Christopher Kevin Waul

A potential approach for monitoring drinking water quality from groundwater systems using organic matter fluorescence as an early warning for contamination events

The fluorescence characteristics of natural organic matter in a groundwater based drinking water supply plant were studied with the aim of applying it as a technique to identify contamination of the water supply. Excitation-emission matrices were measured and modeled using parallel factor analysis (PARAFAC) and used to identify which wavelengths provide the optimal signal for monitoring contamination events. The fluorescence was characterized by four components: three humic-like and one amino acid-like. The results revealed that the relative amounts of two of the humic-like components were very stable within the supply plant and distribution net and changed in a predictable fashion depending on which wells were supplying the water. A third humic-like component and an amino acid-like component did not differ between wells. Laboratory contamination experiments with wastewater revealed that combined they could be used as an indicator of microbial contamination. Their fluorescence spectra did not overlap with the other components and therefore the raw broadband fluorescence at the wavelengths specific to their fluorescence could be used to detect contamination. Contamination could be detected at levels equivalent to the addition of 60 μg C/L in drinking water with a TOC concentration of 3.3 mg C/L. The results of this study suggest that these types of drinking water systems, which are vulnerable to microbial contamination due to the lack of disinfectant treatment, can be easily monitored using online organic matter fluorescence as an early warning system to prompt further intensive sampling and appropriate corrective measures.

Monitoring organic loading to swimming pools by fluorescence excitation-emission matrix with parallel factor analysis (PARAFAC).

Fluorescence Excitation-Emission Matrix spectroscopy combined with parallel factor analysis was employed to monitor water quality and organic contamination in swimming pools. The fluorescence signal of the swimming pool organic matter was low but increased slightly through the day. The analysis revealed that the organic matter fluorescence was characterised by five different components, one of which was unique to swimming pool organic matter and one which was specific to organic contamination. The latter component had emission peaks at 420 nm and was found to be a sensitive indicator of organic loading in swimming pool water. The fluorescence at 420 nm gradually increased during opening hours and represented material accumulating through the day.

Impact of water boundary layer diffusion on the nitrification rate of submerged biofilter elements from a recirculating aquaculture system.

Total ammonia nitrogen (TAN) removal by microbial nitrification is an essential process in recirculating aquaculture systems (RAS). In order to protect the aquatic environment and fish health, it is important to be able to predict the nitrification rates in RASs. The aim of this study was to determine the impact of hydraulic film diffusion on the nitrification rate in a submerged biofilter. Using an experimental batch reactor setup with recirculation, active nitrifying biofilter units from a RAS were exposed to a range of hydraulic flow velocities. Corresponding nitrification rates were measured following ammonium chloride, NH₄Cl, spikes and the impact of hydraulic film diffusion was quantified. The nitrification performance of the tested biofilter could be significantly increased by increasing the hydraulic flow velocity in the filter. Area based first order nitrification rate constants ranged from 0.065 m d⁻¹ to 0.192 m d⁻¹ for flow velocities between 2.5 m h⁻¹ and 40 m h⁻¹ (18 °C). This study documents that hydraulic film diffusion may have a significant impact on the nitrification rate in fixed film biofilters with geometry and hydraulic flows corresponding to our experimental RAS biofilters. The results may thus have practical implications in relation to the design, operational strategy of RAS biofilters and how to optimize TAN removal in fixed film biofilter systems.

Long term studies on the anaerobic biodegradability of MTBE and other gasoline ethers.

Anaerobic biodegradation of methyl tert-butyl ether (MTBE) using electron acceptors such as nitrate, Fe(III), sulfate and bicarbonate, may be more cost effective and feasible compared to aerobic treatment methods, for dealing with the MTBE problem. Currently, there are a few reports in the literature which have documented anaerobic biodegradation of MTBE in batch studies. However, some of the reports have been controversial, additionally many other studies have failed to document anaerobic biodegradation. Experiments were conducted over a long term period in both batch and continuous reactors to investigate the anaerobic biodegradability of MTBE and other gasoline ethers. Inoculums collected from various environments were used, along with different electron acceptors. Only one set of the batch experiments showed a 30-60% conversion of MTBE to tert-butyl alcohol under Fe(III)-reducing conditions, using complexed Fe(III). The use of complexed Fe(III) created an initial low pH of 1-2 in these batches due to its acidic nature, therefore, the removal may be due to acid hydrolysis rather than biological processes. Based on the findings obtained, caution should be applied in the interpretation of experimental data in which complexed Fe(III) is used for bioremediation of MTBE.

Modeling the competitive effect of ammonium oxidizers and heterotrophs on the degradation of MTBE in a packed bed reactor

A mathematical model was used to study effects on the degradation of methyl tert-butyl ether (MTBE) in a packed bed reactor due to the presence of contaminants such as ammonium, and the mix of benzene, toluene, ethylbenzene and xylenes (BTEX). It was shown that competition between the slower growing MTBE degraders and the co-contaminant oxidizers prevented MTBEs degradation when oxygen was limited. In this event, the co-contaminant oxidizers out-competed the MTBE degraders in the reactors biofilm. However, if the oxygen supply was sufficient, MTBE would be fully degraded after the zone where the co-contaminants were oxidized. The results of the model further indicate that contradicting findings in the literature about the effects of BTEX on the degradation of MTBE are mainly due to differences in the study methodologies. Effects such as short-term toxicity of BTEX and the lack of steady-state conditions may also add to contradictions among reports.

Model description and kinetic parameter analysis of MTBE biodegradation in a packed bed reactor

A dynamic modeling approach was used to estimate in-situ model parameters, which describe the degradation of methyl tert-butyl ether (MTBE) in a laboratory packed bed reactor. The measured dynamic response of MTBE pulses injected at the reactors inlet was analyzed by least squares and parameter response surface methodologies. Response surfaces were found to be statistically significant and thus suitable for estimating the global minimum as well as the 95% parameter uncertainty regions. The linear parameter uncertainty estimates for the half-saturation constant (K(S)) and the maximum growth rate (micro(max)) were: 0<K(S)<10 mg COD/L and 0.12<micro(max)<0.25 d(-1). Obtaining reliable parameters is a necessary step towards model application in order to study practical reactor operational problems such as the competition between the relatively slow growing MTBE degraders and the oxidizers of other groundwater co-contaminants such as ammonium, benzene, toluene, ethylbenzene and xylenes.

HS-SPME-GC-MS analysis of antioxidant degradation products migrating to drinking water from PE materials and PEX pipes

Polyethylene (PE) and cross-linked polyethylene (PEX) pipes are frequently used in water supply systems. Such pipes contain added antioxidants with phenolic structures, e.g. Irgafos 168, Irganox 1010 and 1076, in order to improve durability. However, phenol, ketone and quinone antioxidant degradation products may leach and enter drinking water. The aim of this investigation was to develop a method for measuring these degradation products with a performance meeting the drinking water quality criteria of 20 µg L−1. Using headspace solid phase microextraction coupled to a gas chromatograph with a mass spectrometer, a method was established revealing limits of detection and quantification less than 0.4 and 1 µg L−1 respectively. The method was applied to migration experiments for two PEX pipes and one PE material, quantifying the release of two degradation products. Highest concentrations were observed for 2,6-di-tert-butyl-p-benzoquinone which in one of the two pipes was found in concentrations of 18–57 µg L−1 in each of eight consecutive release experiments.

Microbial Degradation of MTBE in Reactors

The use of methyl tert-butyl ether (MTBE) has resulted in serious contamination of many groundwater supplies worldwide. Literature investigations were performed with the aim of improving knowledge on the use of bioreactors for removal of MTBE from contaminated groundwater. Among the important findings were: membrane bioreactors and fluidized bed reactors had the highest volumetric removal rates of all reactors studied, in the order of 1000 mg/(l d); competition for oxygen, nutrients and occupancy between MTBE degraders and oxidisers of co-contaminants such as, ammonium and the group of benzene, toluene, ethylbenzene and xylenes, may reduce the removal rates of MTBE, or prevent its removal in reactors. With mathematical modelling, the long startup time required for some MTBE degrading reactors could be predicted. Long startup times of up to 200 days were due to the low maximum growth rate of the MTBE degraders, in the order of 0.1 d–1 or less, at 25 ◦C. However, despite this, high volumetric MTBE removal rates were found to be possible after the startup period when the biomass concentration reached a steady state.

Estimation of the fraction of biologically active methyl tert-butyl ether degraders in a heterogeneous biomass sample

The fraction of biologically active methyl tert-butyl ether degraders in reactors is just as important for prediction of removal rates as knowledge of the kinetic parameters. The fraction of biologically active methyl tert-butyl ether degraders in a heterogeneous biomass sample, taken from a packed bed reactor, was determined using a batch kinetic based approach. The procedure involved modeling of methyl tert-butyl ether removal rates from batch experiments followed by parameter estimations. It was estimated to be 5–14% (w/w) of the measured volatile suspended solids concentration in the reactor.