Aki Sebastian Ruhl

Selection of organic process and source indicator substances for the anthropogenically influenced water cycle

An increasing number of organic micropollutants (OMP) is detected in anthropogenically influenced water cycles. Source control and effective natural and technical barriers are essential to maintain a high quality of drinking water resources under these circumstances. Based on the literature and our own research this study proposes a limited number of OMP that can serve as indicator substances for the major sources of OMP, such as wastewater treatment plants, agriculture and surface runoff. Furthermore functional indicators are proposed that allow assessment of the proper function of natural and technical barriers in the aquatic environment, namely conventional municipal wastewater treatment, advanced treatment (ozonation, activated carbon), bank filtration and soil aquifer treatment as well as self-purification in surface water. These indicator substances include the artificial sweetener acesulfame, the anti-inflammatory drug ibuprofen, the anticonvulsant carbamazepine, the corrosion inhibitor benzotriazole and the herbicide mecoprop among others. The chemical indicator substances are intended to support comparisons between watersheds and technical and natural processes independent of specific water cycles and to reduce efforts and costs of chemical analyses without losing essential information.

Pilot-scale investigation of drinking water ultrafiltration membrane fouling rates using advanced data analysis techniques.

A pilot-scale investigation of the performance of biofiltration as a pre-treatment to ultrafiltration for drinking water treatment was conducted between 2008 and 2010. The objective of this study was to further understand the fouling behaviour of ultrafiltration at pilot scale and assess the utility of different foulant monitoring tools. Various fractions of natural organic matter (NOM) and colloidal/particulate matter of raw water, biofilter effluents, and membrane permeate were characterized by employing two advanced NOM characterization techniques: liquid chromatography - organic carbon detection (LC-OCD) and fluorescence excitation-emission matrices (FEEM) combined with principal component analysis (PCA). A framework of fouling rate quantification and classification was also developed and utilized in this study. In cases such as the present one where raw water quality and therefore fouling potential vary substantially, such classification can be considered essential for proper data interpretation. The individual and combined contributions of various NOM fractions and colloidal/particulate matter to hydraulically reversible and irreversible fouling were investigated using various multivariate statistical analysis techniques. Protein-like substances and biopolymers were identified as major contributors to both reversible and irreversible fouling, whereas colloidal/particulate matter can alleviate the extent of irreversible fouling. Humic-like substances contributed little to either reversible or irreversible fouling at low level fouling rates. The complementary nature of FEEM-PCA and LC-OCD for assessing the fouling potential of complex water matrices was also illustrated by this pilot-scale study.

Impact of EfOM size on competition in activated carbon adsorption of organic micro-pollutants from treated wastewater.

The competitive impacts of different fractions of wastewater treatment plant effluent organic matter (EfOM) on organic micro-pollutant (OMP) adsorption were investigated. The fractionation was accomplished using separation by nanofiltration (NF). The waters resulting from NF were additionally treated to obtain the same dissolved organic carbon (DOC) concentrations as the initial water. Using size exclusion chromatography (LC-OCD) it could be shown that the NF treatment resulted in an EfOM separation by size. Adsorption tests showed different competitive effects of the EfOM fractions with the OMP. While large EfOM compounds that were retained in NF demonstrated a reduced competition as compared to the raw water, the NF-permeating EfOM compounds showed an increased competition with the majority of the measured OMP. The effects of small size EfOM are particularly negative for OMP which are weak/moderate adsorbates. Adsorption analysis was carried out for the differently fractionized waters. The small sized EfOM contain better adsorbable compounds than the raw water while the large EfOM are less adsorbable. This explains the observed differences in the EfOM competitiveness. The equivalent background compound (EBC) model was applied to model competitive adsorption between OMP and EfOM and showed that the negative impacts of EfOM on OMP adsorption increase with decreasing size of the EfOM fractions. The results suggest that direct competition for adsorption sites on the internal surface of the activated carbon is more substantial than indirect competition due to pore access restriction by blockage. Another explication for reduced competition by large EfOM compounds could be the inability to enter and block the pores due to size exclusion.

Anthropogenic organic micro-pollutants and pathogens in the urban water cycle: assessment, barriers and risk communication (ASKURIS)

In urban areas, water often flows along a partially closed water cycle in which treated municipal wastewater is discharged into surface waters which are one source of raw waters used for drinking water supply. A number of organic micro-pollutants (OMP) can be found in different water compartments. In the near future, climatic and demographic changes will probably contribute to an increase of OMP and antibiotic-resistant pathogens in aquatic ecosystems. The occurrence of OMP, possible adverse effects on aquatic organisms and human health and the public perception must be carefully assessed to properly manage and communicate potentially associated risks and to implement appropriate advanced treatment options at the optimum location within the water cycle. Therefore, the interdisciplinary research project ASKURIS focuses on identification and quantification, toxicological assessment and removal of organic micro-pollutants and antibiotic-resistant pathogens in the Berlin water cycle, life cycle-based economic and environmental assessment, public perception and management of potential risks.

Pilot-Scale Investigation of Micropollutant Removal with Granular and Powdered Activated Carbon

Activated carbon is investigated as adsorptive barrier for organic micropollutants (OMP) within the Berlin water cycle. In a pilot plant using granular activated carbon (GAC) as upper layer in dual-media filtration, OMP concentrations in treated wastewater could be reduced without any negative impact on filtration efficiency. OMP breakthroughs occurred after shorter runtimes than estimated according to isotherm experiments with powdered activated carbon (PAC). Batch adsorption tests comparing the used GAC to new GAC showed that the capacity of the used GAC was not exhausted, indicating that besides direct site competition, pore blocking is also responsible for the poor GAC performance. A pilot plant application of PAC of the same type as GAC showed significantly higher OMP removals at lower dosages, taking advantage of immobilization of PAC particles in the filters. Both PAC and GAC applications can be integrated into tertiary wastewater treatment without significant constructional changes.

Influence of dissolved inorganic carbon and calcium on gas formation and accumulation in iron permeable reactive barriers.

Uncertainties in long-term reactivity and gas accumulation in Fe(0) permeable reactive barriers still hinder a broad application of this groundwater remediation technology. In this study long-term column experiments were conducted under varying geochemical conditions. Generation of hydrogen by anaerobic corrosion in Fe(0) reactive filters was mainly influenced by the mass flux of dissolved inorganic carbon. Both increased concentrations and volume flows led to a substantial rise in gas generation but only to slight differences of gas accumulation within the pores of the reactive filter. Comparisons of columns with different lengths showed higher averaged corrosion rates in the shorter and lower corrosion rates in the longer columns. Calcium in conjunction with dissolved inorganic carbon formed compact and localized aragonite minerals, while in the absence of calcium chukanovite dominated, which covered and passivated the reactive surface to a higher extent. Magnetite was the major crystalline corrosion product in the absence of carbonate and no decline in long term corrosion rates was observed within up to 700 days of operation. Total gas yields of columns were restricted by passivation and approached a volume of approximately 13.5 mL/g granulated cast iron.

Impacts of coagulation on the adsorption of organic micropollutants onto powdered activated carbon in treated domestic wastewater

The application of powdered activated carbon (PAC) as an advanced wastewater treatment step for the removal of organic micropollutants (OMP) necessitates complete separation of the PAC particles, e.g. by coagulation. In this study, potential positive or negative indirect or direct effects of coagulation on the adsorption of OMPs onto PAC in treated wastewater were investigated. Although the concentration of dissolved organic matter (DOM) was significantly reduced by coagulation, the selective removal of mainly larger DOM components such as biopolymers and humic substances did not improve subsequent OMP adsorption onto PAC, demonstrating that coagulation has minor effects on DOM constituents that are relevant for direct competition or pore blocking. The combination of coagulation and adsorption yielded the sum of the individual removals, as adsorption predominantly affected smaller compounds. While the formation of flocs led to visible incorporation of PAC particles, no significant mass transfer limitations impeded the OMP adsorption. As a result, the dosing sequence of coagulant and PAC is not critical for efficient adsorption of OMPs onto PAC. The relationships between adsorptive OMP removal and corresponding reduction of UV absorption at 254 nm (UVA254) as a promising surrogate correlation for the real-time monitoring and PAC adjustment were affected by coagulation, leading to individual correlations depending on the water composition. Correcting for UVA254 reduction by coagulation produces adsorptive UVA254 removal, which correlates highly with OMP removal for different WWTP effluents and varying coagulant doses and can be applied in combined adsorption/coagulation processes to predict OMP removal and control PAC dosing.

Rapid small-scale column testing of granular activated carbon for organic micro-pollutant removal in treated domestic wastewater.

This study investigates the applicability of the rapid small-scale column test (RSSCT) concept for testing of granular activated carbon (GAC) for organic micro-pollutants (OMPs) removal from wastewater treatment plant (WWTP) effluent. The chosen experimental setup was checked using pure water, WWTP effluent, different GAC products, and variable hydrodynamic conditions with different flow velocities and differently sized GAC, as well as different empty bed contact times (EBCTs). The setup results in satisfying reproducibility and robustness. RSSCTs in combination with WWTP effluent are effective when comparing the OMP removal potentials of different GAC products and are a useful tool for the estimation of larger filters. Due to the potentially high competition between OMPs and bulk organics, breakthrough curves are likely to have unfavorable shapes when treating WWTP effluent. This effect can be counteracted by extending the EBCT. With respect to the strong competition observed in GAC treatment of WWTP effluent, the small organic acid and neutral substances are retained longer in the RSSCT filters and are likely to cause the majority of the observed adsorption competition with OMPs.

How to dose powdered activated carbon in deep bed filtration for efficient micropollutant removal

Direct addition of powdered activated carbon (PAC) to the inlet of a deep bed filter represents an energy- and space-saving option to remove organic micropollutants (OMPs) during advanced wastewater treatment or drinking water purification. In this lab-scale study, continuous dosing, preconditioning a filter with PAC and combinations thereof were investigated as possible dosing modes with respect to OMP adsorption efficiency. Continuous dosing resulted in decreasing effluent concentrations with increasing filter runtime due to adsorption onto accumulating PAC in the filter bed. Approximately constant removal levels were achieved at longer filter runtimes, which were mainly determined by the dose of fresh PAC, rather than the total PAC amount embedded. The highest effluent concentrations were observed during the initial filtration stage. Meanwhile, preconditioning led to complete OMP adsorption at the beginning of filtration and subsequent gradual OMP breakthrough. PAC distribution in the pumice filter was determined by the loss on ignition of PAC and pumice and was shown to be relevant for adsorption efficiency. Preconditioning with turbulent upflow led to a homogenous PAC distribution and improved OMP adsorption significantly. Combining partial preconditioning and continuous dosing led to low initial effluent concentrations, but ultimately achieved concentrations similar to filter runs without preconditioning. Furthermore, a dosing stop prior to the end of filtration was suitable to increase PAC efficiency without affecting overall OMP removals.

Impacts of backwashing on granular activated carbon filters for advanced wastewater treatment.

The use of granular activated carbon (GAC) in fixed bed filters is a promising option for the removal of organic micropollutants (OMP) from wastewater treatment plant effluents. Frequent backwashing of the filter bed is inevitable, but its effect on potential filter stratification is not well understood yet and thus has been evaluated in the present study for two commercial GAC products. Backwashing of GAC filters was simulated with 10 or 100 filter bed expansions of 20 or 100% at backwash velocities of 12 and 40 m/h, respectively. Five vertical fractions were extracted and revealed a vertical stratification according to grain sizes and material densities. Sieve analyses indicated increasing grain sizes towards the bottom for one GAC while grain sizes of the other GAC were more homogeneously distributed throughout the filter bed. The apparent densities of the top sections were significantly lower than that of the bottom sections of both products. Comparative long term fixed bed adsorption experiments with the top and bottom sections of the stratified GAC showed remarkable differences in breakthrough curves of dissolved organic carbon, UV light absorption at 254 nm wavelength (UVA254) and OMP. GAC from the upper section showed constantly better removal efficiencies than GAC from the bottom section, especially for weakly adsorbing OMP such as sulfamethoxazole. Furthermore correlations between UVA254 reductions and OMP removals were found.