Impact of the reductive deiodination on the sorption of iodinated X-ray contrast media to filter sand and activated carbon.

Iodinated X-ray contrast media (ICM) and their aerobic transformation products (TPs) are widespread in the aquatic environment due to their persistent and mobile character. In a previous lab study, we have shown that the reductive (partial) deiodination of selected triiodobenzene derivatives increases the sorption to aquifer sand and loam soil, since iodine affects the compounds by steric hindrance, repulsive forces, resonance and inductive effects. These results suggest that the (partial) deiodination generally occurring to ICM and aerobic ICM TPs during anoxic/anaerobic bank filtration has a potential to increase their removal by sorption to natural sorbents. To basically assess the sorption potential to technically applied materials for drinking water treatment subsequent to bank filtration, we investigated the sorption of iopromide, diatrizoate and 5-amino-2,4,6-triiodoisophtalic acid and their di, mono and deiodinated structures to used filter sand from a waterworks and different fresh powdered activated carbons in batch tests using Berlin drinking water. The filter material, coated by iron and manganese oxides as well as organic material (including biofilm), preferentially removed monoiodinated derivatives, but diffusion through the organic layer heavily slowed the sorption. Therefore, the removal potential by sorption in rapid sand filters of waterworks for (partially) deiodinated benzene derivatives is suggested to be low. The deiodination of iopromide and diatrizoate significantly increased the sorption affinity to activated carbon and the competitiveness with regard to drinking water DOC. Despite the large atom radius of iodine, no clear correlation was found between the pore characteristics of the activated carbons and the molecular size of the compounds. This study emphasises the importance of anoxic/anaerobic conditions for the removal of persistent and mobile ICM and ICM TPs during drinking water treatment.

Settling Velocities of Small Microplastic Fragments and Fibers.

There is only sparse empirical data on the settling velocity of small, nonbuoyant microplastics thus far, although it is an important parameter governing their vertical transport within aquatic environments. This study reports the settling velocities of 4031 exemplary microplastic particles. Focusing on the environmentally most prevalent particle shapes, irregular microplastic fragments of four different polymer types (9-289 µm) and five discrete length fractions (50-600 µm) of common nylon and polyester fibers are investigated, respectively. All settling experiments are carried out in quiescent water by using a specialized optical imaging setup. The method has been previously validated in order to minimize disruptive factors, e.g., thermal convection or particle interactions, and thus enable the precise measurements of the velocities of individual microplastic particles (0.003-9.094 mm/s). Based on the obtained data, ten existing models for predicting a particle's terminal settling velocity are assessed. It is concluded that models, which were specifically deduced from empirical data on larger microplastics, fail to provide accurate predictions for small microplastics. Instead, a different approach is highlighted as a viable option for computing settling velocities across the microplastics continuum in terms of size, density, and shape.

Impact of natural organic matter and inorganic ions on the stabilization of polystyrene micro-particles.

The orthokinetic coagulation of irregularly shaped polystyrene micro-particles (PS-MP) was investigated in solutions of inorganic cations with different valence (NaCl, CaCl2, LaCl3) using a coagulation jar test set-up combined with light extinction particle counting. The stabilizing effect of model natural organic matter (NOM from reverse-osmosis (RO-NOM), humic (HA) & fulvic acid (FA)) and of surface water components (SW-NOM) was studied. Collision efficiencies were calculated from the decrease in particle concentration applying first order reaction kinetics. The coagulation of PS-MP followed Derjaguin-Landau-Verwey-Overbeek (DLVO) theory with regard to ionic charge in solution. Highest collision efficiencies were obtained close to the suspected critical coagulation concentrations for CaCl2 (12 mM) and LaCl3 (5.5 mM) whereas for NaCl no CCC was found within the applied concentration range (10-1000 mM). The addition of NOM effectively stabilized PS-MP at low ionic strength (10 mM NaCl) in the order HA > RO-NOM > FA > SW-NOM at concentrations of dissolved organic carbon (DOC) as low as 0.2-0.5 mg/L DOC through electrostatic repulsion. PS-MP were effectively stabilized in 6.1 mg DOC/L of SW-NOM even at high ionic strength (100 mM MgCl2). Coagulation at intermediate ionic strength (10 mM MgCl2) was only observed for SW-NOM concentrations below 0.6 mg/L DOC. The results showed that even low NOM concentrations prevent PS-MP from orthokinetic coagulation in the presence of high ion concentrations. The study provides further insight in the orthokinetic coagulation behavior of PS-MP in the presence of NOM and highlights the importance of NOM for the stabilization of microplastics in aquatic suspensions. Further research is needed to elucidate the behavior of MP in turbulent systems to predict the mobility MP in aquatic systems such as rivers.

Influence of low oxygen concentrations on biological transformations of trace organic chemicals in sand filter systems.

Managed aquifer recharge systems for drinking water reclamation are challenged by trace organic chemicals (TOrCs) since some of them are poorly retained. Although a lot of research has been done to investigate biological transformation of TOrCs in sand filter systems, there are still uncertainties to predict the removal. A laboratory column system with two different filter sands was set up to test TOrC transformation, the influence of low oxygen concentrations as well as the adaptation and influence of spiked TOrC influent concentrations. Bioactivity was quantified with the fluorescence tracer resazurin. In the experiment, a low elimination performance in the first column segment, defined as lag zone, was observed, implying incomplete adaptation or inhibiting co-factors. To assess these lag zones and to determine the dissipation time DT50 for 50% removal, a modified Gompertz model was applied. For acesulfame, formylaminoantipyrine, gabapentin, sulfamethoxazole, and valsartan acid DT50 of less than 10 h were observed, even when influent oxygen concentrations decreased to 0.5 mg/L. In general, TOrC transformations in technical sand with lower bioactivity and especially valsartan acid transformation responded very sensitive to low influent oxygen concentrations of 0.5 mg/L. However, in well adapted sand originating from soil aquifer treatment (SAT) with sufficient bioactivity, TOrC removal was hardly affected by such suboxic conditions. Furthermore, increasing the influent concentrations of TOrCs to 10 µg/L was found to promote adaptation especially for acesulfame and sulfamethoxazole. Benzotriazole, carbamazepine, diclofenac and venlafaxine were recalcitrant under the applied experimental conditions.

Pilot-scale removal of persistent and mobile organic substances in granular activated carbon filters and experimental predictability at lab-scale.

Present knowledge about the fate of persistent and mobile (PM) substances in drinking water treatment is limited. Hence, this study assesses the potential of fixed-bed granular activated carbon (GAC) filters to fill the treatment gap for PM substances and the elimination predictability from lab-scale experiments. Two parallel pilot filters (GAC bed height 2 m, diameter 15 cm) with different GAC were operated for 1.5 years (ca. 47,000 BV throughput) alongside rapid small-scale column tests (RSSCT) designed based on the proportional diffusivity (PD) and the constant diffusivity (CD) approaches. Background dissolved organic matter (DOM) and a set of 17 target substances were investigated, among them 2-acrylamido-2-methylpropane sulfonate (AAMPS), adamantan-1-amine (ATA), melamine (MEL) and trifluoromethanesulfonic acid (TFMSA). Nine substances were predominantly present in the drinking water used as pilot filter influent (frequencies of detection above 80 %, median concentrations 0.003-1.868 µg/L) and their breakthrough behaviors could be observed: TFMSA was not retained at all, four substances including AAMPS and ATA reached complete breakthrough below 20,000 BV, three compounds were partially retained until the end of operation and oxypurinol was retained completely. The comparable PM candidate and DOM removal performances of both GAC aligns with their very similar surface characteristics and elemental compositions. The agreement of results between RSSCT with the pilot-scale filters were substance specific and no superior RSSCT design could be identified. However, CD-RSSCT provide a conservative removal prediction for most studied compounds. MEL adsorption was significantly underestimated by both RSSCT designs. Using the criterion of a carbon usage rate (with respect to 50 % breakthrough) below 25 mgGAC/Lwater for an economic retention by fixed-bed GAC filters, five (out of nine) substances met the requirement.

Can reductive deiodination improve the sorption of iodinated X-ray contrast media to aquifer material during bank filtration?

Iodinated X-ray contrast media (ICM) as well as their aerobic transformation products (TPs), are highly polar triiodobenzoic acid derivatives, ubiquitously found in the urban water cycle. Based on their polarity, their sorption affinity to sediment and soil is negligible. However, we hypothesize that the iodine atoms bound to the benzene ring play a decisive role for sorption, due to their large atom radius, high electron number and symmetrical positioning within the aromatic system. The aim of this study is to investigate, if the (partial) deiodination, occurring during anoxic/anaerobic bank filtration, improves the sorption to aquifer material. Tri, di, mono and deiodinated structures of two ICMs (iopromide and diatrizoate) and one precursor/TP of ICM (5-amino-2,4,6-triiodoisophtalic acid) were tested in batch experiments, using two aquifer sands and a loam soil with and without organic matter. The di, mono and deiodinated structures were produced by (partial) deiodination of the triiodinated initial compounds. The results demonstrated that the (partial) deiodination increases the sorption to all tested sorbents, even though the theoretical polarity increases with decreasing number of iodine atoms. Whereas lignite particles positively affected the sorption, mineral components decreased it. Kinetics tests show biphasic sorption for the deiodinated derivatives. We have concluded that iodine affects the sorption by sterical hindrance, repulsive forces, resonance and inductive effects, depending on the number and position of iodine, side chain characteristics and composition of the sorbent material. Our study has revealed an increased sorption potential of ICMs and their iodinated TPs to aquifer material during anoxic/anaerobic bank filtration as a result of (partial) deiodination, whereby a complete deiodination is not necessary for efficient removal by sorption. Furthermore, it suggests that the combination of an initial aerobic (side chain transformations) and a subsequent anoxic/anaerobic (deiodination) redox milieu supports the sorption potential.

Is adsorption onto activated carbon a feasible drinking water treatment option for persistent and mobile substances?

Persistent and mobile (PM) substances among the organic micropollutants have gained increasing interest since their inherent properties enable them to enrich in water cycles. This study set out to investigate the potential of adsorption onto activated carbon as a drinking water treatment option for 19 PM candidates in batch experiments in a drinking water matrix using a microporous and a mesoporous activated carbon. Overall, adsorption of PM candidates proved to be very variable and the extent of removal could not be directly related to molecular properties. At an activated carbon dose of 10 mg/L and 48 h contact time, five (out of 19) substances were readily removed (≥ 80%), among them N-(3-(dimethylamino)-propyl)methacrylamide, which was investigated for the first time. For five other substances, no or negligible removal (< 20%) was observed, including 2-methyl-2-propene-1-sulfonic acid and 4­hydroxy-1-(2-hydroxyethyl)-2,2,6,6,-tetramethylpiperidine. For the former, current state of the art adsorption processes may pose a sufficient barrier. Additionally, substance specific surrogate correlations between removals and UVA254 abatements were established to provide a cheap and fast estimate for PM candidate elimination. Adsorption onto activated carbon could contribute significantly to PM substance elimination as part of multi barrier approaches, but assessments for individual substances still require clarification, as demonstrated for the investigated PM candidates.

Impacts of autochthonous particulate organic matter on redox-conditions and elimination of trace organic chemicals in managed aquifer recharge.

Autochthonous carbon fixation by algae and subsequent deposition of particulate organic matter can have significant effects on redox conditions and elimination of trace organic chemicals (TOrCs) in managed aquifer recharge (MAR). This study investigated the impacts of different algae loadings (0-160 g/m2) and infiltration rates (0.06-0.37 m/d) on overall oxygen consumption and elimination of selected TOrCs (diclofenac, formylaminoantipyrine, gabapentin, and sulfamethoxazole) in adapted laboratory sand columns. An infiltration rate of 0.37 m/d in conjunction with an algae load of 80 g/m2 (dry weight) sustained oxic conditions in the sand bed and did not affect the degradation of TOrCs. Thus, the availability of easily degradable organic carbon from algae did not influence the removal of TOrCs at an influent concentration of 1 µg/L. In contrast, a lower infiltration rate of 0.20 m/d in combination with a higher algae loading of 160 g/m2 caused anoxic conditions for 30 days and significantly impeded the degradation of formylaminoantipyrine, gabapentin, sulfamethoxazole, and diclofenac. Especially the elimination of gabapentin did not fully recover within 130 days after pulsed algae deposition. Hence, measures like micro-sieving or nutrient control are required at bank filtration or soil aquifer treatment sites with low infiltration rates.

A quick test method for predicting the adsorption of organic micropollutants on activated carbon.

Controlling the contamination of water cycles with organic micropollutants (OMPs) has been targeted in many regions. Adsorption with activated carbon is an effective technology to remove OMPs from different water matrices. To efficiently design or operate the adsorption process, the adsorption of OMPs should be properly assessed, usually with time-consuming batch adsorption tests and sophisticated analyses. In this study, a quick adsorption test method has been developed by loading powdered activated carbon (PAC) into a syringe filter which can be used subsequently to filtrate the water sample in short time (<60 s). Treated wastewater was applied to compare the quick test method and conventional batch test regarding the adsorption of 14 frequently detected OMPs, the abatement of UV254, and changes in fractions of dissolved organic matter (DOM). Similar adsorption patterns of individual OMPs, total OMPs, and DOM fractions was found with two methods. UV254 can predict the removal of total OMPs and most individual OMPs in both methods. Both the abatement of UV254 or the removal of OMPs determined in the quick test led to a highly accurate prediction of OMP adsorption in the conventional adsorption tests. The novel quick test method thus could help operators and researchers quickly monitor the adsorption capacity of PAC products.

Identification and quantification of microplastic particles in drinking water treatment sludge as an integrative approach to determine microplastic abundance in a freshwater river.

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.

Varying attenuation of trace organic chemicals in natural treatment systems - A review of key influential factors.

The removal of trace organic chemicals (TOrCs) from treated wastewater and impacted surface water through managed aquifer recharge (MAR) has been extensively studied under a variety of water quality and operating conditions and at various experimental scales. The primary mechanism thought to dictate removal over the long term is biodegradation by microorganisms present in the system. This review of removal percentages observed in biologically active filtration systems reported in the peer-reviewed literature may serve as the basis to identify future indicators for persistence, as well as variable and efficient removal in MAR systems. A noticeable variation in reported removal percentages (standard deviation above 30%) was observed for 24 of the 49 most commonly studied TOrCs. Such variations suggest a rather inconsistent capacity of biologically active filter systems to remove these TOrCs. Therefore, operational parameters such as the change in dissolved organic carbon (ΔDOC) during treatment, hydraulic retention time (HRT), filter material, and redox conditions were correlated to the associated TOrC removal percentages to determine whether a data-based relationship could be elucidated. Interestingly, 11 out of the 24 compounds demonstrated increased removal with increasing ΔDOC concentrations. Furthermore, 10 compounds exhibited a positive correlation with HRT. Based on the evaluated data, a minimum HRT of 0.5-1 day is recommended for removal of most compounds.

Specific adsorption sites and conditions derived by thermal decomposition of activated carbons and adsorbed carbamazepine.

The adsorption of organic micropollutants onto activated carbon is a favourable solution for the treatment of drinking water and wastewater. However, these adsorption processes are not sufficiently understood to allow for the appropriate prediction of removal processes. In this study, thermogravimetric analysis, alongside evolved gas analysis, is proposed for the characterisation of micropollutants adsorbed on activated carbon. Varying amounts of carbamazepine were adsorbed onto three different activated carbons, which were subsequently dried, and their thermal decomposition mechanisms examined. The discovery of 55 different pyrolysis products allowed differentiations to be made between specific adsorption sites and conditions. However, the same adsorption mechanisms were found for all samples, which were enhanced by inorganic constituents and oxygen containing surface groups. Furthermore, increasing the loadings led to the evolution of more hydrated decomposition products, whilst parts of the carbamazepine molecules were also integrated into the carbon structure. It was also found that the chemical composition, especially the degree of dehydration of the activated carbon, plays an important role in the adsorption of carbamazepine. Hence, it is thought that the adsorption sites may have a higher adsorption energy for specific adsorbates, when the activated carbon can then potentially increase its degree of graphitisation.

Deiodination in the presence of Dehalococcoides mccartyi strain CBDB1: comparison of the native enzyme and co-factor vitamin B12.

Triiodinated benzoic acid derivatives are widely used as contrast media for medical examinations and are found at high concentrations in urban aquatic environments. During bank filtration, deiodination of iodinated contrast media has been observed under anoxic/anaerobic conditions. While several bacterial strains capable of dechlorination and debromination have been isolated and characterized, deiodination has not yet been shown for an isolated strain. Here, we investigate dehalogenation of iodinated contrast media (ICM), triiodobenzoic acids (TIBA), and analogous chlorinated compounds by Dehalococcoides mccartyi strain CBDB1 and its corrinoid co-factor vitamin B12. No cell growth of CBDB1 was observed using iodinated compounds as electron acceptor. Only negligible deiodination occurred for ICM, whereas 2,3,5-TIBA was nearly completely deiodinated by CBDB1 without showing cell growth. Furthermore, TIBA inhibited growth with hexachlorobenzene which is usually a well-suited electron acceptor for strain CBDB1, indicating that TIBA is toxic for CBDB1. The involvement of CBDB1 enzymes in the deiodination of TIBA was verified by the absence of deiodination activity after heat inactivation. Adding iodopropane also inhibited the deiodination of TIBA by CBDB1 cells, indicating the involvement of a corrinoid-enzyme in the reductive TIBA deiodination. The results further suggest that the involved electron transport is decoupled from proton translocation and therefore growth. Graphical abstract.

Reaction kinetics of corrinoid-mediated deiodination of iodinated X-ray contrast media and other iodinated organic compounds.

Iodinated contrast media (ICM) are found at considerably higher concentrations than any other pharmaceutical in waste water, surface water and bank filtrate. While the compounds are persistent to deiodination in aerobic environments, field data from bank filtration transects have demonstrated a partial deiodination in reducing soil-water environments. In a previous lab study, we have shown that this reductive deiodination is abiotically catalyzed by (free) corrinoids. To achieve a better understanding of the incomplete deiodination in the environment, we now investigated the reaction kinetics based on the decrease of the iodinated compound, the formation of deiodinated transformation products and the iodide release. The deiodination follows first-order kinetics and consists of three partial reactions for the release of three iodine atoms. The deiodination rate decreased with decreasing iodination degree with the deiodination rate constants k1 > k2 > k3. In contrast to the ICM, 2,4,6- and 2,3,5-triiodobenzoic acid, 5-amino-2,4,6-triiodoisophthalic acid and monoiodobenzoic acids did not show a complete deiodination under the same test conditions. Our results show that the deiodination strongly depends on the substitution pattern of the bound iodine atoms as well as on adjacent functional groups. Iodine atoms in ortho-position to another iodine atom or a carboxyl group were released more easily while an amino group in ortho-position inhibited the deiodination. Tests in tap water in the presence of B12 showed a much slower deiodination than in ultrapure water, most likely caused by competitive electron acceptors in the water matrix.

Organic micropollutant desorption in various water matrices - Activated carbon pore characteristics determine the reversibility of adsorption.

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.

Impact of different DOM size fractions on the desorption of organic micropollutants from activated carbon.

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.

Abiotic reductive deiodination of iodinated organic compounds and X-ray contrast media catalyzed by free corrinoids.

Iodinated X-ray contrast media are known for their stability concerning deiodination in the aquatic environment under aerobic conditions. In this study, we demonstrate the abiotic reductive deiodination of the iodinated contrast media iopromide, iopamidol and diatrizoate in the presence of corrinoids. In addition, triiodinated benzoic acid derivatives with iodine atoms bound at different positions were investigated. Corrinoids like cyanocobalamin (vitamin B12) and dicyanocobinamide served as electron shuttles and as catalysts between the reducing agent (e.g., titanium (III) citrate) and the electron accepting iodinated compound. The concentration decrease of the iodinated compounds followed first-order kinetics with rate constant kobs depending on the iodinated compound. A linear correlation between the rate of iodide release and the corrinoid concentration was observed, with deiodination rates for dicyanocobinamide twice as high as for vitamin B12. Reducing agents with a less negative standard redox potential like dithiothreitol or cysteine caused slower deiodination as the cobalt center was only reduced to its CoII oxidation state. With a temperature increase from 11 to 23 °C, the concentrations of released iodide doubled. A complete deiodination was only observed for the iodinated contrast media but not for structurally similar iodinated benzoic acid derivatives.

Quantification and isotherm modelling of competitive phosphate and silicate adsorption onto micro-sized granular ferric hydroxide.

Adsorption onto ferric hydroxide is a known method to reach very low residual phosphate concentrations. Silicate is omnipresent in surface and industrial waters and reduces the adsorption capacity of ferric hydroxides. The present article focusses on the influences of silicate concentration and contact time on the adsorption of phosphate to a micro-sized iron hydroxide adsorbent (µGFH) and fits adsorption data to multi-component adsorption isotherms. In Berlin drinking water (DOC of approx. 4 mg L-1) at pH 7.0, loadings of 24 mg g-1 P (with 3 mg L-1 initial PO4 3--P) and 17 mg L-1 Si (with 9 mg L-1 initial Si) were reached. In deionized water, phosphate shows a high percentage of reversible bonds to µGFH while silicate adsorption is not reversible probably due to polymerization. Depending on the initial silicate concentration, phosphate loadings are reduced by 27, 33 and 47% (for equilibrium concentrations of 1.5 mg L-1) for 9, 14 and 22 mg L-1 Si respectively. Out of eight tested multi-component adsorption models, the Extended Freundlich Model Isotherm (EFMI) describes the simultaneous adsorption of phosphate and silicate best. Thus, providing the means to predict and control phosphate removal. Longer contact times of the adsorbent with silicate prior to addition of phosphate reduce phosphate adsorption significantly. Compared to 7 days of contact with silicate (c 0 = 10 mg L-1) prior to phosphate (c 0 = 3 mg L-1) addition, 28 and 56 days reduce the µGFH capacity for phosphate by 21 and 43%, respectively.

Fast empirical lab method for performance projections of large-scale powdered activated carbon re-circulation plants.

Powdered activated carbon (PAC) for organic micro-pollutant (OMP) removal can be applied effectively on wastewater treatment plant (WWTP) effluents by using re-circulation schemes, accumulating the PAC in the system. This technique is complex because several factors are unknown: (i) the PAC concentration in the system, (ii) specific and average contact times of PAC particles, and (iii) PAC particle loadings with target compounds/competing water constituents. Thus, performance projections (e.g. in the lab) are very challenging. We sampled large-scale PAC plants with PAC sludge re-circulation on eight different WWTPs. The PAC plant-induced OMP removals were notably different, even when considering PAC concentrations in proportion to background organic sum parameters. The variability is likely caused by differing PAC products, varying water composition, differently effective plant/re-circulation operation, and variable biodegradation. Plant PAC samples and parts of the PAC plant influent samples were used in laboratory tests, applying multiples (0.5, 1, 2, 4) of the respective large-scale "fresh" PAC doses, and several fixed contact times (0.5, 1, 2, 4, 48 h). The aim was to empirically identify suitable combinations of lab PAC dose (as multiples of the plant PAC dose) and contact time, which represent the PAC plant performances in removing OMPs (for specific OMPs at single locations, and for averages of different OMPs at all locations). E.g., for five well adsorbing, little biodegradable OMPs, plant performances can be projected by using a lab PAC dose of twice the respective full-scale PAC dose and 4 h lab contact time (standard deviation of 13 %-points).

The challenge in preparing particle suspensions for aquatic microplastic research.

The occurrence of small particles consisting of organic polymers, so-called microplastic (MP), in aquatic environments attracts increasing interest in both public and science. Recent sampling campaigns in surface waters revealed substantial numbers of particles in the size range from a few micrometers to a few millimeters. In order to validate sample preparation, identification and quantification and to investigate the behavior of MP particles and potential toxic effects on organisms, defined MP model particles are needed. Many studies use spherical compounds that probably behave differently compared to irregularly shaped MP found in environmental samples. However, preparation and handling of MP particles are challenging tasks and have been systematically investigated in the present study. Polystyrene (PS) as a commonly found polymer with a density slightly above that of water was selected as polymer type for milling and fractionation studies. A cryogenic ball mill proved to be practical and effective to produce particles in the size range from 1 to 200 µm. The yield of small particles increased with increasing pre-cooling and milling durations. Depending on the concentration and the size, PS particles do not completely disperse in water and particles partly creep vertically up along glass walls. Stabilized MP suspensions without use of surfactants that might harm organisms are needed for toxicological studies. The stabilization of PS particle suspensions with ozone treatment reduced the wall effect and increased the number of dispersed PS particles but increased the dissolved organic carbon concentration and changed the size distribution of the particles.