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.

Temperature, turbidity, and the inner filter effect correction methodology for analyzing fluorescent dissolved organic matter in urban sewage.

Dissolved organic matter (DOM) will be increasingly monitored by means of in situ fluorescence spectroscopy devices in order to supervise wastewater treatment plant efficiency, due to their ease of implementation and high-frequency measurement capacity. However, fluorescence spectroscopy measurements are reported to be sensitive to the sample matrix effects of temperature, the inner filter effect (IFE), and turbidity. Matrix effect estimation tests and signal correction have been developed for DOM (tyrosine-like, tryptophan-like, and humic substances-like fluorescent compounds) fluorescence measurements in unfiltered urban sewage samples. All such tests are conducted in temperature, absorbance, and turbidity ranges representative of urban sewage. For all fluorophores studied, an average of 1% fluorescence intensity decrease per degree (°C) of temperature increase could be observed. Protein-like fluorescent compound signals were found to be significantly affected by turbidity (0 to 210 NTU) and IFE (absorbance 254 nm > 0.200). Only temperature needs to be corrected for humic substances-like fluorescent compounds since other effects were not observed over the studied ranges of absorbance and turbidity. The fluorescence intensity correction method was applied first to each matrix effect separately and then combined by using a sequential mathematical correction methodology. An efficient methodology for determining the matrix effect correction equations for DOM fluorescence analysis into unfiltered urban sewage samples has been highlighted and could be used for in situ fluorescence measurement devices.

An environmentally friendly surrogate method for measuring the soluble chemical oxygen demand in wastewater: use of three-dimensional excitation and emission matrix fluorescence spectroscopy in wastewater treatment monitoring.

Gaining rapid knowledge of dissolved organic matter (DOM) proves to be decisive for wastewater treatment plant operators in efforts to achieve good treatment efficiency in light of current legislation. DOM can be monitored by application of fluorescence spectroscopy both online and in real time in order to derive an assessment of DOM oxidation potential. This work presents an eco-friendly alternative method for measuring the soluble chemical oxygen demand (COD) in raw sewage by means of three-dimensional fluorescence spectroscopy. A peak-picking approach has been developed based on a previous parallel factor analysis (PARAFAC) model dedicated to Paris raw sewage. Fluorescence spectroscopy parameters were used to obtain a good prediction model of soluble COD (r2 = 0.799; p < 0.0001; n = 80) for raw sewage. The approach employed in this study serves as a guideline for purposes of implementing online wastewater monitoring and conducting environmentally friendly soluble COD measurements in the laboratory.

Cationic poly(cyclodextrin)/alginate nanocapsules: From design to application as efficient delivery vehicle of 4-hydroxy tamoxifen to podocyte in vitro.

Most of the drug molecules are partially insoluble in aqueous solution and then may accumulate in fat tissues hampering efficient therapy. Innovative drug delivery strategies have emerged in industry or academia over the last decades, however preserving the activity of the encapsulated drug, having high drug loading capacity and controlling drug release kinetics, are still challenging. In this context, we explored the preparation of new nanocarriers, namely nanocapsules, via a templating method, and using polysaccharides exhibiting biological functions. Cationic poly(cyclodextrin) (P(CD+)) and alginate (alg-) were initially self-assembled layer-by-layer on colloidal gold nanoparticles. Removal of gold nanoparticles was then induced thorough cyanide-assisted hydrolysis, enabling the recovery of nanocapsules. A hydrophobic drug known to allow the mutation of genes inside cells, namely 4-hydroxy-tamoxifen, was loaded within the nanocapsules' shell via inclusion with the cyclodextrin cavities. The so-designed nanomaterials were incubated with immortalized podocytes to investigate i) their incorporation inside cells and ii) their efficiency for in vitro 4-hydroxy-tamoxifen-induced CreERT2 recombination. This work undoubtedly highlights a proof-of-concept for drug delivery using polysaccharides-based capsules with host properties.

Towards a better control of the wastewater treatment process: excitation-emission matrix fluorescence spectroscopy of dissolved organic matter as a predictive tool of soluble BOD5 in influents of six Parisian wastewater treatment plants.

The online monitoring of dissolved organic matter (DOM) in raw sewage water is expected to better control wastewater treatment processes. Fluorescence spectroscopy offers one possibility for both the online and real-time monitoring of DOM, especially as regards the DOM biodegradability assessment. In this study, three-dimensional fluorescence spectroscopy combined with a parallel factor analysis (PARAFAC) has been investigated as a predictive tool of the soluble biological oxygen demand in 5 days (BOD5) for raw sewage water. Six PARAFAC components were highlighted in 69 raw sewage water samples: C2, C5, and C6 related to humic-like compounds, along with C1, C3, and C4 related to protein-like compounds. Since the PARAFAC methodology is not available for online monitoring, a peak-picking approach based on maximum excitation-emission (Ex-Em) localization of the PARAFAC components identified in this study has been used. A good predictive model of soluble BOD5 using fluorescence spectroscopy parameters was obtained (r2 = 0.846, adjusted r2 = 0.839, p < 0.0001). This model is quite straightforward, easy to automate, and applicable to the operational field of wastewater treatment for online monitoring purposes.