Snapshot Sampling May Not Be Enough to Obtain Robust Estimates for Riverine Microplastic Loads.

Wastewater treatment plants (WWTPs) have been described as key contributors of microplastics (MPs) to aquatic systems, yet temporal fluctuations in MP concentrations and loads downstream are underexplored. This study investigated how different sampling frequencies (hourly, weekly, and monthly) affect MP estimates in a stream linked to a single WWTP. Utilizing fluorescence microscopy and Raman spectroscopy, considerable hourly variations in MP concentrations were discovered, while the polymer composition remained consistent. This temporal variability in MP loads was influenced by MP concentration, discharge rates, or a mix of both. These results show a high uncertainty, as relying on sparse snapshot samples combined with annual discharge data led to significant uncertainties in MP load estimates (over- and/or underestimation of emissions by 3.8 billion MPs annually at this site). Our findings stress the necessity of higher-frequency sampling for better comprehending the hydrodynamic factors influencing MP transport. This improved understanding enables a more accurate quantification of MP dynamics, crucial for downstream impact assessments. Therefore, preliminary reconnaissance campaigns are essential for designing extended, representative site-monitoring programs and ensuring more precise trend predictions on a larger scale.

Prevailing impacts of river management on microplastic transport in contrasting US streams: Rethinking global microplastic flux estimations.

While microplastic inputs into rivers are assumed to be correlated with anthropogenic activities and to accumulate towards the sea, the impacts of water management on downstream microplastic transport are largely unexplored. A comparative study of microplastic abundance in Boulder Creek (BC), and its less urbanized tributary South Boulder Creek (SBC), (Colorado USA), characterized the downstream evolution of microplastics in surface water and sediments, evaluating the effects of urbanization and flow diversions on the up-to-downstream profiles of microplastic concentrations and loads. Water and sediment samples were collected from 21 locations along both rivers and microplastic properties determined by fluorescence microscopy and Raman spectroscopy. The degree of catchment urbanization affected microplastic patterns, as evidenced by greater water and sediment concentrations and loads in BC than the less densely populated SBC, which is consistent with the differences in the degree of urbanization between both catchments. Microplastic removal through flow diversions was quantified, showing that water diversions removed over 500 microplastic particles per second from the river, and caused stepwise reductions of downstream loads at diversion points. This redistribution of microplastics back into the catchment should be considered in large scale models quantifying plastic fate and transport to the oceans.

Microplastic accumulation in endorheic river basins - The example of the Okavango Panhandle (Botswana).

The Okavango Panhandle is the main influent watercourse of the Okavango Delta, an inland sink of the entire sediment load of the Cubango-Okavango River Basin (CORB). The sources of pollution in the CORB, and other endorheic basins, are largely understudied when compared to exorheic systems and the world's oceans. We present the first study of the distribution of microplastic (MP) pollution in surface sediments of the Okavango Panhandle in Northern Botswana. MP concentrations (64 µm-5 mm size range) in sediment samples from the Panhandle range between 56.7 and 399.5 particles kg-1 (dry weight) when analysed with fluorescence microscopy. The concentrations of MP in the 20 µm to 5 mm grain size range (analysed with Raman spectroscopy) range between 1075.7 and 1756.3 particles kg-1. One shallow core (15 cm long) from an oxbow lake suggests that MP size decreases with depth while MP concentration increases downcore. Raman Spectroscopy revealed that the compositions of the MP are dominated by polyethene terephthalate (PET), polypropylene (PP), polyethene (PE), polystyrene (PS), and polyvinyl chloride (PVC). From this novel data set it was possible to estimate that 10.9-336.2 billion particles could be transported into the Okavango Delta annually, indicating that the region represents a significant sink for MP, raising concerns for the unique wetland ecosystem.

Microplastic distribution and characteristics across a large river basin: Insights from the Neuse River in North Carolina, USA.

While microplastics (MP) have been found in aquatic ecosystems around the world, the understanding of drivers and controls of their occurrence and distribution have yet to be determined. In particular, their fate and transport in river catchments and networks are still poorly understood. We identified MP concentrations in water and streambed sediment at fifteen locations across the Neuse River Basin in North Carolina, USA. Water samples were collected with two different mesh sizes, a trawl net (>335 µm) and a 64 µm sieve used to filter bailing water samples. MPs >335 µm were found in all the water samples with concentrations ranging from 0.02 to 221 particles per m3 (p m-3) with a median of 0.44 p m-3. The highest concentrations were observed in urban streams and there was a significant correlation between streamflow and MP concentration in the most urbanized locations. Fourier Transform Infrared (FTIR) analysis indicated that for MPs >335 µm the three most common polymer types were polyethylene, polypropylene, and polystyrene. There were substantially more MP particles observed when samples were analyzed using a smaller mesh size (>64 µm), with concentrations ranging from 20 to 130 p m-3 and the most common polymer type being polyethylene terephthalate as identified by Raman spectroscopy. The ratio of MP concentrations (64 µm to 335 µm) ranged from 35 to 375, indicating the 335 µm mesh substantially underestimates MPs relative to the 64 µm mesh. MPs were detected in 14/15 sediment samples. Sediment and water column concentrations were not correlated. We estimate MP (>64 µm) loading from the Neuse River watershed to be 230 billion particles per year. The findings of this study help to better understand how MPs are spatially distributed and transported through a river basin and how MP concentrations are impacted by land cover, hydrology, and sampling method.

Easy and accessible way to calibrate a fluorescence microscope and to create a microplastic identification key.

We present here a technique for setting up detection limits on any fluorescent microscope in conjunction with the fluorophore Nile Red for microplastic identification. Our method also describes a rigorous morphology-specific identification key for microplastics to reduce subjectivity between researchers. The detection limits were established for nine common polymer types and five natural substrates which could result in false-positive signals when using Nile Red for microplastic identification. This method was then applied to real freshwater samples and identified particles were validated with micro-FTIR or Raman spectroscopy. This approach may reduce subjectivity in microplastic identification and counting and enhances transparency, repeatability and harmonization within microplastic research community.•Instructions for calibration of detection limits for microplastics on fluorescence microscope systems described•Microplastic identification key developed and tested to reduce false positive detection•Lower subjectivity for microplastic identification obtained using the detection limits & identification key.

Microplastic accumulation in riverbed sediment via hyporheic exchange from headwaters to mainstems.

In rivers, small and lightweight microplastics are transported downstream, but they are also found frequently in riverbed sediment, demonstrating long-term retention. To better understand microplastic dynamics in global rivers from headwaters to mainstems, we developed a model that includes hyporheic exchange processes, i.e., transport between surface water and riverbed sediment, where microplastic retention is facilitated. Our simulations indicate that the longest microplastic residence times occur in headwaters, the most abundant stream classification. In headwaters, residence times averaged 5 hours/km but increased to 7 years/km during low-flow conditions. Long-term accumulation for all stream classifications averaged ~5% of microplastic inputs per river kilometer. Our estimates isolated the impact of hyporheic exchange processes, which are known to influence dynamics of naturally occurring particles in streams, but rarely applied to microplastics. The identified mechanisms and time scales for small and lightweight microplastic accumulation in riverbed sediment reveal that these often-unaccounted components are likely a pollution legacy that is crucial to include in global assessments.

A systematic approach to understand hydrogeochemical dynamics in large river systems: Development and application to the River Ganges (Ganga) in India.

Large river systems, such as the River Ganges (Ganga), provide crucial water resources for the environment and society, yet often face significant challenges associated with cumulative impacts arising from upstream environmental and anthropogenic influences. Understanding the complex dynamics of such systems remains a major challenge, especially given accelerating environmental stressors including climate change and urbanization, and due to limitations in data and process understanding across scales. An integrated approach is required which robustly enables the hydrogeochemical dynamics and underpinning processes impacting water quality in large river systems to be explored. Here we develop a systematic approach for improving the understanding of hydrogeochemical dynamics and processes in large river systems, and apply this to a longitudinal survey (> 2500 km) of the River Ganges (Ganga) and key tributaries in the Indo-Gangetic basin. This framework enables us to succinctly interpret downstream water quality trends in response to the underpinning processes controlling major element hydrogeochemistry across the basin, based on conceptual water source signatures and dynamics. Informed by a 2019 post-monsoonal survey of 81 river bank-side sampling locations, the spatial distribution of a suite of selected physico-chemical and inorganic parameters, combined with segmented linear regression, reveals minor and major downstream hydrogeochemical transitions. We use this information to identify five major hydrogeochemical zones, characterized, in part, by the inputs of key tributaries, urban and agricultural areas, and estuarine inputs near the Bay of Bengal. Dominant trends are further explored by investigating geochemical relationships (e.g. Na:Cl, Ca:Na, Mg:Na, Sr:Ca and NO3:Cl), and how water source signatures and dynamics are modified by key processes, to assess the relative importance of controls such as dilution, evaporation, water-rock interactions (including carbonate and silicate weathering) and anthropogenic inputs. Mixing/dilution between sources and water-rock interactions explain most regional trends in major ion chemistry, although localized controls plausibly linked to anthropogenic activities are also evident in some locations. Temporal and spatial representativeness of river bank-side sampling are considered by supplementary sampling across the river at selected locations and via comparison to historical records. Limitations of such large-scale longitudinal sampling programs are discussed, as well as approaches to address some of these inherent challenges. This approach brings new, systematic insight into the basin-wide controls on the dominant geochemistry of the River Ganga, and provides a framework for characterising dominant hydrogeochemical zones, processes and controls, with utility to be transferable to other large river systems.

Citizen science reveals microplastic hotspots within tidal estuaries and the remote Scilly Islands, United Kingdom.

The identification of microplastic hotspots is vital to our long-term understanding of their environmental fate and distribution. Although case studies have increased globally, sampling campaigns are often restricted geographically, with poor spatial resolution. Here, we use citizen science to increase our geographical reach, which improved our understanding of microplastic distribution in estuarine and beach sediment along the south-west coast of England. Hotspots (>700 particles per kg dry sediment) were identified on the Scilly Islands and in close proximity to major metropolitan hubs (i.e. Falmouth and Plymouth). Particles extracted from the Scilly Island sites were composed of polyethylene and polypropylene. With low population density on the Isle of Scilly, hotspots may suggest that microplastics originate from distant sources, while Falmouth and Plymouth, on mainland UK, are locally supplied. This information supports the design of future campaigns and targeted mitigation strategies in areas of highest concentrations.

Transport and retention of engineered silver nanoparticles in carbonate-rich sediments in the presence and absence of soil organic matter.

The transport and retention behavior of polymer- (PVP-AgNP) and surfactant-stabilized (AgPURE) silver nanoparticles in carbonate-dominated saturated and unconsolidated porous media was studied at the laboratory scale. Initial column experiments were conducted to investigate the influence of chemical heterogeneity (CH) and nano-scale surface roughness (NR) arising from mixtures of clean, positively charged calcium carbonate sand (CCS), and negatively charged quartz sands. Additional column experiments were performed to elucidate the impact of CH and NR arising from the presence and absence of soil organic matter (SOM) on a natural carbonate-dominated aquifer material. The role of the nanoparticle capping agent was examined under all conditions tested in the column experiments. Nanoparticle transport was well described using a numerical model that facilitated blocking on one or two retention sites. Results demonstrate that an increase in CCS content in the artificially mixed porous medium leads to delayed breakthrough of the AgNPs, although AgPURE was much less affected by the CCS content than PVP-AgNPs. Interestingly, only a small portion of the solid surface area contributed to AgNP retention, even on positively charged CCS, due to the presence of NR which weakened the adhesive interaction. The presence of SOM enhanced the retention of AgPURE on the natural carbonate-dominated aquifer material, which can be a result of hydrophobic or hydrophilic interactions or due to cation bridging. Surprisingly, SOM had no significant impact on PVP-AgNP retention, which suggests that a reduction in electrostatic repulsion due to the presence of SOM outweighs the relative importance of other binding mechanisms. Our findings are important for future studies related to AgNP transport in shallow unconsolidated calcareous and siliceous sands.

Reductive dechlorination of 1,2-dichloroethane in the presence of chloroethenes and 1,2-dichloropropane as co-contaminants.

1,2-Dichloroethane (1,2-DCA) is one of the most abundant manmade chlorinated organic contaminants in the world. Reductive dechlorination of 1,2-DCA by organohalide-respiring bacteria (OHRB) can be impacted by other chlorinated contaminants such as chloroethenes and chloropropanes that can co-exist with 1,2-DCA at contaminated sites. The aim of this study was to evaluate the effect of chloroethenes and 1,2-dichloropropane (1,2-DCP) on 1,2-DCA dechlorination using sediment cultures enriched with 1,2-DCA as the sole chlorinated compound (EA culture) or with 1,2-DCA and tetrachloroethene (PCE) (EB culture), and to model dechlorination kinetics. Both cultures contained Dehalococcoides as most predominated OHRB, and Dehalogenimonas and Geobacter as other known OHRB. In sediment-free enrichments obtained from the EA and EB cultures, dechlorination of 1,2-DCA was inhibited in the presence of the same concentrations of either PCE, vinyl chloride (VC), or 1,2-DCP; however, concurrent dechlorination of dual chlorinated compounds was achieved. In contrast, 1,2-DCA dechlorination completely ceased in the presence of cis-dichloroethene (cDCE) and only occurred after cDCE was fully dechlorinated. In turn, 1,2-DCA did not affect dechlorination of PCE, cDCE, VC, and 1,2-DCP. In sediment-free enrichments obtained from the EA culture, Dehalogenimonas 16S rRNA gene copy numbers decreased 1-3 orders of magnitude likely due to an inhibitory effect of chloroethenes. Dechlorination with and without competitive inhibition fit Michaelis-Menten kinetics and confirmed the inhibitory effect of chloroethenes and 1,2-DCP on 1,2-DCA dechlorination. This study reinforces that the type of chlorinated substrate drives the selection of specific OHRB, and indicates that removal of chloroethenes and in particular cDCE might be necessary before effective removal of 1,2-DCA at sites contaminated with mixed chlorinated solvents.

Transport and retention of surfactant- and polymer-stabilized engineered silver nanoparticles in silicate-dominated aquifer material.

Packed column experiments were conducted to investigate the transport and blocking behavior of surfactant- and polymer-stabilized engineered silver nanoparticles (Ag-ENPs) in saturated natural aquifer media with varying content of material < 0.063 mm in diameter (silt and clay fraction), background solution chemistry, and flow velocity. Breakthrough curves for Ag-ENPs exhibited blocking behavior that frequently produced a delay in arrival time in comparison to a conservative tracer that was dependent on the physicochemical conditions, and then a rapid increase in the effluent concentration of Ag-ENPs. This breakthrough behavior was accurately described using one or two irreversible retention sites that accounted for Langmuirian blocking on one site. Simulated values for the total retention rate coefficient and the maximum solid phase concentration of Ag-ENPs increased with increasing solution ionic strength, cation valence, clay and silt content, decreasing flow velocity, and for polymer-instead of surfactant-stabilized Ag-ENPs. Increased Ag-ENP retention with ionic strength occurred because of compression of the double layer and lower magnitudes in the zeta potential, whereas lower velocities increased the residence time and decreased the hydrodynamics forces. Enhanced Ag-ENP interactions with cation valence and clay were attributed to the creation of cation bridging in the presence of Ca2+. The delay in breakthrough was always more pronounced for polymer-than surfactant-stabilized Ag-ENPs, because of differences in the properties of the stabilizing agents and the magnitude of their zeta-potential was lower. Our results clearly indicate that the long-term transport behavior of Ag-ENPs in natural, silicate dominated aquifer material will be strongly dependent on blocking behavior that changes with the physicochemical conditions and enhanced Ag-ENP transport may occur when retention sites are filled.

Natural attenuation of chlorinated ethenes in hyporheic zones: A review of key biogeochemical processes and in-situ transformation potential.

Chlorinated ethenes (CEs) are legacy contaminants whose chemical footprint is expected to persist in aquifers around the world for many decades to come. These organohalides have been reported in river systems with concerning prevalence and are thought to be significant chemical stressors in urban water ecosystems. The aquifer-river interface (known as the hyporheic zone) is a critical pathway for CE discharge to surface water bodies in groundwater baseflow. This pore water system may represent a natural bioreactor where anoxic and oxic biotransformation process act in synergy to reduce or even eliminate contaminant fluxes to surface water. Here, we critically review current process understanding of anaerobic CE respiration in the competitive framework of hyporheic zone biogeochemical cycling fuelled by in-situ fermentation of natural organic matter. We conceptualise anoxic-oxic interface development for metabolic and co-metabolic mineralisation by a range of aerobic bacteria with a focus on vinyl chloride degradation pathways. The superimposition of microbial metabolic processes occurring in sediment biofilms and bulk solute transport delivering reactants produces a scale dependence in contaminant transformation rates. Process interpretation is often confounded by the natural geological heterogeneity typical of most riverbed environments. We discuss insights from recent field experience of CE plumes discharging to surface water and present a range of practical monitoring technologies which address this inherent complexity at different spatial scales. Future research must address key dynamics which link supply of limiting reactants, residence times and microbial ecophysiology to better understand the natural attenuation capacity of hyporheic systems.

Kinetics of dechlorination by Dehalococcoides mccartyi using different carbon sources.

Stimulated anaerobic dechlorination is generally considered a valuable step for the remediation of aquifers polluted with chlorinated ethenes (CEs). Correct simulation and prediction of this process in situ, however, require good knowledge of the associated biological reactions. The aim of this study was to evaluate the dechlorination reaction in an aquifer contaminated with trichloroethene (TCE) and its daughter products, discharging into the Zenne River. Different carbon sources were used in batch cultures and these were related to the dechlorination reaction, together with the monitored biomarkers. Appropriate kinetic formulations were assessed. Reductive dechlorination of TCE took place only when external carbon sources were added to microcosms, and occurred concomitant with a pronounced increase in the Dehalococcoides mccartyi cell count as determined by 16S rRNA gene-targeted qPCR. This indicates that native dechlorinating bacteria are present in the aquifer of the Zenne site and that the oligotrophic nature of the aquifer prevents a complete degradation to ethene. The type of carbon source, the cell number of D. mccartyi or the reductive dehalogenase genes, however, did not unequivocally explain the observed differences in degradation rates or the extent of dechlorination. Neither first-order, Michaelis-Menten nor Monod kinetics could perfectly simulate the dechlorination reactions in TCE spiked microcosms. A sensitivity analysis indicated that the inclusion of donor limitation would not significantly enhance the simulations without a clear process understanding. Results point to the role of the supporting microbial community but it remains to be verified how the complexity of the microbial (inter)actions should be represented in a model framework.

10 years after rio-concepts on the contribution of chemistry to a sustainable development.

The principles of the United Nations Conference on Environment and Development (UNCED), held in June 1992 in Rio de Janeiro, and Agenda 21, the comprehensive plan of action for the 21st century, adopted 10 years ago by more than 170 governments, address the pressing problems of today and also aim at preparing the world for the challenges of this century. The conservation and management of resources for development are the main focus of interest, to which the sciences will have to make a considerable contribution. Natural, economic, and social sciences will have to be integrated in order to achieve this aim. In their future programs, the associations of the chemical industries in Europe, Japan, and the USA have explicitly accepted their obligation to foster a sustainable development. In this review we investigate innovations in chemistry exemplarily for such a development with regard to their ecological, economical, and social dimensions from an integrated and interdisciplinary perspective. Since base chemicals are produced in large quantities and important product lines are synthesized from them, their resource-saving production is especially important for a sustainable development. This concept has been shown, amongst others, by the example of the syntheses of propylene oxide and adipic acid. In the long run, renewable resources that are catalytically processed could replace fossil raw materials. Separation methods existing today must be improved considerably to lower material and energy consumption. Chemistry might become the pioneer of an innovative energy technique. The design of chemical products should make possible a sustainable processing and recycling and should prevent their bio-accumulation. Methods and criteria to assess their contribution to a sustainable development are necessary. The time taken to introduce the new more sustainable processes and products has to be diminished by linking their development with operational innovation management and with efficient environmental-political control procedures.