Efficiency of five samplers to trap suspended particulate matter and microplastic particles of different sizes.

Suspended particulate matter (SPM) plays a major role in nutrient cycles and for the transport of pollutants within local and transboundary water catchments. Obtaining representative SPM samples from rivers, lakes, inland and coastal waters is crucial for quantitative and qualitative chemical analyses to correctly describe the chemical status of a water body. However, a representative sampling of SPM over time is challenging due to the heterogeneity of SPM particles sizes, their non-uniform distribution in rivers, and a variety of sampling devices being in use. Therefore, we investigated the efficiencies of five different sampling devices commonly used in national and international monitoring programs to collect representative SPM samples. We tested three passive sedimentation-based samplers (SBSs: sedimentation box, SB; sedimentation tank, ST; Raetz Sampler, RS), and two active separation techniques (continuous flow centrifuge, CFC; vacuum filtration, VF) in an experimental laboratory setup using in-house SPM standard suspensions (mineral, organic, and microplastic particles) with defined particle sizes. The mass-based efficiencies of the three examined SBSs were 0-66% for the mineral and organic particles <75 µm, where the mean particle sizes of collected samples were always shifted to bigger sizes compared to the initial suspensions. The efficiencies of the three SBSs to collect microplastic particles <80 µm were <20% due to the lower densities of microplastic compared to organic and mineral particles. In contrast to the SBSs, VF and CFC units showed excellent efficiencies >86% for all tested materials, with similar particle size distributions of the sampled material compared to those of the inlet suspensions. In conclusion, SPM sampling efficiencies of sampling units have to be carefully considered and compared to the respective aims of the monitoring approaches, especially when statements are derived from quantitative results on SPM.

Cross-continental importance of CH4 emissions from dry inland-waters.

Despite substantial advances in quantifying greenhouse gas (GHG) emissions from dry inland waters, existing estimates mainly consist of carbon dioxide (CO2) emissions. However, methane (CH4) may also be relevant due to its higher Global Warming Potential (GWP). We report CH4 emissions from dry inland water sediments to i) provide a cross-continental estimate of such emissions for different types of aquatic systems (i.e., lakes, ponds, reservoirs, and streams) and climate zones (i.e., tropical, continental, and temperate); and ii) determine the environmental factors that control these emissions. CH4 emissions from dry inland waters were consistently higher than emissions observed in adjacent uphill soils, across climate zones and in all aquatic systems except for streams. However, the CH4 contribution (normalized to CO2 equivalents; CO2-eq) to the total GHG emissions of dry inland waters was similar for all types of aquatic systems and varied from 10 to 21%. Although we discuss multiple controlling factors, dry inland water CH4 emissions were most strongly related to sediment organic matter content and moisture. Summing CO2 and CH4 emissions revealed a cross-continental average emission of 9.6 ± 17.4 g CO2-eq m-2 d-1 from dry inland waters. We argue that increasing droughts likely expand the worldwide surface area of atmosphere-exposed aquatic sediments, thereby increasing global dry inland water CH4 emissions. Hence, CH4 cannot be ignored if we want to fully understand the carbon (C) cycle of dry sediments.

Spatially Resolved Measurements of CO2 and CH4 Concentration and Gas-Exchange Velocity Highly Influence Carbon-Emission Estimates of Reservoirs.

The magnitude of diffusive carbon dioxide (CO2) and methane (CH4) emission from man-made reservoirs is uncertain because the spatial variability generally is not well-represented. Here, we examine the spatial variability and its drivers for partial pressure, gas-exchange velocity (k), and diffusive flux of CO2 and CH4 in three tropical reservoirs using spatially resolved measurements of both gas concentrations and k. We observed high spatial variability in CO2 and CH4 concentrations and flux within all three reservoirs, with river inflow areas generally displaying elevated CH4 concentrations. Conversely, areas close to the dam are generally characterized by low concentrations and are therefore not likely to be representative for the whole system. A large share (44-83%) of the within-reservoir variability of gas concentration was explained by dissolved oxygen, pH, chlorophyll, water depth, and within-reservoir location. High spatial variability in k was observed, and kCH4 was persistently higher (on average, 2.5 times more) than kCO2. Not accounting for the within-reservoir variability in concentrations and k may lead to up to 80% underestimation of whole-system diffusive emission of CO2 and CH4. Our findings provide valuable information on how to develop field-sampling strategies to reliably capture the spatial heterogeneity of diffusive carbon fluxes from reservoirs.

Molecular Fractionation of Dissolved Organic Matter in a Shallow Subterranean Estuary: The Role of the Iron Curtain.

Iron that precipitates under aerobic conditions in natural aquatic systems scavenges dissolved organic matter (DOM) from solution. Subterranean estuaries (STEs) are of major importance for land-ocean biogeochemical fluxes. Their specific redox boundaries, coined the "iron curtain" due to the abundance of precipitated iron(III) (oxy)hydroxides, are hot spots for the removal and redissolution of iron, associated nutrients, and DOM. We used ultra-high-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry to molecularly characterize the iron-coagulating fractions of 32 groundwater and seawater DOM samples along a salinity gradient from a shallow STE on Spiekeroog Island, North Sea, Germany, and linked our findings to trace metal and nutrient concentrations. We found systematic iron coagulation of large (>450 Da), oxygen-rich, and highly aromatic DOM molecules of terrestrial origin. The extent of coagulation increased with growing terrestrial influence along the salinity gradient. Our study is the first to show that the iron curtain may be capable of retaining terrigenous DOM fractions in marine sediments. We hypothesize that the iron curtain serves as an inorganic modulator for the supply of DOM from groundwaters to the sea, and that the STE has the potential to act as a temporal storage or even sink for terrigenous aromatic DOM compounds.