John van Leeuwen

The impact of alum coagulation on the character, biodegradability and disinfection by-product formation potential of reservoir natural organic matter (NOM) fractions

Natural Organic Matter (NOM) from Myponga Reservoir, South Australia, was separated into four organic fractions based on their hydrophobic and hydrophilic properties using a sequence of non-ionic and ionic resins. NOM fractions were isolated for the purpose of determining the impact of alum coagulation on removal of these fractions in conventional water treatment, and their potential as precursors in the formation of disinfection by-products (DBP) and in supporting microbial growth. The NOM comprised VHA (very hydrophobic acids), SHA (slightly hydrophobic acids), CHA (charged hydrophilics) and NEU (neutral hydrophilics) fractions. These fractions were then jar tested with alum using low (50 mg/L), operational (100 mg/L) and very high (200 mg/L) doses to assess the removal capacities for these fractions in a conventional treatment plant. High-performance size exclusion chromatography-UV-DOC (HPSEC-UV-DOC) revealed that alum removed more of the hydrophobic and higher molecular weight components of NOM, but less of the NEU fraction and lower molecular weight components of NOM. Determination of biodegradable dissolved organic carbon (BDOC) indicated that the NEU fraction had the highest biodegradability, followed by the CHA, SHA and VHA fractions. The VHA fraction had the highest total-trihalomethane formation potential (t-THMFP), followed by NEU, SHA and CHA. The NOM not removed by alum coagulation had the potential to support microbial growth (NEU fraction), and disinfection by-product (DBP) formation (VHA and NEU fractions). To obtain treated water with lower overall residual NOM, other treatment methods would need to be applied in addition to alum coagulation in order to reduce the concentration of the neutral fraction.

pH modeling for maximum dissolved organic matter removal by enhanced coagulation

Correlations between raw water characteristics and pH after enhanced coagulation to maximize dissolved organic matter (DOM) removal using four typical coagulants (FeCl3, Al2(SO4)3, polyaluminum chloride (PACl) and high performance polyaluminum chloride (HPAC)) without pH control were investigated. These correlations were analyzed on the basis of the raw water quality and the chemical and physical fractionations of DOM of thirteen Chinese source waters over three seasons. It was found that the final pH after enhanced coagulation for each of the four coagulants was influenced by the content of removable DOM (i.e. hydrophobic and higher apparent molecular weight (AMW) DOM), the alkalinity and the initial pH of raw water. A set of feed-forward semi-empirical models relating the final pH after enhanced coagulation for each of the four coagulants with the raw water characteristics were developed and optimized based on correlation analysis. The established models were preliminarily validated for prediction purposes, and it was found that the deviation between the predicted data and actual data was low. This result demonstrated the potential for the application of these models in practical operation of drinking water treatment plants.

Prediction of DOM removal of low specific UV absorbance surface waters using HPSEC combined with peak fitting

High performance size exclusion chromatography (HPSEC) is used in water quality research primarily to determine the molecular weight distribution of the dissolved organic matter (DOM), but by applying peak fitting to the chromatogram, this technique can also be used as a tool to model and predict DOM removal. Six low specific UV absorbance (SUVA) source waters were treated using coagulation with alum and both the source and treated water samples were analysed using HPSEC. By comparing the molecular weight profiles of the source and treated waters, it was established that several DOM components were not effectively removed by alum coagulation even after high dosage alum treatment. A peak-fitting technique was applied based on the concept of linking the character (molecular weight profile) of the recalcitrant organics in the treated water with those of the source water. This was then applied to predict DOM treatability by determining the areas of the peaks which were assigned to removable organics from the source water molecular weight profile after peak fitting, and this technique quantified the removable and non-removable organics. The prediction was compared with the actual dissolved organic carbon (DOC) removal determined from jar testing and showed good agreement, with variance between 2% and 10%. This confirmed that this prediction approach, which was originally developed for high SUVA waters, can also be applied successfully to predict DOC removal in low SUVA waters.

Changes in the quality of river water before, during and after a major flood event associated with a La Nina cycle and treatment for drinking purposes

The treatment of organics present in the lower reaches of a major river system (the Murray-Darling Basin, Australia) before (March-July 2010), during (December 2010-May 2011) and after (April-December 2012) a major flood period was investigated. The flood period (over 6months) occurred during an intense La Niña cycle, leading to rapid and high increases in river flows and organic loads in the river water. Dissolved organic carbon (DOC) increased (2-3 times) to high concentrations (up to 16mg/L) and was found to correlate with river flow rates. The treatability of organics was studied using conventional jar tests with alum and an enhanced coagulation model (mEnCo©). Predicted mean alum dose rates (per mg DOC) were higher before (9.1mg alum/mg DOC) and after (8.5mg alum/mg DOC) than during the flood event (8.0mg alum/mg DOC), indicating differences in the character of the organics in raw waters. To assess the character of natural organic matter present in raw and treated waters, high performance size exclusion chromatography with UV and fluorescence detectors were used. During the flood period, high molecular weight UV absorbing compounds (>2kDa) were mostly detected in waters collected, but were not evident in waters collected before and afterwards. The relative abundances of humic-like and protein-like compounds during and following the flood period were also investigated and found to be of a higher molecular weight during the flood period. The treatability of the organics was found to vary over the three climate conditions investigated.

Characterization of dissolved organic matter for prediction of trihalomethane formation potential in surface and sub-surface waters.

Dissolved organic matter (DOM) in surface waters used for drinking purposes can vary markedly in character dependent on their sources within catchments. The character of DOM further influences the formation of disinfection by products when precursor DOM present in drinking water reacts with chlorine during disinfection. Here we report the development of models that describe the formation potential of trihalomethanes (THMFP) dependent on the character of DOM in waters from discrete catchments with specific land-use and soil textures. DOM was characterized based on UV absorbance at 254 nm, apparent molecular weight and relative abundances of protein-like and humic-like compounds. DOM character and Br concentration (up to 0.5 mg/L) were used as variables in models (R(2)>0.93) of THMFP, which ranged from 19 to 649 μg/L. Chloroform concentration (12-594 μg/L) and relative abundance (27-99%) were first modeled (R(2)>0.85) and from these, the abundances of bromodichloromethane and chlorodibromomethane estimated using power and exponential functions, respectively (R(2)>0.98). From these, the abundance of bromoform is calculated. The proposed model may be used in risk assessment of catchment factors on formation of trihalomethanes in drinking water, in context of treatment efficiency for removal of organic matter.

The effect of vegetation and soil texture on the nature of organics in runoff from a catchment supplying water for domestic consumption.

The influence of vegetation and soil texture on the concentration and character of dissolved organic matter (DOM) present in runoff from the surface and sub-surface of zero order catchments of the Myponga Reservoir-catchment (South Australia) was investigated to determine the impacts of catchment characteristics and land management practices on the quality of waters used for domestic supply. Catchments selected have distinct vegetative cover (grass, native vegetation or pine) and contrasting texture of the surface soil horizon (sand or clay loam/clay). Water samples were collected from three slope positions (upper, middle, and lower) at soil depths of ~30 cm and ~60 cm in addition to overland flows. Filtered (0.45 μm) water samples were analyzed for dissolved organic carbon (DOC) and UV-visible absorbance and by F-EEM and HPSEC with UV and fluorescence detection to characterize the DOM. Surface and sub-surface runoff from catchments with clay soils and native vegetation or grass had lower DOC concentrations and lower relative abundances of aromatic, humic-like and high molecular weight organics than runoff from sandy soils with these vegetative types. Sub-surface flows from two catchments with Pinus radiata had similar DOC concentrations and DOM character, regardless of marked variation in surface soil texture. Runoff from catchments under native vegetation and grass on clay soils resulted in lower DOC concentrations and hence would be expected to have lower coagulant demand in conventional treatment for potable water supply than runoff from corresponding sandy soil catchments. However, organics in runoff from clay catchments would be more difficult to remove by coagulation. Surface waters from the native vegetation and grass catchments were generally found to have higher relative abundance of organic compounds amenable to removal by coagulation compared with sub-surface waters. Biophysical and land management practices combine to have a marked influence on the quality of source water used for domestic supply.

Roles of coagulant species and mechanisms on floc characteristics and filterability

In full scale water treatment operation, the rapid filtration process, as the last step of solid-liquid separation, is largely influenced by floc characteristics. In this study, aluminium sulphate (alum) and nano-Al13 were investigated to understand the influence of coagulant species on the formation and filterability of flocs. At neutral pH, it was found that nano-Al13, a high MW polymer, showed better floc filterability than alum. This is because of the densely compacted and well-distributed size flocs from nano-Al13, even though floc sizes of alum were generally bigger. Al specie distributions of the two coagulants at different pH levels were compared by using electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) to further elucidate the reasons for the superiority of nano-Al13 in floc filterability. Depolymerisation/re-polymerisation of nano-Al13 occurred as pH changed, and Al species from nano-Al13were more abundant than that from alum, especially for the high molecular weight (MW) oligomers such as Al11, Al12, Al13 and Al14. Under the charge neutralisation mechanism, higher MW Al species was found to improve coagulation performance and floc filterability. In addition, breakage resistance and regrowth ability of nano-Al13 was better than alum, at weak acid condition. Flocs formed by the charge neutralisation mechanism readily regenerated after being thoroughly broken up. The floc regrowth ability of nano-Al13 at high shear rates (200 rpm and 300 rpm) was much better than at low shear and better than any shear applied to alum., and the flocs after breakage at 200 rpm and 300 rpm also showed better filterability than other conditions.

Developing a chloramine decay index to understand nitrification: A case study of two chloraminated drinking water distribution systems

The management of chloramine decay and the prevention of nitrification are some of the critical issues faced by water utilities that use chloramine as a disinfectant. In this study, potential association between high performance size exclusion chromatography (HPSEC) data obtained with multiple wavelength Ultraviolet (UV) detection from two drinking water distribution systems in Australia and nitrification occurrence was investigated. An increase in the absorbance signal of HPSEC profiles with UV detection at λ=230nm between apparent molecular weights of 200 to 1000Da was observed at sampling sites that experienced rapid chloramine decay and nitrification while its absorbance signal at λ=254nm decreased. A chloramine decay index (C.D.I) defined as the ratio of area beneath the HPSEC spectra at two different wavelengths of 230 and 254nm, was used in assessing chloramine decay occurrences. The C.D.Is of waters at locations that experienced nitrification were consistently higher than locations not experiencing nitrification. A simulated laboratory study showed that the formation of nitrite/nitrate and/or soluble microbial products and/or the release of extracellular polymeric substances (EPS) during nitrification may contribute to the C.D.I. increase. These findings suggest that C.D.I derived from HPSEC with multiple wavelength UV detection could be an informative index to track the occurrence of rapid chloramine decay and nitrification.

Investigation of the adsorption characteristics of natural organic matter from typical Chinese surface waters onto alumina using quartz crystal microbalance with dissipation.

The adsorption of natural organic matter (NOM) from eight typical Chinese surface waters onto alumina was investigated using quartz crystal microbalance with dissipation monitoring (QCM-D). The adsorbed masses of NOM varied between 25ngcm(-2) and 64ngcm(-2), and these showed significant correlation with geographical location, and NOM character and concentrations. Adsorbed mass correlated with DOC concentration (slope k=0.0676, R(2)=0.61) and hydrophobic acid (HoA) and weakly hydrophobic acid (WHoA) (k=0.0342 and 0.0183; R(2)=0.49 and 0.52 for HoA and WHoA, respectively) constituents present in the water samples. The process of adsorbed layer formation was investigated from changes in the ΔD/Δf ratio and viscosity of adsorbed layer with injected time. The adsorbed layer viscosity increased exponentially with injected time (R(2)>0.99) for most samples. Samples with low DOC concentration (k=-1091.8, R(2)=0.55) and low content of HoA and WHoA (k=-524.33 and -322.76; R(2)=0.41 and 0.64 for HoA and WHoA, respectively), the slope of logarithm viscosity value is steeper, the property of adsorbed layer and NOM is more inconsistent. The QCM-D technique provides a method to view the process of complexation between NOM and coagulant, and can provide useful information to establish a quantitative calculation model of the coagulation process.

Chloramine demand estimation using surrogate chemical and microbiological parameters

A model is developed to enable estimation of chloramine demand in full scale drinking water supplies based on chemical and microbiological factors that affect chloramine decay rate via nonlinear regression analysis method. The model is based on organic character (specific ultraviolet absorbance (SUVA)) of the water samples and a laboratory measure of the microbiological (Fm) decay of chloramine. The applicability of the model for estimation of chloramine residual (and hence chloramine demand) was tested on several waters from different water treatment plants in Australia through statistical test analysis between the experimental and predicted data. Results showed that the model was able to simulate and estimate chloramine demand at various times in real drinking water systems. To elucidate the loss of chloramine over the wide variation of water quality used in this study, the model incorporates both the fast and slow chloramine decay pathways. The significance of estimated fast and slow decay rate constants as the kinetic parameters of the model for three water sources in Australia was discussed. It was found that with the same water source, the kinetic parameters remain the same. This modelling approach has the potential to be used by water treatment operators as a decision support tool in order to manage chloramine disinfection.