Radiocarbon signatures of carbon phases exported by Swiss rivers in the Anthropocene.

Lateral carbon transport through the land-to-ocean-aquatic-continuum (LOAC) represents a key component of the global carbon cycle. This LOAC involves complex processes, many of which are prone to anthropogenic perturbation, yet the influence of natural and human-induced drivers remains poorly constrained. This study examines the radiocarbon (14C) signatures of particulate and dissolved organic carbon (POC, DOC) and dissolved inorganic carbon (DIC) transported by Swiss rivers to assess controls on sources and cycling of carbon within their watersheds. Twenty-one rivers were selected and sampled during high-flow conditions in summer 2021, a year of exceptionally high rainfall. Δ14C values of POC range from -446‰ to -158‰, while corresponding ranges of Δ14C values for DOC and DIC are -377‰ to -43‰ and -301‰ to -40‰, respectively, indicating the prevalence of pre-aged carbon. Region-specific agricultural practices seem to have an influential effect on all three carbon phases in rivers draining the Swiss Plateau. Based on Multivariate Regression Analysis, mean basin elevation correlated negatively with Δ14C values of all three carbon phases. These contrasts between alpine terrain and the lowlands reflect the importance of overriding ecoregional controls on riverine carbon dynamics within Switzerland, despite high spatial variability in catchment properties. This article is part of the Theo Murphy meeting issue 'Radiocarbon in the Anthropocene'.

Microplastic analysis in drinking water based on fractionated filtration sampling and Raman microspectroscopy.

Microplastics (MP) as emerging persistent pollutants were found in raw and drinking water worldwide. Since different methods were used, there is an urgent need for harmonized protocols for sampling, sample preparation, and analysis. In this study, a holistic and validated analytical workflow for MP analysis in aqueous matrices down to 5 µm is presented. For sampling of several cubic meters of water, an easily portable filter cascade unit with different pore sizes (100-20-5 µm) was developed and successfully applied for the sampling of three processed drinking waters, two tap waters and one groundwater. The size distribution and polymer types of MP were determined using a two-step semi-automated Raman microspectroscopy analysis. For quality control, comprehensive process blanks were considered at all times and a recovery test yielded an overall recovery of 81%. The average concentration of identified MP was 66 ± 76 MP/m3 ranging from 1 MP/m3 to 197 MP/m3. All found concentrations were below the limit of quantitation (LOQ) of 1880 MP/m3. The majority consisted of PE (86% ± 111%) while comparatively low numbers of PET (10% ± 25%), PP (3% ± 6%), and PA (1% ± 4%) were found. 79% of all particles were smaller than 20 µm. In summary, this study presents the application of a workflow for sampling and analysis of MP down to 5 µm with first results of no significant contamination in drinking water and groundwater.

Microplastic analysis-are we measuring the same? Results on the first global comparative study for microplastic analysis in a water sample.

This paper presents the results of the first international comparative study of commonly applied analytical methods for microplastic analysis. Although it was shown that the comparability between previously published studies is highly limited, there are ambitious efforts regarding the standardization of microplastic analysis. This comparative study serves as a first step to assess the suitability of frequently used methods in microplastic research. Furthermore, it highlights obstacles when conducting a comparative study for microplastics. Results from 17 laboratories from eight different countries are compared. Samples comprised of five different types of microplastic reference particles with diameters ranging from 8 µm to 140 µm suspended in ultrapure water. Microscopy, Fourier-transform infrared microspectroscopy (µ-FTIR), Raman microspectroscopy (µ-Raman), thermo-extraction-and-desorption- or pyrolysis- combined with gas chromatography coupled to mass spectrometry (Σ-GC/MS), scanning electron microscopy and particle counter were compared regarding results on total particle number, polymer type, number of particles and/or particle mass for each polymer type. In the scope of this comparative study, for the identification of polymer type µ-Raman and Σ-GC/MS performed best. The quantification of polymer mass for identified polymer types was questionable for Σ-GC/MS, whereas other methods failed to determine the correct polymer mass. Quantification of particle number per identified polymer type was evaluated successful for µ-FTIR and the quantification of total particle numbers was best for microscopy and to a lesser extent for µ-FTIR. Remarkable was the large variance of results between the methods but also within the methods. The latter is likely due to individual interpretations of methods and preparation protocols, in particular in regard to the handling of blank values. Results strongly emphasize the need for standardization and validation of analytical methods in microplastic research both on a global scale as well as in the context of individual laboratories.

Repeated detection of polystyrene microbeads in the Lower Rhine River.

Microplastics are emerging pollutants in water bodies worldwide. The environmental entry areas must be studied to localise their sources and develop preventative and remedial solutions. Rivers are major contributors to the marine microplastics load. Here, we focus on a specific type of plastic microbead (diameter 286-954 µm, predominantly opaque, white-beige) that was repeatedly identified in substantial numbers between kilometres 677 and 944 of the Rhine River, one of Europe's main waterways. Specifically, we aimed (i) to confirm the reported abrupt increase in microbead concentrations between the cities of Leverkusen and Duisburg and (ii) to assess the concentration gradient of these particles along this stretch at higher resolution. Furthermore, we set out (iii) to narrow down the putative entry stretch from 81.3 km, as reported in an earlier study, to less than 20 km according to our research design, and (iv) to identify the chemical composition of the particles and possibly reveal their original purpose. Surface water filtration (mesh: 300 µm, n = 9) at regular intervals along the focal river stretch indicated the concentration of these spherules increased from 0.05 to 8.3 particles m-3 over 20 km. This spot sampling approach was supported by nine suspended solid samples taken between 2014 and 2017, encompassing the river stretch between Leverkusen and Duisburg. Ninety-five percent of microbeads analysed (202/212) were chemically identified as crosslinked polystyrene-divinylbenzene (PS-DVB, 146/212) or polystyrene (PS, 56/212) via Raman or Fourier-transform infrared spectroscopy. Based on interpretation of polymer composition, surface structure, shape, size and colour, the PS(-DVB) microbeads are likely to be used ion-exchange resins, which are commonly applied in water softening and various industrial purification processes. The reported beads contribute considerably to the surface microplastic load of the Rhine River and their potential riverine entry area was geographically narrowed down.

Environmental fate and behavior of acesulfame in laboratory experiments.

Acesulfame is a widely used artificial sweetener. It can be discharged into surface water by domestic wastewater due to its incomplete retention during wastewater treatment. Concentrations may reach up to 10 µg/L for smaller rivers. State-of-the-art analysis allows the determination of acesulfame traces (0.01 µg/L) and thus a potential tracking of the presence of wastewater in riverbank filtrate. To evaluate the behavior of acesulfame in the aquatic environment, biodegradation and sorption of acesulfame were tested. Batch experiments yielded low sorption for several soils (estimated solid-water distribution coefficient of acesulfame <0.1 L/kg). Biodegradation in a fixed-bed reactor was not observed at environmental concentrations of 9 µg/L in aqueous compost and soil extract (observation period 56 days). Only in diluted effluent of a wastewater treatment plant did biodegradation start, after 17 days of operation, and acesulfame completely fade, within 28 days. Flow-through column experiments indicated conservative behavior of acesulfame (recovery >83%) and long-term observations at different concentration levels yielded no biodegradation. Overall, laboratory experiments demonstrated a conservative behavior of acesulfame under conditions typical for riverbank filtration. However, there are hints for certain settings which favor an adaptation of the microbial community and facilitate a rapid biodegradation of acesulfame.

Effects of boundary conditions on the cleaning efficiency of riverbank filtration and artificial groundwater recharge systems regarding bulk parameters and trace pollutants.

Drinking water is often produced from surface water by riverbank filtration (RBF) or artificial groundwater recharge (AGR). In this study, an AGR system was exemplarily investigated and results were compared with those of RBF systems, in which the effects of redox milieu, temperature and surface water discharge on the cleaning efficiency were evaluated. Besides bulk parameters such as DOC (dissolved organic carbon), organic trace pollutants including iodinated X-ray contrast media, personal care products, complexing agents, and pharmaceuticals were investigated. At all studied sites, levels of TOC (total organic carbon), DOC, AOX (adsorbable organic halides), SAC (spectral absorption coefficient at 254 nm), and turbidity were reduced significantly. DOC removal was stimulated at higher groundwater temperatures during AGR. Several substances were generally easily removable during both AGR and RBF, regardless of the site, season, discharge or redox regime. For some more refractory substances, however, removal efficiency turned out to be significantly influenced by redox conditions.

Performance of conventional multi-barrier drinking water treatment plants for the removal of four artificial sweeteners.

Due to incomplete removal of artificial sweeteners in wastewater treatment plants some of these compounds end up in receiving surface waters, which are used for drinking water production. The sum of removal efficiency of single treatment steps in multi-barrier treatment systems affects the concentrations of these compounds in the provided drinking water. This is the first systematic study revealing the effectiveness of single treatment steps in laboratory experiments and in waterworks. Six full-scale waterworks using surface water influenced raw water were sampled up to ten times to study the fate of acesulfame, saccharin, cyclamate and sucralose. For the most important treatment technologies the results were confirmed by laboratory batch experiments. Saccharin and cyclamate proved to play a minor role for drinking water treatment plants as they were eliminated by nearly 100% in all waterworks with biologically active treatment units like river bank filtration (RBF) or artificial groundwater recharge. Acesulfame and sucralose were not biodegraded during RBF and their suitability as wastewater tracers under aerobic conditions was confirmed. Sucralose proved to be persistent against ozone and its transformation was < 20% in lab and field investigations. Remaining traces were completely removed by subsequent granular activated carbon (GAC) filters. Acesulfame readily reacts with ozone (pseudo first-order rate constant k = 1.3 x 10(-3) s(-1) at 1 mg L(-1) ozone concentration). However, the applied ozone concentrations and contact times under typical waterworks conditions only led to an incomplete removal (18-60%) in the ozonation step. Acesulfame was efficiently removed by subsequent GAC filters with a low throughput of less than 30 m(3) kg(-1), but removal strongly depended on the GAC preload. Thus, acesulfame was detected up to 0.76 microg L(-1) in finished water.