James A. McDonald

Removal of trace organics by MBR treatment: the role of molecular properties

This study examined the relationship between specific molecular features of trace organic contaminants and their removal efficiencies by a laboratory scale membrane bioreactor (MBR). Removal efficiencies of 40 trace organic compounds were assessed under stable operating conditions. The reported results demonstrate an apparent correlation between chemical structures and the removal of trace organic contaminants by the laboratory scale MBR system. The removal of all 14 very hydrophobic (Log D > 3.2) trace organic compounds selected in this study was consistently high and was above 85%. The occurrence and types of electron withdrawing or donating functional groups appear to be important factors governing their removal by MBR treatment. In this study, all hydrophilic and moderately hydrophobic (Log D<3.2) compounds possessing strong electron withdrawing functional groups showed removal efficiency of less than 20%. In contrast, high removal efficiencies were observed with most compounds bearing electron donating functional groups such as hydroxyl and primary amine groups. A qualitative framework for the assessment of trace organic removal by MBR treatment was proposed to provide further insights into the removal mechanisms.

Sorption of emerging trace organic compounds onto wastewater sludge solids

This work examined the sorption potential to wastewater primary- and activated-sludge solids for 34 emerging trace organic chemicals at environmentally relevant concentrations. These compounds represent a diverse range of physical and chemical properties, such as hydrophobicity and charge state, and a diverse range of classes, including steroidal hormones, pharmaceutically-active compounds, personal care products, and household chemicals. Solid-water partitioning coefficients (K(d)) were measured where 19 chemicals did not have previously reported values. Sludge solids were inactivated by a nonchemical lyophilization and dry-heat technique, which provided similar sorption behavior for recalcitrant compounds as compared to fresh activated-sludge. Sorption behavior was similar between primary- and activated-sludge solids from the same plant and between activated-sludge solids from two nitrified processes from different wastewater treatment systems. Positively-charged pharmaceutically-active compounds, amitriptyline, clozapine, verapamil, risperidone, and hydroxyzine, had the highest sorption potential, log K(d)=2.8-3.8 as compared to the neutral and negatively-charged chemicals. Sorption potentials correlated with a compounds hydrophobicity, however the higher sorption potentials observed for positively-charged compounds for a given log D(ow) indicate additional sorption mechanisms, such as electrostatic interactions, are important for these compounds. Previously published soil-based one-parameter models for predicting sorption from hydrophobicity (log K(ow)>2) can be used to predict sorption for emerging nonionic compounds to wastewater sludge solids.

Performance of a novel osmotic membrane bioreactor (OMBR) system: Flux stability and removal of trace organics

Results reported here highlight the potential and several challenges in the development of a novel osmotic membrane bioreactor (OMBR) process for the treatment of municipal wastewater. Following the initial gradual decline, a stable permeate flux value was obtained after approximately four days of continuous operation. There was evidence of continuous deterioration of biological activity of the OMBR system, possibly due to the build-up of salinity in the reactor. The removal of 25 out of 27 trace organic compounds with molecular weight higher than 266 g/mol was above 80% and was possibly governed by the interplay between physical separation of the FO membrane and biodegradation. In contrast, the removal efficiency values of the other 23 trace organic compounds with molecular weight less than 266 g/mol were very scattered. The removal efficiency of these low molecular weight compounds by OMBR treatment appears to depend mostly on biological degradation.

Effect of mixed liquor pH on the removal of trace organic contaminants in a membrane bioreactor

Experiments were conducted over approximately 7 months to investigate the effects of mixed liquor pH (between pH 5 and 9) on the removal of trace organics by a submerged MBR system. Removal efficiencies of ionisable trace organics (sulfamethoxazole, ibuprofen, ketoprofen, and diclofenac) were strongly pH dependent. However, the underlying removal mechanisms are different for ionisable and non-ionisable compounds. High removal efficiencies of these ionisable trace organics at pH 5 could possibly be attributed to their speciation behaviour. At this pH, these compounds exist predominantly in their hydrophobic form. Consequently, they could readily adsorb to the activated sludge, resulting in higher removal efficiency in comparison to under less acidic conditions in the reactor. Removal efficiencies of the two non-ionisable compounds bisphenol A and carbamazepine were relatively independent of the mixed liquor pH. Results reported here suggest an apparent connection between physicochemical properties of the compounds and their removal efficiencies by MBRs.

Analysis of N-nitrosamines in water by isotope dilution gas chromatography–electron ionisation tandem mass spectrometry

A method has been developed for the determination of eight N-nitrosamines in drinking water and treated municipal effluent. The method uses solid phase extraction (SPE), gas chromatography (GC) and analysis by tandem mass spectrometry (MS-MS) with electron ionization (EI). The target compounds are N-nitrosodimethylamine (NDMA), N-nitrosomethyethylamine (NMEA), N-nitrosodiethylamine NDEA), N-nitrosodipropylamine (NDPA), N-nitrosodi-n-butylamine (NDBuA), N-nitrosodiphenylamine (NDPhA), N-nitrosopyrrolidine (NPyr), N-nitrosopiperidine (NPip), N-nitrosomorpholine (NMorph). The use of direct isotope analogues for isotope dilution analysis of all analytes ensures accurate quantification, accounting for analytical variabilities that may occur during sample processing, extraction and instrumental analysis. Method detection levels (MDLs) were determined to describe analyte concentrations sufficient to provide a signal with 99% certainty of detection. The established MDLs for all analytes were 0.4-4 ng L(-1) in a variety of aqueous matrices. Sample matrices were observed to have only a minor impact on MDLs and the method validation confirmed satisfactory method stability over intra-day and inter-day analyses of tap water and tertiary treated effluent samples.

Is halogen content the most important factor in the removal of halogenated trace organics by MBR treatment

This study investigated the relationship between physicochemical properties (namely halogen content and hydrophobicity) of halogenated trace organics and their removal efficiencies by a laboratory scale membrane bioreactor (MBR) under stable operating conditions. The reported results demonstrated a combined effect of halogen content and hydrophobicity on the removal. Compounds with high halogen content (>0.3) were well removed (>85%) when they possessed high hydrophobicity (Log D>3.2), while those with lower Log D values were also well removed if they had low halogen content (<0.1). General indices such as the BIOWIN index (which is based on only biodegradation) or a more specific index such as the halogen content (which captures a chemical aspect) appeared insufficient to predict the removal efficiency of halogenated compounds in MBR. Experimental data confirmed that the ratio of halogen content and Log D, which incorporates two important physico-chemical properties, is comparatively more suitable.

Development of a predictive framework to assess the removal of trace organic chemicals by anaerobic membrane bioreactor

This study aims to develop a predictive framework to assess the removal and fate of trace organic chemicals (TrOCs) during wastewater treatment by anaerobic membrane bioreactor (AnMBR). The fate of 27 TrOCs in both the liquid and sludge phases during AnMBR treatment was systematically investigated. The results demonstrate a relationship between hydrophobicity and specific molecular features of TrOCs and their removal efficiency. These molecular features include the presence of electron withdrawing groups (EWGs) or donating groups (EDGs), especially those containing nitrogen and sulphur. All seven hydrophobic contaminants were well removed (>70%) by AnMBR treatment. Most hydrophilic TrOCs containing EDGs were also well removed (>70%). In contrast, hydrophilic TrOCs containing EWGs were mostly poorly removed and could accumulate in the sludge phase. The removal of several nitrogen/sulphur bearing TrOCs (e.g., linuron and caffeine) by AnMBR was higher than that by aerobic treatment, possibly due to nitrogen or sulphur reducing bacteria.

Occurrence of trace organic contaminants in wastewater sludge and their removals by anaerobic digestion

This study aims to evaluate the occurrence of trace organic contaminants (TrOCs) in wastewater sludge and their removal during anaerobic digestion. The significant occurrence of 18 TrOCs in primary sludge was observed. These TrOCs occurred predominantly in the solid phase. Some of these TrOCs (e.g. paracetamol, caffeine, ibuprofen and triclosan) were also found at high concentrations (>10,000ng/L) in the aqueous phase. The overall removal of TrOCs (from both the aqueous and solid phase) by anaerobic digestion was governed by their molecular structure (e.g. the presence/absence of electron withdrawing/donating functional groups). While an increase in sludge retention time (SRT) of the digester resulted in a small but clearly discernible increase in basic biological performance (e.g. volatile solids removal and biogas production), the impact of SRT on TrOC removal was negligible. The lack of SRT influence on TrOC removal suggests that TrOCs were not the main substrate for anaerobic digestion.

N-nitrosamine rejection by reverse osmosis membranes: A full-scale study

This study aims to provide longitudinal and spatial insights to the rejection of N-nitrosamines by reverse osmosis (RO) membranes during sampling campaigns at three full-scale water recycling plants. Samples were collected at all individual filtration stages as well as at a cool and a warm weather period to elucidate the impact of recovery and feed temperature on the rejection of N-nitrosamines. N-nitrosodimethylamine (NDMA) was detected in all RO feed samples varying between 7 and 32 ng/L. Concentrations of most other N-nitrosamines in the feed solutions were determined to be lower than their detection limits (3-5 ng/L) but higher concentrations were detected in the feed after each filtration stage. As a notable exception, in one plant, N-nitrosomorpholine (NMOR) was observed at high concentrations in RO feed (177-475 ng/L) and permeate (34-76 ng/L). Overall rejection of NDMA among the three RO systems varied widely from 4 to 47%. Data presented here suggest that the feed temperature can influence rejection of NDMA. A considerable variation in NDMA rejection across the three RO stages (14-78%) was also observed. Overall NMOR rejections were consistently high ranging from 81 to 84%. On the other hand, overall rejection of N-nitrosodiethylamine (NDEA) varied from negligible to 53%, which was considerably lower than values reported in previous laboratory-scale studies. A comparison between results reported here and the literature indicates that there can be some discrepancy in N-nitrosamine rejection data between laboratory- and full-scale studies probably due to differences in water recoveries and operating conditions (e.g. temperature, membrane fouling, and hydraulic conditions).

Quantifying human exposure to contaminants for multiple-barrier water reuse systems.

Reliance upon advanced water treatment processes to provide safe drinking water from relatively compromised sources is rapidly increasing in Australia and other parts of the world. Advanced treatment processes such as reverse osmosis have the ability to provide very effective treatment for a wide range of chemicals when operated under optimal conditions. However, techniques are required to comprehensively validate the performance of these treatment processes in the field. This paper provides a discussion and demonstration of some effective statistical techniques for the assessment and description of advanced water treatment plant performance. New data is provided, focusing on disinfection byproducts including trihalomethanes and N-nitrosamines from a recent comprehensive quantitative exposure assessment for an advanced water recycling scheme in Australia.