The occurrence of antibiotics in an urban watershed: from wastewater to drinking water.

The presence of 28 antibiotics in three hospital effluents, five wastewater treatment plants (WWTPs), six rivers and a drinking water storage catchment were investigated within watersheds of South-East Queensland, Australia. All antibiotics were detected at least once, with the exception of the polypeptide bacitracin which was not detected at all. Antibiotics were found in hospital effluent ranging from 0.01-14.5 microg L(-1), dominated by the beta-lactam, quinolone and sulphonamide groups. Antibiotics were found in WWTP influent up to 64 microg L(-1), dominated by the beta-lactam, quinolone and sulphonamide groups. Investigated WWTPs were highly effective in removing antibiotics from the water phase, with an average removal rate of greater than 80% for all targeted antibiotics. However, antibiotics were still detected in WWTP effluents in the low ng L(-1) range up to a maximum of 3.4 microg L(-1), with the macrolide, quinolone and sulphonamide antibiotics most prevalent. Similarly, antibiotics were detected quite frequently in the low ng L(-1) range, up to 2 microg L(-1) in the surface waters of six investigated rivers including freshwater, estuarine and marine samples. The total investigated antibiotic concentration (TIAC) within the Nerang River was significantly lower (p<0.05) than all other rivers sampled. The absence of WWTP discharge to this river is a likely explanation for the significantly lower TIAC and suggests that WWTP discharges are a dominant source of antibiotics to investigated surface waters. A significant difference (p<0.001) was identified between TIACs at surface water sites with WWTP discharge compared to sites with no WWTP discharge, providing further evidence that WWTPs are an important source of antibiotics to streams. Despite the presence of antibiotics in surface waters used for drinking water extraction, no targeted antibiotics were detected in any drinking water samples.

Is there a risk associated with the insect repellent DEET (N,N-diethyl-m-toluamide) commonly found in aquatic environments?

DEET (N,N-diethyl-m-toluamide) is the active ingredient of most commercial insect repellents. This compound has commonly been detected in aquatic water samples from around the world indicating that DEET is both mobile and persistent, despite earlier assumptions that DEET was unlikely to enter aquatic ecosystems. DEET's registration category does not require an ecological risk assessment, thus information on the ecological toxicity of DEET is sparse. This paper reviews the presence of DEET in aqueous samples from around the world (e.g. drinking water, streams, open seawater, groundwater and treated effluent) with reported DEET concentrations ranging from 40-3000 ng L(-1). In addition, new DEET data collected from 36 sites in coastal waterways from eastern Australia (detections ranging from 8 to 1500 ng L(-1)) are examined. A summary of new and existing toxicity data are discussed with an emphasis on preparing a preliminary risk assessment for DEET in the aquatic environment. Collated information on DEET in the aquatic environment suggests risk to aquatic biota at observed environmental concentrations is minimal. However, the information available was not sufficient to conduct a full risk assessment due to data deficiencies in source characterisation, transport mechanisms, fate, and ecotoxicity studies. These risks warrant further investigation due to the high frequency that this organic contaminant is detected in aquatic environments around the world.

Removal of antibiotics in conventional and advanced wastewater treatment: implications for environmental discharge and wastewater recycling.

Removal of 28 human and veterinary antibiotics was assessed in a conventional (activated sludge) and advanced (microfiltration/reverse osmosis) wastewater treatment plant (WWTP) in Brisbane, Australia. The dominant antibiotics detected in wastewater influents were cephalexin (med. 4.6 microg L(-1), freq. 100%), ciprofloxacin (med. 3.8 microg L(-1), freq. 100%), cefaclor (med. 0.5 microg L(-1), freq. 100%), sulphamethoxazole (med. 0.36 microg L(-1), freq. 100%) and trimethoprim (med. 0.34 microg L(-1), freq. 100%). Results indicated that both treatment plants significantly reduced antibiotic concentrations with an average removal rate from the liquid phase of 92%. However, antibiotics were still detected in both effluents from the low-to-mid ng L(-1) range. Antibiotics detected in effluent from the activated sludge WWTP included ciprofloxacin (med. 0.6 microg L(-1), freq. 100%), sulphamethoxazole (med. 0.27 microg L(-1), freq. 100%) lincomycin (med. 0.05 microg L(-1), freq. 100%) and trimethoprim (med. 0.05 microg L(-1), freq. 100%). Antibiotics identified in microfiltration/reverse osmosis product water included naladixic acid (med. 0.045 microg L(-1), freq. 100%), enrofloxacin (med. 0.01 microg L(-1), freq. 100%), roxithromycin (med. 0.01 microg L(-1), freq. 100%), norfloxacin (med. 0.005 microg L(-1), freq. 100%), oleandomycin (med. 0.005 microg L(-1), freq. 100%), trimethoprim (med. 0.005 microg L(-1), freq. 100%), tylosin (med. 0.001 microg L(-1), freq. 100%), and lincomycin (med. 0.001 microg L(-1), freq. 66%). Certain traditional parameters, including nitrate concentration, conductivity and turbidity of the effluent were assessed as predictors of total antibiotic concentration, however only conductivity demonstrated any correlation with total antibiotic concentration (p=0.018, r=0.7). There is currently a lack of information concerning the effects of these chemicals to critically assess potential risks for environmental discharge and water recycling.

Determination of clenbuterol in bovine urine using gas chromatography-mass spectrometry following clean-up on an ion-exchange resin.

A gas chromatographic-mass spectrometric method was developed for the determination of residues of clenbuterol in bovine urine. The method involves a simple cation-exchange clean-up and concentration of clenbuterol in the acidified urine, followed by ethyl acetate extraction. The analyte is determined as the di-trimethylsilyl derivative and quantitated against an internal standard of penbutolol. Using a 5-ml sample of urine, a detection limit of 0.07 ng/ml can be achieved with recoveries close to 100% for fortification levels of 0.2 and 1 ng/ml. By increasing the sample volume to 50 ml, a detection limit below 0.01 ng/ml was achievable with recovery averaging 70%. The coefficient of variation of the assay ranged from 15% at 0.01 ng/ml (50-ml sample) to 6% at 1 ng/ml (5-ml sample). It was demonstrated that the method can detect the presence of clenbuterol in bovine urine at sub-ppb (ng/ml) levels using low resolution GC-MS with electron impact (EI) ionization.

Gas chromatographic determination of organic acids from fruit juices by combined resin mediated methylation and extraction in supercritical carbon dioxide.

A procedure in which anionic analytes, trapped on ion exchange resin, are simultaneously methylated and released using methyl iodide in either supercritical carbon dioxide or acetonitrile has been extended to polyfunctional organic acids. The combined SFE methylation of fruit juice acids trapped onto ion exchange resin proceeds in good yield producing the methyl esters of fumaric, succinic, malic, tartaric, isocitric and citric acids which are readily separated by GC. Using this procedure low concentrations of one acid can be detected and quantitated in the presence of very high concentrations of another. This new method detects tartaric acid at levels of 10 ppm in juices containing 10,000 ppm citric acid. Quantitation was performed either by using GC-FID with triethyl citrate or diethyl tartrate as internal standards or with the element specific calibration capability of the GC-AED. A simple new technique for the determination of citric/isocitric acid ratio is now available. Also, in contrast to HPLC methods, the identity of an analyte is readily confirmed by GC-MS.

Gas chromatographic determination of residues of thyreostatic drugs in bovine muscle tissue using combined resin mediated methylation and extraction.

A method is described for the assay of residues of the thyreostatic substances 2-thiouracil, 6-methyl-2-thiouracil, 5- and 6-propyl-2-thiouracils and 6-phenyl-2-thiouracil in beef muscle at levels of quantitation down to 25 microg/kg for thiouracil and 15 microg/kg for substituted thiouracils. Analytes are extracted from the muscle matrix with acetonitrile and methylated by absorption onto a macroporous anion exchange resin followed by treatment with methyl iodide in acetonitrile at room temperature. Supercritical carbon dioxide is also a suitable derivatization solvent. Determination is carried out using gas chromatography with mass spectrometric detection. The methyl ester of 2,4,5-trichlorophenoxyacetic acid serves as an internal standard while 5-methyl-2-thiouracil is a suitable surrogate. 5-Ethyl-2-thiouracil is added to minimise losses of the analytes during the analysis. The method exhibits a linear range of 25-625 microg/kg for the substituted thiouracils and 50-1250 microg/kg for 2-thiouracil. Recovery of the analytes ranges from 50% for 6-phenyl-2-thiouracil to 90% for 2-thiouracil with coefficients of variation of less than 10%.