Small-scale granular activated carbon (GAC) tests for the adsorption of organic micro-pollutants (OMP) were conducted with drinking water and wastewater treatment plant (WWTP) effluent. In both ...waters, three influent OMP concentration levels were tested. As long as the influent OMP concentrations are below certain thresholds, the relative breakthrough behavior is not impacted in the respective water. Accordingly, the GAC capacity for OMP is directly proportional to the influent OMP concentration in the corresponding water. The differences between the OMP breakthrough curves in drinking water and WWTP effluent can be attributed to the concentrations of the low molecular weight acid and neutral (LMW) organics of the waters. Presenting the relative OMP concentrations (c/c0) over the specific throughput of the LMW organics (mg LMW organics/g GAC), the OMP breakthrough curves in drinking water and WWTP effluent superimpose each other. This superimposition can be further increased if the UV absorbance at 254 nm (UV254) of the LMW organics is considered. In contrast, using the specific throughput of the dissolved organic carbon (DOC) did not suffice to obtain superimposed breakthrough curves. Thus, the LMW organics are the major water constituent impacting OMP adsorption onto GAC. The results demonstrate that knowing the influent OMP and LMW organics concentrations (and UV254) of different waters, the OMP breakthroughs and GAC capacities corresponding to any water can be applied to all other waters.
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•GAC capacity correlates with organic micro-pollutant (OMP) concentration.•specific throughput of low molecular weight organics as universal x-axis.•alignment of breakthrough curves (BTC) in drinking water and wastewater.•OMP capacities and breakthroughs can be transferred between different waters.
Organic micropollutants (OMPs) may occur ubiquitously in the aquatic environment. In order to protect the ecosystem and drinking water sources from potentially toxic effects, discharges of an ...increasing number of OMPs are being regulated. OMP removal from wastewater treatment plant (WWTP) effluents as a point source is a preferred option with removal by adsorption onto powdered activated carbon (PAC) and OMP transformation to presumably harmless compounds by ozonation as the most promising techniques. In this study, effluents of four WWTPs were treated with PAC and ozone in bench-scale experiments to compare the removal efficiencies of seven relevant OMPs. Concentrations of carbamazepine and diclofenac were reduced by more than 90% with 20 mg/L PAC or 5–7 mg/L ozone (0.5 mg O3 per mg dissolved organic carbon (DOC)). Comparing typical doses for practical applications ozonation proved to be more efficient for abatement of sulfamethoxazole, while removal of benzotriazole and iomeprol was comparatively more efficient with activated carbon. While well known for ozonation, DOC-normalized doses were also applied to PAC and correlated better to relative OMP removal than volume proportional PAC addition. Furthermore, OMP removal efficiencies corresponded well with the reduction of ultraviolet light absorption at 254 nm for both treatment options.
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•Direct comparison of ozone and powdered activated carbon for micropollutant removal.•Ozone and PAC efficiency strongly influenced by effluent DOC concentrations.•Similar OMP removal in four secondary effluents with DOC-normalized PAC doses.•Strong correlations between UV254 reduction and micropollutant removal.
This study provides an overview of established processes as well as recent progress in emerging technologies for advanced oxidation processes (AOPs). In addition to a discussion of major reaction ...mechanisms and formation of by-products, data on energy efficiency were collected in an extensive analysis of studies reported in the peer-reviewed literature enabling a critical comparison of various established and emerging AOPs based on electrical energy per order (EEO) values. Despite strong variations within reviewed EEO values, significant differences could be observed between three groups of AOPs: (1) O3 (often considered as AOP-like process), O3/H2O2, O3/UV, UV/H2O2, UV/persulfate, UV/chlorine, and electron beam represent median EEO values of <1 kWh/m3, while median energy consumption by (2) photo-Fenton, plasma, and electrolytic AOPs were significantly higher (EEO values in the range of 1–100 kWh/m3). (3) UV-based photocatalysis, ultrasound, and microwave-based AOPs are characterized by median values of >100 kWh/m3 and were therefore considered as not (yet) energy efficient AOPs. Specific evaluation of 147 data points for the UV/H2O2 process revealed strong effects of operational conditions on reported EEO values. Besides water type and quality, a major influence was observed for process capacity (lab-vs. pilot-vs. full-scale applications) and, in case of UV-based processes, of the lamp type. However, due to the contribution of other factors, correlation of EEO values with specific water quality parameters such as UV absorbance and dissolved organic carbon were not substantial. Also, correlations between EEO and compound reactivity with OH-radicals were not significant (photolytically active compounds were not considered). Based on these findings, recommendations regarding the use of the EEO concept, including the upscaling of laboratory results, were derived.
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•Short summary of radical generation mechanisms and application of AOPs.•First comparison of published EEO values across different AOPs.•Critical consideration of influencing factors on reported EEO values within UV/H2O2.•Proposal for proper use of the EEO-concept.•Discussion of major oxidation by-product formation mechanisms.
By simulating decreasing inflow concentrations, the extent of desorption of organic micropollutants (OMP) from three activated carbons (AC) was examined in laboratory batch tests. The tested AC ...showed strong differences in pore size distribution and could therefore be characterized as typical micro-, meso- and macroporous AC, respectively. Adsorption and desorption conditions were varied by using drinking water (containing dissolved organic matter (DOM)) and DOM-free pure water as background solutions to examine the influence of DOM on OMP desorption for the different AC. Under ideal conditions (adsorption and desorption in pure water) adsorption of the tested OMP was found to be highly up to completely reversible for all tested AC. Under real conditions (adsorption and desorption in drinking water) additional DOM adsorption affects desorption in different ways depending on the AC pore structure. For the micro- and mesoporous AC, an increased irreversibility of OMP adsorption was found, which shows that DOM adsorption prevents OMP desorption. This could be referred to pore blockage effects that occur during the parallel adsorption of DOM and OMP. For the macroporous AC, DOM adsorption led to an enhanced OMP desorption which could be attributed to displacement processes. These results show that smaller pores tend to be blocked by DOM which hinders OMP from desorption. The overall larger pores of the macroporous AC do not get blocked which could allow (i) OMP to desorb and (ii) DOM to enter and displace OMP.
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•Organic micropollutant (OMP) desorption batch tests with 3 activated carbons (ACs).•Adsorption of OMP onto AC generally reversible.•Dissolved organic matter (DOM) affects OMP desorption from AC.•Enhanced OMP desorption from macroporous AC due to displacement of OMP.•Decreased OMP desorption from micro- and mesoporous AC due to DOM pore blockages.
UV-A (near-UV), UV-C (short-UV) and visible-light assisted Fenton-like treatment of Bisphenol A (BPA) was investigated in pure water and raw freshwater samples spiked with BPA. Treatment performances ...were evaluated in terms of BPA degradation, dissolved organic carbon (DOC) removal and H2O2 consumption rates. Complete BPA degradation accompanied with significant DOC removal was achieved for all studied processes. Increasing the initial solution pH only exhibited a negative effect on treatment efficiencies when bicarbonate alkalinity was used for pH adjustment, whereas the raw freshwater matrix and irradiation type also influenced oxidation rates appreciably. Acute toxicity analysis employing Vibrio fischeri revealed that the inhibitory effect of BPA decreased significantly during the course of Photo-Fenton-like treatment. Several transformation products could be identified via HPLC and GC–MS analyses including hydroxylated phenolic compounds (hydroquinone; 2-methoxy, 1-4-benzenediol; 4-isopropenylphenol; 4′-hydroxy-acetophenone; 1-(4-cyclohexylphenyl) ethanone; 4-isopropylenecatechol; 4-4′-dihydroxybenzophenone; 4-ethyl,1,3-benzenediol), as well as the ring opening products hexanoic acid methyl ester, fumaric, succinic and oxalic acids. A reaction pathway featuring hydroxylation, dimerization and ring opening steps is proposed.
•Photo-Fenton-like treatment of BPA was investigated.•Effect of irradiation type and water matrix was studied.•Complete BPA degradation accompanied with high DOC removals was achieved.•Acute toxicity was mainly attributable to the presence of the mother compound BPA.•Several coupling and ring opening products were identified via HPLC and GC–MS.
Small polymer particles with a diameter of less than 5 mm called microplastics find their way into the environment from polymer debris and industrial production. Therefore a method is needed to ...identify and quantify microplastics in various environmental samples to generate reliable concentration values. Such concentration values, i.e. quantitative results, are necessary for an assessment of microplastic in environmental media. This was achieved by thermal extraction in thermogravimetric analysis (TGA), connected to a solid-phase adsorber. These adsorbers were subsequently analysed by thermal desorption gas chromatography mass spectrometry (TDS-GC-MS). In comparison to other chromatographic methods, like pyrolyse gas chromatography mass spectrometry (Py-GC-MS), the relatively high sample masses in TGA (about 200 times higher than used in Py-GC-MS) analysed here enable the measurement of complex matrices that are not homogenous on a small scale. Through the characteristic decomposition products known for every kind of polymer it is possible to identify and even to quantify polymer particles in various matrices. Polyethylene (PE), one of the most important representatives for microplastics, was chosen as an example for identification and quantification.
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•Using a thermal decomposition method for analysing PE microplastics in environmental matrices in one step.•Direct measuring without a pre selection.•Identification and quantification of polymers in environmental samples.
Whereas the adsorption of organic micropollutants (OMP) onto activated carbon (AC) is relatively well studied, little is known about potential OMP desorption effects, especially in real waters. In ...this study, the impact of different fractions of drinking water DOM on OMP desorption from AC was examined. By different pre-treatments of a raw drinking water, a high molecular weight (hmw) and a low molecular weight (lmw) DOM solution were prepared. These solutions were used as background matrix in AC adsorption/desorption batch tests, simulating a drop of the OMP inflow concentration to a fixed-bed adsorber. The tests were conducted in parallel with three AC of different pore structures (microporous, mesoporous/balanced, macroporous). The tests were evaluated with respect to the extent of OMP adsorption and its reversibility, which represents the potential extent of OMP desorption. In terms of OMP adsorption, the lmw-DOM fraction induced a higher competitive effect on OMP adsorption in comparison to the hmw-DOM fraction. In terms of their impact on OMP desorption extent, both fractions led to very similar results. In case of the macroporous AC, both DOM fractions induce an enhanced OMP desorption that can be attributed to displacement effects in both cases. For the microporous AC, an increased irreversibility of OMP adsorption was found in both cases, which shows that DOM adsorption prevents OMP desorption, independently of the size of the adsorbed DOM compounds. Whereas results from this study as well as from former studies indicate that this effect might be induced by permanent pore blockages by adsorbed DOM, further results show that there could be more complex DOM interactions that lead to the decreased desorption in case of microporous AC. Nonetheless, the very similar impact of the different DOM fractions on the reversibility of OMP adsorption indicates that the potential extent of desorption is similar in different waters (with different DOM composition) and primarily depending on the pore structure of the used AC.
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•Organic micropollutant (OMP) desorption batch tests with 3 activated carbons (AC).•Low (lmw) and high molecular weight (hmw) DOM fractions used as background matrix.•Effects on OMP desorption extent are similar for lmw- and hmw-DOM fraction.•Macroporous AC shows enhanced desorption of OMP, independent of DOM composition.•Microporous AC shows irreversible OMP adsorption, independent of DOM composition.
Ultrafiltration (UF) membranes can be used after conventional wastewater treatment to produce particle free and hygienically safe water for reuse. However, membrane fouling affects the performance of ...UF to a large extent. Stirred cell tests with UF membrane show high flux decline filtering treated domestic wastewater. Investigation on the impact of size fractioned substances indicates that dissolved substances are major foulants affecting water filterability. Dissolved organic substances in feed and permeate samples of the stirred cell tests are analyzed by liquid chromatography with online organic carbon detection (LC-OCD). The resulting chromatograms displayed a significant difference of feed and permeate samples in the range of large molecules identified as biopolymer peak. The substances detected in this peak (mostly macro polysaccharide-like and protein-like molecules) are almost completely retained by UF membranes. Quantified investigation shows that biopolymer concentration influences filterability of corresponding water sample proportionally. The apparent magnitude of delivered biopolymer to membrane has a striking correlation with fouling resistance. The relationship was verified to be reproducible using different water samples. Mechanism analysis demonstrates that based on the delivered biopolymer load to membrane pore blocking or cake/gel fouling is the main fouling mechanism in the present experiment conditions.
The adsorption of organic micropollutants (OMP) onto activated carbon (AC) in real waters is strongly affected by dissolved organic matter (DOM). This study examines the impact of DOM quantity and ...composition in terms of OMP desorption from different AC, by using four different water samples. In batch tests, an OMP concentration drop in the influent of an AC treatment system was simulated. These tests were conducted with six AC products with different internal pore structures. The tests were evaluated with respect to the extent of OMP desorption by interpreting corresponding OMP adsorption and desorption isotherms. For each tested AC and each evaluated OMP the isotherms in the different water samples were qualitatively very similar. Thus, despite different DOM composition very similar OMP desorption extents can be expected in different waters. Among the AC products a clear trend can be seen in all waters, namely that increasing pore size results in increasing desorption. The OMP desorption extent was quantified by a simple Freundlich equation-based approach, expressing the relative position of corresponding adsorption and desorption isotherms via the ratio KF, Des/KF, Ads. Plotting KF, Des/KF, Ads of any given substance for the different tested AC in one water over the average AC pore size shows a linear correlation. This confirms that the OMP desorption extent in real waters is strongly impacted by the AC pore structure. Furthermore, it indicates that the average AC pore size might be a good tool to assess the vulnerability of treatment systems towards desorption.
•Adsorption/desorption batch tests with 4 water samples and 6 activated carbons (AC).•Desorption extent of organic micropollutants (OMP) independent of DOM composition.•Increasing OMP desorption extent with rising AC pore size in all tested waters.•Quantification of the desorption extent by a simple Freundlich based approach.•Linear correlation between OMP desorption extent and average AC pore size.
Microplastic (MP) has been detected ubiquitously in freshwater systems. Until now MP sampling, however, is predominantly based on short-term net or pumping and filtration systems which can only ...provide snapshots of MP abundance; especially in flowing water bodies. To improve representativeness in the determination of MP occurrences in these aquatic compartments, an integrative approach that covers larger water volumes for a longer period of time is required. In this regard, surface water supplied drinking water treatment plants (DWTPs) represent an opportunity. In DWTPs, suspended solids from thousands of cubic metres of raw water are continuously removed over several hours and enriched in coagulation/flocculation and filtration processes. Our hypothesis was that MP is also removed to a full extent, like suspended solids, and that an integrative approach for identification and quantification in raw water can be derived from the analysis of MP in the treatment sludge. To prove this hypothesis, treatment sludge from a riverside DWTP (Warnow river, North-Eastern Germany) was analysed for MP > 50 μm. A sample purification protocol overcoming potential matrix effects caused by coagulants and flocculants was developed and validated. MP was analysed using micro-Raman spectroscopy. MP occurrence determined for the Warnow river was compared with in situ reference sampling using an established pumping and filtration system at relatively stable flow conditions. As result, the number of MP particles derived from treatment sludge was extrapolated to 196 ± 42 m−3 for the Warnow river and is statistically insignificantly different from 233 ± 36 m−3 identified by conventional water sampling. In addition, the polymer distribution and particles shape indicated the validity of the integrative concept. Consequently, the determination of MP abundance for freshwater systems based on DWTP treatment sludge represents an adequate method to estimate MP concentrations in flowing waters in an integrative way.
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•Riverside MP abundance was integratively determined by DWTP sludge analysis.•A purification protocol was developed and validated for spectroscopic MP detection.•Results reflect MP concentration and composition derived from reference samplings.•Integrative approach useful for long term monitoring of MP loads in rivers.
MP abundance for freshwater systems based on DWTP treatment sludge represents an adequate method to estimate MP concentrations in flowing waters in an integrative way.
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