Removal of antibiotics from urban wastewater by constructed wetland optimization.

Seven mesocosm-scale constructed wetlands (CWs), differing in their design characteristics, were set up in the open air to assess their efficiency to remove antibiotics from urban raw wastewater. A conventional wastewater treatment plant (WWTP) was simultaneously monitored. The experiment took place in autumn. An analytical methodology including HPLC-MS/MS was developed to measure antibiotic concentrations in the soluble water fraction, in the suspended solids fraction and in the WWTP sludge. Considering the soluble water fraction, the only easily eliminated antibiotics in the WWTP were doxycycline (61±38%) and sulfamethoxazole (60±26%). All the studied types of CWs were efficient for the removal of sulfamethoxazole (59±30-87±41%), as found in the WWTP, and, in addition, they removed trimethoprim (65±21-96±29%). The elimination of other antibiotics in CWs was limited by the specific system-configuration: amoxicillin (45±15%) was only eliminated by a free-water (FW) subsurface flow (SSF) CW planted with Typha angustifolia; doxycycline was removed in FW systems planted with T. angustifolia (65±34-75±40%), in a Phragmites australis-floating macrophytes system (62±31%) and in conventional horizontal SSF-systems (71±39%); clarithromycin was partially eliminated by an unplanted FW-SSF system (50±18%); erythromycin could only be removed by a P. australis-horizontal SSF system (64±30%); and ampicillin was eliminated by a T. angustifolia-floating macrophytes system (29±4%). Lincomycin was not removed by any of the systems (WWTP or CWs). The presence or absence of plants, the vegetal species (T. angustifolia or P. australis), the flow type and the CW design characteristics regulated the specific removal mechanisms. Therefore, CWs are not an overall solution to remove antibiotics from urban wastewater during cold seasons. However, more studies are needed to assess their ability in warmer periods and to determine the behaviour of full-scale systems.

Biogenic metals for the oxidative and reductive removal of pharmaceuticals, biocides and iodinated contrast media in a polishing membrane bioreactor.

Pharmaceutical and personal care products, biocides and iodinated contrast media (ICM) are persistent compounds, which appear in ng to µg L(-1) in secondary effluents of sewage treatment plants (STPs). In this work, biogenic metals manganese oxides (BioMnOx) and bio-palladium (Bio-Pd) were applied in lab-scale membrane bioreactors (MBR) as oxidative and reductive technologies, respectively, to remove micropollutants from STP-effluent. From the 29 substances detected in the STP-effluent, 14 were eliminated in the BioMnOx-MBR: ibuprofen (>95%), naproxen (>95%), diuron (>94%), codeine (>93%), N-acetyl-sulfamethoxazole (92%), chlorophene (>89%), diclofenac (86%), mecoprop (81%), triclosan (>78%), clarithromycin, (75%), iohexol (72%), iopromide (68%), iomeprol (63%) and sulfamethoxazole (52%). The putative removal mechanisms were the chemical oxidation by BioMnOx and/or the biological removal by Pseudomonas putida and associated bacteria in the enriched biofilm. Yet, the removal rates (highest value: 2.6 µg diclofenac L(-1) d(-1)) need to improve by a factor 10 in order to be competitive with ozonation. ICM, persistent towards oxidative techniques, were successfully dehalogenated with a novel reductive technique using Bio-Pd as a nanosized catalyst in an MBR. Iomeprol, iopromide and iohexol were removed for >97% and the more recalcitrant diatrizoate for 90%. The conditions favorable for microbial H(2)-production enabling the charging of the Pd catalyst, were shown to be important for the removal of ICM. Overall, the results indicate that Mn oxide and Pd coupled to microbial catalysis offer novel potential for advanced water treatment.

Ecotoxicologial evaluation of wastewater ozonation based on detritus-detritivore interactions.

Advanced oxidation technologies such as ozonation have been proposed to improve removal efficiency of micropollutants during wastewater treatment. In a meta-analysis of peer-reviewed literature, we found no ecotoxicological effects of wastewater ozonation on invertebrates (n=82), but significant adverse effects on bacteria (n=24) and fish (n=5). As information on functional endpoints or trophic interactions is lacking, we applied a bioassay relating to leaf litter decomposition to fill this gap. Leaf discs exposed to ozone-treated wastewater with a high (1.04 mg O3 (mg DOC)(-1), n=49) ozone concentration were significantly preferred by an aquatic detritivore, Gammarus fossarum, over discs conditioned in wastewater not treated with ozone. This effect might have been mediated by reduced bacterial and elevated fungal biomass, and appears to be the first demonstration of wastewater ozonation impacts on invertebrates and an associated ecosystem process. In accordance with the food-choice trials, chemical analyses revealed significantly decreased concentrations of organic micropollutants in wastewater treated with ozone at high concentrations. Thus, food-choice trials as applied here hold promise to assess environmental effects of advanced oxidation technologies in wastewater treatment and appear to be a valuable complement to the ecotoxicological toolbox in general.

Environmental risk assessment of ivermectin: A case study.

The veterinary parasiticide ivermectin was selected as a case study compound within the project ERAPharm (Environmental Risk Assessment of Pharmaceuticals). Based on experimental data generated within ERAPharm and additional literature data, an environmental risk assessment (ERA) was performed mainly according to international and European guidelines. For the environmental compartments surface water, sediment, and dung, a risk was indicated at all levels of the tiered assessment approach. Only for soil was no risk indicated after the lower tier assessment. However, the use of effects data from additional 2-species and multispecies studies resulted in a risk indication for collembolans. Although previously performed ERAs for ivermectin revealed no concern for the aquatic compartment, and transient effects on dung-insect populations were not considered as relevant, the present ERA clearly demonstrates unacceptable risks for all investigated environmental compartments and hence suggests the necessity of reassessing ivermectin-containing products. Based on this case study, several gaps in the existing guidelines for ERA of pharmaceuticals were shown and improvements have been suggested. The action limit at the start of the ERA, for example, is not protective for substances such as ivermectin when used on intensively reared animals. Furthermore, initial predicted environmental concentrations (PECs) of ivermectin in soil were estimated to be lower than refined PECs, indicating that the currently used tiered approach for exposure assessment is not appropriate for substances with potential for accumulation in soil. In addition, guidance is lacking for the assessment of effects at higher tiers of the ERA, e.g., for field studies or a tiered effects assessment in the dung compartment.

Assessing effects of the pharmaceutical ivermectin on meiobenthic communities using freshwater microcosms.

Ivermectin is a widely applied veterinary pharmaceutical that is highly toxic to several non-target organisms. So far, little is known about its impact on benthic freshwater species, although its rapid sorption to sediment particles and high persistence in aquatic sediments have raised concerns about the risk for benthic organisms. In the present study, indoor microcosms were used to assess the impact of ivermectin on freshwater meiobenthic communities over a period of 224 days. Microcosm sediments were directly spiked with ivermectin to achieve nominal concentrations of 0.9, 9, and 45 microg kg(-1) dw. Initially measured ivermectin concentrations (day 0) were 0.6, 6.2, and 31 microg kg(-1) dw. In addition to abundance of major meiobenthic organism groups, the nematode community was assessed on the species level, assuming a high risk for free-living nematodes due to their close phylogenetic relationship to the main target organisms of ivermectin, parasitic nematodes. Benthic microcrustaceans (cladocerans, ostracods) and nematodes showed the most sensitive response to ivermectin, while tardigrades profited from the presence of the pharmaceutical. The most pronounced effects on the meiofauna community composition occurred at the highest treatment level (31 microg kg(-1) dw), leading to a no observed effect concentration (NOEC(Community)) of 6.2 microg kg(-1) dw. However, the nematode community was already seriously affected at a concentration of 6.2 microg kg(-1) dw with two bacterivorous genera, Monhystera and Eumonhystera, being the most sensitive, whereas species of omnivorous genera (Tripyla, Tobrilus) increased in abundance after the application of ivermectin. Thus, a NOEC(Community) of 0.6 microg kg(-1) dw was derived for nematodes. Direct and indirect effects of ivermectin on meiobenthic communities could be demonstrated. The pharmaceutical is likely to pose a high risk, because its NOECs are close to predicted environmental concentrations (PECs) in sediments (0.45-2.17 microg kg(-1) dw), resulting in worst case risk quotients (RQs) of 1.05-36.2. This observation lends support to efforts aimed at preventing the repeated entry of ivermectin in aquatic environments and thus its accumulation in sediments. Moreover, this study points out that model ecosystem studies should be part of environmental risk assessments (ERAs) of veterinary medicinal products (VMPs).

Comparison of electrospray ionization and atmospheric pressure chemical ionization for multi-residue analysis of biocides, UV-filters and benzothiazoles in aqueous matrices and activated sludge by liquid chromatography-tandem mass spectrometry.

This paper describes the development of a multi-residue method for the determination of 36 emerging organic pollutants (26 biocides, 5 UV-filters and 5 benzothiazoles) in raw and treated wastewater, activated sludge and surface water using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The target analytes were enriched from water samples adjusted to pH 6 by solid-phase extraction (SPE) on Oasis HLB 200mg cartridges and eluted with a mixture of methanol and acetone (60/40, v/v). Extraction of freeze-dried sludge samples was accomplished by pressurized liquid extraction (PLE) using a mixture of methanol and water (50/50, v/v) as extraction solvent followed by SPE. LC-tandem MS detection was compared using electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) in positive and negative ionization mode. ESI exhibited strong ion suppression for most target analytes, while APCI was generally less susceptible to ion suppression but partially leading to ion enhancement of up to a factor of 10. In general, matrix effects could be compensated using stable isotope-labeled surrogate standards, indicated by relative recoveries ranging from 70% to 130%. In wastewater, activated sludge and surface water up to 33 analytes were detected. Maximum concentrations up to 5.1 and 3.9mugL(-1) were found in raw wastewater for the water-soluble UV-filters benzophenone-4 (BZP-4) and phenylbenz-imidazole sulfonic acid (PBSA), respectively. For the first time, the anti-dandruff climbazole was detected in raw wastewater and in activated sludge with concentrations as high as 1.4 microg L(-1) and 1.2 microg gTSS(-1), respectively. Activated sludge is obviously a sink for four benzothiazoles and two isothiazolones, as concentrations were detected in activated sludge between 120 ng gTSS(-1) (2-n-octyl-4-isothiazolin-3-one, OIT) to 330 ng gTSS(-1) (benzothiazole-2-sulfonic acid, BTSA).

Effects of ivermectin-spiked cattle dung on a water-sediment system with the aquatic invertebrates Daphnia magna and Chironomus riparius.

A two-species test using a water-sediment test system was performed to investigate chronic effects of the parasiticide ivermectin on Daphnia magna and Chironomus riparius. To simulate exposure by direct excretion of cattle into surface waters, ivermectin was applied via spiked cattle dung. The parasiticide was applied once, at concentrations ranging from 11 to 1314 microg kg(-1) dung dry weight. The highest concentration corresponds to the maximum concentration in dung 3 days after topical application to cattle. Test vessels were stocked with chironomid larvae and daphnids of defined, mixed age. Replicates were sampled 10, 24, 38 and 51 days post application. Survival, growth and emergence of chironomids, and abundance and biomass of daphnids were evaluated. In case of extinction of the D. magna population in all replicates of a concentration level, daphnids were re-introduced into the remaining vessels of this concentration to simulate immigration. In addition, a second batch of chironomid larvae was introduced into the vessels on day 27 post application. At 1314 microg ivermectin kg(-1) dung dry weight, survival, larval growth and emergence of the initially stocked chironomids were strongly affected. A significant effect on emergence was also observed for the second batch of chironomids. The two highest test concentrations led to 100% mortality of the initially stocked daphnids. At 1314 microg kg(-1) dung dry weight, no daphnids survived following re-introduction on days 11, 28 and 42. At 263 microg kg(-1) dung dry weight, the daphnids that were re-introduced on day 11 survived and reproduced, but abundance and biomass were reduced. The results of the present study indicate that following single application, toxic ivermectin concentrations persisted for an extended period. Possible effects on aquatic invertebrates, which may be caused by direct excretion of ivermectin-containing dung into surface water, deserve further attention.

Fate of beta blockers in aquatic-sediment systems: sorption and biotransformation.

The fate of beta blockers (atenolol, acebutolol, bisoprolol, celiprolol, metoprolol, nadolol, pindolol, propranolol, and sotalol) was studied in surface water-sediment systems. A new analytical method was developed to determine the beta blockers in sediments by LC-ESI-tandem MS detection. The relative recoveries in sediments ranged from 89 +/- 7% (acebutolol) to 102 +/- 3% (nadolol) using deuterated surrogate standards. Beta blockers were present with concentrations up to 86 ng/g (bisoprolol) in the sediments of small German streams containing an elevated percentage of treated wastewater. Biotransformation studies and sorption isotherms of the beta blockers were performed with two natural river sediments ("Burgen", "Dausenau") differing in organic carbon content and particle size distribution. Biotransformation of beta blockers in the surface water-sediment systems exhibited a low to high persistence with 90% disappearance (DT(90)) ranging from 0.4-10 d (pindolol, atenolol) to >100 d (sotalol, propranolol or celiprolol). For sorption studies neither NaN(3) addition nor autoclavation led to a complete mass balance of the beta blockers, probably due to biotransformation. Isotherms at 6 h (apparent equilibrium, measuring aqueous and sediment phase) fitted by the Freundlich equation show that sorption of all beta blockers to the Burgen sediment were linear or close to it (i.e., n-values between 0.93 and 1.13), while in the Dausenau sediment the sorptions were slightly non linear (i.e., n-values 0.77-0.91). In river water the sorbed fraction is negligible in comparison to the dissolved fraction. Nevertheless, beta blockers can be detected with concentrations up to 86 ng/g (bisoprolol) in sediments of small streams containing more than 50% treated wastewater.

The fate of selected micropollutants in a single-house MBR.

Membrane bioreactor (MBR) technology is an interesting option for single-house wastewater treatment or small communities. Because typically a very high effluent quality is achieved with respect to pathogens, suspended solids, organics and nitrogen, the permeate is well suited for reuse. Little is known about the fate of micropollutants in such small systems. The differences between centralized and decentralized biological wastewater treatment with respect to micropollutants are manifold: besides the operational parameters like hydraulic and sludge retention time, the main difference is in the load variation. While the influent load is expected to be more or less constant in large catchments, it varies strongly in small MBRs due to irregular consumption (e.g. of medication by individuals). Concentrations of micropollutants are higher by a factor 50-1000 than in centralized treatment. It is also unknown how reliable degradation of micropollutants is in case of irregular exposure. In this study, two experiments were conducted in a small MBR treating the wastewater of a three-person household. During normal operation of the treatment plant, 25 pharmaceuticals (antibiotics, antiphlogistics, lipid regulators, iodinated contrast media and hormones) that had not been used by members of the household were added in concentrations typical for municipal wastewater. The removal of most substances was in the same range as for centralized wastewater treatment. It was shown that biological transformation was the main elimination process while adsorption to the activated sludge was negligible for most substances due to the low sludge production at high sludge retention time. No appreciable lag for inducing biological degradation was observed. The high hydraulic and sludge residence time had a positive effect on the elimination of slowly degradable substances, but this was partly compensated by the lower biological activity. An experiment with antibiotics concentrations typical for decentralized treatment (between 500 and 1000 microg l(-1); sulfamethoxazole, sulfapyridine, trimethoprim, clarithromycin, roxithromycin) did not show an inhibitory effect on either nitrification or denitrification.

Sorption behavior of potential organic wastewater indicators with soils.

Soil-aquifer treatment is a wastewater treatment and reclamation option to facilitate beneficial water reuse. The fate of wastewater originated micropollutants in the soil-aquifer system is important to understand. In the study the sorption behavior of potential wastewater indicators such as two antiepileptic drugs (carbamazepine, primidone), one sulfonamide (sulfamethoxazole), and one corrosion inhibitor (benzotriazole) were determined with three natural soils (Lufa 2.2, Euro Soil 5, and Wulpen sand) that differed in pH, organic carbon content and particle size distribution. As aqueous phase a 0.01M CaCl(2) solution as well as the effluent of a municipal wastewater treatment plant was used. Affinities of all analytes to the soil increased from Wulpen sand, over Lufa 2.2 to Euro Soil 5, indicating that the organic carbon contents might be crucial for sorption. Isotherms were well described by the Freundlich model. Sorption was mainly close to linear (n=0.93-1.07) for most target compounds and soils. Desorption gave rise to a small hysteresis only for Euro Soil 5 which was likely artificial, due to slow desorption kinetics beyond 24h used in the experiment. All sorption studies confirmed that Carbamazepine, Benzotriazole and Primidone are appropriate to be used as wastewater indicator substances based on their low sorption affinity to soils, while the suitability of Sulfamethoxazole is limited due to the formation of non-extractable residues, especially at lower pH values.

Fate of beta blockers and psycho-active drugs in conventional wastewater treatment.

The removal of beta blockers and psycho-active drugs was investigated in a representative conventional German WWTP by long-term measurement campaigns along different biological treatment processes. The activated sludge treatment with an elevated SRT of 18 d was the only process which led to a significant removal of certain beta blockers and psycho-active drugs. The removal efficiency was below 60% for all compounds except for the natural opium alkaloids codeine and morphine being removed by more than 80%. Primary biological transformation and sorption onto sludge as the main removal mechanisms were examined in lab-scale batch experiments. Sorption onto activated sludge was found to be negligible (<3%). The biological transformation could be described by pseudo-first order kinetics and the transformation constants k(biol) were used to predict the removal of beta blockers and psycho-active drugs in an activated sludge unit with a model. For most compounds the removal efficiencies measured on the full-scale WWTP were within the 95% confidence intervals predicted by the model. The results from full-scale measurements and modeling indicate that biological transformation in the nitrification tank together with parameters such as the sludge retention time and the temperature is crucial regarding the biological transformation of beta blockers and psycho-active drugs in conventional WWTPs.

Analysis and sorption of psychoactive drugs onto sediment.

An analytical method was developed to analyze eight psychoactive pharmaceuticals--including the antiepileptic carbamazepine, the opiates morphine, codeine, dihydrocodeine, the opiode tramadol, and the tranquilizers diazepam, oxazepam, temazepam--and the antibiotic sulfamethoxazole as well as three metabolites (10,11-dihydrocarbamazepine (DHC), 10,11-dihydroxy-10, 11-dihydrocarbamazepine, and N4-acetylsulfamethoxazole) in river sediments. Relative recoveries of all analytes exceeded 97% using either deuterated or 13C15N-labeled surrogate standards. Sorption isotherms of all analytes were constructed at pH 6.5-6.6 on two natural river sediments (Burgen and Dausenau) that differed in organic carbon contents and particle size distributions. Affinities of all analytes were up to an order of magnitude higher for the Dausenau sediment in comparison to the Burgen sediment. Isotherms were well described by the Freundlich model. Sorption of all analytes was linear on the Burgen sediment except for structurally similar carbamazepine (n = 0.90) and DHC (n = 0.88). Conversely, most analytes showed pronounced nonlinear sorption to the Dausenau sediment (n = 0.77-0.92) except for positively charged codeine, dihydrocodeine, and tramadol. Linear sorption of the latter was taken to arise from concentration-independent electrostatic interactions of the organocations with negatively charged surfaces on clay minerals or in the sediment organic matter. Desorption gave rise to hysteresis in 13 out of 16 investigated analyte-sorbent systems. Hysteresis was likely due to slow desorption kinetics beyond 24 h used in the experiment.

Determination of the solid-water distribution coefficient (Kd) for pharmaceuticals, estrogens and musk fragrances in digested sludge.

This work determined the solid-water distribution coefficient (K(d)) and the organic carbon normalized distribution coefficient (K(oc)) of several pharmaceuticals (carbamazepine, ibuprofen, naproxen, diclofenac, iopromide, sulfamethoxazole and roxithromycin), three estrogens (estrone, 17beta-estradiol and 17alpha-ethinylestradiol) and two musk fragrances (HHCB and AHTN) in digested sludge. These sorption coefficients can be used to evaluate the fate of these substances during sludge treatment, thus avoiding the expensive and time-consuming analysis in the sludge phase. For determining the K(d) and K(oc) values of the target compounds in digested sludge, their concentrations were measured in the aqueous and solid phase of the effluent of an anaerobic digestion pilot plant run at several operational conditions. The results obtained were compared with the values modelled by using simple K(ow) approaches. The resulting log K(d) values ranged between 3.5 and 4.4 for the two musk fragrances (log K(oc) of 4.5-6.0), between 2.1 and 2.9 for estrogens (log K(oc) of 2.9-4.2) and between 0.8 and 1.9 for the remaining pharmaceuticals (log K(oc) of 1.8-3.5). These values are in the same range as those reported in the literature for primary and secondary sludge and no significant influence of the anaerobic digestion operational conditions was observed. For most compounds, the modelled K(oc) were close or within the lower range of the experimentally determined K(oc). Major deviations of the modelled K(oc) values were found for iopromide, sulfamethoxazole and roxithromycin, which were 1-3 orders of magnitude lower than the measured values.

Effects of the parasiticide ivermectin on the cladoceran Daphnia magna and the green alga Pseudokirchneriella subcapitata.

Although widely used for the treatment of endo- and ectoparasites in livestock and pets, very few data on chronic effects on aquatic organisms are available for the parasiticide ivermectin. In the present study, toxicity of ivermectin to two freshwater organisms, the cladoceran Daphnia magna and the green alga Pseudokirchneriella subcapitata was investigated. For D. magna, a mean LC(50) 48 h of 5.7 ngl(-1) was derived from 10 acute tests. Chronic toxicity of ivermectin to D. magna was extremely high: with 0.001 and 0.0003 ngl(-1), respectively, nominal LOEC and NOEC based on growth and reproduction were far below the analytical limit of detection for this compound. P. subcapitata was considerably less sensitive to ivermectin than D. magna. For both growth rate and yield, EC(50) was >4,000 microgl(-1), LOEC was 1,250 microgl(-1) and NOEC 391microgl(-1). In view of the high toxicity to D. magna, the use of ivermectin might pose a risk to local aquatic ecosystems. Further studies should be carried out to investigate the effects of ivermectin and its degradation products on pelagic and benthic freshwater invertebrates.

Simultaneous determination of psychoactive drugs and their metabolites in aqueous matrices by liquid chromatography mass Spectrometry.

A multi-residue method was developed that allows for the simultaneous determination of psychoactive compounds such as opioids, tranquilizers, antiepileptics (primidone, carbamazepine plus two metabolites),the cocaine metabolite benzoylecgonine, the antidepressant doxepin, as well as the calcium channel blocker verapamil in raw and treated wastewater, surface water, groundwater, and drinking water. After solid-phase extraction with Oasis HLB at neutral pH, the analytes were detected by LC electrospray tandem MS in the positive ion mode. With a few exceptions relative recoveries of the analytes exceeded 70%. The limits of quantification were in the low ng/L range. Matrix effects were compensated by using appropriate deuterated or 13C-15N-labeled surrogate standards. For raw and treated wastewater, concentration factors were lowered to reduce matrix effects. Most analytes (15 of 20) were found in raw and treated wastewater as well as in surface water, and hence, are presumably ubiquitously present in the environment. Antiepileptics, the opium alkaloids morphine and codeine, dihydrocodeine, the two tranquilizers oxazepam and temazepam, the opioid tramadol, doxepin, and verapamil were detected in STP discharges and German rivers at concentrations up to the microg/L range. In drinking water, only carbamazepine, its metabolite 10,11-dihydroxy-10,11-dihydrocarbamazepine, and primidone were present at concentrations up to 0.020 microg/L.