Influence of granular activated carbon media properties on natural organic matter and disinfection by-product precursor removal from drinking water.

Operational and financial constraints challenge effective removal of natural organic matter (NOM), and specifically disinfection by-product (DBP) precursors, at remote and/or small sites. Granular activated carbon (GAC) is a widely used treatment option for such locations, due to its relatively low maintenance and process operational simplicity. However, its efficacy is highly dependent on the media capacity for the organic matter, which in turn depends on the media characteristics. The influence of GAC media properties on NOM/DBP precursor removal has been studied using a range of established and emerging media using both batch adsorption tests and rapid small-scale column tests. DBP formation propensity (DBPFP) was measured with reference to trihalomethanes (THMs) and haloacetic acids (HAAs). All GAC media showed no selectivity for specific removal of precursors of regulated DBPs; DBP formation was a simple function of residual dissolved organic carbon (DOC) levels. UV254 was found to be a good surrogate measurement of DBPFP for an untreated water source having a high DOC. Due to the much-reduced concentration of DBP precursors, the correlation was significantly poorer for the coagulation/flocculation-pretreateed water source. Breakthrough curves generated from the microcolumn trials revealed DOC removal and consequent DBP reduction to correlate reasonably well with the prevalence pores in the 5-10 nm range. A 3-6 fold increase in capacity was recorded for a 0.005-0.045 cm3/g change in 5-10 nm-sized pore volume density. No corresponding correlation was evident with other media pore size ranges.

THM and HAA formation from NOM in raw and treated surface waters.

The disinfection by-product (DBP) formation potential (FP) of natural organic matter (NOM) in surface water sources has been studied with reference to the key water quality determinants (WQDs) of UV absorption (UV254), colour, and dissolved organic carbon (DOC) concentration. The data set used encompassed raw and treated water sampled over a 30-month period from 30 water treatment works (WTWs) across Scotland, all employing conventional clarification. Both trihalomethane (THM) and haloacetic acid (HAA) FPs were considered. In addition to the standard bulk WQDs, the DOC content was fractionated and analysed for the hydrophobic (HPO) and hydrophilic (HPI) fractions. Results were quantified in terms of the yield (dDBPFP/dWQD) and the linear regression coefficient R2 of the yield trend. The NOM in the raw waters was found to comprise 30-84% (average 66%) of the more reactive HPO material, with this proportion falling to 18-63% (average 50%) in the treated water. Results suggested UV254 to be as good an indicator of DBPFP as DOC or HPO for the raw waters, with R2 values ranging from 0.79 to 0.82 for THMs and from 0.71 to 0.73 for HAAs for these three determinants. For treated waters the corresponding values were significantly lower at 0.52-0.67 and 0.46-0.47 respectively, reflecting the lower HPO concentration and thus UV254 absorption and commensurately reduced precision due to the limit of detection of the analytical instrument. It is concluded that fractionation offers little benefit in attempting to discern or predict chlorinated carbonaceous DBP yield for the waters across the geographical region studied. UV254 offered an adequate estimate of DBPFP based on a mean yield of ∼2600 and ∼2800 µg per cm-1 absorbance for THMFP for the raw and treated waters respectively and ∼3800 and2900 µg cm-1 for HAAFP, albeit with reduced precision for the treated waters.

Treatment of disinfection by-product precursors.

Formation of harmful disinfection by-products (DBPs), of which trihalomethanes (THMs) and haloacetic acids (HAAs) are the major groups, can be controlled by removal of natural organic matter (NOM) before disinfection. In the literature, removal of precursors is variable, even with the same treatment. The treatment of DBP precursors and NOM was examined with the intention of outlining precursor removal strategies for various water types. Freundlich adsorption parameters and hydroxyl rate constants were collated from the literature to link treatability by activated carbon and advanced oxidation processes (AOPs), respectively, to physico-chemical properties. Whereas hydroxyl rate constants did not correlate meaningfully with any property, a moderate correlation was found between Freundlich parameters and log K(ow), indicating activated carbon will preferentially adsorb hydrophobic NOM. Humic components of NOM are effectively removed by coagulation, and, where they are the principal precursor source, coagulation may be sufficient to control DBPs. Where humic species remaining post-coagulation retain significant DBP formation potential (DBPFP), activated carbon is deemed a suitable process selection. Anion exchange is an effective treatment for transphilic species, known for high carboxylic acid functionality, and consequently is recommended for carboxylic acid precursors. Amino acids have been linked to HAA formation and are important constituents of algal organic matter. Amino acids are predicted to be effectively removed by biotreatment and nanofiltration. Carbohydrates have been found to reach 50% of NOM in river waters. If the carbohydrates were to pose a barrier to successful DBP control, additional treatment stages such as nanofiltration are likely to be required to reduce their occurrence.

Inhibition of three algae species using chemicals released from barley straw.

Algal blooms are a significant problem in the UK, particularly in water sources that supply potable water treatment works. A wide range of methods to control algae have been tested and, whilst many are effective, they all have disadvantages. The use of barley straw to control algal growth in reservoirs is one option that is gaining popularity, but little is known about its mode of action. One suggested mechanism is that, as the straw is broken down, algastatic chemicals such as phenolics are released. Here we have used an algae inhibition test to evaluate the effect of chemicals reported to be released from straw on three common algal species: Chlorella vulgaris, Microcystis aeruginosa and Scenedesmus subspicatus. It was shown that, of the chemicals assessed, many produced an algastatic effect on the growth of the three algal species tested, with 2 phenyl-phenol being the most effective, whilst p-cresol and benzaldehyde were shown to be effective at concentrations similar to those that have been reported downstream of rotted straw. Scenedesmus subspicatus proved to be much more resistant to the chemicals tested than the other species.

Disinfection by-product formation of natural organic matter surrogates and treatment by coagulation, MIEX and nanofiltration.

Potentially the most effective means of controlling disinfection by-products (DBPs) is to remove precursors before disinfection. To understand relationships between physical properties, treatability and DBP formation, nine natural organic matter (NOM) surrogates were studied. Their DBP formation and removal by coagulation, MIEX anion exchange resin and two nanofiltration membranes was measured. Whereas treatability of NOM surrogates was explained in terms of their physicochemical properties, the same was not true of DBP formation. Hence it was not possible to selectively remove compounds which generate high amounts of DBPs. Instead, precursor removal strategies based upon empirical DBP formation potential testing are more apt. Under conditions simulating full-scale performance, MIEX did not offer improved performance over coagulation. A hydrophobic nanofiltration membrane proved successful for removing neutral, hydrophilic surrogates, and hence is also suitable for DBP precursors of this character.

Removal and recovery of phosphate from municipal wastewaters using a polymeric anion exchanger bound with hydrated ferric oxide nanoparticles.

A new type of ion exchange media which is highly selective for phosphate, and can be easily regenerated has been investigated. The media consists of hydrated ferric oxide nanoparticles dispersed within the pore structures of polymeric anion exchanger beads. The media combines the durability and mechanical strength of ion exchange resins with the high sorption capacity of ferric oxide for phosphate. The media was trialled in fixed bed mini column experiments with real final effluent from two UK sewage treatment works, one with treatment based on chemical precipitation with iron chloride salts into an activated sludge process (population >250,000), and one based on trickling filter treatment with no specific phosphorus removal process (population <10,000). Results show that the media has high capacity for removing phosphate, reaching capacity at 4000 and 1300 bed volumes for the chemical precipitation and trickling filter works respectively, with performance greatly exceeding that of a standard anion exchanger, Amberlite IRA-410. Also trialled was the media's ability to elute the phosphorus after breakthrough, with the aim of recovering and processing it into a useful product. A one step regenerative process using a single solution containing 4% NaOH and 2% NaCl was passed through the resin bed and the phosphorus concentration of each bed volume leaving the column analysed. 80% of the phosphorus was eluted in the first bed volume. Subsequent tests investigated the performance of the media after successive partial regenerations of one bed volume of the NaOH/NaCl solution. There was no loss of performance observed after ten regeneration cycles, and levels of eluted phosphate were consistently high. These results suggest that the media has high potential for the removal and recovery of phosphate from wastewater streams. Additionally, the small volume of regenerant required translates to a very small operational footprint.

Disinfection byproduct formation and fractionation behavior of natural organic matter surrogates.

While natural organic matter (NOM) surrogates are established in disinfection byproduct (DBP) research, their use in fractionation studies is rare. To understand how surrogates relate to drinking waters, a range of NOM surrogates were fractionated with XAD resins. Their trihalomethane (THM), haloacetic acid (HAA), haloacetaldehyde, haloacetonitrile, and haloketone formations after chlorination were recorded. While compounds with higher log K(ow) values behaved as hydrophobic acids, fractionation of the more hydrophilic compounds did not clearly correlate to the log K(ow). High HAA formation from ferulic and aspartic acids and 1,1,1-trichloropropanone (1,1,1-TCP) formation from 3-oxopropanoic acid were notable. Three amino acids, asparagine, aspartic acid, and tryptophan, formed significant levels of dichloroacetonitrile (DCAN) and trichloroacetaldehyde (TCA). Formation of DBPs did not correlate to any compound physical property; however, there were several correlations between DBP groups. The most significant were between dichloroacetic acid (DCAA) and dichloroacetonitrile (DCAN), DCAN and TCA, and dichloroacetaldehyde (DCA) and trichloroacetaldehyde, indicating the possibility of similar relationships in natural waters.

Chemical and biological oxidation of NOM surrogates and effect on HAA formation.

Formation of disinfection by-products (DBPs) can be controlled by removal of disinfection by-product precursors before disinfection. Variable success has been reported, depending on the treatment used and water tested. Chemical and biological oxidations are candidate technologies to control DBP formation. Given the uncertainty over the identity of DBP precursors, the use of surrogates of natural organic matter (NOM) allows fundamental probing of the links between compound character, removal and DBP formation. Nine compounds were chosen to represent NOM and their removal by two advanced oxidation processes (AOPs), UV-C irradiation and biological treatment compared while haloacetic acid (HAA) formation before and after treatment was measured. Although AOPs were able to fully remove all compounds, incomplete mineralisation led to increased HAA levels, dramatically in the case of two amino acids. Biological treatment was effective in removing amino acids but also moderately increased the HAA formation potential (HAAFP) of hydrophilic compounds. These findings indicate waters with high amino acid concentrations will be susceptible to raised HAA levels following AOP treatment and careful process selection for HAA control is required in such cases.

Mechanical sludge disintegration: providing an alternative carbon source for nutrient removal.

The primary driver for efficient biological nutrient removal (BNR) in activated sludge treatment is the sufficient supply of soluble carbon. Several methods have been proposed to increase available carbon sources and enhance BNR. This study examines the effect of ultrasonic equipment and mechanical disintegration technologies on surplus activated sludge (SAS), to release additional soluble chemical oxygen demand (SCOD) and volatile fattty acids (VFA), as a carbon food source for BNR. A laboratory sonicator with a maximum power of 550W, a 3KW SONIX radial horn and a deflaker declared to be used in the paper industry were investigated. All caused significant release of SCOD, up to 48 fold. The maximum concentration of VFA reached (from 0-1 mg 1(-1)), was 530 mg 1(-1). To assess the likely impact to BNR, batch (21) anaerobic lab tests examining the use of disintegrated sludge on phosphorus and nitrogen removal were completed. Phosphorus removal was estimated by observing the phosphate release under anaerobic conditions and up to 460% more release was observed relative to controls. In addition, denitrification rates were improved by over 106%. Ultrasonic and mechanical disintegration technologies have been shown to release soluble carbon for BNR, with subsequent laboratory nitrogen and phosphorus removal efficiencies observed to be comparable to acetate.

Struvite crystallisation and recovery using a stainless steel structure as a seed material.

A metallic system acting as a seed substrate has been designed and developed in order to assess its efficiency in recovering phosphorus as struvite. The device, consisting of two concentric stainless steel meshes, was immerged in the upper section of a pilot crystallisation reactor fed with synthetic liquors (MgCl(2) x 6H(2)O, NH(4)H(2)PO(4),) for 2h. Apart from soluble PO(4)-P removals which remained in the range 79-80% with or without application of the metallic system, it was found that under the specific operating conditions tested the meshes were capable of accumulating struvite at a rate of 7.6 gm(-2)h(-1), hence reducing significantly the amount of fine particles remaining in solution from 302.2 to 12 mg L(-1) when compared to trials without mesh.

Mechanical sludge disintegration for the production of carbon source for biological nutrient removal.

The primary driver for a successful biological nutrient removal is the availability of suitable carbon source, mainly in the form of volatile fatty acids (VFA). Several methods have been examined to increase the amount of VFAs in wastewater. This study investigates the mechanism of mechanical disintegration of thickened surplus activated sludge by a deflaker technology for the production of organic matter. This equipment was able to increase the soluble carbon in terms of VFA and soluble chemical oxygen demand (SCOD) with the maximum concentration to be around 850 and 6530 mgl(-1), for VFA and SCOD, respectively. The particle size was reduced from 65.5 to 9.3 microm after 15 min of disintegration with the simultaneous release of proteins (1550 mgl(-1)) and carbohydrates (307 mgl(-1)) indicating floc disruption and breakage. High performance size exclusion chromatography investigated the disintegrated sludge and confirmed that the deflaker was able to destroy the flocs releasing polymeric substances that are typically found outside of cells. When long disintegration times were applied (>or=10 min or >or=9000 kJkg(-1)TS of specific energy) smaller molecular size materials were released to the liquid phase, which are considered to be found inside the cells indicating cell lysis.

Ammonium removal from solution using ion exchange on to MesoLite, an equilibrium study.

This paper investigates the potential of MesoLite ion exchange media for ammonium (NH(4)(+)) removal from solution in the presence of competing cations. Batch tests were performed under a range of conditions to assess the effect of contact time, solution pH and solution concentration on the performance and capacity of the media for this application. The data obtained was fitted to the Langmuir and Freundlich isotherm models with the Langmuir model providing the better description of the process. Results indicate a maximum equilibrium capacity of 49g NH(4)(+)Nkg(-1) of media is achievable under the experimental conditions studied. A detailed examination of the data shows that increasing solution concentration and increased contact time provide the best performance at an optimum pH of between 6 and 7.

Kinetics of struvite precipitation: effect of the magnesium dose on induction times and precipitation rates.

The presence of white deposits in specific areas of wastewater treatment plants is generally the consequence of the spontaneous formation of a mineral called struvite. Struvite forms when the levels of phosphate, ammonium and magnesium naturally available in wastewater effluents reach a minimum molar ratio 1:1:1 under specific conditions of pH, temperature and mixing energy. Originally regarded as a phenomenon to be controlled or eliminated, struvite has been lately identified as an alternative way of removing and recovering P from wastewater effluents and generating a product identified as an excellent base for the production of slow release fertilisers. Chemical and physical principles of struvite precipitation and the development of crystallisation technologies have been widely investigated. However, little interest has been given to kinetics of struvite precipitation. In the present work the kinetics of struvite formation have been investigated at both laboratory and pilot scale in synthetic solutions containing Mg(2+), NH4(+), and PO4(3-) ions in a molar ratio 1:2:2 at room temperature. These different tests have used pH measurements to assess the impact of water chemistry on induction times, and more precisely the influence of magnesium levels on kinetic rates. Experimental results and kinetic calculations revealed that the control of the magnesium dose initially present in solution is decisive of the speed at which struvite nucleates.

Impact of reactor operation on success of struvite precipitation from synthetic liquors.

A pilot scale reactor was designed and developed to study struvite crystallisation principles. The present work focuses on the possible impact of the reactor's operating parameters on struvite characteristics, and evaluates the performances of the process in removing phosphorus. Struvite precipitation from synthetic liquors was investigated under various situations including: pH, magnesium dosing, addition of foreign ions such as calcium and increasing retention time. Small variations of all these parameters were found to have significant effects on struvite crystal characteristics and/or production. For instance, an increase of pH from 10.0 to 10.5 favoured the formation of Mg3(PO4)2.22H2O rather than struvite. For molar ratios Ca:Mg above 1:1, calcium ions competed with magnesium to form an amorphous calcium phosphate, hence inhibiting struvite formation. With regards to crystal growth, the process showed some limitations. Indeed, large amounts of fines were produced, and crystal rarely grew over 100 microm under optimum conditions. Based on those observations, zeta-potential measurements of struvite crystals were investigated. Results revealed highly negative zeta-potential values for all experiments, indicating that this may be a limitation to struvite tendency for agglomeration.

Ammonium removal from digested sludge liquors using ion exchange.

Liquors arising from the dewatering of digested sludge typically contain ammonium levels in the range 200-700mgl(-1) NH(4)(+)-N. These liquors are frequently recycled to the head of the wastewater treatment works (WwTW) untreated and can constitute >25% of the total nitrogen load entering the works at inlet. This paper investigates the use of a clay-based material, MesoLite, as an ion exchange medium for ammonium removal from recycle streams. Pilot-scale studies performed at Didcot WwTW, part of the Thames Water wastewater treatment network, indicate that MesoLite is highly selective for the ammonium ion. Results show that >95% of ammonium was removed from belt press liquors with an initial ammonium nitrogen concentration >600mgl(-1), with an overall ion exchange capacity >51g NH(4)(+)-Nkg(-1) medium and this resulted in an operating capacity in the range 27-36gNH(4)(+)-Nkg(-1).

Membrane chemical reactor (MCR) combining photocatalysis and microfiltration for grey water treatment.

Urban water recycling is now becoming an important issue where water resources are becoming scarce. This paper looks at reusing grey water; the preference is treatment processes based on biological systems to remove the dissolved organic content. Here, an alternative process, photocatalysis is discussed as it is an attractive technology that could be well-suited for treating the recalcitrant organic compounds found in grey water. The photocatalytic process oxidises organic reactants at a catalyst surface in the presence of ultraviolet light. Given enough exposure time, organic compounds will be oxidized into CO2 and water. The best contact is achieved in a slurry reactor but a second step to separate and recover the catalyst is need. This paper discusses a new membrane chemical reactor (MCR) combining photocatalysis and microfiltration for grey water treatment.

A spectrophotometer-based study of magnetic water treatment: assessment of ionic vs. surface mechanisms.

A technique previously used to study the effects of magnetic fields on calcium carbonate (CaCO3) precipitate is revisited in order to investigate the two most widely reported mechanisms. The laboratory-based study tested the effect of treating solutions and particulates of CaCO3 and showed that a repeatable magnetic effect on precipitation is observed, but only when CaCO3 particulates are exposed to magnetic fields, and not when a solution of sodium carbonate (Na2CO3) is exposed to magnetic fields. Issues regarding the reproducibility of the test are also discussed.

A review of floc strength and breakage.

The main focus of the paper is to review current understanding of floc structure and strength. This has been done by reviewing current theoretical understanding of floc growth and breakage and an analysis of different techniques used for measuring floc strength. An overview has also been made of the general trends seen in floc strength analysis. The rate of floc formation is a balance between breakage and aggregation with flocs eventually reaching a steady-state size for a given shear rate. The steady-state floc size for a particular shear rate can, therefore, be a good indicator of floc strength. This has resulted in the development of a range of techniques to measure floc size at different applied shear levels using a combination of one or more of the following tools: light scattering and transmission; microscopy; photography; video and image analysis software. Floc strength may be simply quantified using the initial floc size for a given shear rate and the floc strength factor. More complex techniques have used theoretical modelling to determine whether flocs break by large-scale fragmentation or smaller-scale surface erosion effects, although this interpretation is open to debate. Impeller-based mixing, ultrasound and vibrating columns have all been used to provide a uniform, accurate and controllable dissipation of energy onto a floc suspension to determine floc strength. Other more recent techniques have used sensitive micromanipulators to measure the force required to break or compress individual flocs, although these techniques have been limited to the measurement of only a few hundred flocs. General trends emerge showing that smaller flocs tend to have greater strength than larger flocs, whilst the use of polymer seems to give increased strength to only some types of floc. Finally, a comparison of the strength of different types of floc (activated sludge flocs, organic matter flocs, sweep flocs and charge neutralised flocs) has been made highlighting differences in relative floc strength.

Integrated odour modelling for sewage treatment works.

Odours from sewage treatment works are a significant source of environmental annoyance. There is a need for tools to assess the degree of annoyance caused, and to assess strategies for mitigation of the problem. This is the role of odour modelling. Four main stages are important in the development of an odour problem. Firstly, the odorous molecules must be formed in the liquid phase. They must then transfer from the liquid to the gaseous phase. They are then transported through the atmosphere to the population surrounding the odour source, and are then perceived and assessed by that population. Odour modelling as currently practised tends to concentrate on the transportation of odorants through the atmosphere, with the other areas receiving less attention. Instead, odour modelling should consider each stage in an integrated manner. This paper describes the development of integrated odour models for annoyance prediction. The models describe the liquid-phase transformations and emission of hydrogen sulphide from sewage treatment processes. Model output is in a form suitable for integration with dispersion models, the predictions of which can in turn be used to indicate the probability of annoyance. The models have been applied to both hypothetical and real sewage treatment works cases. Simulation results have highlighted the potential variability of emission rates from sewage treatment works, resulting from flow, quality and meteorological variations. Emission rate variations can have significant effects on annoyance predictions, which is an important finding, as they are usually considered to be fixed and only meteorological variations are considered in predicting the odour footprint. Areas for further development of integrated odour modelling are discussed, in particular the search for improved links between analytical and sensory measurements, and a better understanding of dose/response relationships for odour annoyance.

Combination of ferric and MIEX for the treatment of a humic rich water.

Seasonal periods of high rainfall have been shown to cause elevated natural organic matter (NOM) loadings at treatment works. These high levels lead to difficulties in removing sufficient NOM to meet trihalomethane (THM) standards, and hence better alternative treatments are required. Here the removal of NOM was investigated by a new ion exchange process (MIEX) using both bulk and fractionated NOM. Initial results showed that in excess of 80% of the raw water dissolved organic carbon (DOC) and greater than 85% of the UV absorbance from the bulk raw water could be removed by the use of MIEX alone. It was also seen that the removal of the more recalcitrant isolated fractions was increased. When MIEX was combined with a significantly reduced dose of coagulant a slight improvement on the overall DOC and UV removals was observed, however a significant decrease in the amount of THM formation potential (THMFP) in the final water was seen. This combined with the reduction in coagulant would imply a more efficient process during the times when the water becomes increasingly difficult to treat.