Fluorescence excitation/emission matrices as a tool to monitor the removal of organic micropollutants from wastewater effluents by adsorption onto activated carbon.

Monitoring the removal of organic micropollutants (OMPs) in advanced wastewater treatment facilities requires expensive and time-consuming analytical methods that cannot be installed online. Spectroscopic techniques such as fluorescence excitation/emission spectroscopy were demonstrated to offer the potential for monitoring OMPs removal in conventional wastewater treatment plants or ozonation pilots but their application to activated carbon (AC) adsorption processes was only investigated at lab scale and not in real treatment facilities. In this study, indexes from fluorescence emission/excitation matrices (EEMs) were used to find correlations with the removal of 28 OMPs from a large-scale AC pilot in fluidized bed employed for wastewater advanced treatment, as well as from batch experiments. Differences in OMPs removal could be observed depending on the operational conditions (i.e. pilot or batch experiments, contact time, type of AC) and the physico-chemical properties of the molecules. 7 PARAFAC components were derived from the fluorescence EEMs of 60 samples obtained before and after adsorption. Positive correlations were obtained between the removal of fluorescence indexes and most OMPs, and correlation coefficients were much higher than the ones obtained with UV254, confirming the interesting potential of fluorescence spectroscopy to accurately monitor adsorption performances at the industrial scale. The highest correlation coefficients were obtained for OMPs having the best removals while the ones that were refractory to adsorption, as well as to interactions with DOM, exhibited weak correlations. These results suggest that interactions between OMPs and fluorescing DOM and their subsequent co-adsorption onto AC were at the origin of the correlations found. Lower correlations were also found for the most biodegradable OMPs, which indicated that the occurrence of biological effects could make the monitoring of these compounds more challenging.

Influence of dissolved organic matter on the removal of 12 organic micropollutants from wastewater effluent by powdered activated carbon adsorption.

The presence of dissolved organic matter (DOM) in wastewater effluents is recognized as the main factor limiting the adsorption of organic micropollutants (OMPs) onto activated carbon. The degree of the negative effect that DOM, depending on its quality, exerts on OMPs adsorption is still unclear. The influence of the interactions between DOM and OMPs on their removal is also not fully understood. Adsorption isotherms and conventional batch tests were performed in ultra-pure water and in wastewater effluent to study the influence of DOM on the adsorption of 12 OMPs onto powdered activated carbon. Best fit of adsorption pseudo-isotherms was obtained with the Freundlich equation and showed, as expected, that OMPs adsorption was higher in ultra-pure water than in wastewater effluent due to the presence of DOM leading to pore blockage and competition for adsorption sites. LC-OCD analysis revealed that biopolymers and hydrophobic molecules were the most adsorbed fractions while humic acids were not removed after a contact time of either 30 min or 72 h. The presence of DOM had a negative impact on the removal of all OMPs after 30 min of adsorption, but similar removals to ultra-pure water were obtained for 6 OMPs after 72 h of adsorption. This demonstrated that competition between DOM and OMPs for adsorption sites was not a major mechanism as compared to pore blockage, which only slowed down the adsorption and did not prevent it. The charge of OMPs had a clear impact: the adsorption of negatively charged compounds was reduced in the presence of wastewater effluent due to repulsive electrostatic interactions with the adsorbed DOM and the PAC surface. On the other hand, the removal of positively charged compounds was improved. A 24 h pre-equilibrium between OMPs and DOM improved their removal onto PAC, which suggest that OMPs and DOM interacted in solution which decreased the negative effects caused by the presence of DOM, e.g. through co-adsorption of an OMP-DOM complex.

Influence of the properties of 7 micro-grain activated carbons on organic micropollutants removal from wastewater effluent.

Most studies dedicated to organic micropollutants (OMPs) removal from wastewater effluents by adsorption onto activated carbon (AC) only consider a few conventional AC properties. The link between OMPs removal and these properties is often missing, which limits the understanding of the adsorption process and the interpretation of the results. The chemical, physical and textural properties of seven newly commercialized micro-grain activated carbons (µGACs) were determined to assess their influence on the removal of 28 OMPs. Conventional batch tests with wastewater effluent showed that a high percentage of microporous volume (>65%) was detrimental for the removal of 10 OMPs, probably due to a higher blockage of micropores by dissolved organic matter (DOM). The removal of 5 OMPs was correlated with µGACs surface chemistry properties (i.e. charge) which were potentially modified by DOM adsorption or inorganic species, thus favoring the adsorption of positively-charged compounds. A combination of OMPs properties including their charge, hydrophobicity and minimal projection area could explain their removal. Correlations were found between the removal of several OMPs and UV254, suggesting that DOM and OMPs interacted with each other or followed similar adsorption mechanisms. A decrease in µGACs particle size had a positive impact on UV254 removal under continuous-flow conditions in columns representative of a large-scale pilot due to better expansion.

Benefits of ozonation before activated carbon adsorption for the removal of organic micropollutants from wastewater effluents.

Advanced processes for the removal of organic micropollutants (OMPs) from wastewater effluents include adsorption onto activated carbon, ozonation, or a combination of both processes. The removal of 28 OMPs present in a real wastewater effluent was studied by ozonation coupled to activated carbon adsorption and compared to a sole adsorption. The influence of the specific ozone dose (0.09-1.29 gO3/gDOC) and the influence of the powdered activated carbon (PAC) dose (2, 5 and 10 mg/L) were first studied separately. OMPs removal increased with both the specific ozone dose (up to 80% for a dose higher than 0.60 gO3/gDOC) and the PAC dose. Ozonation performances decreased in presence of suspended solids, which were converted to dissolved organic carbon. A correction of the specific ozone dose according to the suspended solids levels, in addition to nitrite, should be considered. The influence of ozonation (0.09, 0.22, 0.94 and 1.29 gO3/gDOC) on OMPs adsorption was then assessed. OMPs adsorption didn't change at low specific ozone doses but increased at higher specific ozone doses due to a decrease in DOM adsorption and competition with OMPs. At low ozone doses followed by adsorption (0.22 gO3/gDOC and 10 mg/L PAC), the two processes appeared complementary as OMPs with a low reactivity toward ozone were well absorbed onto PAC while most OMPs refractory to adsorption were well eliminated by ozone. Improved removals were obtained for all compounds with these selected doses, reaching more than 80% removal for most OMPs while limiting the formation of bromate ion.

Organic micropollutants in a large wastewater treatment plant: What are the benefits of an advanced treatment by activated carbon adsorption in comparison to conventional treatment?

Several advanced treatments, such as ozonation or activated carbon adsorption, are currently considered for the removal of organic micropollutants (OMPs) in wastewater treatment plants (WWTP). However, little is known on the overall performances of a WWTP upgraded with those processes and the benefits provided regarding the elimination of multiple families of OMPs. In this study, 5 sampling campaigns were performed to determine the removal of 48 OMPs in a WWTP followed by an activated carbon pilot. The primary treatment had no effect on OMPs (removals < 20%), whereas the biological treatment removed OMPs that can be easily sorbed onto sludges or biodegraded (>60%). The additional elimination provided by the advanced treatment was not significant (<10%) for OMPs already well removed in the WWTP) but was substantial (>30%) for recalcitrant OMPs. Removals higher than 60% were obtained for all OMPs (except azithromycin and sulfamethoxazole) over the WWTP and the activated carbon pilot. The adsorption conditions (10 g/m3 fresh activated carbon addition) were not sufficient to achieve the 80% removal targeted in Switzerland for compounds suggested as indicator substances for wastewater treatment. A higher dose of activated carbon or the combination with another advanced treatment should be used to achieve a satisfactory removal of those compounds.