Michael Chys

A comparative study on the efficiency of ozonation and coagulation–flocculation as pretreatment to activated carbon adsorption of biologically stabilized landfill leachate

The present work investigates the potential of coagulation-flocculation and ozonation to pretreat biologically stabilized landfill leachate before granular activated carbon (GAC) adsorption. Both iron (III) chloride (FeCl3) and polyaluminium chloride (PACl) are investigated as coagulants. Better organic matter removal is observed when leachate was treated with FeCl3. At a dose of 1mg FeCl3/mg CODo (CODo: initial COD content), the COD and α254 removal was 66% and 88%, respectively. Dosing 1mg PACl/mg CODo resulted in 44% COD and 72% α254 removal. The settle-ability of sludge generated by PACl leveled off at 252mL/g, while a better settle-ability of 154mL/g was obtained for FeCl3 after dosing 1mg coagulant/mg CODo. For ozonation, the percentage of COD and α254 removal increased as the initial COD concentration decreased. Respectively 44% COD and 77% α254 removal was observed at 112mg COD/L compared to 5% COD and 26% α254 removal at 1846mg COD/L. Subsequent activated carbon adsorption of ozonated, coagulated and untreated leachate resulted in 77%, 53% and 8% total COD removal after treatment of 6 bed volumes. Clearly showing the benefit of treating the leachate before GAC adsorption. Mathematical modeling of the experimental GAC adsorption data with Thomas and Yoon-Nelson models show that ozonation increases the adsorption capacity and breakthrough time of GAC by a factor of 2.5 compared to coagulation-flocculation.

Treatment of rainwater runoff in recovery and recycling companies: Lab and pilot-scale testing

Wastewater released from the storage and/or processing of recycling and materials recovery can be characterised as rainwater runoff. Recuperation and recycling companies are confronted with wastewater that has a very fluctuating flow rate and composition. The flow rate mainly depends on the amount of rainfall while the composition additionally depends on what is currently stored on site. An analysis of possible physical-chemical treatment (coagulation/flocculation, sand filtration, activated carbon filtration and sedimentation) methods was performed at two different recycling companies in order to find a robust and economical feasible water treatment system that meets the discharge limits at all times. A violation of some measurement values (Cd, Cr, Ni and acenaphthene) after coagulation/flocculation occurred, which could be further reduced by using sand filtration. Good removal is achieved for common parameters as for mono- and poly-aromatic hydrocarbons (MAH and PAH) and polychlorinated biphenyls (PCB). Applying a coupled sand- and activated carbon filtration on runoff resulted in a removal of over 80% of several measurement values (suspended solids, heavy metals). This clearly indicates the applicability of the physical-chemical treatment techniques.

Leaching behaviour of different scrap materials at recovery and recycling companies: full-, pilot- and lab-scale investigation.

Scrap material recovery and recycling companies are confronted with waste water that has a highly fluctuating flow rate and composition. Common pollutants, such as COD, nutrients and suspended solids, potentially toxic metals, polyaromatic hydrocarbons and poly chlorinated biphenyls can exceed the discharge limits. An analysis of the leaching behaviour of different scrap materials and scrap yard sweepings was performed at full-scale, pilot-scale and lab-scale in order to find possible preventive solutions for this waste water problem. The results of these leaching tests (with concentrations that frequently exceeded the Flemish discharge limits) showed the importance of regular sweeping campaigns at the company, leak proof or covered storage of specific scrap materials and oil/water separation on particular leachates. The particulate versus dissolved fraction was also studied for the pollutants. For example, up to 98% of the polyaromatic hydrocarbons, poly chlorinated biphenyls and some metals were in the particulate form. This confirms the (potential) applicability of sedimentation and filtration techniques for the treatment of the majority of the leachates, and as such the rainwater run-off as a whole.

Performance and kinetic process analysis of an Anammox reactor in view of application for landfill leachate treatment

Anammox has shown its promise and low cost for removing nitrogen from high strength wastewater such as landfill leachate. A reactor was inoculated with nitrification–denitrification sludge originating from a landfill leachate treating waste water treatment plant. During the operation, the sludge gradually converted into red Anammox granular sludge with high and stable Anammox activity. At a maximal nitrogen loading rate of 0.6 g N l−1 d−1, the reactor presented ammonium and nitrite removal efficiencies of above 90%. In addition, a modified Stover–Kincannon model was applied to simulate and assess the performance of the Anammox reactor. The Stover–Kincannon model was appropriate for the description of the nitrogen removal in the reactor with the high regression coefficient values (R2=0.946) and low Theils inequality coefficient (TIC) values (TIC<0.3). The model results showed that the maximal N loading rate of the reactor should be 3.69 g N l−1 d−1.

Surrogate-Based Correlation Models in View of Real-Time Control of Ozonation of Secondary Treated Municipal Wastewater—Model Development and Dynamic Validation

New robust correlation models for real-time monitoring and control of trace organic contaminant (TrOC) removal by ozonation are presented, based on UVA254 and fluorescence surrogates, and developed considering kinetic information. The abatement patterns of TrOCs had inflected shapes, controlled by the reactivity of TrOCs toward ozone and HO• radicals. These novel and generic correlation models will be of importance for WRRF operators to reduce operational costs and minimize byproduct formation. Both UVA254 and fluorescence surrogates could be used to control ΔTrOC, although fluorescence measurements indicated a slightly better reproducibility and an enlarged control range. The generic framework was validated for several WRRFs and correlations for any compound with known kinetic information could be developed solely using the second order reaction rate constant with ozone (kO3). Two distinct reaction phases were defined for which separate linear correlations were obtained. The first was mainly ozone controlled, while the second phase was more related to HO• reactions. Furthermore, parallel factor analysis of the fluorescence spectra enabled monitoring of multiple types of organic matter with different O3 and HO• reactivity. This knowledge is of value for kinetic modeling frameworks and for achieving a better understanding of the occurring changes of organic matter during ozonation.

Physical-chemical treatment of rainwater runoff in recovery and recycling companies: pilot-scale optimization

Pilot-scale optimisation of different possible physical-chemical water treatment techniques was performed on the wastewater originating from three different recovery and recycling companies in order to select a (combination of) technique(s) for further full-scale implementation. This implementation is necessary to reduce the concentration of both common pollutants (such as COD, nutrients and suspended solids) and potentially toxic metals, polyaromatic hydrocarbons and poly-chlorinated biphenyls frequently below the discharge limits. The pilot-scale tests (at 250 L h−1 scale) demonstrate that sand anthracite filtration or coagulation/flocculation are interesting as first treatment techniques with removal efficiencies of about 19% to 66% (sand anthracite filtration), respectively 18% to 60% (coagulation/flocculation) for the above mentioned pollutants (metals, polyaromatic hydrocarbons and poly chlorinated biphenyls). If a second treatment step is required, the implementation of an activated carbon filter is recommended (about 46% to 86% additional removal is obtained).

Dynamic validation of online applied and surrogate-based models for tertiary ozonation on pilot-scale

New robust correlation models for ozonation, based on UVA254 and fluorescence surrogate parameters and developed considering kinetic information, have been applied at pilot-scale. This model framework is validated with the aim for operators to control the ozone dose for the removal of trace organic contaminants (TrOCs) in effluents from full-scale municipal wastewater treatment plants. The inflected correlation model between ΔTrOCs and the surrogates predicts the removal of TrOCs (based on statistical evidence) solely using the 2nd order reaction rate constant with ozone (kO3) and in a more adequate manner than similar single correlation models. This allows the use of this new model for current and future TrOCs under investigation which is highly interesting when imposed discharge limits might include more and other TrOCs in future. The use of UVA254 might be preferable at the current timing for online monitoring of TrOC abatement as the model showed a good predictive power (based on statistical evidence and visual confirmation). Reliable online sensors are more widespread (and commercially) available compared to fluorescence sensors which are still under development, with the exception of a few examples. Nevertheless, the data processing of the fluorescence signals, isolating the different intensities associated with moieties reacting similarly to ozone might even increase the predictive power, given the lower degree of interference (i.e. less scattering).

Effect of oxidation and catalytic reduction of trace organic contaminants on their activated carbon adsorption

The combination of ozonation and activated carbon (AC) adsorption is an established technology for removal of trace organic contaminants (TrOCs). In contrast to oxidation, reduction of TrOCs has recently gained attention as well, however less attention has gone to the combination of reduction with AC adsorption. In addition, no literature has compared the removal behavior of reduction vs. ozonation by-products by AC. In this study, the effect of pre-ozonation vs pre-catalytic reduction on the AC adsorption efficiency of five TrOCs and their by-products was compared. All compounds were susceptible to oxidation and reduction, however the catalytic reductive treatment proved to be a slower reaction than ozonation. New oxidation products were identified for dinoseb and new reduction products were identified for carbamazepine, bromoxynil and dinoseb. In terms of compatibility with AC adsorption, the influence of the oxidative and reductive pretreatments proved to be compound dependent. Oxidation products of bromoxynil and diatrizoic acid adsorbed better than their parent TrOCs, but oxidation products of atrazine, carbamazepine and dinoseb showed a decreased adsorption. The reductive pre-treatment showed an enhanced AC adsorption for dinoseb and a major enhancement for diatrizoic acid. For atrazine and bromoxynil, no clear influence on adsorption was noted, while for carbamazepine, the reductive pretreatment resulted in a decreased AC affinity. It may thus be concluded that when targeting mixtures of TrOCs, a trade-off will undoubtedly have to be made towards overall reactivity and removal of the different constituents, since no single treatment proves to be superior to the other.

Municipal wastewater effluent characterization and variability analysis in view of an ozone dose control strategy during tertiary treatment : the status in Belgium

Ozonation is known for removing trace organic contaminants (TrOCs) from secondary wastewater effluent. However, its implementation and overall efficiency on a broad scale depends on effluent characteristics, which can differ both in time as well as between different treatment plants (nowadays referred to as water resource recovery facilities (WRRFs)). Therefore, water quality was assessed over time at 15 different Belgian sampling locations to increase the understanding of effluent variability in view of online control of the tertiary ozonation step. Conventional and surrogate parameters as well as those specifically related to tertiary ozonation (e.g. instantaneous ozone demand) were assessed. Little differences between the different locations were found for spectral measurements (e.g. UVA254 or fluorescence). The small amount of observed outliers was clearly site or event dependent. A lower variability (for spectral measurements) is advantageous in simplifying the development and application of a generic control framework based on these spectral measurements. In addition, also variations in TrOC concentration levels seemed to be small, as the concentration of most individual compounds resided within one order of magnitude over multiple sampling events at two different WRRFs. The combination of this low variability in TrOC levels in the effluent before ozonation with a control strategy using a TrOC removal efficiency set-point, allows to indicatively assess absolute TrOC levels after ozonation. In contrast, significant variations between different plants (especially smaller sized plants) were observed and could be related to the conventional water quality parameters alkalinity (correlated with the electrical conductivity) and pH which are both known to have an influence on the ozonation process. This confirms that a differential dosing control strategy (i.e. accounting for the matrix reactivity) should be applied instead of one solely based on the (organic) effluent load before ozonation.

Combining ozone with UV and H2O2 for the degradation of micropollutants from different origins: lab-scale analysis and optimization

ABSTRACT The degradation of micropollutants (MPs), including pesticides, herbicides, pharmaceuticals and endocrine disrupting compounds, by ozone-based advanced oxidation techniques (AOP) was investigated in this study. The effect of different factors, such as ozone concentration, hydrogen peroxide concentration and initial pH, on the removal rate was studied in detail. The combination of UV with ozone/ H2O2 increased the MPs degradation. For example, atrazine removal increased from 12.6% to 66.9%. Increasing the concentration of ozone and H2O2 can enhance the degradation efficiency of MPs, while excess H2O2 plays a role as a scavenger for •OH. In addition, the optimizing conditions of degradation of MPs by an ozone-based AOP were investigated in this study. The optimal dosages of ozone for atrazine (ATZ), alachlor (ALA), carbamazepine (CBZ), 17-α-ethinylestradiol (EE2) and pentachlorophenol (PCP), were in the range of 0.6–0.75, while for ATZ a much higher dosage (5.4 mg/l) is needed. The optimal dosages of H2O2 concentration were at 0.75, 0.2, 0.47, 0.75 and 0.63 mM, and pH were at 10, 10, 7, 10 and 10, and reaction time at 38.5, 33.5 43, 6 and 6 min, respectively. Ozone-based AOP and in particular combination of UV with ozone and H2O2 is efficient to degrade atrazine, alachlor, carbamazepine, 17-α-ethinylestradiol and pentachlorophenol, and is attractive for future application of real wastewater treatment. GRAPHICAL ABSTRACT