Removal of micropollutants during tertiary wastewater treatment by biofiltration: Role of nitrifiers and removal mechanisms.

The objective of this study was to determine the extent to which a suite of organic micropollutants (MPs) can be removed by biological filtration and the role of bioavailability and ammonia oxidizing microorganisms (AOMs) in the biodegradation process. During approximately one year, laboratory-scale columns with 8 min empty bed contact time (EBCT) and packed with anthracite as filter media were used for treating a tertiary effluent spiked with a broad range of MPs at a target concentration of 2 µg L(-1). In parallel columns, aerobic biomass growth was inhibited by using either the biocide sodium azide (500 mg L(-1) NaN3) or allylthiourea (5 mg L(-1) ATU), specifically inhibiting nitrifying bacteria. Once the biomass had colonized the media, around 15% of the dissolved organic carbon (DOC) contained in the untreated tertiary effluent was removed by non-inhibited columns. The removal of several MPs increased over time indicating the relevance of biological activity for the removal of MPs, while the negative control, the NaN3 inhibited column, showed no significant removal. Out of 33 MPs, 19 were recalcitrant (<25%) to biodegradation under aerobic conditions with the others exhibiting a diverse range of removal efficiency up to 95%. Through inhibition by ATU it was shown that nitrifying bacteria were clearly having a role in the degradation of several MPs, whereas the removal of other MPs was not affected by the presence of the nitrification inhibitor. A relationship between the qualitative assessment of sorption of MPs on granular activated carbon (GAC) and their removal efficiency by biodegradation on anthracite was observed. This result suggested that the affinity of the MPs for GAC media could be a useful indicator of the bioavailability of compounds during biofiltration on anthracite.

Sorption and biodegradation of organic micropollutants during river bank filtration: a laboratory column study.

This study investigated sorption and biodegradation behaviour of 14 organic micropollutants (OMP) in soil columns representative of the first metre (oxic conditions) of the river bank filtration (RBF) process. Breakthrough curves were modelled to differentiate between OMP sorption and biodegradation. The main objective of this study was to investigate if the OMP biodegradation rate could be related to the physico-chemical properties (charge, hydrophobicity and molecular weight) or functional groups of the OMPs. Although trends were observed between charge or hydrophobicity and the biodegradation rate for charged compounds, a statistically significant linear relationship for the complete OMP mixture could not be obtained using these physico-chemical properties. However, a statistically significant relationship was obtained between biological degradation rates and the OMP functional groups. The presence of ethers and carbonyl groups will increase biodegradability, while the presence of amines, ring structures, aliphatic ethers and sulphur will decrease biodegradability. This predictive model based on functional groups can be used by drinking water companies to make a first estimate whether a newly detected compound will be biodegraded during the first metre of RBF or that additional treatment is required. In addition, the influence of active and inactive biomass (biosorption), sand grains and the water matrix on OMP sorption was found to be negligible under the conditions investigated in this study. Retardation factors for most compounds were close to 1, indicating mobile behaviour of these compounds during soil passage. Adaptation of the biomass towards the dosed OMPs was not observed for a 6 month period, implying that new developed RBF sites might not be able to biodegrade compounds such as atrazine and sulfamethoxazole in the first few months of operation.

Ozonation and biological activated carbon filtration of wastewater treatment plant effluents.

This study investigates the fate of trace organic chemicals (TrOCs) in three full-scale reclamation plants using ozonation followed by biological activated carbon (BAC) filtration to treat wastewater treatment plant effluents. Chemical analysis was used to quantify a wide range of TrOCs and combined with bioanalytical tools to assess non-specific toxicity (Microtox assay) and estrogenicity (E-SCREEN assay). Limited dissolved organic carbon (DOC) removal (<10%) was observed in the ozonation stages showing that oxidation leads to the formation of transformation products rather than mineralization. The quantified TrOCs were removed to a degree highly dependent on the compounds' structures and the specific ozone dose (mg(O3) mg(DOC)(-1)). Non-specific toxicity was reduced by 31-39%, demonstrating that the mixture of remaining parent compounds and their transformation products as well as newly formed oxidation by-products had an overall lower toxic potential than the mixture of parent compounds. Estrogenicity was reduced by more than 87% indicating that the transformation products of the estrogenic chemicals lost their specific toxicity potential. The subsequent BAC filtration removed between 20 and 50% of the DOC depending on the plant configuration, likely due to biodegradation of organic matter. The filtration was also able to reduce the concentrations of most of the remaining TrOCs by up to 99%, and reduce non-specific toxicity by 33-54%. Overall, the combination of ozonation and BAC filtration can achieve removals of 50% for DOC and more than 90% for a wide range of TrOCs as well as a reduction of 70% of non-specific toxicity and more than 95% of estrogenicity. This process combination is therefore suggested as an effective barrier to reduce the discharge of TrOCs into the environment or their presence in water recycling schemes.

Biofiltration of wastewater treatment plant effluent: effective removal of pharmaceuticals and personal care products and reduction of toxicity.

This study investigates biofiltration for the removal of dissolved organic carbon (DOC), pharmaceuticals and personal care products (PPCPs), and for the reduction of non-specific toxicity expressed as baseline toxicity equivalent concentration (baseline-TEQ). Two filtering media, sand and granular activated carbon, were tested. The influence of pre-ozonation and empty-bed contact time (EBCT, from 30 to 120 min) was determined. The experiments were performed at a pilot-scale with real WWTP effluent. A previous study showed that biological activity had developed on the filtering media and dissolved organic removal had reached a steady state before sampling commenced. The results show that biological activated carbon (BAC) has a good potential for the removal of DOC (35-60%), PPCPs (>90%) and baseline-TEQ (28-68%) even without pre-ozonation. On the contrary, the sand shows limited improvement of effluent quality. Varying the EBCT does not influence the performance of the BAC filters; however, dissolved oxygen concentration could be a limiting factor. The performances of the BAC filters were stable for over two years suggesting that the main mechanism of organic matter and PPCPs removal is biodegradation. It is concluded that BAC filtration without pre-ozonation could be implemented as a low cost advanced treatment option to improve WWTP effluent chemical quality.

Oxidation of nitrobenzene by ozone in the presence of faujasite zeolite in a continuous flow gas-liquid-solid reactor.

This work investigates the oxidation of nitrobenzene (NB) by ozone in the presence of faujasite zeolite. Experiments were carried out in a gas-liquid-solid reactor were ozone transfer and NB oxidation took place at the same time. Three configurations of the reactor were compared: empty, filled with inert glass beads and filled with faujasite pellets. First, ozone transfer coefficient (k(L)a) and decomposition rate constant (k(C)) were determined for each configuration. In presence of solid, k(L)a was 2.0 to 2.6 times higher and k(C) was 5.0 to 6.4 times higher compared to the empty reactor. Then, the various configurations were evaluated in terms of NB removal and chemical oxygen demand (COD) decrease. The faujasite reactor showed higher removal of NB and decrease of COD compared to other configurations under the same conditions suggesting that the faujasite increases the oxidation rate of NB. Oxidation of NB in presence of faujasite also proved to be limited by the transfer of ozone from the gas to the liquid phase.

Removal of micropollutants and reduction of biological activity in a full scale reclamation plant using ozonation and activated carbon filtration.

Pharmaceutical compounds are found in secondary treated effluents up to microg L(-1) levels and therefore discharged into surface waters. Since the long term effects of these compounds on the environment and human health are, to date, largely unknown, implementation of advanced treatment of wastewaters is envisaged to reduce their discharge. This is of particular relevance where surface waters are used as drinking water sources and when considering indirect potable reuse. This study aimed at assessing the removal of organic micropollutants and the concurrent reduction of their biological activity in a full scale reclamation plant treating secondary effluent. The treatment consists of 6 stages: denitrification, pre-ozonation, coagulation/flocculation/dissolved air flotation and filtration (DAFF), main ozonation, activated carbon filtration and final ozonation for disinfection. For that purpose, representative 24-hour composite samples were collected after each stage. The occurrence of 85 compounds was monitored by LC/MS-MS. A battery of 6 bioassays was also used as a complementary tool to evaluate non-specific toxicity and 5 specific toxic modes of action. Results show that, among the 54 micropollutants quantified in the influent water, 50 were removed to below their limit of quantification representing more than 90% of concentration reduction. Biological activity was reduced, depending on the specific response that was assessed, from a minimum of 62% (AhR response) to more than 99% (estrogenicity). The key processes responsible for the plant's performances were the coagulation/flocculation/DAFF, main ozonation and activated carbon filtration. The effect of these 3 processes varied from one compound or bioassay to another but their combination was almost totally responsible for the overall observed reduction. Bioassays yielded complementary information, e.g. estrogenic compounds were not detected in the secondary effluent by chemical analysis, but the samples had an estrogenic effect. The main ozonation formed oxidation by-products of the organic micropollutants but decreased the level of non-specific toxicity and other specific toxic modes of action, demonstrating that the mixture of oxidation by-products was less potent than the mixture of the parent compounds for the considered effects.

Monitoring the biological activity of micropollutants during advanced wastewater treatment with ozonation and activated carbon filtration.

A bioanalytical test battery was used to monitor the removal efficiency of organic micropollutants during advanced wastewater treatment in the South Caboolture Water Reclamation Plant, Queensland, Australia. This plant treats effluent from a conventional sewage treatment plant for industrial water reuse. The aqueous samples were enriched using solid-phase extraction to separate some organic micropollutants of interest from metals, nutrients and matrix components. The bioassays were chosen to provide information on groups of chemicals with a common mode of toxic action. Therefore they can be considered as sum indicators to detect certain relevant groups of chemicals, not as the most ecologically or human health relevant endpoints. The baseline toxicity was quantified with the bioluminescence inhibition test using the marine bacterium Vibrio fischeri. The specific modes of toxic action that were targeted with five additional bioassays included aspects of estrogenicity, dioxin-like activity, genotoxicity, neurotoxicity, and phytotoxicity. While the accompanying publication discusses the treatment steps in more detail by drawing from the results of chemical analysis as well as the bioanalytical results, here we focus on the applicability and limitations of using bioassays for the purpose of determining the treatment efficacy of advanced water treatment and for water quality assessment in general. Results are reported in toxic equivalent concentrations (TEQ), that is, the concentration of a reference compound required to elicit the same response as the unknown and unidentified mixture of micropollutants actually present. TEQ proved to be useful and easily communicable despite some limitations and uncertainties in their derivation based on the mixture toxicity theory. The results obtained were reproducible, robust and sensitive. The TEQ in the influent ranged in the same order of magnitude as typically seen in effluents of conventional sewage treatment plants. In the initial steps of the treatment chain, no significant degradation of micropollutants was observed, and the high levels of dissolved organic carbon probably affected the outcome of the bioassays. The steps of coagulation/flocculation/dissolved air flotation/sand filtration and ozonation decreased the effect-based micropollutant burden significantly.