Biological degradation of organic micropollutants in GAC filters-temporal development and spatial variations.

The capacity for organic micropollutant removal in granular activated carbon (GAC) filters for wastewater treatment changes over time. These changes are in general attributed to changes in adsorption, but may in some cases also be affected by biological degradation. Knowledge on the degradation of organic micropollutants, however, is scarce. In this work, the degradation of micropollutants in several full-scale GAC and sand filters was investigated through incubation experiments over a period of three years, using 14C-labeled organic micropollutants with different susceptibilities to biological degradation (ibuprofen, diclofenac, and carbamazepine), with parallel 16S rRNA gene sequencing. The results showed that the degradation of diclofenac and ibuprofen in GAC filters increased with increasing numbers of bed volumes when free oxygen was available in the filter, while variations over filter depth were limited. Despite relatively large differences in bacterial composition between filters, a degradation of diclofenac was consistently observed for the GAC filters that had been operated with high influent oxygen concentration (DO >8 mg/L). The results of this comprehensive experimental work provide an increased understanding of the interactions between microbial composition, filter material, and oxygen availability in the biological degradation of organic micropollutants in GAC filters.

Summary recommendations on "Analytical methods for substances in the Watch List under the Water Framework Directive".

The Watch List (WL) is a monitoring program under the European Water Framework Directive (WFD) to obtain high-quality Union-wide monitoring data on potential water pollutants for which scarce monitoring data or data of insufficient quality are available. The main purpose of the WL data collection is to determine if the substances pose a risk to the aquatic environment at EU level and subsequently to decide whether a threshold, the Environmental Quality Standards (EQS) should be set for them and, potentially to be listed as priority substance in the WFD. The first WL was established in 2015 and contained 10 individual or groups of substances while the 4th WL was launched in 2022. The results of monitoring the substances of the first WL showed that some countries had difficulties to reach an analytical Limit of Quantification (LOQ) below or equal to the Predicted No-Effect Concentrations (PNEC) or EQS. The Joint Research Centre (JRC) of the European Commission (EC) organised a series of workshops to support the EU Member States (MS) and their activities under the WFD. Sharing the knowledge among the Member States on the analytical methods is important to deliver good data quality. The outcome and the discussion engaged with the experts are described in this paper, and in addition a literature review of the most important publications on the analysis of 17-alpha-ethinylestradiol (EE2), amoxicillin, ciprofloxacin, metaflumizone, fipronil, metformin, and guanylurea from the last years is presented.

Assessing the potential of a membrane bioreactor and granular activated carbon process for wastewater reuse - A full-scale WWTP operated over one year in Scania, Sweden.

A full-scale membrane bioreactor (MBR) with ultrafiltration, followed by granular activated carbon (GAC), was examined to determine the potential of reusing treated water as a source of drinking water or for irrigation. The major part of the bacteria removal took place in the MBR, whereas the GAC removed substantial amounts of organic micropollutants. Annual variations in inflow and infiltration resulted in a concentrated influent during summer and a diluted influent in the winter. The removal of E. coli was high throughout the process (average log removal 5.8), with effluent concentrations meeting the threshold for class B water standards for irrigation (EU 2020/741) but exceeding those for drinking water in Sweden. The total bacterial concentration increased over the GAC, indicating the growth and release of bacteria; however, E. coli concentrations declined. The effluent concentrations of metals met the Swedish criteria for drinking water. The removal of organic micropollutants decreased during the initial operation of the treatment plant, but after 1 year and 3 months, corresponding to 15,000 bed volumes, the removal increased. Maturation of the biofilm in the GAC filters might have resulted in biodegradation of certain organic micropollutants, in combination with bioregeneration. Although there is no legislation in Scandinavia with regard to many organic micropollutants in drinking water and water for irrigation, the effluent concentrations were generally in the same order of magnitude as to those in Swedish source waters that are used for drinking water production.

Removal of organic micropollutants from municipal wastewater by aerobic granular sludge and conventional activated sludge.

Removal performances of organic micropollutants by conventional activated sludge (CAS) and aerobic granular sludge (AGS) were investigated at a full-scale wastewater treatment plant. Lab-scale kinetic experiments were performed to assess the micropollutant transformation rates under oxic and anoxic conditions. Transformation rates were used to model the micropollutant removal in the full-scale processes. Metagenomic sequencing was used to compare the microbial communities and antimicrobial resistance genes of the CAS and AGS systems. Higher transformation ability was observed for CAS compared to AGS for most compounds, both at the full-scale plant and in the complementary batch experiments. Oxic conditions supported the transformation of several micropollutants with faster and/or comparable rates compared to anoxic conditions. The estimated transformation rates from batch experiments adequately predicted the removal for most micropollutants in the full-scale processes. While the compositions in microbial communities differed between AGS and CAS, the full-scale biological reactors shared similar resistome profiles. Even though granular biomass showed lower potential for micropollutant transformation, AGS systems had somewhat higher gene cluster diversity compared to CAS, which could be related to a higher functional diversity. Micropollutant exposure to biomass or mass transfer limitations, therefore played more important roles in the observed differences in OMP removal.

Chemically enhanced primary treatment, microsieving, direct membrane filtration and GAC filtration of municipal wastewater: a pilot-scale study.

Chemically enhanced primary treatment (CEPT) followed by microsieving and direct membrane filtration (DMF) as ultrafiltration, was evaluated on pilot scale at a municipal wastewater treatment plant. In addition, a granular activated carbon (GAC) filter downstream of DMF was evaluated for the removal of organic micropollutants. Up to 80% of the total organic carbon (TOC) and 96% of the total phosphorus were removed by CEPT with microsieving. The additional contribution of subsequent DMF was minor, and only five days of downstream GAC filtration was possible due to fouling of the membrane. Of the 21 organic micropollutants analysed, all were removed (≥ 98%) by the GAC filter until 440 bed volumes, while CEPT with microsieving and DMF removed only a few compounds. Measurements of the oxygen uptake rate indicated that the required aeration for supplementary biological treatment downstream of CEPT with microsieving, both with and without subsequent DMF, was 20-25% of that in the influent wastewater. This study demonstrated the potential of using compact physicochemical processes to treat municipal wastewater, including the removal of organic micropollutants.

Ozonation of 14C-labeled micropollutants - mineralization of labeled moieties and adsorption of transformation products to activated carbon.

Ozonation transformation products (OTPs) are largely unknown compounds that are formed during the ozonation of micropollutants, and it is uncertain to which extent these compounds can be removed by subsequent adsorption to activated carbon. Thus, 14C-labeled micropollutants were ozonated to generate 14C-labeled OTPs, for which the adsorption of the sum of all 14C-labeled OTPs to activated carbon could be determined, based on the adsorption of the labeled carbon. Further, 14CO2 traps were used to examine the mineralization of 14C-labeled moieties during ozonation. 14CO2-formation revealed a partial mineralization of the 14C-labeled moieties in all compounds except for propyl-labeled bisphenol A and O-methyl-labeled naproxen. A similar degree of mineralization was noted for different compounds labeled at the same moiety, including the carboxylic carbon in diclofenac and ibuprofen (∼40% at 1 g O3/g DOC) and the aniline ring in sulfamethoxazole and sulfadiazine (∼30% at 1 g O3/g DOC). Aromatic ring cleavage was also confirmed for bisphenol A, sulfamethoxazole, and sulfadiazine through the formation of 14CO2. The adsorption experiments demonstrated increased adsorption of micropollutants to powdered activated carbon after ozonation, which was connected to a decreased adsorption of dissolved organic matter (DOM). Conversely, the OTPs showed a substantial and successive decline in adsorption at increased ozone doses for all compounds, likely due to decreased hydrophobicity and aromaticity of the OTPs. These findings indicate that adsorption to activated carbon alone is not a viable removal method for a wide range of ozonation transformation products.

Pharmaceuticals and other contaminants of emerging concern in Admiralty Bay as a result of untreated wastewater discharge: Status and possible environmental consequences.

Considering how the impact of human activity in Antarctica is growing, the aim of this study was to conduct the first assessment of pharmaceuticals and personal care products (PPCPs), other emerging contaminants (ECs), and antibiotic resistance genes present in the western shore of the Admiralty Bay region of King George Island. In total, more than 170 substances were evaluated to assess the potential environmental risks they pose to the study area. The major evaluated source of pollutants in this study is discharged untreated wastewater. The highest PPCP concentrations in wastewater were found for naproxen (2653 ngL-1), diclofenac (747 ngL-1), ketoconazole (760 ngL-1), ibuprofen (477 ngL-1) and acetaminophen (332 ngL-1). Moreover, the concentrations of benzotriazole (6340 ngL-1) and caffeine (3310 ngL-1) were also high. The Risk Quotient values indicate that azole antifungals (ketoconazole), anti-inflammatories (diclofenac, ibuprofen) and stimulants (caffeine) are the main groups responsible for the highest toxic burden. In addition, antibiotic resistance genes integrons (int 1) and sulphonamide resistance genes (sul 1-2) were detected in wastewater and seawater. These results indicate that regular monitoring of PPCPs and other ECs is of great importance in this environment. Additionally, the following mitigation strategies are suggested: (1) to create a centralised record of the medications prescribed and consumed in situ (to improve knowledge of potential contaminants without analysis); (2) to use more environmentally friendly substitutes both for pharmaceuticals and personal care products when possible (limiting consumption at the source); and (3) to apply advanced systems for wastewater treatment before discharge to the recipient (end-of-pipe technologies as a final barrier).

Digging deep into a GAC filter - Temporal and spatial profiling of adsorbed organic micropollutants.

A large pilot-scale granular activated carbon (GAC) filter was operated downstream in a full-scale wastewater treatment plant to remove organic micropollutants. To describe the spatial and temporal developments of micropollutant adsorption profiles in the GAC filter, micropollutants were extracted from GAC media taken at various filter depths and number of treated bed volumes. At a low number of treated bed volumes (2600 BVs), most micropollutants were adsorbed in the top layers of the filter. At increasing number of treated bed volumes (7300-15,500 BVs), the adsorption front for micropollutants progressed through the filter bed at varying rates, with sulfamethoxazole, fluconazole, and PFOS reaching the bottom layer before carbamazepine and other well-adsorbing micropollutants, such as propranolol and citalopram. Higher amounts of adsorbed micropollutants in the bottom layer of the filter bed resulted in decreased removal efficiencies in the treated wastewater. Mass estimations indicated biodegradation for certain micropollutants, such as naproxen, diclofenac, and sulfamethoxazole. A temporary increase in the concentration of the insecticide imidacloprid could be detected in the filter indicating that extraction of adsorbed micropollutants could provide an opportunity for backtracking of loading patterns.

A comparison of adsorption of organic micropollutants onto activated carbon following chemically enhanced primary treatment with microsieving, direct membrane filtration and tertiary treatment of municipal wastewater.

The adsorption of organic micropollutants onto powdered activated carbon (PAC) was investigated in laboratory scale based on samples from four wastewater process streams (matrices); three from a pilot-scale plant with different degrees of physicochemical treatment of municipal wastewater and one from a full-scale activated sludge plant with post-precipitation. The pilot-scale treatment consisted of chemically enhanced primary treatment with microsieving followed by direct membrane filtration as microfiltration or ultrafiltration. The results showed highest adsorption of micropollutants in the tertiary (biologically and chemically) treated wastewater and lowest adsorption in the microsieve filtrate. Adsorption of micropollutants in the direct membrane microfiltration (200 nm) permeate was generally similar to that in the direct membrane ultrafiltration (3 nm) permeate. The higher adsorption of micropollutants in the tertiary treated wastewater could be related to a lower concentration of dissolved organic carbon (DOC) and lower affinity of DOC for PAC at low dosage (<15 mg PAC/L) in this matrix. At a PAC dose of 10 mg/L, sulfamethoxazole was removed by 33% in the tertiary treated wastewater and 7% in the direct membrane microfiltration permeate. In addition to the PAC experiments, a pilot scale sand filter and a proceeding GAC filter was operated on tertiary treated wastewater from the full-scale treatment plant. Similar removal trends in the PAC and GAC experiments were observed when studying a weighted average micropollutant removal in the GAC filter and a similar dose of activated carbon for both PAC and GAC. Positively charged micropollutants were removed to a higher extent than negatively charged ones by both PAC and GAC.

Tracking 14C-Labeled Organic Micropollutants to Differentiate between Adsorption and Degradation in GAC and Biofilm Processes.

Granular activated carbon (GAC) filters can be used to reduce emissions of organic micropollutants via municipal wastewater, but it is still uncertain to which extent biological degradation contributes to their removal in GAC filters. 14C-labeled organic micropollutants were therefore used to distinguish degradation from adsorption in a GAC-filter media with associated biofilm. The rates and extents of biological degradation and adsorption were investigated and compared with other biofilm systems, including a moving bed biofilm reactor (MBBR) and a sand filter, by monitoring 14C activities in the liquid and gas phases. The microbial cleavage of ibuprofen, naproxen, diclofenac, and mecoprop was confirmed for all biofilms, based on the formation of 14CO2, whereas the degradation of 14C-labeled moieties of sulfamethoxazole and carbamazepine was undetected. Higher degradation rates for diclofenac were observed for the GAC-filter media than for the other biofilms. Degradation of previously adsorbed diclofenac onto GAC could be confirmed by the anaerobic adsorption and subsequent aerobic degradation by the GAC-bound biofilm. This study demonstrates the potential use of 14C-labeled micropollutants to study interactions and determine the relative contributions of adsorption and degradation in GAC-based treatment systems.

Total Release of 21 Indicator Pharmaceuticals Listed by the Swedish Medical Products Agency from Wastewater Treatment Plants to Surface Water Bodies in the 1.3 Million Populated County Skåne (Scania), Sweden.

In 2017, the Swedish Environmental Protection Agency published a report on advanced wastewater treatment for the removal of pharmaceutical residues and stated that advanced treatment should be implemented where it will make the largest difference from an environmental perspective. However, the report also concluded that this need cannot be specified with existing data, but consideration must be made of local conditions. Two considerations are (1) the discharged amount of pharmaceutical into receiving water bodies and (2) the turnover of water in the recipient, where the highest risks are related to recipients with a low water turnover and low dilution. The current project comprised eight different WWTPs distributed throughout the entire County Skåne (Scania) in Sweden, with a population of ca. 1,300,000 persons. In total, 21 of 22 pharmaceuticals were analyzed according to the list proposed by the Swedish Medical Products Agency 2015. The results show that large amounts of pharmaceuticals are released from the WWTPs yearly to Scanian recipients. The total discharge of pharmaceuticals from the eight treatment plants adds up to 71 kg of these 21 substances alone, mainly comprising metoprolol, which is a drug that lowers blood pressure, and the analgesic drug diclofenac. Additionally, carbamazepine, losartan, naproxen and oxazepam were present in significant concentrations. These represented three illnesses that are very common: high blood pressure, inflammation/pain and depression/anxiety. The concentrations were generally in line with previous national Swedish screenings. It was estimated that, when one million cubic meters (1,000,000 m3) of wastewater is discharged, almost 4 kg of the 21 pharmaceuticals is released. The total volume wastewater release by the >90 WWTPs in Scania was estimated to 152,887,000 m3, which corresponded to 590 kg/year. The investigated 21 drugs cover only a small part of many hundred pharmaceuticals that are in use in Sweden. Thus, most likely, one or several tons of pharmaceuticals leak out to the Scanian recipients annually. The analysis of river samples shows that the dilution of wastewater is a key parameter in reducing concentrations. However, some locations have remarkably high concentrations, which occur when the volume wastewater is large in relation to the flow in the river. These kinds of regional results are of importance when selecting where advanced treatment should be prioritized in a first instance, as requested by the Swedish EPA.

High Flow-Rate Sample Loading in Large Volume Whole Water Organic Trace Analysis Using Positive Pressure and Finely Ground Sand as a SPE-Column In-Line Filter.

By using an innovative, positive pressure sample loading technique in combination with an in-line filter of finely ground sand the bottleneck of solid phase extraction (SPE) can be reduced. Recently published work by us has shown the proof of concept of the technique. In this work, emphasis is put on the SPE flow rate and method validation for 26 compounds of emerging environmental concern, mainly from the 1st and 2nd EU Watch List, with various physicochemical properties. The mean absolute recoveries in % and relative standard deviations (RSD) in % for the investigated compounds from spiked pure water samples at the three investigated flow rates of 10, 20, and 40 mL/min were 63.2% (3.2%), 66.9% (3.3%), and 69.0% (4.0%), respectively. All three flow rates produced highly repeatable results, and this allowed a flow rate increase of up to 40 mL/min for a 200 mg, 6 mL, reversed phase SPE cartridge without compromising the recoveries. This figure is more than four times the maximum flow rate recommended by manufacturers. It was indicated that some compounds, especially pronounced for the investigated macrolide molecules, might suffer when long contact times with the sample glass bottle occurs. A reduced contact time somewhat decreases this complication. A very good repeatability also held true for experiments on both spiked matrix-rich pond water (high and low concentrations) and recipient waters (river and wastewater) applying 40 mL/min. This work has shown that, for a large number of compounds of widely differing physicochemical properties, there is a generous flow rate window from 10 to 40 mL/min where sample loading can be conducted. A sample volume of 0.5 L, which at the recommended maximum flow rate speed of 10 mL/min, would previously take 50 min, can now be processed in 12 min using a flow rate of 40 mL/min. This saves 38 min per processed sample. This low-cost technology allows the sample to be transferred to the SPE-column, closer to the sample location and by the person taking the sample. This further means that only the sample cartridge would need to be sent to the laboratory, instead of the whole water sample, like today's procedure.

Increased electrospray ionization intensities and expanded chromatographic possibilities for emerging contaminants using mobile phases of different pH.

In this work the habitual behaviour of low pH in environmental organic trace analysis is challenged by investigating the full potential of building a multi-component UHPLC-ESI-MS/MS method adapted to cover common emerging contaminants of many different polarities, minimizing the elements of compromise in the performance of the final analytical separation and detection. Contributes have been made by taking advantage of common commercially available technology in understanding the impact from solvent components and the ionization of analytes which can facilitate future development of robust, sensitive and precise UHPLC-MS/MS methods. All contaminants were evaluated and optimized without prejudices regarding historical residence in terms of chromatographic conditions and ESI mode; increasing multi-method's flexibility that can be implemented in routine analysis in response to new requests as well as to emerging contaminants yet to be discovered. Our data strongly supports the questioning of the assumption that equilibrium concentrations of ions in solution reflect those produced during the electrospray process. ESI responses of [M+H](+) and limits of detection were comparable, or often better at high pH compared to acidic eluents. Presence of nitrogen basic groups such as tertiary and secondary amines in a compound increased the intensity of the ESI+ signal, and was even further elevated in basic eluent. The proton affinity probably changes for many nitrogen-containing compounds during the ionization process, making the gas-phase processes very important in generation of these ions by ESI+. There were also an unexpected large number of compounds showing their highest response at pH 7 and weak ionic strength. A flow optimized, buffert free, neutral UHPLC-MS/MS method enhanced the sensitivity for the environmental important synthetic hormone ethinyl estradiol significantly.

Pharmaceutical Residues Affecting the UNESCO Biosphere Reserve Kristianstads Vattenrike Wetlands: Sources and Sinks.

This study is the first to investigate the pharmaceutical burden from point sources affecting the UNESCO Biosphere Reserve Kristianstads Vattenrike, Sweden. The investigated Biosphere Reserve is a >1000 km(2) wetland system with inflows from lakes, rivers, leachate from landfill, and wastewater-treatment plants (WWTPs). We analysed influent and treated wastewater, leachate water, lake, river, and wetland water alongside sediment for six model pharmaceuticals. The two WWTPs investigated released pharmaceutical residues at levels close to those previously observed in Swedish monitoring exercises. Compound-dependent WWTP removal efficiencies ranging from 12 to 100 % for bendroflumethiazide, oxazepam, atenolol, carbamazepine, and diclofenac were observed. Surface-water concentrations in the most affected lake were ≥100 ng/L for the various pharmaceuticals with atenolol showing the highest levels (>300 ng/L). A small risk assessment showed that adverse single-substance toxicity on aquatic organisms within the UNESCO Biosphere Reserve is unlikely. However, the effects of combinations of a large number of known and unknown pharmaceuticals, metals, and nutrients are still unknown.

Describing sorption of pharmaceuticals to lake and river sediments, and sewage sludge from UNESCO Biosphere Reserve Kristianstads Vattenrike by chromatographic asymmetry factors and recovery measurements.

Over the past 30 years a vast number of studies have demonstrated the presence of pharmaceutical residues in the environment. But still knowledge is scarce regarding the interaction of these emerging pollutants with various matrices in nature. A chromatographic system with on-line detection was developed to perform a sorption study of six selected pharmaceuticals to four natural sediments and dewatered digested sewage treatment plant sludge with differing physicochemical characteristics. Sorption effects, measured as asymmetry factors and recoveries, differed pronouncedly among the pharmaceuticals and between the matrices, which could be explained by basic physicochemical properties of the investigated compounds in relation to matrix characteristics. Protonated and deprotonated molecular properties had the greatest importance for sorbate-sorbent interactions. Atenolol, with cationic properties, showed the highest degree of sorption regardless of the matrix studied. Diclofenac and furosemide, both acids, showed the least tendency towards interactions to natural matrices. Among the neutral compounds bendroflumethiazide, carbamazepine and oxazepam, weaker forces, such as van der Waals, aromatic electron donor-acceptor interactions, and hydrogen forces, seemed more important to determine sorption differences. Results revealed that sorption of pharmaceuticals on natural sediments decreased in the order: atenolol (+)>bendroflumethiazide>oxazepam>carbamazepine>diclofenac (-)>furosemide (-). The matrix content of organic matter measured as total organic carbon (TOC) clearly dictated drug sorption. Beside from studying matrix interaction, these results and the developed technique and methodology might find use in the development of new removal processes of pharmaceuticals from wastewater based on improved knowledge concerning chemical interactions to filter materials.