2 of membrane from 6.372 x 10(-3) (NTR 729HF) and 4.979 x 10(-3) (LF 10) mg EfOM/cm2 of membrane. The MW of the solute fraction of biologically treated sewage effluent (BTSE) ranged from 250 daltons to about 3573 (the most important being 250-520 daltons). The weight-averaged MW values of the foulants on the NTR 729HF membrane reduced from 304 daltons without pre-treatment to 208 daltons with pretreatment. In the case of EfOM, the small molecules (MW 300 to 500 daltons) are mainly responsible for the membrane fouling. Thus, the MW distribution of organic matter in the effluent and in the foulant can be used as a representative tool to evaluate the efficiency of pretreatment and NF and in the selection of their operating conditions.

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.