Removal of persistent and mobile organic micropollutants from drinking water utilizing a synthesized waste-derived adsorbent.

Persistent and mobile (PM) substances refer to a wide range of organic micropollutants (OMPs) with high persistence and mobility in water. So far, only a few methods have been explored for the removal of PM substances from drinking water. In this work, a new adsorbent based on spent coffee grounds and aluminum waste was synthesized and utilized to remove 25 OMPs, including 22 PM substances, from drinking water. Different characterization methods, including powder X-ray diffraction (XRD), analyses according to Brunauer-Emmett-Teller (BET), field-emission scanning electron microscopy (FE-SEM) and energy dispersive X-ray spectroscopy (EDS), were applied to describe the adsorbent's textural and structural characteristics. The results revealed that the adsorbent is highly effective in removing OMPs. Common OMPs (i.e. carbamazepine, sulfamethoxazole and diclofenac) were completely removed from drinking water. Also, many of the PM substances were removed by more than 80% using an adsorbent dosage of 0.1 g/L. A strong relation between abatement of ultraviolet light absorbance at 254 nm (UV254) and OMP removal was observed. Therefore, UV254 abatement is a useful surrogate for a quick estimation of OMP removals.

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.

Automated scraping and analyses of drinking water quality data.

Drinking water quality data, though regularly monitored, is not available in Germany as national overview, but only decentralized from the water suppliers. On the national level, only the number of limit exceedances are reported. An overview on drinking water qualities as complete as possible however is necessary to assess and develop regulations and helpful for authorities, political decision makers, the public and the scientific community. Due to the fragmented nature of the data sources, web-scraping was used in the present study to mitigate aforementioned challenges and knowledge gaps. Data from 502 water supply areas were compiled and further evaluated. The extent and form of reported values varied strongly, as did the availability of data for the different water supply areas. The results show, that the scraped values were not close to but well below associated legal limits or guidance values. For organic parameters, the reported values were mostly below the respective limits of quantification. However, further developments are needed to cover more water supply areas in Germany and internationally.

Fates of potentially persistent and mobile organic substances in embedded outdoor columns for artificial groundwater recharge simulation.

Persistent and mobile organic micropollutants (OMP) are ubiquitously found in the aquatic environment and have a high propensity to distribute in water resources and are difficult to remediate. Managed aquifer recharge systems such as artificial groundwater recharge, produce high-quality drinking water by removing numerous OMP from the source water. In this study, the fates of selected emerging and potentially persistent and mobile OMP were investigated in outdoor columns for artificial groundwater recharge simulation. Breakthrough curves of OMP were modeled to differentiate between sorption and bio-transformation. The study showed that selected OMP were persistent in the surface water and no photo-degradation was observed, except for diclofenac. The trends of dissolved organic carbon concentrations and UV light absorption at 254 nm wavelength suggest elevated biological activity in the first 0.3 m of the columns. The study revealed that the bio-transformation of cyanoguanidine, valsartan acid and diclofenac correlated with the biological activity in the sand columns. Benzyltrimethylammonium, n-(3-(dimethylamino)-propyl)methacrylamide, 1,3-di-o-tolylguanidine, 1,3-diphenylguanidine and melamine were completely eliminated within the first 0.3 m, likely due to sorption. Less mobile compounds such as carbamazepine and adamantan-1-amine also showed sorption. Sorption was also observed for diclofenac, likely due to decreased pH along the column depth. Retardation factors of several OMP were higher in the first 0.3 m of the columns, likely due to higher organic carbon contents compared to the remaining depth. Six organic substances (for example 2-acrylamido-2-methylpropane sulfonate and dimethylbenzene sulfonate) were persistent and mobile throughout the experiment. Overall, this study reveals the vital role of pH and sand organic carbon for sorption and residence time and biological activity for OMP elimination.

Fates of selected pharmaceuticals in a large recirculated mesocosm with a pond and bank filtration.

Pharmaceuticals such as carbamazepine (CBZ), sulfamethoxazole (SMX) and diclofenac (DCF) are detected at a high frequency in the aquatic environment. The fates of these compounds in bank filtration (BF), a nature-based water treatment system, have been extensively studied, mainly in batch and laboratory column studies. This study, for the first time, investigated the fates of CBZ, SMX and DCF in a large recirculated mesocosm with a pond and subsequent BF. Changes in dissolved organic carbon (DOC) in the pond and bank filtrate were also observed. The averaged spiking concentration of CBZ, SMX and DCF was 1 µg/L at the pond influent and the hydraulic retention time of surface water in the pond was 15 days to reach at the bank. The infiltrated surface water travelled through two parallel subsurface layers and a combined effluent (from both layers) was collected (35 m from the bank) and recirculated as an influent of the pond. The redox conditions in both layers were significantly different (p < 0.05) and correlated with temperature (R2 = 0.91, p < 0.05). The results revealed that CBZ was persistent in the surface water and groundwater passage, SMX was persistent in surface water and removed entirely through BF within 50 days of operation. DCF was completely removed after infiltration and groundwater passage (within 2 m). The DOC in the surface water showed insignificant variations between the influent and the bank. A significant reduction of DOC was observed within the first 5 m after infiltration, and the reduction was associated with the removal of biopolymers. This work shows that the selected organic micropollutants in surface water were not affected by sunlight intensity, water chemistry and water depth. In addition, recirculation mesocosm BF confirms the potential environmental risk and predictive concentrations of organic micropollutants in the aquatic environment.

Transformation of potentially persistent and mobile organic micropollutants in column experiments.

The occurrence of potentially persistent and mobile (PM) organic micropollutants (OMP) in the aquatic environment is recognized as a severe threat to water resources and drinking water suppliers. The current study investigated long-term fate (persistency and bio-transformation) of several emerging contaminants in a simulated bank filtration (BF) for the first time. In parallel, four sand column systems were operated with groundwater and continuously spiked with an average concentration of 1 µg/L for 24 OMP. Each column system consisted of two sand columns connected in series. Presumably, biological activities in the first column were higher than in the second column, as dissolved oxygen utilization, dissolved organic matter (DOM) and UV absorbance at 254 nm (UV254) reduction rates were high in the first column. This study revealed that 9 out of 24 OMP were persistent and mobile throughout the study under oxic conditions and within a hydraulic retention time (HRT) of 12 days. However, 2 (out of 9) OMP were persistent but showed sorption behavior. 15 (out of 24) OMP displayed bio-transformation, 4 were eliminated entirely within 4.5 days of HRT. Others showed constant or improved degradation with the adaptation (or operation) time. Improved degradation with adaption was high in the bioactive sand columns. However, 8 OMP showed improved elimination at high HRT, even in low biologically active columns. In addition, no significant effect of the DOM on the eliminations of OMP was found except for 4-hydroxy-1-(2-hydroxyethyl)-2,2,6,6,-tetramethylpiperidine (HHTMP), 2-methyl-2-propene-1-sulfonic acid (MPSA) and sulfamethoxazole (SMX). The eliminations of HHTMP (Pearson's r > 0.80, p < 0.05), MPSA (Pearson's r > 0.70) and SMX (Pearson's r > 0.80) correlated with the removals of humic substances in the sand columns. Overall, adaptation time and HRT play a crucial role in the elimination of emerging OMP through BF, yet at the same time several OMP exhibit persistent behavior.

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.

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.

The fate of nitrification and urease inhibitors in simulated bank filtration.

The application of nitrification and urease inhibitors (NUI) in conjunction with nitrogen (N) fertilizers improves the efficiency of N fertilizers. However, NUI are frequently found in surface waters through leaching or surface runoff. Bank filtration (BF) is considered as a low-cost water treatment system providing high quality water by efficiently removing large amounts of organic micropollutants from surface water. The fate of NUI in managed aquifer recharge systems such as BF is poorly known. The aim of this work was to investigate sorption and degradation of NUI in simulated BF under near-natural conditions. Besides, the effect of NUI on the microbial biomass of slowly growing microorganisms and the role of microbial biomass on NUI removal was investigated. Duplicate sand columns (length 1.7 m) fed with surface water were spiked with a pulse consisting of four nitrification (1,2,4-triazole, dicyanodiamide, 3,4-dimethylpyrazole and 3-methylpyrazole) and two urease inhibitors (n-butyl-thiophosphoric acid triamide and n-(2-nitrophenyl) phosphoric triamide). The average spiking concentration of each NUI was 5 µg/L. Experimental and modeled breakthrough curves of NUI indicated no retardation for any of the inhibitors. Therefore, biodegradation was identified as the main elimination pathway for all substances and was highest in zones of high microbial biomass. Removal of 1,2,4-triazole was 50% and n-butyl-thiophosphoric acid triamide proved to be highly degradable and was completely removed after a hydraulic retention time (HRT) of 24 h. 50% of the mass recovery for nitrification inhibitors except for 3,4-dimethylpyrazole was observed at the effluent (4 days HRT). In addition, a mild effect of NUI on microbial biomass was noted. This study highlights that the degradation of NUI in BF depends on HRT and microbial biomass.

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.

Bisphenol A removal in treated wastewater matrix at neutral pH using magnetic graphite intercalation compounds as persulfate activators.

Effluents of municipal wastewater treatment plants (WWTPs) are major sources for releasing contaminants of emerging concern (CECs) into the aquatic environment, which can result in negative effects on aquatic ecosystems and, as a consequence, on humans. Herein, the graphite intercalation concept was used to synthesize heterogeneous catalysts to degrade bisphenol A (BPA) as a model CEC in municipal WWTP effluents at neutral pH. The catalyst was synthesized using the simple molten salt method and showed several benefits, such as iron leaching prevention and stability in environmental matrices. Different methods were applied to describe the catalyst's structural characteristics. The proposed system removed 99.3% of BPA in 75 min using 2 g/L of the synthesized catalyst and 1.19 g/L (5 mM) persulfate at neutral pH. Quenching experiments showed that catalytic activities and BPA removals were significantly aided by both radical and non-radical pathways through the generation of free radicals and singlet oxygen (1 O2 ). Furthermore, the reuse of recycled synthesized catalyst was investigated on treated urban wastewater, and the results showed that the catalyst could degrade BPA from the wastewater in consecutive cycles, demonstrating its applicability under real conditions. PRACTITIONER POINTS: BPA was effectively removed from the effluents of municipal WWTPs at neutral pH. A new catalyst (magnetic GIC) was fabricated for heterogeneous catalytic systems. The catalyst activates persulfate to generate free radicals and 1 O2 , indicating that radical and non-radical pathways contribute to BPA degradation. The catalyst showed the ability to remove BPA even in the sixth cycle of use, demonstrating its stability and reusability.

Screening for 26 per- and polyfluoroalkyl substances (PFAS) in German drinking waters with support of residents.

The occurrence of per- and polyfluoroalkyl substances (PFAS) in water cycles poses a challenge to drinking water quality and safety. In order to counteract the large knowledge gap regarding PFAS in German drinking water, 89 drinking water samples from all over Germany were collected with the help of residents and were analyzed for 26 PFAS by high-performance liquid chromatography with tandem mass spectrometry (HPLC-MS/MS). The 20 PFAS recently regulated by sum concentration (PFAS∑20), as well as six other PFAS, were quantified by targeted analysis. In all drinking water samples, PFAS∑20 was below the limit of 0.1 µg/L, but the sum concentrations ranged widely from below the limit of quantification up to 80.2 ng/L. The sum concentrations (PFAS∑4) of perfluorohexanesulfonate (PFHxS), perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and perfluorononanoate of 20 ng/L were exceeded in two samples. The most frequently detected individual substances were PFOS (in 52% of the samples), perfluorobutanesulfonate (52%), perfluorohexanoate (PFHxA) (44%), perfluoropentanoate (43%) and PFHxS (35%). The highest single concentrations were 23.5 ng/L for PFHxS, 15.3 ng/L for PFOS, and 10.1 ng/L for PFHxA. No regionally elevated concentrations were identified, but some highly urbanized areas showed elevated levels. Concentrations of substitution PFAS, including 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propanoate and 2,2,3-trifluor-3-[1,1,2,2,3,3-hexafluor-3-(trifluormethoxy)propoxy]-propanoate (anion of ADONA), were very low compared to regulated PFAS. The most frequently detected PFAS were examined for co-occurrences, but no definite correlations could be found.

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.

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.

Tire and road wear particles in road environment - Quantification and assessment of particle dynamics by Zn determination after density separation.

In this study, a method for the determination of tire and road wear particle (TRWP) contents in particulate samples from road environment was developed. Zn was identified as the most suitable elemental marker for TRWP, due to its high concentration in tire tread and the possibility of separation from other Zn sources. The mean concentration of 21 tire samples was 8.7 ± 2.0 mg Zn/g. Before quantification in samples from road environment, TRWP were separated from the particulate matrix by density separation. Method development was conducted using shredded tread particles (TP) as a surrogate for TRWP. Recovery of TP from spiked sediment was 95 ± 17% in a concentration range of 2 - 200 mg TP/g. TP determination was not affected by other Zn containing solids or spiked Zn-salts. By adjusting the density of the separation solution to 1.9 g/cm³, more than 90% of total TRWP were separated from the sample matrix. TRWP concentrations in particulate matter collected in two road runoff treatment systems ranged from 0.38 to 150 mg TRWP/g. Differences in quantified TRWP contents of the two systems indicate changes in particle dynamics due to ageing and aggregation processes. The developed method allows TRWP determination in road runoff and in environments that are influenced by road traffic. The validated separation procedure can also be applied for TRWP characterization in future studies.

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.

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).

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.

Competition in chromate adsorption onto micro-sized granular ferric hydroxide.

Hexavalent chromium is highly toxic and elaborate technology is necessary for ensured removal during drinking water production. The present study aimed at estimating the potential of a micro-sized iron hydroxide (µGFH] adsorbent for chromate removal in competition to ions presents in drinking water. Freundlich and Langmuir models were applied to describe the adsorption behaviour. The results show a high dependency on the pH value with increasing adsorption for decreasing pH values. The adsorption capacity in deionized water (DI) at pH 7 was 5.8 mg/g Cr(VI) while it decreased to 1.9 mg/g Cr(VI) in Berlin drinking water (DW) at initial concentrations of 1.2 mg/L. Desorption experiments showed reversible adsorption indicating ion exchange and outer sphere complexes as main removal mechanisms. Competing ions present in DW were tested for interfering effects on chromate adsorption. Bicarbonate was identified as main inhibitor of chromate adsorption. Sulfate, silicate and phosphate also decreased chromate loadings, while calcium enhanced chromate adsorption. Adsorption kinetics were highly dependent on particle size and adsorbent dose. Adsorption equilibrium was reached after 60 min for particles smaller than 63 µm, while 240 min were required for particles from 125 µm to 300 µm. Adsorption kinetics in single solute systems could be modelled using the homogeneous surface diffusion model (HSDM) with a surface diffusion coefficient of 4∙10 -14 m2/s. Competitive adsorption could be modelled using simple equations dependent on time, adsorption capacity and concentrations only.