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.

Monitoring freshwater fish communities in large rivers using environmental DNA metabarcoding and a long-term electrofishing survey.

Monitoring freshwater fish communities in a large human-impacted river is a challenging task. The structure of fish assemblages has been monitored yearly in the Marne and the Seine Rivers, across the Paris conurbation, France, using traditional electrofishing (EF) surveys since 1990, in accordance with the European Water Framework Directive. In addition, metabarcoding of DNA extracted from environmental samples (eDNA) was concomitantly conducted in nine sampling sites in 2017 and in 2018 to compare the estimates of species richness and relative abundance among three methods: annual, long-term EF monitoring and eDNA. The present study confirms better detection of fish species using eDNA compared to annual EF. eDNA metabarcoding was also more efficient for species detection than a 3-6-year EF survey but was similar or less efficient than a long-term EF survey of 14 years of monitoring. In addition, the numbers of reads per species relative to the total number of reads significantly increased with (a) increasing relative abundance (relative percentage of individuals caught per species) and (b) increasing number of years that a fish species was detected during the 2000-2018 period. These results suggest that eDNA could reflect local population persistence.

Are boron isotopes a reliable tracer of anthropogenic inputs to rivers over time?

This study aims at determining how the boron signal of the Seine River evolved in terms of concentration and isotopic signatures over eighteen years (1994-95 and 2006-12) and if boron isotopes can reliably trace anthropogenic inputs over time. In the anthropised Seine River watershed, boron is widely released by human activities, and even if boron concentrations ([B]) are below the potability limit, our study confirms the potential of boron isotopes (δ11B) to trace urban anthropogenic contaminations. Between 1994 and 2012, [B] have decreased across the anthropised part of the Seine River basin (and by a factor of two in Paris) while δ11B has increased. This means either that urban inputs have been reduced or that the boron signature of urban inputs has changed over time. Both hypotheses are in agreement with the decrease of perborate consumption in Europe over 15years and are not mutually exclusive. Results of a thorough analysis of urban effluents from the sewage network of Paris conurbation that are in fine released to the Seine River suggest a shift of the urban δ11B from -10‰ in 1994 to 1.5±2.0‰ in 2012, in agreement with our second hypothesis. We attribute this change to the removal of perborates from detergents rather than to the modernisation of wastewater treatment network, because it does not significantly impact the wastewater boron signatures. Eighteen years after the first assessment and despite the decreased use of perborates, geochemical and isotopic mass budgets confirm, that boron in the Seine River basin is mainly released from urban activities (60-100%), especially in Paris and the downstream part of the basin. Contrastingly, in headwaters and/or tributaries with low urbanisation, the relative boron input to river from agricultural practices and rains increased, up to 10% and by 10 to 30%, respectively.

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.

N2O emissions from full-scale nitrifying biofilters.

A full-scale nitrifying biofilter was continuously monitored during two measurement periods (September 2014; February 2015) during which both gaseous and liquid N2O fluxes were monitored on-line. The results showed diurnal and seasonal variations of N2O emissions. A statistical model was run to determine the main operational parameters governing N2O emissions. Modification of the distribution between the gas phase and the liquid phase was observed related to the effects of temperature and aeration flow on the volumetric mass transfer coefficient (kLa). With similar nitrification performance values, the N2O emission factor was twice as high during the winter campaign. The increase in N2O emissions in winter was correlated to higher effluent nitrite concentrations and suspected increased biofilm thickness.

Full-scale post denitrifying biofilters: sinks of dissolved N2O?

In this study, nitrous oxide (N2O) emissions from a full-scale denitrifying biofilter plant were continuously monitored over two periods (summer campaign in September 2014 and winter campaign in February 2015). Results of the summer campaign showed that the major part (>99%) of N2O flux was found in the liquid phase and was discharged with the effluent. N2O emissions were highly variable and represented in average 1.28±1.99% and 0.22±0.31% of the nitrate uptake rate during summer and winter campaigns, respectively. Denitrification was able to consume a large amount of dissolved N2O coming from the upstream nitrification stage. In the absence of methanol injection failure and with an influent BOD/NO3-N ratio higher than 3, average reduction of N2O was estimated to be of 93%. The control of exogenous carbon dosage is essential to minimize N2O production from denitrifying biofilters, in correlation to NO2-N concentrations in the filter.

Early assessment of a rapid alternative method for the estimation of the biomethane potential of sewage sludge.

This short communication briefly presents a rapid method using a fluorescent redox indicator, similar to resazurin, in order to estimate the biodegradability of sewage sludge during anaerobic digestion (AD). The biodegradability and by extension the Biochemical Methane Potential (BMP) of nineteen municipal sludge samples (primary, biological and tertiary) were investigated and estimated in only 48 h. Results showed the relevance to follow the metabolic activity of anaerobic sludge by the kinetic of probe reduction. The extended lag phase of inoculum indicated an impact of pre-treatments on enzyme activity. The comparison with Automatic Methane Potential Test System II (AMPTS) confirmed the estimated values of BMP according to an uncertainty limit of 25%. These first results highlight the interest of this rapid assay as a preliminary tool of the biodegradability of sewage sludge in anaerobic digestion.

Nitrite accumulation during denitrification depends on the carbon quality and quantity in wastewater treatment with biofilters.

This study aims to understand the mechanisms of nitrite appearance during wastewater denitrification by biofilters, focusing on the role of the carbon source. Experiments were carried out at lab-scale (batch tests) and full-scale plant (Parisian plant, capacities of 240,000 m(3) day(-1)). Results showed that the nature of the carbon source affects nitrite accumulation rates. This accumulation is low, 0.05 to 0.10 g N-NO2(-) per g N-NO3(-) eliminated, for alcohols such as methanol, ethanol, or glycerol. The utilization of glycerol leads to fungal development causing clogging of the biofilters. This fungal growth and consequent clogging exclude this carbon source, with little nitrite accumulation, as carbon source for denitrification. Whatever the carbon source, the C/N ratio in the biofilter plays a major role in the appearance of residual nitrite; an optimal C/N ratio from 3.0 to 3.2 allows a complete denitrification without any nitrite accumulation.

Modelling the nitrification in a full-scale tertiary biological aerated filter unit.

A wastewater biofiltration model is used to assess its capacity to reproduce the treatment behaviour of a plant-sized tertiary nitrifying biofilter unit. It is calibrated on two different types of datasets collected at the Seine-Aval biofiltration plant (Achères, France): grab samples at several heights inside the media bed and a long-term daily plant monitoring over a 1-year period. The model parameters are first calibrated to fit the dynamics observed in the media bed, after which the model is compared to the second dataset. Further parameter changes are then made if necessary and the model is once again compared to both datasets to ensure its ability to predict the treatment behaviour on both size scales. The calibrated model provides correct predictions for most observed nutrient variables for both datasets. An overestimation of the oxygen transfer under a summer, low ammonia load period however leads to a slight underestimation of the nitrifying efficiency of the biofilters. Statistical score computation corroborates the model accuracy as the mean error scores usually remain low. They also point to a certain weakness of the model regarding the suspended solids filtration. Both datasets are overall correctly modelled using a single parameter set. Most of this parameter set is close to or contained in value ranges found in the literature. The parameters related to aeration, however, seem to be slightly higher than what is reported elsewhere.

Municipal wastewater treatment by biofiltration: comparisons of various treatment layouts. Part 1: assessment of carbon and nitrogen removal.

One of the largest wastewater treatment plants in the Paris conurbation (240,000 m(3)/d) has been studied over several years in order to provide technical and economical information about biological treatment by biofiltration. Biofiltration systems are processes in which carbon and nitrogen pollution of wastewater are treated by ascendant flow through immersed fixed cultures. This paper, focused on technical information, aims: (1) to compare performances of the three biological treatment layouts currently used in biofiltration systems: upstream denitrification (UD), downstream denitrification (DD) and combined upstream-downstream denitrification (U-DD) layouts; and (2) to describe in detail each treatment step. Our study has shown that more than 90% of the carbon and ammoniacal pollution is removed during biological treatment, whatever the layout used. Nitrate, produced during nitrification, is then reduced to atmospheric nitrogen. This reduction is more extensive when the denitrification stage occurs downstream from the treatment (DD layout with methanol addition), whereas it is only partial when it is inserted upstream from the treatment (UD layout - use of endogenous carbonaceous substrate). So, the UD layout leads to a nitrate concentration that exceeds the regulatory threshold in the effluent, and the treatment must be supplemented with a post-denitrification step (U-DD layout). Our work has also shown that the optimal ammonium-loading rate is about 1.1-1.2 kg N-NH(4)(+) per m(3) media (polystyrene) and day. For denitrification, the optimal nitrate-loading rate is about 2.5 kg N per m(3) media (expanded clay) and day in the case of DD with methanol, and is about 0.25 kg N-NO(3)(-) per m(3) media and day in the case of UD with exogenous carbonaceous substrate.