Occurrence and fate of an emerging drug pollutant and its by-products during conventional and advanced wastewater treatment: Case study of furosemide.

Conventional wastewater treatment systems are not designed to remove pharmaceutical compounds from wastewater. These compounds can be degraded into many other transformation products which are hardly, if at all, studied. In this context, we studied the occurrence and degradation of furosemide, a very frequently detected diuretic, along with its known degradation products in several types of wastewater. Influent and effluent from the Seine-Centre Wastewater Treatment Plant (WWTP) (Paris, France) as well as outlet of residential care homes (Dordogne, France) were analyzed by Ultra-Performance Liquid Chromatography-tandem Mass Spectrometry (UPLC-MS/MS) to quantify furosemide and its known degradation products, saluamine and pyridinium of furosemide. Oxidation experiments (chlorination, ozonation and UV photolysis with hydrogen peroxide) were then performed on furosemide solutions and on water from residential care facilities to study the degradation of furosemide by potential advanced processes, and also to identify unknown oxidation products by high-resolution mass spectrometry. Furosemide was well degraded in Seine-Centre WWTP (>75%) but did not increase the concentrations of its main degradation products. Saluamine and pyridinium of furosemide were already present at similar concentrations to furosemide in the raw wastewater (∼2.5-3.5 µg.L-1), and their removal in the WWTPs were very high (>80%). Despite their removal, the three compounds remained present in treated wastewater effluents at concentrations of hundreds of nanograms per liter. Chlorination degraded furosemide without pyridinium production unlike the other two processes. Chlorination and ozonation were also effective for the removal of furosemide and pyridinium in residential care home water, but they resulted in the production of saluamine. To our knowledge this is the first evidence of saluamine and pyridinium of furosemide in real water samples in either the particulate or dissolved phase.

Microplastic and microfiber fluxes in the Seine River: Flood events versus dry periods.

Studies on the influence of hydrodynamic conditions on anthropogenic microfiber (MF) and microplastic (MP) distributions in freshwater environments are sparse. In this study, we evaluated the influence of urbanisation gradient on the spatial variability of MFs and MPs. Temporal variability was also assessed by comparing the concentrations and fluxes of MFs and MPs under low flow conditions with those during the January-February 2018 flood event. For each period, Seine river water was collected upstream and downstream of Greater Paris and filtered through an 80 µm net at three different sampling sites. MFs were counted using a stereomicroscope, while MPs were analysed using micro-Fourier transform infrared spectroscopy coupled with siMPle analysis software. The highest concentrations of MFs and MPs were reported at the furthest downstream sites during both periods. However, high water flowrates and urbanisation gradient did not significantly impact MF and MP concentrations, sizes, or polymer distributions. The median MF and MP concentrations were 2.6 and 15.5 items/L and their interquartile ranges were 1.6 and 4.9 items/L (n = 10), respectively, illustrating relatively stable concentrations in spite of the urbanisation gradient and variations in the flowrate. In contrast to the concentration, size, and polymer distribution characteristics, MP mass fluxes were strongly affected by river flow. MF and MP fluxes show increases in the number and mass of particles from upstream to downstream. The downstream site presents high MP mass fluxes, which range between 924 and 1675 tonnes/year. These results may indicate significant MP inputs from the Paris Megacity through wastewater treatment plant effluents and untreated stormwater. The January-February 2018 flood event, which represented 14.5% of the year (in terms of time), contributed 40% of the yearly MP mass fluxes. Thus, flood events contribute strongly to MP fluxes.

Microplastics and microfibers in urban runoff from a suburban catchment of Greater Paris.

Microplastics (MPs) and microfibers (MFs) in stormwater have been poorly investigated. Data on their intra and inter rain events variability over time are still sparse. For the first time, the variability of microlitter concentrations in stormwater has been studied. MF and MP concentrations were investigated in stormwater runoff at the outlet of the suburban catchment at Sucy-en-Brie (a suburb of Paris, France), during four rain events. Median MF and MP concentrations were 1.9 and 29 items/L, with an interquartile range of 2.3 and 36 items/L, respectively (N = 18). A different pattern was observed between MFs and MPs. While no relationship or trends were observed for MFs, the highest MP concentrations were observed before the flow rate peak of the rain events. This could indicate a difference in the behaviour between MFs and MPs. We estimated the median MP mass concentration to be 56 µg/L with an interquartile range of 194 µg/L, whereas the mass concentration of macroplastics was estimated to be 31 µg/L with an interquartile range of 22 µg/L at the same sampling site, in a previous study. For this sampling site, MPs and macroplastics have the same order of magnitude. This study may have strong implications on microplastic assessment in urban waters.

Retention and transport processes of particulate and dissolved micropollutants in stormwater biofilters treating road runoff.

Road runoff is contaminated by various micropollutants and may be treated using low impact development techniques, such as stormwater biofilters. Better understanding the processes, such as filtration, sorption and leaching, which affect pollutants in these systems is essential to reliably predicting treatment performance and optimizing system design. Field data from an in situ monitoring campaign, wherein dissolved and particulate concentrations of a wide range of micropollutants (trace metals, polycyclic aromatic hydrocarbons, bisphenol-A, alkylphenols and phthalates) were characterized in untreated road runoff and biofilter outlets for 19 rain events, are used to explore transport and retention processes. Although retention of the particulate phase of pollutants was generally quite effective, unusually high particle concentrations were observed at biofilter outlets for three winter events. Particle characterization in road runoff and outlet waters revealed that this degraded performance was due to poor filtration rather than particle erosion, which was attributed to the relative abundance of small (<10 µm) particles during this period, along with possible preferential flows. Dissolved pollutants were less effectively removed in general. To better understand this behavior, field results were combined with laboratory sorption and leaching tests. Dissolved concentrations of trace metals were shown to be influenced by organic carbon; leaching from road-originated particles may also influence their transport. Removal of the dissolved phase of organic micropollutants was limited by the contamination of the filter media, either before installation or during the first period of operation, due to emissions from construction materials.

Field performance of two biofiltration systems treating micropollutants from road runoff.

The treatment efficiency of a vegetative filter strip and a biofiltration swale treating heavily loaded road runoff are evaluated. Concentrations measured in water drained from the two systems are compared to those in untreated road runoff collected from a reference catchment for a wide range of contaminants including organic carbon, nutrients (N and P), trace metals, and organic micropollutants (polycyclic aromatic hydrocarbons (PAH), total petroleum hydrocarbons (TPH), alkylphenols, bisphenol-A, phthalates), in both total and dissolved phases. Predominantly particulate pollutants, including Pb, Zn and PAH, were very efficiently removed (around 90%) for most events. However, poor particulate removal was observed during a winter period. Relatively few pollutants were significantly removed in the dissolved phase and observed concentration reductions tended to be lower than those of suspended solids and associated pollutants; as such, lower removals were observed for total concentrations of moderately particulate micropollutants, including bisphenol-A, alkylphenols and phthalates. In addition, some pollutants appear to be emitted from various biofilter components (filter media, drainage and lining materials), as low or negative concentration removals were observed during the first months of operation of the biofiltration swale.