Nhat Le-Minh

Fate of antibiotics during municipal water recycling treatment processes

Municipal water recycling processes are potential human and environmental exposure routes for low concentrations of persistent antibiotics. While the implications of such exposure scenarios are unknown, concerns have been raised regarding the possibility that continuous discharge of antibiotics to the environment may facilitate the development or proliferation of resistant strains of bacteria. As potable and non-potable water recycling schemes are continuously developed, it is imperative to improve our understanding of the fate of antibiotics during conventional and advanced wastewater treatment processes leading to high-quality water reclamation. This review collates existing knowledge with the aim of providing new insight to the influence of a wide range of treatment processes to the ultimate fate of antibiotics during conventional and advanced wastewater treatment. Although conventional biological wastewater treatment processes are effective for the removal of some antibiotics, many have been reported to occur at 10-1000 ng L(-1) concentrations in secondary treated effluents. These include beta-lactams, sulfonamides, trimethoprim, macrolides, fluoroquinolones, and tetracyclines. Tertiary and advanced treatment processes may be required to fully manage environmental and human exposure to these contaminants in water recycling schemes. The effectiveness of a range of processes including tertiary media filtration, ozonation, chlorination, UV irradiation, activated carbon adsorption, and NF/RO filtration has been reviewed and, where possible, semi-quantitative estimations of antibiotics removals have been provided.

Determination of six sulfonamide antibiotics, two metabolites and trimethoprim in wastewater by isotope dilution liquid chromatography/tandem mass spectrometry

A highly sensitive method for the analysis of six sulfonamide antibiotics (sulfadiazine, sulfathiazole, sulfapyridine, sulfamerazine, sulfamethazine and sulfamethoxazole), two sulfonamide metabolites (N(4)-acetyl sulfamethazine and N(4)-acetyl sulfamethoxazole) and the commonly co-applied antibiotic trimethoprim was developed for the analysis of complex wastewater samples. The method involves solid phase extraction of filtered wastewater samples followed by liquid chromatography-tandem mass spectral detection. Method detection limits were shown to be matrix-dependent but ranged between 0.2 and 0.4 ng/mL for ultrapure water, 0.4 and 0.7 ng/mL for tap water, 1.4 and 5.9 ng/mL for a laboratory-scale membrane bioreactor (MBR) mixed liquor, 0.7 and 1.7 ng/mL for biologically treated effluent and 0.5 and 1.5 ng/g dry weight for MBR activated sludge. An investigation of analytical matrix effects was undertaken, demonstrating the significant and largely unpredictable nature of signal suppression observed for variably complex matrices compared to an ultrapure water matrix. The results demonstrate the importance of accounting for such matrix effects for accurate quantitation, as done in the presented method by isotope dilution. Comprehensive validation of calibration linearity, reproducibility, extraction recovery, limits of detection and quantification are also presented. Finally, wastewater samples from a variety of treatment stages in a full-scale wastewater treatment plant were analysed to illustrate the effectiveness of the method.

The application of membrane bioreactors as decentralised systems for removal of endocrine disrupting chemicals and pharmaceuticals.

The concentrations of some important endocrine disrupting chemicals and pharmaceuticals after various stages of wastewater treatment were investigated. The endocrine disrupting chemicals included natural and synthetic estrogenic and androgenic steroids. The pharmaceuticals included a series of sulfonamide antibiotics and trimethoprim. The removal efficiency of a membrane bioreactor (MBR) was investigated and compared with a conventional activated sludge (CAS) system. Samples were analysed by liquid chromatography tandem mass spectrometry. Results showed that the MBR and CAS systems effectively removed steroidal estrogens and androgens, but only partially eliminated the target antibiotics from wastewater. The MBR was shown to be more effective than the CAS system which was possibly attributed to the high solid retention time and concentration of biosolids in the MBR. The results highlight the potential wider application of MBRs for the removal of trace chemical contaminants in wastewater and their potential for use as decentralised wastewater treatment systems.

Fate and levels of steroid oestrogens and androgens in waste stabilisation ponds: quantification by liquid chromatography-tandem mass spectrometry.

The capacity for removing wastewater-borne endocrine disrupting chemicals (EDCs) was investigated for two wastewater treatment plants (WWTPs) incorporating waste stabilisation ponds (WSPs) as the principal treatment technology. Samples were analysed for a number of steroidal oestrogens and androgens using liquid chromatography-tandem mass spectrometry (LC/MS/MS). Removal efficiency for steroid androgens was high for both WWTPs (93-100%) but WSP treatment was observed to be less effective for removing steroid oestrogens, particularly oestriol.

Distribution and sensorial relevance of volatile organic compounds emitted throughout wastewater biosolids processing

A diverse range of volatile organic compounds (VOCs) are emitted from wastewater biosolids processing. Odorous emissions are predominately made up of volatile sulfur compounds (VSCs) which are typically the only odorants measured. However, a range of VOCs are known to contribute to malodours yet previous studies often overlook the contribution of VOCs in comparison with VSCs. This study aims to evaluate how emissions are affected by different biosolids processing configurations, and if any non-sulfur VOCs should be included in odour measurement and management. Non-sulfur VOCs emitted from biosolids throughout six wastewater treatment plants in the Sydney, Australia region were measured at six locations on average twice each week over 2-3weeks at each site. Variations in types of VOCs emitted throughout and between the sites were assigned to differences in WWTP processing configurations, plant operation and variations in industrial and municipal flows to the sewer network, referred to as sewer catchments. The presence of VOCs is likely due to biotic generation as well as industrial or residential additions to the sewer network. The dewatered and stored biosolids samples had the highest levels of VOC emissions. Sensorially important odorants were p-cresol and butanoic acid, based on the frequency of detection and odour activity values. Other compounds with a high risk of nuisance impacts were trimethylamine, indole and phenol emitted from the dewatered and stored biosolids, and volatile fatty acids from the anaerobic digester inlet and outlet at one particular site. The findings show that non-sulfur VOCs should be added to odorant monitoring campaigns at WWTPs. Identification of VOCs as sensorially important odorants opens opportunities for the more efficient management of nuisance odours, through targeted odour control or process improvement.

Occurrence of ectoparasiticides in Australian beef cattle feedlot wastes

A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for the simultaneous analysis of 6 ectoparasiticides - 2 synthetic pyrethroids (deltamethrin, cypermethrin) and 4 macrocyclic lactones (abamectin, doramectin, ivermectin and eprinomectin) in biosolids. The method was used to investigate the occurrence of these ectoparasiticides in beef cattle feedlot wastes in Australia from 5 commercial feedlot operations which employ varying waste management practices. Deltamethrin and cypermethrin were not detected in any of the samples while abamectin, ivermectin, doramectin and eprinomectin were detected in some of the samples with concentrations ranging from 1 to 36 μg/kg dry weight (d.w.) freeze dried feedlot waste. Levels of macrocyclic lactones detected in the feedlot wastes varied and were dependent on sample type. The effect of seasonal variations and waste management practices were also investigated in this study.

Emissions of volatile sulfur compounds (VSCs) throughout wastewater biosolids processing

Volatile sulfur compounds (VSCs) are important contributors to nuisance odours from the processing of wastewater sludge and biosolids. However, emission characteristics are difficult to predict as they vary between sites and are likely to be affected by biosolids processing configuration and operation. VSC emissions from biosolids throughout 6 wastewater treatment plants (WWTPs) in Sydney, Australia were examined in this study. H2S was the VSC found at the highest concentrations throughout the WWTPs, with concentrations ranging from 7 to 39,000μg/m3. Based on odour activity values (OAVs), H2S was typically also the most dominant odorant. However, methyl mercaptan (MeSH) was also found to be sensorially important in the biosolids storage areas given its low odour detection threshold (ODT). High concentrations of VOSCs such as MeSH in the storage areas were shown to potentially interfere with H2S measurements using the Jerome 631-X H2S sensor and these interferences should be investigated in more detail. The VSC composition of emissions varied throughout biosolids processing as well as between the different WWTPs. The primary sludge and biosolids after dewatering and during storage, were key stages producing nuisance odours as judged by the determination of OAVs. Cluster analysis was used to group sampling locations according to VSC emissions. These groups were typically the dewatered and stored biosolids, primary and thickened primary sludge, and waste activated sludge (WAS), thickened WAS, digested sludge and centrate. Effects of biosolids composition and process operation on VSC emissions were evaluated using best subset regression. Emissions from the primary sludge were dominated by H2S and appeared to be affected by the presence of organic matter, pH and Fe content. While volatile organic sulfur compounds (VOSCs) emitted from the produced biosolids were shown to be correlated with upstream factors such as Fe and Al salt dosing, anaerobic digestion and dewatering parameters.

Dynamics of Volatile Sulfur Compounds and Volatile Organic Compounds in Sewer Headspace Air

A 2-year monitoring study was conducted at a sewer pumping station to investigate volatile sulfur compound (VSC) and volatile organic compound (VOC) emission dynamics over a range of timescales to gain an understanding of how they impact the design and execution of sewer odorant monitoring. It is demonstrated that the sewer system was highly dynamic and influenced by a range of processes at different time scales. Based upon odor activity values, hydrogen sulfide and methyl mercaptan had strong potential to be odorous, while dimethyl sulfide and dimethyl disulfide were potentially odorous at source concentrations. In general, VOCs were not likely to be odorous at source concentrations, although some episodic elevations in aromatic hydrocarbon and terpene concentrations to potentially odorous levels were observed and as a result VSCs are the primary targets for sewer odor abatement. A strong diurnal emission cycle was observed, with dynamic ranges (ratio of peak to average concentration) between 2.34 and 4.55 for specific VSCs and 1.82 to 10.6 for specific VOCs. Interday variability over a 1-week period was relatively low for many VSCs, with coefficients of variance generally ranging from 11 to 30%, while VOC emissions had greater variability, with coefficients of variance ranging from 29 to 220%.

Odorous volatile organic compound (VOC) emissions from ageing anaerobically stabilised biosolids

Opportunities for the beneficial re-use of biosolids are limited by nuisance odour emissions. Volatile organic compounds (VOCs) from anaerobically stabilised biosolids were measured to identify compounds that could contribute to the overall odour character of nuisance emissions. Flux hood sampling and chemical analysis were used to identify VOCs emitted from biosolids as they were stored in ambient conditions. Compounds emitted varied as the biosolid cakes were stored for a period of 50 days. VOCs detected in the biosolids are likely to occur from catchment sources as well as abiotic and biotic generation in the wastewater processing and the biosolids as they are stored. Odour activity values (OAVs) were used to compare odorants. Trimethylamine was the only VOC detected that exceeded the sulfur compounds in terms of OAVs. Other compounds such as limonene, ethyl methyl benzene and acetic acid were detected at concentrations exceeding their olfactory detection limits, however at lower OAVs than sulfur compounds.

Identification of VOCs from natural rubber by different headspace techniques coupled using GC-MS

Different extraction procedures were evaluated to assess their potential for measuring volatile organic compounds (VOCs) from raw rubber materials. Four headspace sampling techniques (SHS, DHS, HS-SPME and µ-CTE) were studied. Each method was firstly optimised to ensure their reliability in performance. Passive sampling was also compared as a rapid identification of background VOCs. 352 VOCs were identified, 71 from passive sampling and 281 from active headspace sampling, with 62 not previously reported (hexanenitrile, octanone, decanal, indole, aniline, anisole, alpha-pinene as well as pentanol and butanol). The volatiles belonged to a broad range of chemical classes (ketones, aldehydes, aromatics, acids, alkanes, alcohol and cyclic) with their thermal effects (lower boiling points) greatly affecting their abundance at a higher temperature. Micro-chamber (µ-CTE) was found to be the most suitability for routine assessments due to its operational efficiency (rapidity, simplicity and repeatability), identifying 115 compounds from both temperatures (30 °C and 60 °C). Whereas, HS-SPME a widely applied headspace technique, only identified 75 compounds and DHS identified 74 VOCs and SHS only 17 VOCs. Regardless of the extraction technique, the highest extraction efficiency corresponded to aromatics and acids, and the lowest compound extraction were aldehyde and hydrocarbon. The interaction between techniques and temperature for all chemical groups were evaluated using two-way ANOVA (p-value is 0.000197) explaining the highly significant interactions between factors.