Applications of Online UV-Vis Spectrophotometer for Drinking Water Quality Monitoring and Process Control: A Review.

Water quality monitoring is an essential component of water quality management for water utilities for managing the drinking water supply. Online UV-Vis spectrophotometers are becoming popular choices for online water quality monitoring and process control, as they are reagent free, do not require sample pre-treatments and can provide continuous measurements. The advantages of the online UV-Vis sensors are that they can capture events and allow quicker responses to water quality changes compared to conventional water quality monitoring. This review summarizes the applications of online UV-Vis spectrophotometers for drinking water quality management in the last two decades. Water quality measurements can be performed directly using the built-in generic algorithms of the online UV-Vis instruments, including absorbance at 254 nm (UV254), colour, dissolved organic carbon (DOC), total organic carbon (TOC), turbidity and nitrate. To enhance the usability of this technique by providing a higher level of operations intelligence, the UV-Vis spectra combined with chemometrics approach offers simplicity, flexibility and applicability. The use of anomaly detection and an early warning was also discussed for drinking water quality monitoring at the source or in the distribution system. As most of the online UV-Vis instruments studies in the drinking water field were conducted at the laboratory- and pilot-scale, future work is needed for industrial-scale evaluation with ab appropriate validation methodology. Issues and potential solutions associated with online instruments for water quality monitoring have been provided. Current technique development outcomes indicate that future research and development work is needed for the integration of early warnings and real-time water treatment process control systems using the online UV-Vis spectrophotometers as part of the water quality management system.

Stormwater monitoring using on-line UV-Vis spectroscopy.

Stormwater runoff contains a myriad of pollutants, including faecal microbes, and can pose a threat to urban water supplies, impacting both economic development and public health. Therefore, it is a necessity to implement a real-time hazard detection system that can collect a substantial amount of data, assisting water authorities to develop preventive strategies to ensure the control of hazards entering drinking water sources. An on-line UV-Vis spectrophotometer was applied in the field to collect real-time continuous data for various water quality parameters (nitrate, DOC, turbidity and total suspended solids) during three storm events in Mannum, Adelaide, Australia. This study demonstrated that the trends for on-line and comparative laboratory-analysed samples were complimentary through the events. Nitrate and DOC showed a negative correlation with water level, while turbidity and total suspended solids indicated a positive correlation with water level during the high rainfall intensity. The correlations among nitrate, DOC, turbidity, total suspended solids and water level are the opposite during low rainfall intensity. Nitrate, one of the main pollutants in stormwater, was investigated and used as a surrogate parameter for microbial detection. However, the microbiological data (Escherichia coli) from captured storm events showed poor correlations to nitrate and other typical on-line parameters in this study. This is possibly explained by the nature of the stormwater catchment outside of rain events, where the sources of bacteria and nutrients may be physically separated until mixed during surface runoff as a result of rainfall. In addition, the poor correlations among the microbiological data and on-line parameters could be due to the different sources of bacteria and nutrients that were transported to the stormwater drain where sampling and measurement were conducted.

Evaluation of the impact of suspended particles on the UV absorbance at 254 nm (UV254) measurements using a submersible UV-Vis spectrophotometer.

There is an increasing need to use online instrumentation for continuous monitoring of water quality. However, industrial applications using online instruments, such as submersible UV-Vis spectrophotometers, may require the use of alternative techniques to remove particle effect rather than performing a physical filtration step. Some submersible UV-Vis spectrophotometers have built-in generic particle compensation algorithms to remove the filtration step. This work studied the influence of suspended particles on the measurements of a submersible UV-Vis spectrophotometer as well as the performance of the built-in particle compensation technique under laboratory-controlled conditions. Simulated water samples were used in the combinations of standard particles from laboratory chemical and natural particles extracted from water systems with ultrapure water and treated water from a drinking water treatment plant. Particle contributions to the UV absorbance at 254 nm (UV254) measurements of water samples varied differently when particle types or concentrations changed. The compensated UV254, measured by the submersible instrument using the built-in generic particle compensation algorithms, was compared with laboratory UV254, analysed by the bench-top instrument with the physical filtration method. The results indicated that the built-in generic compensation algorithms of the submersible UV-Vis spectrophotometer may generate undercompensated UV254 or overcompensated UV254 for various surface waters. These findings provide in-depth knowledge about the impact of suspended particles on the measurements of submersible UV-Vis spectrophotometers; source water dependence; and why site-specific calibration is often needed to get accurate measurements.

Influence of coagulation mechanisms and floc formation on filterability.

Minimizing particles in water is a key goal for improving drinking water quality and safety. The media filtration process, as the last step of the solid-liquid separation process, is largely influenced by the characteristics of flocs, which are formed and controlled within the coagulation process. In a laboratory-based study, the impacts of the physical characteristics of flocs formed using aluminum sulfate on the filtration treatment of two comparative water samples were investigated using a photometric dispersion analyzer and a filterability apparatus. In general, the optimum dosage for maximizing filterability was higher than that for minimizing turbidity under neutral pH conditions. For a monomeric aluminum-based coagulant, the charge neutralization mechanism produced better floc characteristics, including floc growth speed and size, than the sweep flocculation mechanism. In addition, the charge neutralization mechanism showed better performance compared to sweep flocculation in terms of DOC removal and floc filterability improvement for both waters, and showed superiority in turbidity removal only when the raw water had high turbidity. For the different mechanisms, the ways that floc characteristics impacted on floc filterability also differed. The low variation in floc size distribution obtained under the charge neutralization mechanism resulted in the flocs being amenable to removal by filtration processes. For the sweep flocculation mechanism, increasing the floc size improved the settling ability of flocs, resulting in higher filter efficiency.

Effect of increasing bromide concentration on toxicity in treated drinking water.

Research is increasingly indicating the potential chronic health effects of brominated disinfection by-products (DBPs). This is likely to increase with elevated bromide concentrations resulting from the impacts of climate change, projected to include extended periods of drought and the sudden onset of water quality changes. This will demand more rigorous monitoring throughout distribution systems and improved water quality management at water treatment plants (WTPs). In this work the impact of increased bromide concentration on formation of DBPs following conventional treatment and chlorination was assessed for two water sources. Bioanalytical tests were utilised to determine cytotoxicity of the water post disinfection. Coagulation was shown to significantly reduce the cytotoxicity of the water, indicating that removal of natural organic matter DBP precursors continues to be an important factor in drinking water treatment. Most toxic species appear to form within the first half hour following disinfectant addition. Increasing bromide concentration across the two waters was shown to increase the formation of trihalomethanes and shifted the haloacetic acid species distribution from chlorinated to those with greater bromine substitution. This correlated with increasing cytotoxicity. This work demonstrates the challenges faced by WTPs and the possible effects increasing levels of bromide in source waters could have on public health.

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.

Surface analysis of pilot distribution system pipe autopsies: The relationship of organic and inorganic deposits to input water quality.

Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) surface analysis was conducted to characterise deposits in polyethylene pipes used in a novel pilot water distribution system (PDS). The system consisted of four (4) parallel distribution systems receiving water from different treatment processes, ranging from conventional coagulation through to an advanced membrane filtration system. After two years of operation, the distribution system was shut down and samples of pipe were collected for autopsy analysis. Inlet and outlet samples from each PDS were collected for purpose of comparison. ToF-SIMS was used to assess chemical differences in surface biofilm accumulation and particulate deposition, which resulted as a consequence of the treatment method and operational mode of each system. These data supplemented previously collected bacteriological and chemical water quality data. Results from the inorganic analysis of the pipes were consistent with corrosion and contamination events that occurred upstream in the corresponding treatment systems. Principal component analysis of data on organic constituents showed oxygen and nitrogen containing fragments were associated with the treatment inlet and outlet samples. These types of signals can often be ascribed to biofilm polysaccharides and proteins. A trend was observed when comparing samples from the same PDS, showing an association of lower molecular weight (MW) organic fragments with the inlet and higher MW organic fragments with the outlet samples.

Assessing the impact of water treatment on bacterial biofilms in drinking water distribution systems using high-throughput DNA sequencing.

Biofilm control in drinking water distribution systems (DWDSs) is crucial, as biofilms are known to reduce flow efficiency, impair taste and quality of drinking water and have been implicated in the transmission of harmful pathogens. Microorganisms within biofilm communities are more resistant to disinfection compared to planktonic microorganisms, making them difficult to manage in DWDSs. This study evaluates the impact of four unique drinking water treatments on biofilm community structure using metagenomic DNA sequencing. Four experimental DWDSs were subjected to the following treatments: (1) conventional coagulation, (2) magnetic ion exchange contact (MIEX) plus conventional coagulation, (3) MIEX plus conventional coagulation plus granular activated carbon, and (4) membrane filtration (MF). Bacterial biofilms located inside the pipes of each system were sampled under sterile conditions both (a) immediately after treatment application ('inlet') and (b) at a 1 km distance from the treatment application ('outlet'). Bacterial 16S rRNA gene sequencing revealed that the outlet biofilms were more diverse than those sampled at the inlet for all treatments. The lowest number of unique operational taxonomic units (OTUs) and lowest diversity was observed in the MF inlet. However, the MF system revealed the greatest increase in diversity and OTU count from inlet to outlet. Further, the biofilm communities at the outlet of each system were more similar to one another than to their respective inlet, suggesting that biofilm communities converge towards a common established equilibrium as distance from treatment application increases. Based on the results, MF treatment is most effective at inhibiting biofilm growth, but a highly efficient post-treatment disinfection regime is also critical in order to prevent the high rates of post-treatment regrowth.

Drought to flood: a comparative assessment of four parallel surface water treatments during the 2010-2012 inflows to the Murray-Darling Basin, South Australia.

Four treatment processes; conventional coagulation, magnetic ion exchange (MIEX)/coagulation, with and without granular activated carbon (GAC), and membrane treatment combining microfiltration (MF) and nanofiltration (NF), were operated in parallel using the same source water from the Murray-Darling basin in South Australia. During the two year study, high levels of natural organic matter and turbidity arising from floods affecting the Murray-Darling basin in 2010-2012 challenged the four processes. The comparative study indicated that all four processes could effectively meet basic water quality guidelines of turbidity and colour despite challenging source water quality but that the more advanced treatments improved overall organic and bacterial removal. Interestingly, the high organics and turbidity arising from the floods resulted in improved treatment efficiency for all treatments incorporating coagulation to the extent that, despite flood conditions, treated water quality could remain comparatively constant provided that the process was operated and optimised effectively.

Using reverse phase high performance liquid chromatography as an alternative to resin fractionation to assess the hydrophobicity of natural organic matter.

Resin fractionation is the most widely used technique to isolate and characterize natural organic matter (NOM) based on its hydrophobicity and hydrophilicity, however, it is also recognized as a time consuming technique. This paper describes the use of reverse phase high performance liquid chromatography (RPHPLC) as a rapid assessment technique to determine the hydrophobicity/hydrophilicity of NOM. The optimum column separation condition was achieved and without the need for concentrating the sample prior to analysis and with good reproducibility of the peak retention time and the peak area. The characterization results were further compared with the traditional resin fractionation technique using DAX-8 and XAD-4 resins. The results demonstrated that the polarities defined by the two methods were different but consistent and also that the fractions absorbed onto XAD-4 were less hydrophobic than those absorbed onto DAX-8. The difference in definition between resin fractionation and RPHPLC were further investigated.

Comparison of drinking water treatment process streams for optimal bacteriological water quality.

Four pilot-scale treatment process streams (Stream 1 - Conventional treatment (coagulation/flocculation/dual media filtration); Stream 2 - Magnetic ion exchange (MIEX)/Conventional treatment; Stream 3 - MIEX/Conventional treatment/granular activated carbon (GAC) filtration; Stream 4 - Microfiltration/nanofiltration) were commissioned to compare their effectiveness in producing high quality potable water prior to disinfection. Despite receiving highly variable source water quality throughout the investigation, each stream consistently reduced colour and turbidity to below Australian Drinking Water Guideline levels, with the exception of Stream 1 which was difficult to manage due to the reactive nature of coagulation control. Of particular interest was the bacteriological quality of the treated waters where flow cytometry was shown to be the superior monitoring tool in comparison to the traditional heterotrophic plate count method. Based on removal of total and active bacteria, the treatment process streams were ranked in the order: Stream 4 (average log removal of 2.7) > Stream 2 (average log removal of 2.3) > Stream 3 (average log removal of 1.5) > Stream 1 (average log removal of 1.0). The lower removals in Stream 3 were attributed to bacteria detaching from the GAC filter. Bacterial community analysis revealed that the treatments affected the bacteria present, with the communities in streams incorporating conventional treatment clustering with each other, while the community composition of Stream 4 was very different to those of Streams 1, 2 and 3. MIEX treatment was shown to enhance removal of bacteria due to more efficient flocculation which was validated through the novel application of the photometric dispersion analyser.

Changes in character of organics in the receiving environment of effluent from a sulphite pulp mill.

PURPOSE: The characteristics of organics in sulphite pulp mill effluent and in the receiving environment of effluent discharge were investigated to assess the basis for the persistence or attenuation of colour. METHODS: Characterization of organics was conducted through determination of SUVA, specific colour, and molecular weight distribution of organics using high performance size exclusion chromatography and by solid-state (13) C cross polarization (CP) NMR. The characteristics of organics from mill wastewater before and after secondary aerobic treatment, followed by lime treatment and from the receiving environment, an enclosed brackish lake were compared. Changes in the character of organics in lake water over a period of 14 years were studied in the context of changes in mill processing and climate impacts. RESULTS: High colour in mill effluent and in receiving waters correlated with high SUVA and specific colour levels, high molecular weight range and aromatic content. Conversely, lake waters with low colour had UV absorbing compounds of much lower molecular weight range and low relative abundance of aromatic compounds. Attenuation of colour and changes in the character of organics in the receiving environment coincided with increased concentrations of metal cations. CONCLUSIONS: These increased concentrations appear to be due to the effects of climate change, lake management and their presence in mill effluent, with subsequent discharge to the lake. Attenuation of colour was found to be predominantly through removal of high molecular weight aromatic compounds where the removal processes could be through adsorption and co-precipitation with divalent metals, as well as through dilution processes.

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.

Characterization of dissolved organic matter from Australian and Chinese source waters by combined fractionation techniques.

The character of dissolved organic matter (DOM) in source waters from two countries (Australia and China) was investigated using an extended fractionation technique by combining resin adsorption, ultrafiltration and high performance size exclusion chromatography. There are distinctive chemical characteristics associated with DOM origins. Australian sourced DOM had higher hydrophobic acid (HoA) content and exhibited a more pronounced humic character, indicating a higher influence from allochthonous organics (decayed plant bodies from vegetated catchments). The higher content of hydrophobic base and neutral components found in Chinese DOM, may be attributed to the effects of increasing pollution caused by the rapid urbanization in China. The molecular weights (MWs) of aquatic HoA are predominantly in the moderate (e.g., 1-10 kDa) or small (e.g., < 1 kDa) ranges. This suggests that aquatic HOA should not be assumed as high MW organics without experimental validation. It is also found that some of the low MW compounds in our samples were hydrophobic, which could explain the observation of low MW organic compounds being able to be removed by conventional treatment processes.

Multi-wavelength spectroscopic and chromatography study on the photocatalytic oxidation of natural organic matter.

The effect of TiO2 photocatalytic oxidation on the natural organic matter (NOM) properties of two Australian surface waters were quantified using UV-vis spectroscopy, high performance size exclusion chromatography (HPSEC) with a multi-wavelength UV detector, liquid chromatography with organic carbon detector (LC-OCD), and trihalomethane formation potential (THMFP) analyses. Both the UV absorbance at wavelengths greater than 250 nm and dissolved organic carbon (DOC) content decreased significantly with treatment, although complete mineralization of NOM could not be achieved. Multi-wavelength UV detection of HPSEC analysis was shown to be useful to display further changes to NOM composition and molecular weight profiles because the organic molecules was transformed into compounds that absorb weakly at the typical detection wavelength of 250-260 nm. The multi-wavelength HPSEC results also revealed that photocatalytic oxidation yields by-products with a low aromaticity and low molecular weight. The LC-OCD chromatograms indicated that low molecular acids and neutral compounds remained after photocatalytic oxidation. Those groups of compounds did not seem to contribute significantly to the formation of trihalomethanes.

Absorbance spectroscopy-based examination of effects of coagulation on the reactivity of fractions of natural organic matter with varying apparent molecular weights.

Absorbance spectra of fractions of natural organic matter (NOM) with varying apparent molecular weights (AMWs) were examined in this study. Size exclusion chromatography (SEC) was employed to obtain AMW distributions for three Australian water sources which represented low- and high-dissolved organic carbon (DOC) surface waters and a source with highly degraded NOM. These waters were coagulated with alum and other coagulants. Effects of coagulation on AMW distributions were quantified based on an absorbance slope index (ASI) calculated using NOM absorbance measured at 220, 230, 254 and 272 nm. This index can be calculated for any AMW fraction of NOM. Similarly to SUVA(254), ASI values decrease consistently in coagulated waters and are correlated with trihalomethane yields. Comparison of ASI indexes in different water sources indicates the presence of both common trends and differences indicative of NOM site-specificity.

Assessing natural organic matter treatability using high performance size exclusion chromatography.

This paper reports the use of high performance size exclusion chromatography (HPSEC) as a tool to assess NOM removal by coagulation. Quantitative information such as percentage removal can be determined after "peak-fitting" the HPSEC molecular weight profile of the source water. A peak-fitting approach was developed based on the molecular weight profile of dissolved organic matter from surface water. A sequential jar testing procedure with five treatment steps was used to characterize organics and to confirm that several NOM components were recalcitrant to coagulation with alum. Despite differences found in both the concentration and character of NOM in three surface waters studied, the final concentrations and characteristics (e.g., molecular weight profile) were very similar after five treatment stages. The molecular weight profiles of the recalcitrant organics were subsequently used to build a peak-fitting technique for NOM removal. The approach was validated by further jar test results of several other water sources, such as ground and river waters, including one found to be very difficult to treat in terms of NOM removal by alum treatment. Predictions of removable and nonremovable organic fractions by coagulation using this peak fitting technique were found to be within 10% of actual values.

TiO2 photocatalysis of natural organic matter in surface water: impact on trihalomethane and haloacetic acid formation potential.

In this study, changes in the physical and structural properties of natural organic matter (NOM) during titanium dioxide photocatalytic oxidation process were investigated using several complementary analytical techniques. Potential of the treated water to form trihalomethanes (THMs) and haloacetic acids (HAAs) was also studied. High-performance size exclusion chromatography analysis showed that NOM with apparent molecular weights of 1-4 kDa were preferentially degraded, leading to the formation of lower molecular weight organic compounds. Resin fractionation of the treated water demonstrated that the photocatalytic oxidation changed the affinity of the bulk organic character from predominantly hydrophobic to more hydrophilic. Short chain aldehydes and ketones were identified by mass spectroscopy as one of the key degradation products. The addition of hydrogen peroxide to photocatalysis was found to increase the degradation kinetics but did not affect the reaction pathway, thus producing similar degradation end products. The amount of THMs normalized per dissolved organic carbon (specific THM) formed upon chlorination of NOM treated with photocatalytic oxidation was reduced from 56 to 10 microg/mg. In contrast, the specific HAAs formation potential of the treated water remained relatively unchanged from the initial value of 38 microg/mg, which could be due to the presence of hydrophilic precursor compounds that were formed as a result of the photocatalytic oxidation process.

Comparison of NOM character in selected Australian and Norwegian drinking waters.

Observations from many countries around the world during the past 10-20 years indicate increasing natural organic matter (NOM) concentration levels in water sources, due to issues such as global warming, changes in soil acidification, increased drought severity and more intensive rain events. In addition to the trend towards increasing NOM concentration, the character of NOM can vary with source and time (season). The great seasonal variability and the trend towards elevated NOM concentration levels impose challenges to the water industry and the water treatment facilities in terms of operational optimisation and proper process control. The aim of this investigation was to compare selected raw and conventionally treated drinking water sources from different hemispheres with regard to NOM character which may lead to better understanding of the impact of source water on water treatment. Results from the analyses of selected Norwegian and Australian water samples showed that Norwegian NOM exhibited greater humic nature, indicating a stronger bias of allochthonous versus autochthonous organic origin. Similarly, Norwegian source waters had higher average molecular weights than Australian waters. Following coagulation treatment, the organic character of the recalcitrant NOM in both countries was similar. Differences in organic character of these source waters after treatment were found to be related to treatment practice rather than origin of the source water. The characterisation techniques employed also enabled identification of the coagulation processes which were not necessarily optimised for dissolved organic carbon (DOC) removal. The reactivity with chlorine as well as trihalomethane formation potential (THMFP) of the treated waters showed differences in behaviour between Norwegian and Australian sources that appeared to be related to residual higher molecular weight organic material. By evaluation of changes in specific molecular weight regions and disinfection parameters before and after treatment, correlations were found that relate treatment strategy to chlorine demand and DBP formation.

Removal of humic acid using TiO2 photocatalytic process--fractionation and molecular weight characterisation studies.

The photocatalytic removal of humic acid (HA) using TiO2 under UVA irradiation was examined by monitoring changes in the UV(254) absorbance, dissolved organic carbon (DOC) concentration, apparent molecular weight distribution, and trihalomethane formation potentials (THMFPs) over treatment time. A resin fractionation technique in which the samples were fractionated into four components: very hydrophobic acids (VHA), slightly hydrophobic acids, hydrophilic charged (CHA) and hydrophilic neutral (NEU) was also employed to elucidate the changes in the chemical nature of the HA components during treatment. The UVA/TiO2 process was found to be effective in removing more than 80% DOC and 90% UV(254) absorbance. The THMFPs of samples were decreased to below 20 microg l(-1) after treatments, which demonstrate the potential to meet increasingly stringent regulatory level of trihalomethanes in water. Resin fractionation analysis showed that the VHA fraction was decreased considerably as a result of photocatalytic treatments, forming CHA intermediates which were further degraded with increased irradiation time. The NEU fraction, which comprised of non-UV-absorbing low molecular weight compounds, was found to be the most persistent component.