Luca Rossi

Treatment of micropollutants in municipal wastewater: Ozone or powdered activated carbon?

Many organic micropollutants present in wastewater, such as pharmaceuticals and pesticides, are poorly removed in conventional wastewater treatment plants (WWTPs). To reduce the release of these substances into the aquatic environment, advanced wastewater treatments are necessary. In this context, two large-scale pilot advanced treatments were tested in parallel over more than one year at the municipal WWTP of Lausanne, Switzerland. The treatments were: i) oxidation by ozone followed by sand filtration (SF) and ii) powdered activated carbon (PAC) adsorption followed by either ultrafiltration (UF) or sand filtration. More than 70 potentially problematic substances (pharmaceuticals, pesticides, endocrine disruptors, drug metabolites and other common chemicals) were regularly measured at different stages of treatment. Additionally, several ecotoxicological tests such as the Yeast Estrogen Screen, a combined algae bioassay and a fish early life stage test were performed to evaluate effluent toxicity. Both treatments significantly improved the effluent quality. Micropollutants were removed on average over 80% compared with raw wastewater, with an average ozone dose of 5.7 mg O3 l(-1) or a PAC dose between 10 and 20 mg l(-1). Depending on the chemical properties of the substances (presence of electron-rich moieties, charge and hydrophobicity), either ozone or PAC performed better. Both advanced treatments led to a clear reduction in toxicity of the effluents, with PAC-UF performing slightly better overall. As both treatments had, on average, relatively similar efficiency, further criteria relevant to their implementation were considered, including local constraints (e.g., safety, sludge disposal, disinfection), operational feasibility and cost. For sensitive receiving waters (drinking water resources or recreational waters), the PAC-UF treatment, despite its current higher cost, was considered to be the most suitable option, enabling good removal of most micropollutants and macropollutants without forming problematic by-products, the strongest decrease in toxicity and a total disinfection of the effluent.

Urban stormwater contamination by polychlorinated biphenyls (PCBs) and its importance for urban water systems in Switzerland

Like other persistent organic pollutants (POPs), polychlorinated biphenyls (PCBs) are still present in the environment despite their almost worldwide prohibition. A study was conducted over 1 year in Switzerland to analyze the source and load of PCBs in urban stormwater and their importance in urban water systems. The mean PCB concentrations of 89 rain events were determined in five different strictly separate drainage systems (three in Lausanne and two in Geneva). The mean concentrations of PCBs in stormwater ranged from values below the detection limit (0.11-0.24 ng/l) to 403 ng/l. A model for the wet and dry deposition of PCBs based on these results estimates that their concentration in rainwater has remained practically constant (35 ng/l) over a period of 12 years. A mass balance of Swiss levels estimates a total input load of PCBs in the urban water systems at 110-125 kg/year. The contribution of stormwater is 75-94 kg/year in combined sewer systems and 23-34 kg in separate sewer systems. This mass balance illustrates that a major part of the PCB load in the environment or in WWTP sludges originates from urban stormwater. This result was confirmed by a fingerprint of PCB congeners in stormwater, which showed a pattern identical to that found in sewage sludge in combined sewer systems.

Influence of treatment conditions on the oxidation of micropollutants by Trametes versicolor laccase

Many organic compounds present at low concentrations in municipal wastewater, such as various pharmaceuticals and biocides, are recalcitrant in conventional wastewater treatment plants (WWTPs). To improve their biodegradation, oxidoreductase enzymes such as laccases were tested. The goal was to find optimal conditions for the transformation of two anti-inflammatory pharmaceuticals (diclofenac (DFC) and mefenamic acid (MFA)), one biocide (triclosan (TCN)) and one plastic additive (bisphenol A (BPA)) by Trametes versicolor laccase. Experiments were conducted in spiked solutions at different pH values (from 3 to 9), enzyme concentrations (70-1400 Ul(-1)), reaction times (0-26 hours) and temperatures (10, 25 and 40°C) following a Doehlert experimental design. A semi-empirical model was developed to understand better the combined effects of the four factors and to determine optimal values. This model was able to fit well the experimental data (R(2)>0.97) and showed good predictive ability. All four factors had a significant effect on the micropollutant oxidation with the greatest influence shown by pH. Results for single compounds were different from those obtained for mixtures of micropollutants. For instance, DFC transformation occurred at much higher rates in mixtures under alkaline conditions. Optimal conditions were compound-dependent, but were found to be between pH 4.5 to 6.5 and between 25°C to more than 40°C. A laccase concentration of 730 Ul(-1) was sufficient to obtain a high removal rate (>90%) of the four individual compounds (range of times: 40 min to 5 hours), showing the potential of laccases to improve biodegradation of environmentally persistent compounds.

Temporal dynamics of antibiotics in wastewater treatment plant influent

A yearlong field experimental campaign was conducted to reveal time scales over which antibiotic fluxes vary in the influent of a wastewater treatment plant (WTP). In particular, sampling was carried out to ascertain the amplitudes of monthly, daily and hourly fluctuations of several antibiotics. A total of 180 samples was collected at the entrance of a WTP in Lausanne, Switzerland. Sample concentrations were multiplied by flow rate to obtain monthly, daily and hourly mass fluxes of six antibiotics (trimethoprim, norfloxacin, ciprofloxacin, ofloxacin, clindamycin and metronidazole). Seasonality in mass fluxes was observed for all substances, with maximum values in winter being up to an order of magnitude higher than in summer. The hourly measurements of the mass flux of antibiotics were found to have a period of 12h. This was due to peaks in toilet use in the morning and early evening. In particular, the morning peak in flushing coincided with high concentrations (and hence high mass fluxes) due to overnight accumulation of substances in urine. However, little variation was observed in the average daily flux. Consequently, fluctuations in mass fluxes of antibiotics were mainly evident at the monthly and hourly time scales, with little variation on the day-week time scale. These results can aid in optimizing removal strategies and future sampling campaigns focused on antibiotics in wastewater.

Temporal Variability of Antibiotics Fluxes in Wastewater and Contribution from Hospitals

Significant quantities of antibiotics are used in all parts of the globe to treat diseases with bacterial origins. After ingestion, antibiotics are excreted by the patient and transmitted in due course to the aquatic environment. This study examined temporal fluctuations (monthly time scale) in antibiotic sources (ambulatory sales and data from a hospital dispensary) for Lausanne, Switzerland. Source variability (i.e., antibiotic consumption, monthly data for 2006–2010) were examined in detail for nine antibiotics – azithromycin, ciprofloxacin, clarithromycin, clindamycin, metronidazole, norfloxacin, ofloxacin, sulfamethoxazole and trimethoprim, from which two main conclusions were reached. First, some substances – azithromycin, clarithromycin, ciprofloxacin – displayed high seasonality in their consumption, with the winter peak being up to three times higher than the summer minimum. This seasonality in consumption resulted in seasonality in Predicted Environmental Concentrations (PECs). In addition, the seasonality in PECs was also influenced by that in the base wastewater flow. Second, the contribution of hospitals to the total load of antibiotics reaching the Lausanne Wastewater Treatment Plant (WTP) fluctuated markedly on a monthly time scale, but with no seasonal pattern detected. That is, there was no connection between fluctuations in ambulatory and hospital consumption for the substances investigated.

Sediment contamination assessment in urban areas based on total suspended solids

Sediment represents an important compartment in surface waters. It constitutes a habitat or spawning site for many organisms and is an essential trophic resource for higher level organisms. It can be impacted by anthropogenic activities, particularly through urban wet-weather discharges like stormwater and combined sewer overflows. An approach was presented for assessing the risks caused by urban wet-weather discharges to the sediment compartment based on total suspended solids (TSS). TSS is routinely measured in field surveys and can be considered as a tracer for urban wet-weather contamination. Three assessment endpoints linked with TSS were proposed: a) siltation of the riverbed, b) oxygen demand due to organic matter degradation and c) accumulation of ecotoxic contaminants on the riverbed (heavy metals, PAHs). These criteria were translated in terms of the maximal TSS accumulation load and exposure time (percentage of time exceeding the accumulation criteria) to account for sediment accumulation dynamics and resuspension in streams impacted by urban wet-weather discharges. These assessment endpoints were implemented in a stochastic model that calculates TSS behavior in receiving waters and allows therefore an assessment of potential impacts. The approach was applied to three Swiss case studies. For each, good agreement was found between the risk predictions and the field measurements confirming the reliability of the approach.

Substance flow analysis as a tool for mitigating the impact of pharmaceuticals on the aquatic system

Pharmaceuticals constitute an important environmental issue for receiving waters. A holistic approach, taking into consideration the sources of these compounds (hospitals, domestic use), discharges (wastewater effluent, combined sewer overflows) and related risks to the environment, is therefore needed to develop the best protection strategy. The substance flow analysis (SFA) approach, applied, for example, to the city of Lausanne, Switzerland, is an ideal tool to tackle these issues. Four substances were considered: one antibiotic (ciprofloxacin), an analgesic (diclofenac), and two anti-epileptics (carbamazepine and gabapentin). Consumption data for the main hospital of the city (916 beds) and for the population were available. Micropollutant concentrations were measured at different points of the system: wastewater inlet and outlet (WWTP), combined sewer overflows (CSO) and in the receiving waters (Vidy Bay, Lake Geneva). Measured and predicted concentrations were in agreement, except for diclofenac, for which analytical uncertainties were expected. Seven different scenarios were considered (supplementary treatment at the WWTP, at the hospital or at both places, etc.). Based on the results obtained, the supplementary treatment at the WWTP decreases the load of pharmaceuticals reaching surface water by a factor between 2 and 27, depending on the compound and on the technique. The treatment at the hospitals only influences the amount of ciprofloxacin reaching the environment and decreases the release by one third. The contribution of CSO to surface water pollution is low compared to that of the WWTP for the selected compounds. Regarding the risk for the receiving waters, ciprofloxacin was found to be the most problematic compound, with a risk quotient far above 1. In this particular case, a treatment at the WWTP is not sufficient to reduce the risk, and additional measures at the CSO or at the hospital should be considered. SFA is an ideal tool for developing the best strategy for pharmaceutical elimination, but its application depends on data availability and local conditions.

Real-life efficiency of urine source separation

Urine source separation (NoMix technology) is a promising innovation in wastewater management. To improve and further develop NoMix technology, it has been implemented in four Swiss households and at our research institute (Eawag). We conducted measurements during one year on frequency of toilet usage (in households 5.2/person/day for weekdays, and 6.3/person/day for weekends), flushing behavior (30-85% small flushes), and recovered urine. We calculate the amount of urine effectively recovered per voiding in NoMix toilets (138 ml/flush in households; 309 ml/flush in womens toilets at Eawag), and waterfree urinals (225 ml/usage). We estimate urine recovery in the households to be maximally 70-75% of the expected quantity, leaving room for technical and behavioral improvements. Based on sampling of N and P concentrations, we suspect nitrogen losses in the extended urine piping system. For households and workplaces, the daily and weekly flushing pattern is recorded. Our results are in accordance with literature data from a shorter period but with more people. These results represent a good dimensioning basis for future urine source separation applications. An example of extrapolation to an entire watershed is presented. The flushing pattern corresponds well with the typical nitrogen loading of a treatment plant.

Population Normalization with Ammonium in Wastewater-Based Epidemiology: Application to Illicit Drug Monitoring

Fluctuations in ammonium (NH4+), measured as NH4-N loads using an ion-selective electrode installed at the inlet of a sewage treatment plant, showed a distinctive pattern which was associated to weekly (i.e., commuters) and seasonal (i.e., holidays) fluctuations of the population. Moreover, population size estimates based on NH4-N loads were lower compared to census data. Diurnal profiles of benzoylecgonine (BE) and 11-nor-9-carboxy-Δ9-tetrahydrocannabinol (THC-COOH) were shown to be strongly correlated to NH4-N. Characteristic patterns, which reflect the prolonged nocturnal activity of people during the weekend, could be observed for BE, cocaine, and a major metabolite of MDMA (i.e., 4-hydroxy-3-methoxymethamphetamine). Additional 24 h composite samples were collected between February and September 2013. Per-capita loads (i.e., grams per day per 1000 inhabitants) were computed using census data and NH4-N measurements. Normalization with NH4-N did not modify the overall pattern, suggesting that the magnitude of fluctuations in the size of the population is negligible compared to those of illicit drug loads. Results show that fluctuations in the size of the population over longer periods of time or during major events can be monitored using NH4-N loads: either using raw NH4-N loads or population size estimates based on NH4-N loads, if information about site-specific NH4-N population equivalents is available.

Dynamics and environmental risk assessment of the herbicide glyphosate and its metabolite AMPA in a small vineyard river of the Lake Geneva catchment

The use of pesticides may lead to environmental problems, such as surface water pollution, with a risk for aquatic organisms. In the present study, a typical vineyard river of western Switzerland was first monitored to measure discharged loads, identify sources, and assess the dynamic of the herbicide glyphosate and its metabolite aminomethylphosphonic acid (AMPA). Second, based on river concentrations, an associated environmental risk was calculated using laboratory tests and ecotoxicity data from the literature. Measured concentrations confirmed the mobility of these molecules with elevated peaks during flood events, up to 4970 ng/L. From April 2011 to September 2011, a total load of 7.1 kg was calculated, with 85% coming from vineyards and minor urban sources and 15% from arable crops. Compared with the existing literature, this load represents an important fraction (6-12%) of the estimated amount applied because of the steep vineyard slopes (∼10%). The associated risk of these compounds toward aquatic species was found to be negligible in the present study, as well as for other rivers in Switzerland. A growth stimulation was nevertheless observed for the algae Scenedesmus vacuolatus with low concentrations of glyphosate, which could indicate a risk of perturbation in aquatic ecosystems, such as eutrophication. The combination of field and ecotoxicity data allowed the performance of a realistic risk assessment for glyphosate and AMPA, which should be applied to other pesticide molecules.