Determination of fluoroquinolone antibiotics in wastewater effluents by liquid chromatography-mass spectrometry and fluorescence detection

The occurrence of quinolone antibiotics (QAs) was investigated in wastewater effluents and surface river/lake waters in the US and Canada by using solid-phase extraction with mixed phase cation exchange disk cartridge and liquid chromatography-mass spectrometry (LC-MS) and liquid chromatography fluorescence detection (LC-FLD). Ofloxacin (OFL) was detected in secondary and final effluents of a wastewater treatment plant (WWTP) in East Lansing, Michigan, at concentrations of 204 and 100 ng/l, respectively. The mass flow calculation, estimated by multiplying the OFL concentration in the final effluent by the average influent volume of the WWTP, showed that the discharge of OFL to the river was 4.8 g/day. The OFL concentrations in wastewater effluents measured in this study are comparable to or less than those observed in several European countries. QAs were not detected in river and lake waters analyzed in this study, which may due to dilution effects and to the higher detection limits, relative to those reported previously. OFL concentrations were approximately 1-2 orders of magnitude lower than the EC50 concentrations for environmental bacterium. However, greater concentrations of other QAs in sewage sludge from WWTPs may result in cumulative effects. Considering that the sewage sludge is applied to the land as fertilizers, soil-dwelling organisms could experience greater exposures to such antibiotics. Monitoring studies of QAs in sewage from WWTPs and in sediment/soil near aquaculture facilities and livestock farms will be necessary for the evaluation of the environmental distribution and risk of these compounds.     

Input/output balance of estrogenic active compounds in a major municipal sewage plant in Germany

24 h samples of untreated and treated wastewater were taken in parallel from a modern municipal sewage plant in southern Germany in March and June 1998. After solid phase extraction, total estrogenic activity was quantitatively measured with a miniaturized E-screen assay and the levels of nine estrogenic phenolic chemicals analyzed by HRGC/LRMS. 17Beta-estradiol equivalent concentrations (EEQ) were 58 and 70 ng/l in the influent and 6 ng/l in the effluent, indicating that the load of estrogenic activity of the wastewater was reduced by about 90% in the sewage plant. Less than 3% of the estrogenic activity was found in the sludge. 4-t-octylphenol, 4-nonylphenol, bisphenol A, 2-hydroxybiphenyl, and 4-chloro-3-methylphenol were detected in the untreated wastewater at levels from 0.13 to 3.6 microg/l. 4-t-octylphenol, 4-nonylphenol, and bisphenol A were present in the effluent at concentrations from 0.16 to 0.36 microg/l, 2-hydroxybiphenyl and 4-chloro-3-methylphenol were not detectable. The contribution of the quantified levels of phenolic xenoestrogens to total estrogenic activity in the sewage was 0.7-4.3%.     

Determination of commonly used polar herbicides in agricultural drainage waters in Australia by HPLC

The present study describes the application of different extraction techniques for the preconcentration of ten commonly found acidic and non-acidic polar herbicides (2,4-D, atrazine, bensulfuron-methyl, clomazone, dicamba, diuron, MCPA, metolachlor, simazine and triclopyr) in the aqueous environment. Liquid-liquid extraction (LLE) with dichloromethane, solid-phase extraction (SPE) using Oasis HLB cartridges or SBD-XC Empore disks were compared for extraction efficiency of these herbicides in different matrices, especially water samples from contaminated agricultural drainage water containing high concentrations of particulate matter. Herbicides were separated and quantified by high performance liquid chromatography (HPLC) with an ultraviolet detector. SPE using SDB-XC Empore disks was applied to determine target herbicides in the Murrumbidgee Irrigation Area (NSW, Australia) during a two-week survey from October 2005 to November 2005. The daily aqueous concentrations of herbicides from 24-h composite samples detected at two sites increased after run-off from a storm event and were in the range of: 0.1-17.8 microg l(-1), < 0.1-0.9 microg l(-1) and 0.2-17.8 microg l(-1) at site 1; < 0.1-3.5 microg l(-1), < 0.1-0.2 microg l(-1) and < 0.2-3.2 microg l(-1) at site 2 for simazine, atrazine and diuron, respectively.     

Evaluating the vulnerability of surface waters to antibiotic contamination from varying wastewater treatment plant discharges

Effluents from three wastewater treatment plants with varying wastewater treatment technologies and design were analyzed for six antibiotics and caffeine on three sampling occasions. Sulfamethoxazole, trimethoprim, ciprofloxacin, tetracycline, and clindamycin were detected in the effluents at concentrations ranging from 0.090 to 6.0 microg/L. Caffeine was detected in all effluents at concentrations ranging from 0.19 to 9.9 microg/L. These findings indicate that several conventional wastewater management practices are not effective in the complete removal of antibiotics, and their discharges have a large potential to affect the aquatic environment. To evaluate the persistence of antibiotics coming from the wastewater discharges on the surrounding surface waters, samples were collected from the receiving streams at 10-, 20- and 100-m intervals. Ciprofloxacin, sulfamethoxazole, and clindamycin (0.043 to 0.076 microg/L) were found as far as 100 m from the discharge point, which indicates the persistence of these drugs in surface waters.     

Evaluation of municipal sewage treatment systems for pollutant removal efficiency by measuring levels of micropollutants

In order to evaluate the municipal sewage treatment systems used at Harbin municipal sewage treatment plant for their pollutant removal efficiency, raw sewage and effluent samples at different treatment stages from the sewage treatment systems were taken, priority pollutants (PPs) were identified and quantified using gas chromatography-mass spectrometry (GC-MS) and inductively coupled plasma-atomic emission spectrograph (ICP-AES). The test results indicated that there were one hundred and fifty species of organic pollutants identified in the raw sewage sample, and only ten species of PPs in all the sewage samples. The levels of dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), di-n-octyl phthalate (DnOP) in the sewage samples were 0.779-0.111 microg l(-1), 1.977-0.022 microg l(-1), 6.411-2.194 microg l(-1) and 7.152-2.953microg l(-1), respectively, and most of these phthalate esters (PAEs) were removed through anaerobic/aerobic (A/O) process; The levels of alachlor, acetochlor, atrazine were 0.074-0.021 microg l(-1), 0.160-0.096 microg l(-1) and 0.238-0.184 microg l(-1), respectively, and the total removal efficiency of atrazine was poorest through the sewage treatment systems. The levels of Cu, Cr, Se, Hg, Ni and Zn were 0.0030-0.2327 mg l(-1). It is therefore concluded from these results that the sewage treatment systems were efficient in removing most of the organic and inorganic compounds in this study, and so, the discharged effluent could cause little of the secondary pollution of the aquatic environment.     

Agricultural reuse of reclaimed water and uptake of organic compounds: pilot study at Mutah University wastewater treatment plant, Jordan

The residues of polynuclear aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), chlorinated benzenes (CBs) and phenols were investigated for soil, wastewater, groundwater and plants. The uptake concentration of these compounds was comparatively determined using various plant types: Zea mays L., Helianthus annus L., Capsicum annum L., Abelmoschus esculentus L., Solanum melongena L. and Lycopersicon esculentum L. which were grown in a pilot site established at Mutah University wastewater treatment plant, Jordan. Soil, wastewater, groundwater and various plant parts (roots, leaves and fruits) samples were extracted in duplicate, cleaned up by open-column chromatography and analyzed by a multi-residue analytical methods using gas chromatography equipped with either mass selective detector (GC/MS), electron capture detector (GC/ECD), or flame ionization detector (FID). Environmentally relevant concentrations of targeted compounds were detected for wastewater much higher than for groundwater. The overall distribution profiles of PAHs and PCBs appeared similar for groundwater and wastewater indicating common potential pollution sources. The concentrations of PAHs, PCBs and phenols for different soils ranged from 169.34 to 673.20 microg kg(-1), 0.04 to 73.86 microg kg(-1) and 73.83 to 8724.42 microg kg(-1), respectively. However, much lower concentrations were detected for reference soil. CBs were detected in very low concentrations. Furthermore, it was found that different plants have different uptake and translocation behavior. As a consequence, there are some difficulties in evaluating the translocation of PAHs, CBs, PCBs and phenols from soil-roots-plant system. The uptake concentrations of various compounds from soil, in which plants grown, were dependent on plant variety and plant part, and they showed different uptake concentrations. Among the different plant parts, roots were found to be the most contaminated and fruits the least contaminated.     

Analysis of acidic pesticides using in situ derivatization with alkylchloroformate and solid-phase microextraction (SPME) for GC-MS.

A solid-phase microextraction (SPME) method was developed for the analysis of acidic pesticide residues in water. The method utilizes in situ derivatization with butylchloroformate (BuCF), followed by on-line SPME extraction using a PDMS fibre, and analysis by GC-MS. Derivatives of the phenoxy acids mechlorprop (MCPP), dichlorprop (DCPP), MCPA and 2,4-D and their phenol degradation products 4-chloro-2-methylphenol and 2,4-dichlorophenol (DCP) were identified. Detection limits at 0.16-2.3 microg/l were achieved. Optimization of derivatization, ion strength, extraction time, SPME-fibre, desorption time and temperature are described. Standard curves in the range 0.5-10.0 microg/l were fitted to a second-degree polynomial. Standard deviation (n = 5) was below 10% for the phenol derivatives, but 20-50% for the phenoxy acids. For method verification groundwater samples from a field experiment were screened for content of MCPP and compared to the results from the HPLC analysis. A good agreement was obtained with respect to identification of positive samples, even though concentrations measured by the SPME were lower than with HPLC. Even if the precision and accuracy do not meet the demands for a strictly quantitative analysis, the SPME method is suitable for screening, because it is cheap, it can be automated, and uses smaller amounts of potential harmful solvents. Also, the method is less labour-intensive, as it requires a minimum of sample preparation when compared to traditional analyses. The acidic pesticides bentazon, dicamba, bromoxynil, ioxynil, dinoseb and DNOC were included in the study but could not be analysed by the current method.     

LC-MS-MS analysis and occurrence of octyl- and nonylphenol, their ethoxylates and their carboxylates in Belgian and Italian textile industry, waste water treatment plant effluents and surface waters

Alkylphenols (APs), alkylphenol ethoxylates (APEOs), ethoxycarboxylate metabolites (APECs) and bisphenol A were determined in surface water using solid-phase extraction (SPE) followed by triple-quadrupole LC-MS-MS. APs were separated by LC from APECs using an acetonitrile-water-gradient without the addition of any buffer. Nonylphenol ethoxycarboxylates (NPECs) interfere in the detection of nonylphenols (NPs) when using an acidic mobile phase, because they produce the same MS-MS fragment ions (219>133 and 147). 4n-NP shows the characteristic transition 219>106; it is well suited as internal standard. Nonylphenol ethoxylates NPE(n)Os (n=1-17) were analysed separately in a second run by positive ionization using an ammonium acetate mobile phase. Textile industry discharges, the corresponding wastewater treatment plant (WWTP) effluents and the receiving rivers in Belgium and Italy were analysed. Among the substances investigated, NPE1C and NPE2O exhibited the highest concentrations in the water samples, up to 4.5 microg l(-1) NPE1C in a WWTP effluent and 3.6 microg l(-1) NPE2O in a river. The highest NP levels were found in the receiving rivers (max. 2.5 microg l(-1)). The predicted no-effect concentration (PNEC) for NP of 0.33 microg l(-1) for water species was frequently exceeded in the surface waters investigated, suggesting potential adverse effects to the aquatic environment.     

Pharmaceutical contamination in residential, industrial, and agricultural waste streams: risk to aqueous environments in Taiwan

This is a comprehensive study of the occurrence of antibiotics, hormones and other pharmaceuticals in water sites that have major potential for downstream environmental contamination. These include residential (hospitals, sewage treatment plants, and regional discharges), industrial (pharmaceutical production facilities), and agricultural (animal husbandries and aquacultures) waste streams. We assayed 23 Taiwanese water sites for 97 targeted compounds, of which a significant number were detected and quantified. The most frequently detected compounds were sulfamethoxazole, caffeine, acetaminophen, and ibuprofen, followed closely by cephalexin, ofloxacin, and diclofenac, which were detected in >91% of samples and found to have median (maximum) concentrations of 0.2 (5.8), 0.39 (24.0), 0.02 (100.4), 0.41 (14.5), 0.15 (31.4), 0.14 (13.6) and 0.083 (29.8) microg/L, respectively. Lincomycin and acetaminophen had high measured concentrations (>100 microg/L), and 35 other pharmaceuticals occurred at the microg/L level. These incidence and concentration results correlate well with published data for other worldwide locations, as well as with Taiwanese medication usage data, suggesting a human contamination source. Many pharmaceuticals also occurred at levels exceeding predicted no-effect concentrations (PNEC), warranting further investigation of their occurrence and fate in receiving waters, as well as the overall risks they pose for local ecosystems and human residents. The information provided here will also be useful for development of strategies for regulation and remediation.     

Determination of estrogenic compounds in wastewater using liquid chromatography-tandem mass spectrometry with electrospray and atmospheric pressure photoionization following desalting extraction

Two complementary LC-MS ionization methods, electrospray (ESI) and atmospheric pressure photoionization (APPI), have been optimized to determine three natural estrogenic compounds (estrone, 17beta-estradiol and estriol) and two synthetic estrogenic compounds (17alpha-ethynylestradiol and diethylstilbestrol) in the influent and effluent of wastewater treatment plants (WWTPs). The wastewater samples were first subjected to solid-phase extraction coupled with desalting extraction to remove matrix interference. The analytes were then detected using liquid chromatography-tandem mass spectrometry (LC-MS-MS) with ESI and dopant-assisted (DA) APPI to evaluate the ion suppression effect and to complement the detection and quantification of estrogenic compounds in complex wastewater samples. The average ion suppression factors for the extracts of the WWTP influent analyzed using ESI and APPI were 52+/-5% and 27+/-7%, respectively. The sensitivity and ionization efficiency of the LC-ESI-MS-MS system decreased dramatically when a complex matrix was present in the WWTP influent sample. Estrogenic compounds could be detected in the WWTP influent and effluent samples at concentrations below the parts-per-billion level. The lower detection limits obtained when using ESI and the higher matrix tolerance of the APPI method allowed the complete quantification of estrogenic compounds in very complex samples in a complementary manner.     

Determination of beta-adrenergic receptor blocking pharmaceuticals in United States wastewater effluent

Beta adrenergic receptor antagonists (beta-Blockers) are frequently prescribed medications in the United States and have been identified in European municipal wastewater effluent, however no studies to date have investigated these compounds in United States wastewater effluent. Municipal wastewater effluent was collected from treatment facilities in Mississippi, Texas, and New York to investigate the occurrence of metoprolol, nadolol, and propranolol. Propranolol was identified in all wastewater samples analyzed (n = 34) at concentrations < or = 1.9 microg/l. Metoprolol and nadolol were identified in > or = 71% of the samples with concentrations of metoprolol < or = 1.2 microg/l and nadolol < or = 0.36 microg/l. Time course studies at both Mississippi plants and the Texas plant indicate that concentrations of propranolol, metoprolol, and nadolol remain relatively constant at each sampling period. This study indicates that beta-Blockers are present in United States wastewater effluent in the ng/l to microg/l range.     

Comparison of the occurrence of antibiotics in four full-scale wastewater treatment plants with varying designs and operations

The occurrence of ciprofloxacin, sulfamethoxazole, tetracycline, and trimethoprim antibiotics in four full-scale wastewater treatment plants (WWTPs) that differ in design and operating conditions was determined. The WWTPs chosen utilized a variety of secondary removal processes, such as a two stage activated sludge process with a nitrification tank, extended aeration, rotating biological contactors, and pure oxygen activated sludge. Several of the WWTPs also employed an advanced treatment process, such as chlorination and UV radiation disinfection. The detected concentrations (microg/l) ranged from 0.20 to 1.4 for ciprofloxacin, 0.21 to 2.8 for sulfamethoxazole, 0.061 to 1.1 for tetracycline, and 0.21 to 7.9 for trimethoprim. The overall percent difference in the concentrations of the antibiotics in the effluent and influent of these antibiotics differed between plants and ranged from 33% to 97%. Based on these four full-scale WWTPs evaluated, the apparent removal of organic micropollutants in wastewater is dependent on a combination of biological and physico-chemical treatment processes and operating conditions of the treatment system.     

The occurrence of antihistamines in sewage waters and in recipient rivers

Background, aim and scope  Each year, large quantities of pharmaceuticals are consumed worldwide for the treatment and prevention of human and animal diseases. Although the drugs and the metabolites observed in the wastewaters and in the environment are present at concentrations several orders of magnitude lower than the concentrations required to exert their effects in humans or animals, their long-term impact on the environment is commonly not known. In this study, the occurrence of six antihistamines, which are used for the relief of allergic reactions such as hay fever, was determined in sewage treatment plants wastewaters and in recipient river waters. Materials and methods  The occurrence of the antihistamines cetirizine, acrivastine, fexofenadine, loratadine, desloratadine and ebastine in sewage treatment plants wastewaters and in recipient river waters was studied. The analytical procedure consisted of solid-phase extraction of the water samples followed by liquid chromatography separation and detection by a triple-quadrupole mass spectrometer in the multiple reaction mode. Results  Cetirizine, acrivastine and fexofenadine were detected in both influent and effluent wastewater samples at concentration levels ranging from about 80 to 220 ng/L, while loratadine, desloratadine and ebastine could not be detected in any samples. During sewage treatment, the concentration of the antihistamines dropped by an average of 16–36%. Furthermore, elevated concentrations of antihistamines were observed in samples collected during the season of most intensive plant pollen production, i.e. in May. In the river water samples, the relative pattern of occurrence of cetirizine, acrivastine and fexofenadine was similar to that in the wastewater samples; although the concentration of the compounds was substantially lower (4–11 ng/L). The highest concentrations of the studied drugs were observed near the discharging point of the sewage treatment plant. Discussion  The highest concentrations of antihistamines in STP wastewaters correlate with the outbreak of allergic reaction caused by high amounts of plant pollens in the air. The analysis results of the river water samples show that the antihistamines are carried far away from the effluent discharge points. They may account for a part of the mix of pharmaceuticals and of pharmaceutical metabolites that occur downstream of STPs. Conclusions  Antihistamines are poorly degraded/eliminated under the biological treatment processes applied in the wastewater treatment plants and, consequently, they are continuously being discharged along with other drugs to the aquatic environment. Recommendations and perspectives  As a huge quantity and variety of drugs and their metabolites are continuously discharged to rivers and the sea, the compounds should be considered as contaminants that may possess risks to the aquatic ecosystem. Further studies are urgently needed on the environmental fate of the antihistamines and other pharmaceuticals in the aquatic environment. These studies should be concerned with the stability of the compounds, their transformation reactions and the identity of the transformation products, the distribution of drugs and their uptake and effects in organisms. On the basis of these studies, the possible environmental hazards of pharmaceuticals may be assessed.     

Considerations about the enantioselective transformation of polycyclic musks in wastewater, treated wastewater and sewage sludge and analysis of their fate in a sequencing batch reactor plant

The present work consists of two distinct parts: in the first part enantioselective GC was used to separate the different enantiomeric/diastereomeric polycyclic musks, PCMs (HHCB, AHTN, AHDI, ATII and DPMI) including the main transformation product of HHCB, HHCB-lactone, in wastewater and sewage sludge. After optimization all PCMs were resolved on a cyclodextrin containing Rt-BDEXcst capillary GC column. Enantiomeric ratios of PCMs in a technical mixture were determined and compared to those obtained from enantioselective separation of wastewater and sewage sludge samples. In general, enantiomeric ratios were similar for most materials in influent, effluent and stabilized sewage sludge. However, the ratios for HHCB, AHDI and particularly ATII suggest some stereospecific removal of these compounds. In the second part, a field study was conducted on a wastewater treatment plant comprising a sequencing batch reactor. Concentrations of HHCB, AHTN, ADBI, AHDI, ATII, DPMI and HHCB-lactone were determined by non-enantioselective GC in daily samples of influent, effluent and activated sludge during one week. Mean concentrations in influent were 6900 and 1520 ng/l for HHCB and AHTN, respectively. The other PCMs exhibited contents 200 ng/l. Mean percent removal was between 61% (AHDI) and 87% (HHCB) resulting in mean effluent concentrations below 860 ng/l. HHCB-lactone concentration increased during wastewater treatment with a mean in the influent of 430 ng/l and in the effluent of 900 ng/l, respectively, indicating a degradation of HHCB.     

Non-steroidal anti-inflammatory drugs in Indian rivers

Pharmaceutical concentration data for Indian surface waters are currently scarce. Sewage often enters Indian rivers without prior treatment, and so previously reported environmental concentrations from regions with routinely implemented sewage treatment cannot simply be used to predict concentrations in Indian surface water. Improved knowledge of pharmaceutical concentrations in Indian waters would enable determination of potential risks posed to aquatic wildlife and human health in this region. The concentrations of five common non-steroidal anti-inflammatory drugs (NSAIDs; diclofenac, ketoprofen, naproxen, ibuprofen, and acetylsalicylic acid) were determined in surface waters from 27 locations of the Kaveri, Vellar, and Tamiraparani Rivers in southern India. The samples were extracted by solid-phase extraction and analyzed by GC-MS. The measured concentrations of four of the five drugs in this reconnaissance were relatively similar to those reported elsewhere (ND–200 ng/l); however, acetylsalicylic acid, the most readily degradable of the investigated drugs, was found at all sites and at considerably higher concentrations (up to 660 ng/l) than reported in European surface waters. This is the first report on the occurrence of NSAIDs in Indian rivers. The finding of elevated concentrations of acetylsalicylic acid is most likely a result of direct discharges of untreated sewage. Therefore, readily degradable pharmaceuticals may present larger concern in regions without consistent sewage treatment. Based on measured environmental concentrations, the risks of direct toxicity to aquatic wildlife and of humans consuming the water are discussed.     

Determination of polycyclic musks in sewage sludge from Guangdong, China using GC-EI-MS

Polycyclic musks [Cashmeran (DPMI), Celestolide (ADBI), Phantolide (AHMI), Traseolide (ATII), Tonalide (AHTN) and Galaxolide (HHCB)] were Soxhlet extracted, separated and analyzed in sewage sludge from six different wastewater treatment plants from Guangdong, China, using GC and GC-EI-MS. DPMI, ADBI, HHCB, AHTN were found in all samples, and ATII was not found in any sample. AHMI was detected in five out of six samples. HHCB and AHTN were the two major polycyclic musks found in highest concentrations in sludge. The sludge from municipal wastewater treatment plants contained HHCB, AHTN and DPMI at concentrations between 5.416 and 21.214, 0.715 and 6.195 and 0.599 and 2.870 mg/kg (dry), respectively. The highest concentration was found in sludge from one cosmetic plant at 703.681 mg HHCB/kg (dry). The results indicate that there are two sources of polycyclic musks: domestic sewage and industrial wastewater.     

Multivariate optimization of solid-phase extraction applied to iron determination in finished waters

In this work, Amberlite XAD-4 resin functionalized with salicylic acid was synthetized, characterized and applied as a new packing material for an on-line system to iron determination in aqueous samples. The detection method is based on the sorption of Fe(III) ions in a minicolumn containing the synthesized resin, followed by a desorption step using an acid solution and measurement of iron by vis-spectrophotometry (CAS method). The optimization of the solid-phase extraction system was performed using factorial design and Doehlert matrix considering six variables: sample percolation rate (0.5-9 ml min(-1)), sample metal concentration (20-200 microg l(-1)), flow-through sample volume (0-5 ml) (all three directly linked to the extraction step), elution flow-rate (0.5-9 ml min(-1)), concentration and volume of eluent (HCl 0.1-0.5M) (all three directly linked to the elution step). The aim of this study was to obtain a set of operating ranges for the six variables tested in order to obtain--by means of a mathematical function allowing maximisation of each response (desirability function)--at least 90% of iron recovery rates. Using the experimental conditions defined in the optimization, the method allowed iron determination with achieved detection limit of 2.3 microgl(-1) and precision (assessed as the relative standard deviation) of 9.3-2.8% for iron solutions of 10.0-150 microgl(-1). Real samples (coming from a water treatment unit) were used successfully when evaluating potentialities of the developed SPE procedure coupled to a spectrophotometric determination.     

Primary biodegradation of veterinary antibiotics in aerobic and anaerobic surface water simulation systems

The primary aerobic and anaerobic biodegradability at intermediate concentrations (50-5000 microg/l) of the antibiotics olaquindox (OLA), metronidazole (MET), tylosin (TYL) and oxytetracycline (OTC) was studied in a simple shake flask system simulating the conditions in surface waters. The purpose of the study was to provide rate data for primary biodegradation in the scenario where antibiotics pollute surface waters as a result of run-off from arable land. The source of antibiotics may be application of manure as fertilizer or excreta of grazing animals. Assuming first-order degradation kinetics, ranges of half-lives for aerobic degradation of the four antibiotics studied were 4-8 days (OLA), 9.5-40 days (TYL), 14-104 days (MET) and 42-46 days (OTC). OLA and OTC were degraded with no initial lag phase whereas lag phases from 2 to 34 days (MET) and 31 to 40 days (TYL) were observed for other substances. The biodegradation behaviour was influenced by neither the concentrations of antibiotics nor the time of the year and location for sampling of surface water. Addition of 1 g/l of sediment or 3 mg/l of activated sludge from wastewater treatment increased the biodegradation potential which is believed to be the result of increased bacterial concentration in the test solution. Biodegradation was significantly slower in tests conducted in absence of oxygen. Assessments of the toxic properties of antibiotics by studying the influence on the biodegradation rates of 14C-aniline at different concentrations of antibiotics showed that no tests were conducted at toxic concentrations.     

Concentrations and specific loads of UV filters in sewage sludge originating from a monitoring network in Switzerland

Many substances related to human activities end up in wastewater and accumulate in sewage sludge. The present study focuses on the analysis of widely used UV filters 3-(4-methylbenzylidene) camphor (4-MBC), octyl-methoxycinnamate (OMC), octocrylene (OC) and octyl-triazone (OT) in sewage sludge originating from a monitoring network in Switzerland. Mean concentrations in stabilised sludge from 14 wastewater treatment plants were 1780, 110, 4840 and 5510 microg/kg dry matter for 4-MBC, OMC, OC and OT, respectively. Specific loads in sewage sludge show that UV filters originate mainly from private households, but surface runoff and industries may be considered as additional sources. This indicates that besides use for sunscreens and cosmetics UV filters might occur in plastics and other materials and be released to the environment by volatilization or leaching. Differences between the modeled per capita loads of UV filters in sewage sludge and the observed specific loads in sewage sludge are probably due to erroneous figures of production volumes, degradation and sorption during wastewater treatment as well as degradation processes during transport in the sewer or sludge treatment. Thus, further research is needed to elucidate the fate of UV filters after application and release into the environment. Other compounds used as UV filters should be included in future studies.     

Determination of selected antibiotics in the Victoria Harbour and the Pearl River, South China using high-performance liquid chromatography-electrospray ionization tandem mass spectrometry

Nine selected antibiotics in the Victoria Harbour of Hong Kong and the Pearl River at Guangzhou, South China, were analyzed using high-performance liquid chromatography-electrospray ionization tandem mass spectrometry. The results showed that the concentrations of antibiotics were mainly below the limit of quantification (LOQ) in the marine water of Victoria Harbour. However, except for amoxicillin, all of the antibiotics were detected in the Pearl River during high and low water seasons with the median concentrations ranging from 11 to 67 ng/L, and from 66 to 460 ng/L, respectively; and the concentrations in early spring were about 2-15 times higher than that in summer with clearer diurnal variations. It was suggested that the concentrations of antibiotics in the high water season were more affected by wastewater production cycles due to quick refreshing rate, while those in the low water season may be more sensitive to the water column dynamics controlled by tidal processes in the river.