Alexander Sperlich

Predicting anion breakthrough in granular ferric hydroxide (GFH) adsorption filters

Adsorption of arsenate, phosphate, salicylic acid, and groundwater DOC onto granular ferric hydroxide (GFH) was studied in batch and column experiments. Breakthrough curves were experimentally determined and modelled using the homogeneous surface diffusion model (HSDM) and two of its derivatives, the constant pattern homogeneous surface diffusion model (CPHSDM) and the linear driving force model (LDF). Input parameters, the Freundlich isotherm constants, and mass transfer coefficients for liquid- and solid-phase diffusion were determined and analysed for their influence on the shape of the breakthrough curve. HSDM simulation results predict the breakthrough of all investigated substances satisfactorily, but LDF and CPHSDM could not describe arsenate breakthrough correctly. This is due to a very slow intraparticle diffusion and hence higher Biot numbers. Based on this observation, limits of applicability were defined for LDF and CPHSDM. When designing fixed-bed adsorbers, model selection based on known or estimated Biot and Stanton numbers is possible.

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.

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.

Treatment of membrane concentrates: phosphate removal and reduction of scaling potential

The widespread application of nanofiltration (NF) and reverse osmosis (RO) membranes in wastewater reuse inevitably generates a concentrate stream. Due to high concentrations of phosphate and salts, disposal of membrane concentrates is a problem which seriously constrains the application of this technology, especially in inland applications. There is a need for technologies which facilitate an affordable and environmentally-safe disposal of membrane concentrates. The objectives of this study are to investigate appropriate treatment techniques to (1) increase the recovery of the membrane filtration thus minimising the volume of the concentrate stream, and (2) increase the concentrate quality to enable discharge into surface water bodies. The results show that both adsorption onto granular ferric hydroxide (GFH) and chemical precipitation are generally effective for phosphate removal from NF concentrates. Chemical precipitation by dosing of sodium hydroxide solution is rapid and removes more than 90% of phosphate and calcium ions. By the removal of calcium ions, chemical precipitation can significantly reduce the scaling potential of NF and RO concentrates. This may allow higher recoveries in the NF/RO process.

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.

An integrated wastewater reuse concept combining natural reclamation techniques, membrane filtration and metal oxide adsorption

In a Sino-German research project, a sustainable water reclamation concept was developed for different applications of municipal water reuse at the Olympic Green 2008 in Beijing, China. Results from pilot-scale experiments in Beijing and Berlin show that selective nutrient removal by adsorption onto granular ferric hydroxide (GFH) after a membrane bioreactor (MBR) can maintain a total phosphorus concentration of <0.03 microg L(-1) P, thus preventing eutrophication of artificial lakes. Operation time of GFH adsorption columns can be extended by regeneration using sodium hydroxide solution. A subsequent ultrafiltration (UF) membrane after bank filtration creates an additional barrier for pathogens and allows for further urban reuse applications such as toilet flushing. Short term bank / bio-filtration prior to UF is shown to effectively remove biopolymers and reduce membrane fouling.

Pilot-scale study of powdered activated carbon recirculation for micropollutant removal

Adsorption onto powdered activated carbon (PAC) is a promising technique for the removal of organic micropollutants (OMPs) from treated wastewater. To enhance the adsorption efficiency, PAC is recycled back into the adsorption stage. This technique was examined in pilot scale in comparison to a reference without recirculation. Coagulation with Fe(3+) was carried out simultaneously to adsorption. Extensive OMP measurements showed that recirculation significantly increased OMP eliminations. Thus, significant PAC savings were feasible. The PAC concentration in the contact reactor proved to be an important operating parameter that can be surrogated by the easily measurable total suspended solids (TSS) concentration. OMP eliminations increased with increasing TSS concentrations. At 20 mg PAC L(-1) and 2.8 g TSS L(-1) in the contact reactor, well-adsorbable carbamazepine was eliminated by 97%, moderately adsorbable diclofenac was eliminated by 92% and poorly-adsorbable acesulfame was eliminated by 54% in comparison to 49%, 35% and 18%, respectively, without recirculation. The recirculation system represents an efficient technique, as the PACs adsorption capacity is practically completely used. Small PAC dosages yield high OMP eliminations. Poorly-adsorbable gabapentin was eliminated to an unexpectedly high degree. A laboratory-scale biomass inhibition study showed that aerobic biodegradation removed gabapentin in addition to adsorption.

Stratification of Granular Activated Carbon Filters for Advanced Wastewater Treatment

Advanced wastewater treatment with granular activated carbon (GAC) is a promising option to reduce emissions of organic micropollutants (OMP) into the aquatic environment. Frequent back-washes of the GAC filters are required due to high particle concentration in the treated wastewater but lead to stratification. Differences in adsorption capacities of individual strata are not known. The present study aimed at investigating physical and chemical differences at different filter depths of a stratified GAC filter. Two different commercial products were stratified during repeated filter bed expansions and sectioned into vertical fractions. Bulk densities, grain size distributions and ash contents of the individual fractions differed significantly. Adsorption tests with pulverized GAC from different levels showed great vertical differences in adsorption properties. OMP removals determined in the upper part of a GAC filter therefore cannot be extrapolated downwards. Both physical and chemical vertical heterogeneities with regard to adsorption capacities and residence times at different filter depths should be considered in the filter design, in the monitoring of a GAC filter, and in the interpretation of the GAC filter performance. Good correlations between abatements of UV light absorption and OMP removals were found for the virgin GAC throughout the non-uniform filter.