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.

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.

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.

Importance of Local and Regional Scales in Shaping Mycobacterial Abundance in Freshwater Lakes.

Biogeographical studies considering the entire bacterial community may underestimate mechanisms of bacterial assemblages at lower taxonomic levels. In this context, the study aimed to identify factors affecting the spatial and temporal dynamic of the Mycobacterium, a genus widespread in aquatic ecosystems. Nontuberculous mycobacteria (NTM) density variations were quantified in the water column of freshwater lakes at the regional scale (annual monitoring of 49 lakes in the Paris area) and at the local scale (2-year monthly monitoring in Créteil Lake) by real-time quantitative PCR targeting the atpE gene. At the regional scale, mycobacteria densities in water samples ranged from 6.7 × 103 to 1.9 × 108 genome units per liter. Density variations were primarily explained by water pH, labile iron, and dispersal processes through the connection of the lakes to a river. In Créteil Lake, no spatial variation of mycobacterial densities was noticed over the 2-year monthly survey, except after large rainfall events. Indeed, storm sewer effluents locally and temporarily increased NTM densities in the water column. The temporal dynamic of the NTM densities in Créteil Lake was associated with suspended solid concentrations. No clear seasonal variation was noticed despite a shift in NTM densities observed over the 2012-2013 winter. Temporal NTM densities fluctuations were well predicted by the neutral community model, suggesting a random balance between loss and gain of mycobacterial taxa within Créteil Lake. This study highlights the importance of considering multiple spatial scales for understanding the spatio-temporal dynamic of bacterial populations in natural environments.

Influence of effluent organic matter on copper speciation and bioavailability in rivers under strong urban pressure.

This study focuses on spatiotemporal variations in the type of dissolved organic matter (DOM) and copper binding ability both upstream and downstream of Paris. It also compares the relative influence of both natural DOM upstream of Paris and effluent dissolved organic matter (EfDOM) output from a wastewater treatment plant (WWTP) on trace metal speciation and bioavailability in aquatic systems. In addition to the typical high- and low-affinity binding sites, a third family of very high-affinity binding sites has been highlighted for EfDOM. In receiving waters downstream of Paris during low-flow periods, the percentage of high- and very high-affinity sites originating from EfDOM reaches nearly 60 %. According to the speciation computation, the free copper concentration upstream of Paris exceeds the downstream Paris concentration by a factor of 2 to 4. As regards copper bioavailability, the highest EC50tot values were observed for EfDOM and downstream DOM, with a very low aromaticity and low UV absorbance. This finding suggests that specific ultraviolet absorbance (SUVA) is unlikely to be useful in assessing metal speciation and toxicity in aquatic systems subject to strong urban pressures. These results also highlight that the copper speciation computation for surface water exposed to considerable human pressures should include not only the humic and/or fulvic part of dissolved organic carbon but more hydrophilic fractions as well, originating for example from EfDOM.

Implications of effluent organic matter and its hydrophilic fraction on zinc(II) complexation in rivers under strong urban pressure: aromaticity as an inaccurate indicator of DOM-metal binding.

The zinc binding characteristics of dissolved organic matter (DOM) fractions from the Seine River Basin were studied after being separated and extracted according to their polarity: hydrophobic, transphilic, and hydrophilic. The applied experimental methodology was based on a determination of labile zinc species by means of differential pulse anodic stripping voltammetry (DPASV) at increasing concentrations of total zinc on a logarithmic scale and at fixed levels of: pH, ionic strength, and temperature. Fitting the DOM fractions with two discrete classes of ligands successfully allowed determining the conditional zinc binding constants (Ki) as well as total ligand density (LiT). The binding constants obtained for each DOM fraction were then compared and discussed with respect to the hydrophobic/hydrophilic nature and sample origin. Results highlighted a strong complexation of zinc to the effluent organic matter and especially the most hydrophilic fraction, which also displayed a very low specific UV absorbance. Although the biotic ligand model takes into account the quality of DOM through UV absorbance in the predictions of metal bioavailability and toxicity, this correction is not efficient for urban waters.

Kinetics as a tool to assess the immobilization of soil trace metals by binding phase amendments for in situ remediation purposes.

Many soil remediation techniques consist in decreasing the mobility of trace metals by means of adding trace metal binding phases. For this study, whose aim is to assess the efficiency of soil remediation method by binding phase amendment, a kinetic fractionation method that provides the labile and slowly labile trace metal amounts in soil has been introduced. Manganese oxides (vernadite) and insolubilized humic acids (IHA) have been used as binding phases for the remediation of four heavily polluted soils. Vernadite amendments are effective for lead and cadmium remediation, whereas IHA amendments are only effective for copper remediation. In most cases, the labile metal fractions decrease dramatically in amended soils (up to 50%); on the other hand, the amounts of total extracted metal near the point of thermodynamic equilibrium often show no significant difference between the amended soil and the control soil. These results highlight the utility of kinetic fractionation in assessing the efficiency of soil remediation techniques and, more generally, in evaluating trace metal mobility in soils and its potential advantages compared to extraction schemes performed under equilibrium conditions. In the future, this kinetic method could be considerably simplified so as to consume much less time allowing its routine use.

Accumulation of lead in the roots of grass pea (Lathyrus sativus L.) plants triggers systemic variation in gene expression in the shoots.

The impact of lead nitrate (Pb(NO(3))(2); 0.5mM) on steady-state accumulation of messengers corresponding to stress responsive genes was studied in two local lines of 11-d grass pea (Lathyrus sativus L.) plants exposed for 96 h in a hydroponic system. Real-time reverse transcription polymerase chain reaction technique was used with grass pea-specific primers designed from newly isolated partial cDNA. Increases in accumulation of glutathione reductase, ascorbate peroxidase and glutathione S-transferase transcripts suggested that roots enhanced detoxification mechanisms involving glutathione. In the leaves where no lead was translocated, the pollutant indirectly triggered increases in expression of several genes. This process probably resulted from systemic signals originating from the roots where lead accumulated in large amounts, approximately 150 mg Pbg(-1) dry weight. A preventive and/or adaptive role for the signal is assumed, since it concerned genes implicated in reactive oxygen species scavenging (ascorbate peroxidase), protein protection (heat shock protein 70) and proteolysis (cysteine and aspartic proteases).

Lead accumulation in the roots of grass pea (Lathyrus sativus L.): a novel plant for phytoremediation systems?

Eleven day-old grass pea plants (Lathyrus sativus L.) were grown hydroponically for 96 h in the presence of 0.5 mM lead nitrate (Pb(NO(3))(2)). The survival rate was 100%. The mean lead content (measured by ICP-OES) in root tissues was 153 mg Pb g(-1) dry matter. Over three quarters of the lead was not labile. Compared with control plants, lead-exposed plants showed a six-fold, two-fold and three and a half-fold reduction in their root calcium, zinc and copper contents, respectively. Together, these results suggested that Lathyrus sativus L. was tolerant to a deficiency in essential nutrients and able to store large amounts of lead in its root tissues. Therefore, it could be used for the development of new rhizofiltration systems.

Dissolved organic matter from treated effluent of a major wastewater treatment plant: characterization and influence on copper toxicity.

A combination of reverse osmosis (RO) concentration and DAX-8/XAD-4 resin adsorption techniques is used to isolate the various constituents of urban dissolved organic matter (DOM) from inorganic salts. Three fractions: hydrophobic (HPO), transphilic (TPI) and hydrophilic (HPI) accounting respectively for 35%, 20% and 45% of extracted carbon, are isolated from effluents of a major French wastewater treatment plant. This atypical DOC distribution, in comparison with natural water where the HPO fraction dominates, shows the significance of HPI fraction which often gets neglected because of extraction difficulties. A number of analytical techniques (elemental, spectroscopic: UV, FTIR) allow highlighting the weak aromaticity of wastewater effluent DOM (EfOM) due to fewer degradation and condensation processes and the strong presence of proteinaceous structures indicative of intense microbial activity. Copper toxicity in the presence of DOM is estimated using an acute toxicity test on Daphnia Magna (Strauss). Results reveal the similar protective role of each EfOM fraction compared to reference Suwannee river fulvic acid despite lower EfOM aromaticity (i.e. specific UV absorbance). The environmental implications of these results are discussed with respect to the development of site-specific water quality criteria.

Decrease of atmospheric deposition of heavy metals in an urban area from 1994 to 2002 (Paris, France).

Total atmospheric deposition, i.e. both wet and dry ones, was sampled during three different sampling periods between 1994 and 2002. The aim of this study is to determine the temporal variation of the atmospheric deposition fluxes of four heavy metals (Cd, Cu, Pb and Zn) in an urban area (Paris region, France). The global pattern shows a decrease of the fluxes for most of elements during this period. Indeed, the atmospheric deposition fluxes measured in 2001-2002 were lower than those measured during the 1994-1997 period by factors reaching 16, 2.5, 4 and 7.5 at Créteil and 7, 1, 6 and 4.5 at Chatou for Cd, Cu, Pb and Zn, respectively. At the Paris site, the decreasing factors were 2.5 and 3 for Cd and Pb, respectively while Cu and Zn fluxes were nearly similar during the whole studied period.