Nickel (Ni) is a bio-essential trace metal for marine phytoplankton, serving as a cofactor in key enzymes. Its nutrient-like distribution and the mirrored distribution of δ⁶⁰Ni in seawater suggest that δ⁶⁰Ni could serve as a tracer of biological Ni cycling. However, particulate Ni (pNi) remains understudied despite its important role. Here, we present three coupled dissolved and particulate δ⁶⁰Ni profiles from distinct biogeochemical regimes across the Subtropical Front in the Australian sector of the Southern Ocean.
In surface waters, pNi is isotopically lighter than co-located dissolved Ni, and particulate Ni/P in the mixed layer falls within the range observed for phytoplankton, reflecting an association with organic matter. These results support previous studies suggesting that phytoplankton preferentially remove isotopically light Ni. In the subtropics, higher surface productivity corresponds to elevated mixed layer pNi concentrations, below which pNi declines, associated with the regeneration of organic matter. However, particulate δ⁶⁰Ni shows limited variation, implying minimal isotope fractionation during this process. At subantarctic stations, pNi concentrations remain relatively constant, while particulate δ⁶⁰Ni decreases with depth in the upper 300 m. Moreover, δ⁶⁰Ni offsets between the dissolved and particulate phases are smaller than for the subtropical counterpart, likely associated with different phytoplankton assemblages. At greater depth, particulate Mn/P increases, and Ni/P ratios exceed those of phytoplankton. This suggests a shift in pNi association from organic-rich to Mn-rich phases, with minimal change in total particulate δ⁶⁰Ni. These findings suggest a more complex internal cycling of Ni in the oceans than one driven solely by biological processes.

Harmful cyanobacterial blooms pose increasing threats to aquatic ecosystems and human health; yet, the role of zooplankton grazing in regulating blooms remains understudied. We investigated the seasonal feeding behaviour and fitness consequences of feeding preferences in natural zooplankton communities for toxic (microcystin-producing) versus non-toxic cyanobacteria across temperature gradients in eutrophic Lake Greifen, Switzerland. We conducted monthly experiments from April to October 2023 to test the grazing behaviour of four zooplankton groups (daphnids, calanoid copepods, cyclopoid copepods, and microzooplankton) exposed to mixed diets of green algae and either toxic or non-toxic Microcystis strains at 15 °C and 25 °C.
Contrary to expectations of cyanobacteria avoidance, zooplankton exhibited predominantly non-selective grazing throughout the seasonal succession, consuming both toxic and non-toxic cyanobacteria at similar rates, regardless of temperature. Notably, during the peaks of phytoplankton abundance (April and September), mesozooplankton demonstrated a selective preference for cyanobacteria over green algae, particularly non-toxic strains. Temperature effects were subtle but revealed metabolic constraints: elevated temperatures occasionally triggered selective consumption of cyanobacteria in copepods, while fitness costs (survival) from exposure to toxic species were mostly restricted to transitional bloom periods and high-temperature conditions.
These findings suggest that toxic cyanobacteria may not always evade grazing pressure through secondary metabolite deterrent effects. Our results suggest that zooplankton communities can adapt and graze on cyanobacteria regardless of toxicity under the tested conditions, even during bloom conditions. These observations highlight the potential for zooplankton to interact with cyanobacterial populations, which may have implications for bloom prediction and management strategies, particularly under climate warming scenarios.

Carbon dioxide fluxes associated with weathering and carbon export in river basins are highly spatially variable, with some locations acting as sinks whilst others represent CO₂ sources. Chemical weathering and the associated carbon fluxes are strongly modulated by bedrock geology, with orogenic systems constituting locations where metamorphic lithologies can be found juxtaposed with sedimentary rock mélanges. Hydrological processes also converge in mountain belt interiors, where water in the shallow critical zone can intersect with gas-rich fluids derived from deeper tectonic processes. The Engadin Valley in the Swiss Alps provides a natural geological setting to examine how these competing controls impact weathering and dissolved inorganic carbon (DIC) fluxes in alpine rivers. Using the radiocarbon and stable isotope composition of river DIC, alongside the dissolved products of weathering, we observed an increase in the fractional contribution of riverine DIC derived from metamorphic processes coincident with a distinct lithological transition from the upper to the lower Engadin Valley.
DIC export from the upper Engadin Valley is dominated by silicate weathering of igneous and metamorphic terrains, while Δ¹⁴C_DIC values < -100 ‰ suggest some of this DIC could originate from pre-aged organic sources from soils, permafrost thaw or glaciated catchments. Riverine DIC concentrations increase from headwaters to the most downstream station in the lower Engadin Valley, mirrored by a sharp drop in Δ¹⁴C_DIC values, while the magnitude of this decrease varies seasonally. This decline in Δ¹⁴C_DIC values, which is counter to the trend expected due to increasing exchange with atmospheric CO₂ downstream, is consistent with contributions from geogenic carbon sources, specifically DIC from weathering of carbonate minerals and petrogenic organic carbon (OC), spatially intertwined with inputs CO₂ from metamorphic processes. Overall, seasonal variations in hydrological processes and associated flow pathways appear to modulate DIC contributions from bedrock weathering, while metamorphic CO₂ inputs occur in a quasi-constant manner. This study demonstrates that geogenic CO₂ sources in the shallow critical zone contribute significantly to the riverine DIC pool, leading in the Engadin valley to a potential shift in CO₂ fluxes from uptake via silicate weathering upstream to potential CO₂ release downstream, highlighting both the importance and complexity of carbon cycle processes in mountainous river basins.

Cyanobacteria produce complex mixtures of secondary metabolites (cyano-metabolites), some of which are toxic and pose a growing concern for water utilities. While physical treatments such as filtration can efficiently remove cells, their lysis can release dissolved cyano-metabolites. This study investigated the efficiency of laboratory-scale sand filtration to abate 19 cyano-metabolites representing various structural classes. Furthermore, abatement of cyano-metabolites in a full-scale sand filtration is presented. Most cyano-metabolites showed abatement similar to or higher than the biodegradable benchmark micropollutants atenolol, paracetamol, and valsartan. Among cyano-metabolites, anabaenopeptins and cyanopeptolins had the highest abatement, while cyclamides and microcystin-LR had the lowest abatement. Abiotic controls and formation trends of 10 identified biotransformation products demonstrated that biodegradation played a major role in their removal. Laboratory-scale sand filters showed a sharp increase in biodegradation efficiency within days due to their adaptation to cyano-metabolites. Increasing the contact time and temperature both enhanced the abatement of most compounds, which could be kinetically modeled. High cyano-metabolite concentrations suppressed their own relative abatement, possibly due to metabolic enzyme inhibition or saturation. These findings suggest that sand filtration can serve as a dual-barrier against cyano-metabolites, including particle removal and biodegradation. However, biodegradation will be affected by the temperature and cyano-metabolite intake dynamics.

This review highlights cyanobacteria secondary metabolites reported between 2021 and 2024. Those compounds are categorised into major classes, including peptides, alkaloids, lipids, polyketides, terpenes/terpenoids, and natural products from other classes. For selected compounds, the review provides details of advanced methodologies employed in their discovery, isolation and structure elucidation. Particular attention is placed on techniques for determining the relative and absolute configurations of stereocentres, including computational approaches, chemical derivatisation, and total synthesis. Furthermore, the review outlines the biosynthetic pathway of several newly identified cyanobacterial natural products.

Guanitoxin, a neurotoxin produced by cyanobacteria and the only known naturally occurring organophosphate, poses environmental risks comparable to synthetic organophosphate insecticides. Its effects on aquatic organisms, particularly in combination with compounds sharing similar mechanisms of action, remain poorly understood. This study evaluated the developmental toxicity of guanitoxin, alone and combined with the organophosphate insecticides malathion and trichlorfon, in zebrafish (Danio rerio) embryos and larvae at environmentally relevant concentrations. Developmental, neurobehavioral, and molecular endpoints were assessed. All compounds exhibited dose-dependent toxicity, with mixtures significantly enhancing both lethal and sublethal effects. The trichlorfon + guanitoxin combination was particularly potent, causing embryo coagulation, cardiac arrest, hatching failure, and pronounced pericardial swelling. Sublethal effects were consistently observed across mixtures, including edema, craniofacial malformations, muscle disorganization, and strong hypoactivity. Transcriptomic profiling revealed downregulation of genes critical for muscle contraction, synaptic signaling, energy metabolism and oxidative stress. The highest number of differentially expressed genes was observed in the trichlorfon + guanitoxin mixture (1348 genes). Synergistic interactions were observed, with mixture-induced effects exceeding those of individual compounds. Together, these findings demonstrate that guanitoxin, particularly in combination with synthetic organophosphates, poses a significant ecological risk and highlights the importance of considering mixture toxicity in environmental risk assessments.

Ongoing global warming caused by a steady increase in carbon dioxide in the atmosphere urgently needs to be mitigated. This is possible if phytoplankton biomass is increased in the ocean, as this will remove additional atmospheric CO₂. In the Southern Ocean, Fe is a well-known growth-limiting element, but the role of the other micronutrients remains very unclear. Our aim is to describe the evolution of each nutrient in the Southern Ocean throughout the year and to identify nutrients that limit phytoplankton growth. Therefore, we created a model that calculates nutrient consumption rates and available nutrient pools, fueled by deep winter mixing and diapycnal supply. Annual consumed nutrient amounts are smaller than their labile dissolved pools, but this is not true for limiting elements Fe and Co (from the sub-Antarctic zone [SAZ] to the Antarctic zone [AZ]) and Zn and Si (only in the SAZ). Since we found several limiting elements, fertilization with multiple nutrients would be required to promote large-scale carbon capture.

Winter dissolved nickel (dNi) and particulate nickel (pNi) concentrations were measured in the Southern Ocean (GEOTRACES GIpr07 transect) to investigate biogeochemical cycling within the water column and over seasonal timescales. Concentrations of dNi ranged from 1.98 to 8.21 nmol kg⁻¹ with low surface concentrations and maxima in deepest sampled water masses. Combining our winter data with the GEOTRACES Intermediate Data Product (2021) shows insignificant seasonal dNi variation in surface waters north of the Antarctic Polar Front, indicating the dominance of year-round mixing processes. However, lower summer concentrations than winter in the Antarctic Zone (∆0.23 nmol kg⁻¹) suggest a role for biological processes at high latitudes. For pNi, concentrations ranged from 5 to 49 pmol kg⁻¹ with higher values in surface/near-surface water masses. Vertical attenuation factors (b values) for pNi (0.19 ± 0.06) and particulate phosphorus (pP; 0.43 ± 0.10) suggest a greater retention of Ni in particles than P, invoking scavenging processes or refractory Ni phases. Water mass analysis shows that remineralization of pNi contributes a maximum of 6% of the highest measured dNi. Instead, dNi distributions and macronutrient relationships were largely explained by phytoplankton uptake in surface waters, and mixing and advection of Atlantic and Antarctic origin water masses, each with different preformed nutrient compositions. Winter trace metal measurements provide new perspectives regarding the balance between biological and physical drivers in the Southern Ocean. For Ni, the biological component is small with respect to physical mixing processes and over the timescales in which water masses accumulate Ni during their transport.

Over the last decades, the chromium (Cr) stable isotope system (referred to as δ⁵³Cr) has emerged as a proxy to reconstruct past oxygenation changes in Earth’s atmosphere and oceans. Although Cr is a promising paleoproxy, uncertainties remain as to the modern marine Cr cycle, and limited data are yet available in large swaths of the ocean, including the Atlantic Ocean. Here we present dissolved seawater Cr concentrations ([Cr]) and δ⁵³Cr along a meridional transect from the North to the South Atlantic (AMT 29). Chromium concentrations range from of 2.51 to 3.96 nmol kg⁻¹ (n = 68) and δ⁵³Cr values range from +0.86 ± 0.04 ‰ (2SEM) to +1.20 ± 0.02 ‰ (2SEM) (n = 68). In contrast to data from other ocean basins [Cr] and δ⁵³Cr show only a weak correlation (δ⁵³Cr vs. Ln([Cr]) R² = 0.17), inconsistent with a closed-system Rayleigh distillation model. These results can mainly be explained by horizontal advection and water mass mixing, which our data demonstrate are the dominant processes controlling [Cr] and δ⁵³Cr distributions throughout much of the Atlantic, while the impact of in situ biogeochemical cycling is comparatively minor. There is, indeed no clear impact of biological productivity nor of dysoxic environments in the (sub)tropical Atlantic on the cycling of Cr along the transect. This is likely explained by insufficiently depleted oxygen concentrations and relatively low biological productivity, resulting in these processes being of secondary importance relative to water mass mixing in shaping the distribution of Cr in the low- to mid-latitude Atlantic Ocean.

Toxic cyanobacteria are likely to be favored by global warming and other human impacts, posing significant threats to aquatic ecosystems. While cyanobacterial blooms in eutrophic lakes are widely investigated, the dynamics of cyanobacteria and the effects of their toxins and bioactive metabolites on the plankton communities in mesotrophic and oligotrophic lakes are less well understood. Here we investigated seasonal dynamics of cyanobacteria, eukaryotic algae and cyanotoxins in oligo-mesotrophic Lake Geneva—the largest and deepest lake in western Europe. High-throughput sequencing of the 16S rRNA genes in 143 samples along a water column revealed that Lake Geneva hosts diverse, co-dominant cyanobacterial genera, including Planktothrix, Cyanobium, Pseudanabaena, and Aphanizomenon. The abundance of the mcyA gene marker for microcystin production was highly correlated with total cyanobacteria abundance, obtained from qPCR of the 16S rRNA genes. Targeted LC-HRMS/MS analysis demonstrated peak concentrations of cyanotoxins in September and December 2021 at the deep chlorophyll-a maximum layer, reaching up to 1474 ng/l for anabaenopeptins and 144 ng/l for microcystins. The toxin peaks did not correlate with the abundance or variations in the cyanobacteria or eukaryote community, but they were correlated in time with seasonal lows in the abundances of ciliates (18S rRNA analysis). Laboratory exposure tests demonstrated that growth of the model ciliate Tetrahymena pyriformis was inhibited by Microcystin-RR and Anabaenopeptin A at environmentally relevant concentrations in the ng/l-range, in natural lake water, synthetic freshwater, and growth media spiked with the cyanotoxins. Our findings suggest that even low concentrations (in the ng/l-range) of microcystins and anabaenopeptins, reduce growth of ciliates such as T. pyriformis and can be expected to have wider impacts on the eukaryote communities.

The biogeochemistry of Cr and its cycling in Earth's surface environments is reviewed. A synthesis and critical evaluation of the major processes controlling Cr mobility and isotope composition (δ⁵³Cr) is presented, taking a source to sink view beginning with Cr mobilization from Earth's crust. Transport and cycling in inland waters and input to the oceans are discussed. Anthropogenic mobilization of Cr results in contributions to the atmosphere and inland waters that are of similar orders of magnitude as natural processes. The principal sources of Cr to the oceans are rivers and diffusive fluxes from marine sediments. Internal cycling of Cr in the ocean is largely controlled by reductive removal onto particles, particularly in O₂-depleted waters, and redistribution through ocean circulation. Chromium removal from the oceans occurs primarily in organic carbon-rich, O₂-poor shelf sediments. Despite theoretically poor mobility of Cr(III), reductive removal in anoxic waters is non-quantitative. As a result, isotope fractionation drives δ⁵³Cr offsets in removed Cr as well as residual dissolved Cr(III), which accumulates in anoxic water, compared to the corresponding source. The implications for δ⁵³Cr-based reconstructions are discussed, along with an outlook for future proxy applications based on the processes controlling Cr incorporation into sediments. The roles of different source and sink processes are quantified in an updated mass balance for the global ocean. Finally, priority topics for future research are suggested, which at present are the primary uncertainties of the modern Cr biogeochemical cycle and aspects of the Cr isotope mass balance.

Tintenstrich communities are specialized lithic biofilms dominated by free-living cyanobacteria, also occurring in lichen associations, forming a unique ecological interface between rock environments and aquatic habitats in mountainous areas. To better understand their composition and genetic and metabolic potential, we analyzed 207 samples from the Swiss Alps and Jura Mountains. We determined how key environmental factors shaped cyanobacterial abundance, assessed whether these communities harbor genes for toxin biosynthesis, characterized their taxonomic composition at the family and genus level, and evaluated the actual occurrence of cyanotoxins and other bioactive metabolites. Cyanobacterial abundance proved to be influenced by factors such as elevation, exposure, and their interaction with siliceous rock substrata. Targeted PCR and Sanger sequencing revealed the presence of toxin-encoding genes, particularly for ndaF/mcyE fragments, which may encode microcystin and/or nodularin biosynthesis, while specific genes for microcystins, anatoxins, and cylindrospermopsins were rather rare. Metabarcoding analysis identified 11 cyanobacterial families, with Chroococcaceae, Nostocaceae, and Leptolyngbyaceae being the most abundant. Complementary high-resolution mass spectrometry confirmed the occasional presence of nodularins and microcystins, alongside more frequent detection of other bioactive peptides such as anabaenopeptins and cyanopeptolins. Overall, these findings provide the most comprehensive insight to date into Tintenstrich-associated cyanobacteria, underscoring their environmental significance given their genetic and metabolic potential.

The primary production of fjords across the Arctic and Subarctic is undergoing significant transformations due to the climatically driven retreat of glaciers and ice sheets. However, the implications of these changes for upper trophic levels remain largely unknown. In this study, we employ both bulk and compound-specific stable isotope analyses to investigate how shifts at the base of fjord food webs impact the carbon and energy sources of consumers. Focusing on two rapidly changing fjords in Southern Greenland, we used the migratory Arctic char as an indicator species, sampling populations along environmental gradients within the fjords, building upon the assumption that char populations feed primarily close to their natal stream, thereby integrating a dietary gradient. Our analysis of bulk stable isotopes in Arctic char tissue confirmed this premise, revealing a consistent change in resource use from the outer to the inner fjord, which nonetheless served as preferred feeding grounds. Essential amino acid analysis further indicated shifts in carbon and nitrogen sources, consistent with changes in nutrient use near glacier inputs characterized by low turbidity and high iron levels. Notably, these changes in the source of primary production were associated with shifts in trophic positions and the transfer of polyunsaturated fatty acids, with Arctic char in glacier-influenced inner fjords feeding at lower trophic level (size-corrected) and accumulating higher levels of high-quality docosahexaenoic acid (DHA). These findings highlight the usefulness of new analytical tools in revealing that glacial retreat can substantially alter food web dynamics, enhancing both carbon flow and the nutritional quality of fish in fjord ecosystems. The two Southern Greenland fjords studied could represent the future of other fjords, where retreating glaciers become land-terminating and glacial inputs decrease. Our study underscores the critical role of glacier dynamics in affecting high-level consumers, such as salmonids, with implications for fjords globally.

Cyanobacteria produce toxic and bioactive secondary metabolites, posing risks to ecosystems and human health, yet their transformation pathways in surface waters remain unclear. We assessed biotransformation for 40 cyanopeptides including microcystins, anabaenopeptins and cyanopeptolins in surface waters and in situ enriched biofilm suspensions. In surface waters, most cyanopeptides did not degrade significantly over the course of 7 days. A wide range of biodegradability across cyanopeptides was apparent in biofilm suspensions from three rivers. Increasing the biofilm density shortened the lag time and increased initial removal of cyanopeptides. Increasing the initial cyanopeptide concentration lengthened the lag time and decreased their initial removal, supporting inhibitory effects of cyanopeptides toward enzymes involved in their own transformation. Transformation kinetics and product analysis demonstrated a structure–reactivity relationship across and within cyanopeptide classes. Anabaenopeptins were hydrolyzed at the C-terminus when arginine, tyrosine and (iso)leucine were present, but not when phenylalanine or tryptophan was present. Microcystins showed tetrapeptide formation when adda linked to arginine but not when it linked to alanine, leucine, or tyrosine. Oxidation of tyrosine and deamination of arginine residues showed an interdependence across cyanopeptide classes. These novel insights into biotransformation products and pathways of a wide range of cyanopeptides facilitate assessment of exposure scenarios in surface waters and inform about kinetics and product formation in biological water treatment.

Inland waters play a crucial role in the global carbon cycle, with lakes integrating carbon from various sources within their catchment in addition to that fixed by local primary productivity. Isotopic measurements of carbon pools can differentiate contributions from these sources, with natural abundance radiocarbon (¹⁴C) a particularly powerful tool due to the large range in ¹⁴C characteristics among carbon sources. Here, we present ¹⁴C measurements of dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC) from monthly water column samplings over the course of a year in Lake Geneva, a large oligotrophic hard water perialpine lake in Western Europe. We find that DIC in the lake is significantly ¹⁴C-depleted relative to the atmosphere primarily due to the dissolution of carbonate rocks in the lake's catchment. Variability in DI¹⁴C is largely tied to the Rhône River inflow, where DI¹⁴C values were also found to vary seasonally. DOC has a ¹⁴C signature similar to that of DIC, reflecting the fact that much of the lake DOC pool is autochthonous. However, more ¹⁴C-depleted DOC was observed in July and tied to increased river discharge from snow and glacier melt within the upper Rhône River basin. These observations shed light on carbon sources and dynamics within Lake Geneva and its alpine catchment and highlight the importance of preaged dissolved carbon inputs to the largest natural lake in Western Europe.

Swiss geosciences are at the heart of major national and global challenges that our society is facing, including climate change and weather extremes, long-term environmental trends, natural hazards (e.g. landslides, floods, seismic and volcanic events), the energy transition towards a green and blue economy, sustainable management of natural resources (e.g. water, soils, ecosystems, critical metals, building materials), and the increasing interest towards extra-terrestrial life and resources. In order to remain at the forefront of geosciences research and provide the fertile environment necessary for groundbreaking findings addressing these societal challenges, the Swiss Geosciences Community proposes five large infrastructures, organised into four pillars built on a common datadriven research foundation. [...]

Freshwater pollution is, together with climate change, one of today's most severe and pervasive threats to the global environment. Comprehensive and spatially explicit scenarios covering a wide range of constituents for freshwater quality are currently scarce. In this Global Perspective paper, we propose a novel model-based approach for five water quality constituents relevant for human and ecosystem health (nitrogen, biochemical oxygen demand, anthropogenic chemicals, fecal coliform, and arsenic). To project the driving forces and consequences for emissions and impacts, a set of common data based on the same assumptions was prepared and used in different large-scale water quality models including all relevant demographic, socioeconomic, and cultural changes, as well as threshold concentrations to determine the risk for human and ecosystem health. The analysis portrays the strong links among water quality, socio-economic development, and lifestyle. Internal consistency of assumptions and input data is a prerequisite for constructing comparable scenarios using different models to support targeted policy development.

The highly biodiverse Lake Poso, located in Central Sulawesi, Indonesia, can be considered one of the least studied ancient lakes in the world. Here, we present a comprehensive analysis of Lake Poso's hydrology and hydrochemistry, shedding light on factors that may have contributed to the exceptional biodiversity. Riverine and lake water chemical compositions indicated a soft water lake and relative major cation and anion abundances of Ca²⁺ ≫ Mg²⁺ > Na⁺ > K⁺ and HCO₃^– ≫ SO₄²⁻ > Cl⁻, primarily a result of the high annual precipitation and chemical weathering of calcareous-siliceous metamorphic bedrock. Lake Poso’s nutrient concentrations were low (average DIN/TDP mass ratio of 6.2 and 50.9 for the lake surface water and its tributaries, respectively), indicating that most of the inlets were P-limited and that the lake was likely P-limited as well. Metal pollutants indicated a minor to moderate impact of anthropogenic land use (∼32 % of the catchment area). Water isotopic compositions of the different tributaries clearly delineated rivers draining higher elevation catchments with lower δ²H and δ¹⁸O from those draining lower elevation catchments with higher δ²H and δ¹⁸O. Surface lake water isotopic compositions indicated detectable evaporation from the lake leading toward more enriched isotope compositions than the integrated source signal. Overall, the findings suggested that Lake Poso remains relatively resilient to anthropogenic land use and related nutrient and pollutant inputs. However, ongoing alterations to its hydrological balance due to significant changes in land use may drive the lake towards higher trophic levels in the future.

L'état global de la qualité des lacs en Suisse a tendance à s'améliorer, mais de nombreux problèmes d'oxygénation dans le fond des lacs persistent. Ce phénomène, lié aux concentrations actuelles et passées de phosphore, demeure préoccupant. La modélisation au coeur de cette étude vise à guider le choix d'approches simples mais appropriées pour la gestion des lacs. Deux exemples d'applications pour les lacs de Schiffenen et de Baldegg sont illustrés.

Iron-rich, ferruginous waters were the dominant geochemical regime for most of Earth's history. Modern ferruginous waters are found in stratified, sulfur-poor lakes, and serve as crucial analogs for biogeochemical cycling throughout Earth's past. Here we present the first depth-resolved data of physical structure, nutrients and trace elements from Lake Poso (Indonesia), a deep oligotrophic ancient lake. Lake Poso is ferruginous, with anoxia below ~ 90 m depth, placing it among the world's largest ferruginous lakes. Physical stratification is weaker than other tropical anoxic lakes, indicating sensitivity for paleoclimate reconstructions. Trace elements and nutrients are predominantly shaped by the oxic–anoxic transition. Manganese– and Fe oxyhydroxide–driven biogeochemical cycling occurs at distinct depth horizons, with Co and Ni controlled by Mn and showing shallow release in anoxic waters, while V, Cr, P, and As are controlled by Fe, with release in surface sediments and diffusive transport. Chromium is nonquantitatively removed in anoxic waters, in contrast to widespread assumptions in Cr-based paleoreconstructions. Oxycline U and Se removal corresponds to a local N minimum, suggesting biological reduction and/or uptake. These first ferruginous water Se data also show removal in sediments, indicating sediment signals reflect multiple removal processes and informing Se-based paleoreconstructions, while the absence of sediment U removal contrasts other anoxic basins. A comparison with other ferruginous lakes demonstrates how local influences drive deviations from expectations in other systems, and highlight common, generalizable ferruginous basin features. Therefore, these data will guide research in ferruginous settings across space and time, and improve paleoreconstructions from ferruginous sediment records.

Tintenstrich communities (TCs) mainly comprise Cyanobacteria developing on rock substrates and forming physical structures that are strictly connected to the rock itself. Endolithic and epilithic bacterial communities are important because they contribute to nutrient release within run-off waters flowing on the rock surface. Despite TCs being ubiquitous, little information about their ecology and main characteristics is available. In this study, we characterized the bacterial communities of rock surfaces of TCs in Switzerland through Illumina sequencing. We investigated their bacterial community composition on two substrate types (siliceous rocks [SRs] and carbonate rocks [CRs]) through multivariate models. Our results show that Cyanobacteria and Proteobacteria are the predominant phyla in this environment. Bacterial α-diversity was higher on CRs than on SRs, and the β-diversity of SRs varied with changes in rock surface structure. In this study, we provide novel insights into the bacterial community composition of TCs, their differences from other lithic communities, and the effects of the rock substrate and structure.

Cyanobacterial blooms occur at increasing frequency and intensity, notably in freshwater. This leads to the introduction of complex mixtures of their products, i.e., cyano-metabolites, to drinking water treatment plants. To assess the fate of cyano-metabolite mixtures during ozonation, a novel multicompound ozone (O₃) competition kinetics method was developed. Sixteen competitors with known second-order rate constants for their reaction with O₃ ranging between 1 and 10⁸ M^–1 s^–1 were applied to cover a wide range of the O₃ reactivity. The apparent second-order rate constants (k_app,O3) at pH 7 were simultaneously determined for 31 cyano-metabolites. k_app,O3 for olefin- and phenol-containing cyano-metabolites were consistent with their expected reactivity (0.4–1.7 × 10⁶ M^–1 s^–1) while k_app,O3 for tryptophan- and thioether-containing cyano-metabolites were significantly higher than expected (3.4–7.3 × 10⁷ M^–1 s^–1). Cyano-metabolites containing these moieties are predicted to be well abated during ozonation. For cyano-metabolites containing heterocycles, k_app,O3 varied from <10² to 5.0 × 10³ M^–1 s^–1, giving first insights into the O₃ reactivity of this class of compounds. Due to lower O₃ reactivities, heterocycle- and aliphatic amine-containing cyano-metabolites may be only partially degraded by a direct O₃ reaction near circumneutral pH. Hydroxyl radicals, which are formed during ozonation, may be more important for their abatement. This novel multicompound kinetic method allows a high-throughput screening of ozonation kinetics.

In a warming world, the input of glacier meltwater to inland water ecosystems is predicted to change, potentially affecting their productivity. Meta-ecosystem theory, which posits that the nutrient availability in the recipient ecosystem can determine the extent of cross-ecosystem boundary utilization, can be useful for studying landscape-scale influences of glacier meltwater on inland waters. Here, we investigate how the input of glacier meltwater in a river system in Southern Greenland influences the utilization of marine subsidies in freshwater fish. Our study system comprised four sites, with controls for glacial meltwater and marine subsidies, harboring a partially migrating population of arctic char, meaning that some individuals migrate to the ocean and others remain in freshwaters, and two fully resident populations as a freshwater reference. We assessed the incorporation of marine carbon in freshwater resident char using both bulk and amino acid stable isotope analysis of muscle tissue. In the population with partial migration, marine subsidies were a significant resource for resident char individuals, and estimates of trophic position suggest that egg cannibalism is an important mechanism underlying the assimilation of these marine subsidies. In proglacial streams, namely those with high glacial meltwater, the total dependence on marine subsidies increased and reached 83% because char become cannibals at smaller sizes. In the configuration of our focal meta-ecosystem, our results suggest that the importance of marine subsidies to freshwater fish strengthens within increasing meltwater flux from upstream glaciers.

The UV–vis absorbance spectra, molar extinction coefficients and circular dichroism spectra, as well as NMR and high resolution tandem mass spectrometry spectra were determined for two prominent secondary metabolites from cyanobacteria, namely anabaenopeptin A and anabaenopeptin B. The compounds were extracted from the cyanobacterium Planktothrix rubescens CBT929 and purified by flash chromatography and HPLC. Exact amounts of isolated compounds were assessed by quantitative ¹H-NMR with internal calibrant ethyl 4-(dimethylamino)benzoate in DMSO‑d₆ at 298 K with a recycle delay (d1) of 120 s. UV–vis absorbance spectra were recorded in methanol at room temperature. Molar extinction coefficients were determined at 278 nm as 4190 M⁻¹ cm⁻¹ and 2300 M⁻¹ cm⁻¹ in methanol for anabaenopeptin A and anabaenopeptin B, respectively. Circular dichroism spectra and secondary fragmentation mass spectra are also reported.

The mass proliferation of cyanobacteria, episodes known as blooms, is a concern worldwide. One of the most critical aspects during these blooms is the production of toxic secondary metabolites that are not limited to the four cyanotoxins recognized by the World Health Organization. These metabolites comprise a wide range of structurally diverse compounds that possess bioactive functions. Potential human and ecosystem health risks posed by these metabolites and co-produced mixtures remain largely unknown. We studied acute lethal and sublethal effects measured as impaired mobility on the freshwater microcrustaceans Thamnocephalus platyurus for metabolite mixtures from two cyanobacterial strains, a microcystin (MC) producer and a non-MC producer. Both cyanobacterial extracts, from the MC-producer and non-MC-producer, caused acute toxicity with LC₅₀ (24 h) values of 0.50 and 2.55 mg_{dw_biomass}/mL, respectively, and decreased locomotor activity. Evaluating the contribution of different cyanopeptides revealed that the Micropeptin-K139-dominated fraction from the MC-producer extract contributed significantly to mortality and locomotor impairment of the microcrustaceans, with potential mixture effect with other cyanopeptolins present in this fraction. In the non-MC-producer extract, compounds present in the apolar fraction contributed mainly to mortality, locomotor impairment, and morphological changes in the antennae of the microcrustacean. No lethal or sublethal effects were observed in the fractions dominated by other cyanopetides (Cyanopeptolin 959, Nostoginin BN741). Our findings contribute to the growing body of research indicating that cyanobacterial metabolites beyond traditional cyanotoxins cause detrimental effects. This underscores the importance of toxicological assessments of such compounds, also at sublethal levels.

Per- and polyfluoroalkyl substances (PFAS) pose significant environmental and health risks due to their ubiquitous presence and persistence in water systems. Herein, the efficacy of piezocatalysis using barium titanate nanoparticles under ultrasound irradiation for the degradation and defluorination of perfluorooctane sulfonate (PFOS) in water is investigated. The research demonstrates a substantial 90.5% degradation and 29% defluorination of PFOS after 6 h of treatment, highlighting the potential of piezocatalysis as a promising approach for PFAS degradation. Additionally, the quantification of degradation products elucidates the transformation pathways of PFOS, suggesting a stepwise chain-shortening mechanism. The findings underscore the importance of continued research in optimizing piezocatalytic processes and exploring synergistic approaches with other advanced oxidation methods to effectively address PFAS contamination challenges. These efforts are essential for advancing sustainable water treatment strategies and mitigating the environmental and health hazards associated with PFAS contamination.

Cyanobacterial blooms require monitoring, as they pose a threat to ecosystems and human health, especially by the release of toxins. Along with widely reported microcystins, cyanobacteria coproduce other bioactive metabolites; however, information about their dynamics in surface waters is sparse. We investigated dynamics across full bloom successions throughout a five-year lake monitoring campaign (Greifensee, Switzerland) spanning 150 sampling dates. We conducted extensive suspect screening of cyanobacterial metabolites using the database CyanoMetDB. Across all 850 samples, 35 metabolites regularly co-occurred. Microcystins were present in 70% of samples, with [d-Asp³,(E)-Dhb⁷]MC-RR reaching concentrations of 70 ng/L. Anabaenopeptins, meanwhile, were detected in 95% of all samples with concentrations of Oscillamide Y up to 100-fold higher than microcystins. Based on LC-MS response and frequency, we identified indicator metabolites exclusively produced by one of three cyanobacteria isolated from the lake, these being [d-Asp³,(E)-Dhb⁷]MC-RR from Planktothrix sp. G2020, Microginin 761B from Microcystis sp. G2011, and Ferintoic acid B from Microcystis sp. G2020. These indicators showed distinct temporal trends and peaking seasons that reflect the variance in either the abundance of the producing cyanobacteria or their toxin production dynamics. Our approach demonstrates that selecting high LC-MS response and frequent and species-specific indicator metabolites can be advantageous for cyanobacterial monitoring.

Dissolved iron (dFe) availability limits the uptake of atmospheric CO₂ by the Southern Ocean (SO) biological pump. Hence, any change in bioavailable dFe in this region can directly influence climate. On the basis of Fe uptake experiments with Phaeocystis antarctica, we show that the range of dFe bioavailability in natural samples is wider (<1 to ~200% compared to free inorganic Fe′) than previously thought, with higher bioavailability found near glacial sources. The degree of bioavailability varied regardless of in situ dFe concentration and depth, challenging the consensus that sole dFe concentrations can be used to predict Fe uptake in modeling studies. Further, our data suggest a disproportionately major role of biologically mediated ligands and encourage revisiting the role of humic substances in influencing marine Fe biogeochemical cycling in the SO. Last, we describe a linkage between in situ dFe bioavailability and isotopic signatures that, we anticipate, will stimulate future research.

Special attention has been given to chromium (Cr) as a paleoproxy tracing redox cycling throughout Earth’s history, due to differences in the solubility of its primary redox species at Earth’s surface (Cr(III) and Cr(VI)) and isotope fractionation associated with their interconversion. In turn, chromium’s paleoproxy potential has motivated studies of the modern ocean to better understand which processes drive its cycling and to constrain their impact on the Cr isotope composition (δ⁵³Cr) of seawater. Here, we present total dissolved seawater Cr concentrations and δ⁵³Cr along the GEOTRACES GP13 section. This section is a zonal transect extending from Australia in the subtropical southwest Pacific Ocean. Surface signals of local biological Cr cycling are minimal, in agreement with distributions of dissolved major nutrients as well as biologically-controlled trace metals in this low productivity, oligotrophic environment. Depth profiles have Cr concentration minima in surface waters and maxima at depth, and are largely shaped by the advection of nutrient- and Cr-rich subsurface waters rather than vertically-driven processes. Samples close to the sediment-water interface indicate important benthic Cr fluxes across the section.
The GP13 transect crosses the hydrothermally-active Kermadec Arc. Hydrothermal fluids (consisting of <15% background seawater) were collected from three venting sites at the Brothers Volcano (along the Kermadec Arc). These fluids yielded near-crustal δ⁵³Cr values (-0.17 to +0.08‰) and elevated [Cr] (7.5-23 nmol kg^-1, hydrothermal endmember [Cr] ≈ 8-27 nmol kg^-1), indicating that the Kermadec Arc may be an isotopically light Cr source. Dissolved [Fe] enrichments have been reported previously in deep waters (∼1600-3000 m) along the GP13 transect, east of the Kermadec Arc. These same waters show elevated [Cr] compared to Circumpolar Deep Water ([Cr] = 3.88 ± 0.11, δ⁵³Cr = 0.89 ± 0.08, n = 32), with an average [Cr] accumulation of 0.71 ± 0.11 nmol kg^-1 (1 SD), and an estimated δ⁵³Cr of +0.46 ± 0.30‰ (2 SD, n = 9) for the accumulated Cr. Comparing high-temperature vent and neutrally buoyant plume data, hydrothermal-sourced Cr is likely negligable compared to Cr contributions from other processes (benthic fluxes, release from particles), and the advection of more Cr-rich Pacific Deep Water. It is unlikely that hydrothermal vents would be a major contributor within the regional or global biogeochemical Cr cycle, even if hydrothermal fluxes change by orders of magnitude, and therefore δ⁵³Cr trends in the paleorecord may be attributable, at least in part, to major changes in other controls on Cr (e.g. widespread anoxia).

Identifying a chemical's potential for biotransformation in the aquatic environment is crucial to predict its fate and manage its potential hazards. Due to the complexity of natural water bodies, especially river networks, biotransformation is often studied in laboratory experiments, assuming that study outcomes can be extrapolated to compound behavior in the field. Here, we investigated to what extent outcomes of laboratory simulation studies indeed reflect biotransformation kinetics observed in riverine systems. To determine in-field biotransformation, we measured loads of 27 wastewater treatment plant effluent-borne compounds along the Rhine and its major tributaries during two seasons. Up to 21 compounds were detected at each sampling location. Measured compound loads were used in an inverse model framework of the Rhine river basin to derive k'_bio,field values – a compound-specific parameter describing the compounds' average biotransformation potential during the field studies. To support model calibration, we performed phototransformation and sorption experiments with all the study compounds, identifying 5 compounds that are susceptible towards direct phototransformation and determining K_oc values covering four orders of magnitude. On the laboratory side, we used a similar inverse model framework to derive k'_bio,lab values from water-sediment experiments run according to a modified OECD 308-type protocol. The comparison of k'_bio,lab and k'_bio,field revealed that their absolute values differed, pointing towards faster transformation in the Rhine river basin. Yet, we could demonstrate that relative rankings of biotransformation potential and groups of compounds with low, moderate and high persistence agree reasonably well between laboratory and field outcomes. Overall, our results provide evidence that laboratory-based biotransformation studies using the modified OECD 308 protocol and k'_bio values derived thereof bear considerable potential to reflect biotransformation of micropollutants in one of the largest European river basins.

Cyanobacterial blooms affect aquatic ecosystems across the globe and one major concern relates to their toxins such as microcystins (MC). Yet, the ecotoxicological risks, particularly non-lethal effects, associated with other co-produced secondary metabolites remain mostly unknown. Here, we assessed survival, morphological alterations, swimming behaviour and cardiovascular functions of zebrafish (Danio rerio) upon exposure to cyanobacterial extracts of two Brazilian Microcystis strains. We verified that only MIRS-04 produced MCs and identified other co-produced cyanopeptides also for the MC non-producer NPCD-01 by LC-HRMS/MS analysis. Both cyanobacterial extracts, from the MC-producer and non-producer, caused acute toxicity in zebrafish with LC₅₀ values of 0.49 and 0.98 mg_{dw_biomass}/mL, respectively. After exposure to MC-producer extract, additional decreased locomotor activity was observed. The cyanopeptolin (micropeptin K139) contributed 52% of the overall mortality and caused oedemas of the pericardial region. Oedemas of the pericardial area and prevented hatching were also observed upon exposure to the fraction with high abundance of a microginin (Nostoginin BN741) in the extract of the MC non-producer. Our results further add to the yet sparse understanding of lethal and sublethal effects caused by cyanobacterial metabolites other than MCs and the need to better understand the underlying mechanisms of the toxicity. We emphasize the importance of considering mixture toxicity of co-produced metabolites in the ecotoxicological risk assessment of cyanobacterial bloom events, given the importance for predicting adverse outcomes in fish and other organisms.

Empirical evidence demonstrates that lakes and reservoirs are warming across the globe. Consequently, there is an increased need to project future changes in lake thermal structure and resulting changes in lake biogeochemistry in order to plan for the likely impacts. Previous studies of the impacts of climate change on lakes have often relied on a single model forced with limited scenario-driven projections of future climate for a relatively small number of lakes. As a result, our understanding of the effects of climate change on lakes is fragmentary, based on scattered studies using different data sources and modelling protocols, and mainly focused on individual lakes or lake regions. This has precluded identification of the main impacts of climate change on lakes at global and regional scales and has likely contributed to the lack of lake water quality considerations in policy-relevant documents, such as the Assessment Reports of the Intergovernmental Panel on Climate Change (IPCC). Here, we describe a simulation protocol developed by the Lake Sector of the Inter-Sectoral Impact Model Intercomparison Project (ISIMIP) for simulating climate change impacts on lakes using an ensemble of lake models and climate change scenarios for ISIMIP phases 2 and 3. The protocol prescribes lake simulations driven by climate forcing from gridded observations and different Earth system models under various representative greenhouse gas concentration pathways (RCPs), all consistently bias-corrected on a 0.5^∘ × 0.5^∘ global grid. In ISIMIP phase 2, 11 lake models were forced with these data to project the thermal structure of 62 well-studied lakes where data were available for calibration under historical conditions, and using uncalibrated models for 17 500 lakes defined for all global grid cells containing lakes. In ISIMIP phase 3, this approach was expanded to consider more lakes, more models, and more processes. The ISIMIP Lake Sector is the largest international effort to project future water temperature, thermal structure, and ice phenology of lakes at local and global scales and paves the way for future simulations of the impacts of climate change on water quality and biogeochemistry in lakes.

Chromium stable isotope composition (δ⁵³Cr) is a promising tracer for redox conditions throughout Earth's history; however, the geochemical controls of δ⁵³Cr have not been assessed in modern redox-stratified basins. We present new chromium (Cr) concentration and δ⁵³Cr data in dissolved, sinking particulate, and sediment samples from the redox-stratified Lake Cadagno (Switzerland), a modern Proterozoic ocean analog. These data demonstrate isotope fractionation during incomplete (non-quantitative) reduction and removal of Cr above the chemocline, driving isotopically light Cr accumulation in euxinic deep waters. Sediment authigenic Cr is isotopically distinct from overlying waters but comparable to average continental crust. New and published data from other redox-stratified basins show analogous patterns. This challenges assumptions from δ⁵³Cr paleoredox applications that quantitative Cr reduction and removal limits isotope fractionation. Instead, fractionation from non-quantitative Cr removal leads to sedimentary records offset from overlying waters and not reflecting high δ⁵³Cr from oxidative continental weathering.

The frequency and intensity of cyanobacterial blooms continue to increase in freshwater systems across the globe. Cyanobacteria can release toxins and several bioactive secondary metabolites and analytical methods are needed to effectively assess their concentrations in surface waters. Since booms can evolve rapidly in parts of a lake, high resolution of spatial and temporal sampling increases the complexity of monitoring efforts. Here, we present the validation of an automated, online-solid phase extraction (SPE) high performance liquid chromatography (HPLC)-high resolution tandem mass spectrometry (HRMS/MS) method. This online-SPE HPLC-HRMS/MS methods enables quantitative monitoring of surface waters for 17 cyanobacterial peptides (cyanopeptides), spanning 5 distinct cyanopeptide classes, including: microcystins, anabaenopeptins, nodularins, cyclamides and cyanopeptolins. The method can quantify these cyanopeptides in the low ng/L-range with high accuracy (85-116%) and low relative matrix effects (<25%). We demonstrated its application to Swiss lake waters (Zürichsee, Hallwilersee, Greifensee), which also highlighted the value of adding cyanopeptides beyond common microcystins when monitoring surface waters for cyanobacteria.

Cyanobacteria, also known as blue-green algae, are photosynthetic bacteria that can colonize different habitats, including extreme ones. They are of great interest to the scientific community, especially because of their ability to produce cyanotoxins: toxic secondary metabolites potentially harmful to organisms especially when released to surface waters.

Background: The NORMAN Association (https://www.norman-network.com/) initiated the NORMAN Suspect List Exchange (NORMAN-SLE; https://www.norman-network.com/nds/SLE/) in 2015, following the NORMAN collaborative trial on non-target screening of environmental water samples by mass spectrometry. Since then, this exchange of information on chemicals that are expected to occur in the environment, along with the accompanying expert knowledge and references, has become a valuable knowledge base for “suspect screening” lists. The NORMAN-SLE now serves as a FAIR (Findable, Accessible, Interoperable, Reusable) chemical information resource worldwide.
Results: The NORMAN-SLE contains 99 separate suspect list collections (as of May 2022) from over 70 contributors around the world, totalling over 100,000 unique substances. The substance classes include per- and polyfluoroalkyl substances (PFAS), pharmaceuticals, pesticides, natural toxins, high production volume substances covered under the European REACH regulation (EC: 1272/2008), priority contaminants of emerging concern (CECs) and regulatory lists from NORMAN partners. Several lists focus on transformation products (TPs) and complex features detected in the environment with various levels of provenance and structural information. Each list is available for separate download. The merged, curated collection is also available as the NORMAN Substance Database (NORMAN SusDat). Both the NORMAN-SLE and NORMAN SusDat are integrated within the NORMAN Database System (NDS). The individual NORMAN-SLE lists receive digital object identifiers (DOIs) and traceable versioning via a Zenodo community (https://zenodo.org/communities/norman-sle), with a total of > 40,000 unique views, > 50,000 unique downloads and 40 citations (May 2022). NORMAN-SLE content is progressively integrated into large open chemical databases such as PubChem (https://pubchem.ncbi.nlm.nih.gov/) and the US EPA’s CompTox Chemicals Dashboard (https://comptox.epa.gov/dashboard/), enabling further access to these lists, along with the additional functionality and calculated properties these resources offer. PubChem has also integrated significant annotation content from the NORMAN-SLE, including a classification browser (https://pubchem.ncbi.nlm.nih.gov/classification/#hid=101).
Conclusions: The NORMAN-SLE offers a specialized service for hosting suspect screening lists of relevance for the environmental community in an open, FAIR manner that allows integration with other major chemical resources. These efforts foster the exchange of information between scientists and regulators, supporting the paradigm shift to the “one substance, one assessment” approach. New submissions are welcome via the contacts provided on the NORMAN-SLE website (https://www.norman-network.com/nds/SLE/).

From winter 2013–14 to the end of 2015–16, a high pressure atmospheric system induced elevated sea surface temperatures in the offshore subarctic northeast Pacific, resulting in a marine heatwave. Increased stratification due to the heatwave resulted in shoaling of the winter mixed layer and a decrease in nutrient re-supply to the euphotic zone. Here, we investigate relationships between dissolved iron (dFe) and macronutrients, net community production (NCP), (micro)nutrient uptake ratios, and phytoplankton community composition in the winter and summer from 2012 to 2015 to gain insight into coupled biogeochemical responses to the heatwave. Our investigation highlights the importance of external dFe supply during marine heatwave events, as a more shallow mixed layer reduces the transport of essential (micro)macronutrients to the surface layer. We conclude that recycled dFe did not contribute to NCP in 2014, but rather the vertical displacement of dFe rich water unrelated to mixed layer deepening played a major role. In 2015, such transport was not detected, resulting in abnormally low dFe and shift toward higher biomass of pico- and nano-phytoplankton size-classes.

Within the natural products field there is an increasing emphasis on the study of compounds from microbial sources. This has been fuelled by interest in the central role that microorganisms play in mediating both interspecies interactions and host-microbe relationships. To support the study of natural products chemistry produced by microorganisms we released the Natural Products Atlas, a database of known microbial natural products structures, in 2019. This paper reports the release of a new version of the database which includes a full RESTful application programming interface (API), a new website framework, and an expanded database that includes 8128 new compounds, bringing the total to 32 552. In addition to these structural and content changes we have added full taxonomic descriptions for all microbial taxa and have added chemical ontology terms from both NP Classifier and ClassyFire. We have also performed manual curation to review all entries with incomplete configurational assignments and have integrated data from external resources, including CyanoMetDB. Finally, we have improved the user experience by updating the Overview dashboard and creating a dashboard for taxonomic origin. The database can be accessed via the new interactive website at https://www.npatlas.org.

Background: Bloom-forming cyanobacteria occur globally in aquatic environments. They produce diverse bioactive metabolites, some of which are known to be toxic. The most studied cyanobacterial toxins are microcystins, anatoxin, and cylindrospermopsin, yet more than 2000 bioactive metabolites have been identified to date. Data on the occurrence of cyanopeptides other than microcystins in surface waters are sparse.
Results: We used a high-performance liquid chromatography–high-resolution tandem mass spectrometry/tandem mass spectrometry (HPLC–HRMS/MS) method to analyse cyanotoxin and cyanopeptide profiles in raw drinking water collected from three freshwater reservoirs in the United Kingdom. A total of 8 cyanopeptides were identified and quantified using reference standards. A further 20 cyanopeptides were identified based on a suspect-screening procedure, with class-equivalent quantification. Samples from Ingbirchworth reservoir showed the highest total cyanopeptide concentrations, reaching 5.8, 61, and 0.8 µg/L in August, September, and October, respectively. Several classes of cyanopeptides were identified with anabaenopeptins, cyanopeptolins, and microcystins dominating in September with 37%, 36%, and 26%, respectively. Samples from Tophill Low reservoir reached 2.4 µg/L in September, but remained below 0.2 µg/L in other months. Samples from Embsay reservoir did not exceed 0.1 µg/L. At Ingbirchworth and Tophill Low, the maximum chlorophyll-a concentrations of 37 µg/L and 22 µg/L, respectively, and cyanobacterial count of 6 × 10⁴ cells/mL were observed at, or a few days after, peak cyanopeptide concentrations. These values exceed the World Health Organization’s guideline levels for relatively low probability of adverse health effects, which are defined as 10 µg/L chlorophyll-a and 2 × 10⁴ cells/mL.
Conclusions: This data is the first to present concentrations of anabaenopeptins, cyanopeptolins, aeruginosins, and microginins, along  with microcystins, in U.K. reservoirs. A better understanding of those cyanopeptides that are abundant in drinking water reservoirs can inform future monitoring and studies on abatement efficiency during water treatment.

Harmful cyanobacterial blooms, which frequently contain toxic secondary metabolites, are reported in aquatic environments around the world. More than two thousand cyanobacterial secondary metabolites have been reported from diverse sources over the past fifty years. A comprehensive, publically-accessible database detailing these secondary metabolites would facilitate research into their occurrence, functions and toxicological risks. To address this need we created CyanoMetDB, a highly curated, flat-file, openly-accessible database of cyanobacterial secondary metabolites collated from 850 peer-reviewed articles published between 1967 and 2020. CyanoMetDB contains 2010 cyanobacterial metabolites and 99 structurally related compounds. This has nearly doubled the number of entries with complete literature metadata and structural composition information compared to previously available open access databases. The dataset includes microcytsins, cyanopeptolins, other depsipeptides, anabaenopeptins, microginins, aeruginosins, cyclamides, cryptophycins, saxitoxins, spumigins, microviridins, and anatoxins among other metabolite classes. A comprehensive database dedicated to cyanobacterial secondary metabolites facilitates: (1) the detection and dereplication of known cyanobacterial toxins and secondary metabolites; (2) the identification of novel natural products from cyanobacteria; (3) research on biosynthesis of cyanobacterial secondary metabolites, including substructure searches; and (4) the investigation of their abundance, persistence, and toxicity in natural environments.

To assess the risks associated with cyanobacterial blooms, the persistence and fate processes of cyanotoxins and other bioactive cyanobacterial metabolites need to be evaluated. Here, we investigated the reaction with photochemically produced singlet oxygen (¹O₂) for 30 cyanopeptides synthesized by Dolichospermum flos aquae, including 9 anabaenopeptins, 18 microcystins, 2 cyanopeptolins, and 1 cyclamide. All compounds were stable in UVA light alone but in the presence of a photosensitizer we observed compound-specific degradation. A strong pH effect on the decay was observed for 18 cyanopeptides that all contained tyrosine or structurally related moieties. We can attribute this effect to the reaction with ¹O₂ and triplet sensitizer that preferentially react with the deprotonated form of tyrosine moieties. The contribution of ¹O₂ to indirect phototransformation ranged from 12 to 39% and second-order rate constants for 9 tyrosine-containing cyanopeptides were assessed. Including the pH dependence of the reaction and system-independent second-order rate constants with ¹O₂ will improve the estimation of half-lives for multiclass cyanopeptide in surface waters. Our data further indicates that naturally occurring triplet sensitizers are likely to oxidize deprotonated tyrosine moieties of cyanopeptides and the specific reactivity and its pH dependence needs to be investigated in future studies.

Background: Cyanobacteria and their toxins occur in high concentrations during the so-called bloom events in surface waters. To be able to assess the risks associated with cyanobacterial blooms, we need to understand the persistence and fate processes of these toxins and other bioactive metabolites. In this study, we investigated the photochemical fate of 54 cyanopeptides extracted from two strains of Microcystis aeruginosa (PCC7806 and UV006), Planktothrix rubescens, and Dolichospermum flos aquae. We determined half-lives during sunlight exposure in lake water and inspected the effect of pH on transformation kinetics for 27 microcystins, 8 anabaenopeptins, 14 cyanopeptolins, 2 cyclamides, and 3 aeruginosins.
Results: For cyanopeptides from D. flos aquae and P. rubescens, we observed the highest removal of 28 and 26%, respectively, after 3-h sunlight exposure. Most cyanopeptides produced by the two M. aeruginosa strains were rather persistent with only up to 3% removal. The more reactive cyanopeptides contained amino acids known to undergo phototransformation, including methionine and tyrosine moieties or their derivatives. Photochemical half-lives of 14 tyrosine-containing cyanopeptides decreased by one order of magnitude from nearly persistent conditions at pH 7 (half-life > 70 h) to shorter half-lives at pH 10 (< 10 h).
Conclusions: More work is needed to distinguish the contribution of different photochemical reaction pathways including the contributions to the pH effect. To the best of our knowledge, this is the first assessment of transformation kinetics of such a wide range of cyanopeptides. The abundant and persistent cyanopeptides that have not been studied in detail yet should be prioritized for the evaluation of their ecosystem and human health risks and for their abatement during drinking water treatment.

Antimicrobial peptides (AMPs) are increasingly important as a last resort against multi-drug resistant bacteria due to resistance formation towards conventional antibiotics. However, many AMPs were introduced to the market before environmental risk assessment was required, e.g., by the European Medicines Agency (EMA) since 1998. While AMPs have been administered as antibiotics and growth promotors in feedstock since the 1960s and were reconsidered for human medicine by the EMA in 2013, details about their mobility and persistence in the environment remain unknown. This study investigated the environmental fate of three commonly used AMPs: bacitracins, daptomycin, and polymyxins B and E (Colistin). We observed moderate sorption affinity of daptomycin to standard European soils (K_d = 20.6–48.6), while polymyxins adsorbed irreversibly. Bacitracin variants sorbed slightly to sandy soil (K_d = 5.8–8) and significantly to clayey soil (K_d = 169–250). We further investigated photochemical and microbial transformation processes relevant in surface waters. We demonstrated that phototransformation of all AMPs was enhanced in the presence of dissolved organic matter and fast bimolecular reaction rate constant with singlet oxygen contributed largely to indirect phototransformation (15–41%). Phototransformation product analysis for daptomycin was consistent with expected modifications of the tryptophan and kynurenine moieties. Moreover, riverine biofilm communities demonstrated biotransformation potential for all AMPs. Our findings of sorption behaviour, photo- and biotransformation suggest that these processes play a critical role in the fate of bacitracins, daptomycin, and polymyxins in environmental systems.

Extracellular enzymes are master recyclers of organic matter, and to predict their functional lifetime, we need to understand their environmental transformation processes. In surface waters, direct and indirect photochemical transformation is a known driver of inactivation. We investigated molecular changes that occur along with inactivation in aminopeptidase, an abundant class of extracellular enzymes. We studied the inactivation kinetics and localized oxidation caused by singlet oxygen, ¹O₂, a major photochemically derived oxidant toward amino acids. Aminopeptidase showed second-order inactivation rate constants with ¹O₂ comparable to those of free amino acids. We then visualized site-specific oxidation kinetics within the three-dimensional protein and demonstrated that fastest oxidation occurred around the active site and at other reactive amino acids. However, second-order oxidation rate constants did not correlate strictly with the ¹O₂-accessible surface areas of those amino acids. We inspected site-specific processes by a comprehensive suspect screening for 723,288 possible transformation products. We concluded that histidine involved in zinc coordination at the active site reacted slower than what was expected by its accessibility, and we differentiated between two competing reaction pathways of ¹O₂ with tryptophan residues. This systematic analysis can be directly applied to other proteins and transformation reactions.

Harmful cyanobacterial blooms in freshwater ecosystems produce bioactive secondary metabolites including cyanopeptides that pose ecological and human health risks. Only adverse effects of one class of cyanopeptides, microcystins, have been studied extensively and have consequently been included in water quality assessments. Inhibition is a commonly observed effect for enzymes exposed to cyanopeptides and has mostly been investigated for human biologically relevant model enzymes. Here, we investigated the inhibition of ubiquitous aquatic enzymes by cyanobacterial metabolites. Hydrolytic enzymes are utilized in the metabolism of aquatic organisms and extracellularly by heterotrophic bacteria to obtain assimilable substrates. The ubiquitous occurrence of hydrolytic enzymes leads to the co-occurrence with cyanopeptides especially during cyanobacterial blooms. Bacterial leucine aminopeptidase and alkaline phosphatase were exposed to cyanopeptide extracts of different cyanobacterial strains (Microcystis aeruginosa wild type and microcystin-free mutant, Planktothrix rubescens) and purified cyanopeptides. We observed inhibition of aminopeptidase and phosphatase upon exposure, especially to the apolar fractions of the cyanobacterial extracts. Exposure to the dominant cyanopeptides in these extracts confirmed that purified microcystins, aerucyclamide A and cyanopeptolin A inhibit the aminopeptidase in the low mg L^-1 range while the phosphatase was less affected. Inhibition of aquatic enzymes can reduce the turnover of nutrients and carbon substrates and may also impair metabolic functions of grazing organisms.

Chlorothalonil, a fungicide applied for decades worldwide, has recently been banned in the European Union (EU) and Switzerland due to its carcinogenicity and the presence of potentially toxic transformation products (TPs) in groundwater. The spread and concentration range of chlorothalonil TPs in different drinking water resources was examined (73 groundwater and four surface water samples mainly from Switzerland). The chlorothalonil sulfonic acid TPs (R471811, R419492, R417888) occurred more frequently and at higher concentrations (detected in 65-100% of the samples, ≤2200 ngL^-1) than the phenolic TPs (SYN507900, SYN548580, R611968; detected in 10-30% of the samples, ≤130 ngL^-1). The TP R471811 was found in all samples and even in 52% of the samples above 100 ngL^-1, the drinking water standard in Switzerland and other European countries. Therefore, the abatement of chlorothalonil TPs was investigated in laboratory and pilot-scale experiments and along the treatment train of various water works, comprising aquifer recharge, UV disinfection, ozonation, advanced oxidation processes (AOPs), activated carbon treatment, and reverse osmosis. The phenolic TPs can be abated during ozonation (second order rate constant k_O3 ∼10⁴ M^-1s^-1) and by reaction with hydroxyl radicals (OH) in AOPs (k_OH ∼10⁹ M^-1s^-1). In contrast, the sulfonic acid TPs, which occurred in higher concentrations in drinking water resources, react only very slowly with ozone (k_O3 <0.04 M^-1s^-1) and OH (k_OH <5.0 × 10⁷ M^-1s^-1) and therefore persist in ozonation and OH-based AOPs. Activated carbon retained the very polar TP R471811 only up to a specific throughput of 25 m³kg^-1 (20% breakthrough), similarly to the X-ray contrast agent diatrizoic acid. Reverse osmosis was capable of removing all chlorothalonil TPs by ≥98%.

Intensified cyanobacterial bloom events are of increasing global concern because of adverse effects associated with the release of bioactive compounds, including toxic cyanopeptides. Cyanobacteria can produce a variety of cyanopeptides, yet our knowledge about their abundance and co-production remains limited. We applied a suspect-screening approach, including 700 structurally known cyanopeptides, and identified 11 cyanopeptides in Microcystis aeruginosa and 17 in Dolichospermum flos-aquae. Total cyanopeptide concentrations ranged from high nmol to μmol g_dry^-1 with slightly higher cell quotas in the mid-exponential growth phase. Relative cyanopeptide profiles were unchanged throughout the growth cycle. We demonstrate that quantification based on microcystin-LR equivalents can introduce an error of up to 6-fold and recommend a class-equivalent approach instead. In M. aeruginosa, rarely studied cyclamides dominated (>80%) over cyanopeptolins and microcystins. While all nutrient reductions caused less growth, only lowering phosphorous and micronutrients reduced cyanopeptide production by M. aeruginosa. Similar trends were observed for D. flos-aquae and only lowering nitrogen decreased cyanopeptide production while the relative abundance of individual cyanopeptides remained stable. The synchronized production of other cyanopeptides along with microcystins emphasizes the need to make them available as reference standards to encourage more studies on their occurrence in blooms, persistence, and potential toxicity.

Cyanobacterial bloom events that produce natural toxins occur in freshwaters across the globe, yet the potential risk of many cyanobacterial metabolites remains mostly unknown. Only microcystins, one class of cyanopeptides, have been studied intensively and the wealth of evidence regarding exposure concentrations and toxicity led to their inclusion in risk management frameworks for water quality. However, cyanobacteria produce an incredible diversity of hundreds of cyanopeptides beyond the class of microcystins. The question arises, whether the other cyanopeptides are in fact of no human and ecological concern or whether these compounds merely received (too) little attention thus far. Current observations suggest that an assessment of their (eco)toxicological risk is indeed relevant: First, other cyanopeptides, including cyanopeptolins and anabaenopeptins, can occur just as frequently and at similar nanomolar concentrations as microcystins in surface waters. Second, cyanopeptolins, anabaenopeptins, aeruginosins and microginins inhibit proteases in the nanomolar range, in contrast to protein phosphatase inhibition by microcystins. Cyanopeptolins, aeruginosins, and aerucyclamide also show toxicity against grazers in the micromolar range comparable to microcystins. The key challenge for a comprehensive risk assessment of cyanopeptides remains their large structural diversity, lack of reference standards, and high analytical requirements for identification and quantification. One way forward would be a prevalence study to identify the priority candidates of tentatively abundant, persistent, and toxic cyanopeptides to make comprehensive risk assessments more manageable.

The kinetic solvent isotope effect (KSIE) is typically utilized in environmental photochemistry to elucidate whether a compound is susceptible to photooxidation by singlet oxygen (¹O₂), due to its known difference in lifetime in water (H₂O) versus heavy water (D₂O). Here, the overall indirect photodegradation rates of diarylamines in the presence of dissolved organic matter (DOM) were enhanced in D₂O to a greater extent than expected based on their reactivity with ¹O₂. For each diarylamine, the relative contribution of reaction with ¹O₂ to the observed KSIE was determined from high resolution data of ¹O₂ lifetimes by time-resolved infrared luminescence spectroscopy. The additional enhancement in D₂O beyond reaction with ¹O₂ contributed significantly to the observed KSIE for diarylamines (8–65%) and diclofenac (100%). The enhancement was ascribed to slower reduction of transient radical species of the diarylamines due to H/D exchange at DOM's phenolic antioxidant moieties. A slower second-order reaction rate constant with a model antioxidant was verified for mefenamic acid radicals using transient absorption spectroscopy. Changes in lifetime and reactivity with triplet sensitizers were not responsible for the additional KSIE. Other pollutants with quenchable radical intermediates may also be susceptible to such an additional KSIE, which has to be considered when using the KSIE as a diagnostic tool.

Extracellular enzymes are major drivers of biogeochemical nutrient and carbon cycling in surface water. While photoinactivation is regarded as a major inactivation process of these enzymes, the underlying molecular changes have received little attention. This study demonstrate how light exposure leads to a rapid loss of phosphatase, aminopeptidase and glucosidase activities of biofilm samples and model enzymes. Here, an optimized proteomics approach allowed simultaneous observation of inactivation and molecular changes. Site-specific fingerprints of degradation kinetics have been generated and visualized in the three-dimensional proteins. Oxidation of tryptophan, the chromophoric target, initiated secondary reactions. Evidence was obtained that tyrosine residues act as intramolecular antioxidants, reflected in decelerated decay of tryptophan- and enhanced decay of tyrosine-containing peptides. In addition, subsequent methionine oxidation and disulfide reduction contribute to heterogeneous photodamage. The proximity to tryptophan residues explains >95% of the photodamage across the protein structures. The presence of redox-active organic matter or a model antioxidant in solution quenched not only photoinactivation and tryptophan oxidation but also all subsequent damage. The developed analytical approach can be applied to other research questions in environmental sciences where site-specific damage in a protein is essential.

Fenamates are a class of non-steroidal anti-inflammatory drugs (NSAIDs) that are not fully removed during wastewater treatment and can be released to surface waters. Here, near-surface photochemical half-lives were evaluated to range from minutes to hours of four fenamates and the closely related diclofenac. While quantum yields for direct photochemical reactions at the water surface vary widely from 0.071 for diclofenac to <0.001 for mefenamic acid, all fenamates showed significant reactivity towards singlet oxygen and hydroxyl radical with bimolecular reaction rate constants of 1.3-2.8 x 10⁷ M^-1 s^-1 and 1.1-2.7 x 10¹⁰ M^-1 s^-1, respectively. Photodecay rates increased in the presence of dissolved organic matter (DOM) for diclofenac (+19%), tolfenamic acid (+9%), and mefenamic acid (+95%), but decreased for flufenamic acid (-2%) and meclofenamic acid (-14%) after accounting for light screening effects. Fast reaction rate constants of all NSAIDs with model triplet sensitizers were quantified by laser flash photolysis. Here, the direct observation of diphenylamine radical intermediates by transient absorption spectroscopy demonstrates one-electron oxidation of all fenamates. Quenching rate constants of these radical intermediates by ascorbic acid, a model antioxidant, were also quantified. These observations suggest that the balance of oxidation by photoexcited triplet DOM and quenching of the formed radical intermediates by antioxidant moieties determines whether net sensitization or net quenching by DOM occurs in the photochemical degradation of fenamates.

A central question in microbial ecology is whether microbial interactions are predominantly cooperative or competitive. The secretion of siderophores, microbial iron chelators, is a model system for cooperative interactions. However, siderophores have also been shown to mediate competition by sequestering available iron and making it unavailable to competitors. The details of how siderophores mediate competition are not well understood, especially considering the complex distribution of iron phases in the environment. One pertinent question is whether sequestering iron through siderophores can indeed be effective in natural conditions; many natural environments are characterized by large pools of precipitated iron, and it is conceivable that any soluble iron that is sequestered by siderophores is replenished by the dissolution of these precipitated iron sources. Our goal here was to address this issue, and investigate the magnitude and mechanism of siderophore-mediated competition in the presence of precipitated iron. We combined experimental work with thermodynamic modeling, using Pseudomonas aeruginosa as a model system and ferrihydrite precipitates as the iron source with low solubility. Our experiments show that competitive growth inhibition by the siderophore pyochelin is indeed efficient, and that inhibition of a competitor can even have a stronger growth-promoting effect than solubilization of precipitated iron. Based on the results of our thermodynamic models we conclude that the observed inhibition of a competitor is effective because sequestered iron is only very slowly replenished by the dissolution of precipitated iron. Our research highlights the importance of competitive benefits mediated by siderophores, and underlines that the dynamics of siderophore production and uptake in environmental communities could be a signature of competitive, not just cooperative, dynamics.

Here, we present a community perspective on how to explore, exploit and evolve the diversity in aquatic ecosystem models. These models play an important role in understanding the functioning of aquatic ecosystems, filling in observation gaps and developing effective strategies for water quality management. In this spirit, numerous models have been developed since the 1970s. We set off to explore model diversity by making an inventory among 42 aquatic ecosystem modellers, by categorizing the resulting set of models and by analysing them for diversity. We then focus on how to exploit model diversity by comparing and combining different aspects of existing models. Finally, we discuss how model diversity came about in the past and could evolve in the future. Throughout our study, we use analogies from biodiversity research to analyse and interpret model diversity. We recommend to make models publicly available through open-source policies, to standardize documentation and technical implementation of models, and to compare models through ensemble modelling and interdisciplinary approaches. We end with our perspective on how the field of aquatic ecosystem modelling might develop in the next 5–10 years. To strive for clarity and to improve readability for non-modellers, we include a glossary.

The worldwide distribution of toxicants is an important yet understudied driver of biodiversity, and the mechanisms relating toxicity to diversity have not been adequately explored. Here, we present a community model integrating demography, dispersal and toxicant-induced effects on reproduction driven by intraspecific and interspecific variability in toxicity tolerance. We compare model predictions to 458 species abundance distributions (SADs) observed along concentration gradients of toxicants to show that the best predictions occur when intraspecific variability is five and ten times higher than interspecific variability. At high concentrations, lower settings of intraspecific variability resulted in predictions of community extinction that were not supported by the observed SADs. Subtle but significant species losses at low concentrations were predicted only when intraspecific variability dominated over interspecific variability. Our results propose intraspecific variability as a key driver for biodiversity sustenance in ecosystems challenged by environmental change.

East Africa’s Lake Victoria provides resources and services to millions of people on the lake’s shores and abroad. In particular, the lake’s fisheries are an important source of protein, employment, and international economic connections for the whole region. Nonetheless, stock dynamics are poorly understood and currently unpredictable. Furthermore, fishery dynamics are intricately connected to other supporting services of the lake as well as to lakeshore societies and economies. Much research has been carried out piecemeal on different aspects of Lake Victoria’s system; e.g., societies, biodiversity, fisheries, and eutrophication. However, to disentangle drivers and dynamics of change in this complex system, we need to put these pieces together and analyze the system as a whole. We did so by first building a qualitative model of the lake’s social-ecological system. We then investigated the model system through a qualitative loop analysis, and finally examined effects of changes on the system state and structure. The model and its contextual analysis allowed us to investigate system-wide chain reactions resulting from disturbances. Importantly, we built a tool that can be used to analyze the cascading effects of management options and establish the requirements for their success. We found that high connectedness of the system at the exploitation level, through fisheries having multiple target stocks, can increase the stocks’ vulnerability to exploitation but reduce society’s vulnerability to variability in individual stocks. We describe how there are multiple pathways to any change in the system, which makes it difficult to identify the root cause of changes but also broadens the management toolkit. Also, we illustrate how nutrient enrichment is not a self-regulating process, and that explicit management is necessary to halt or reverse eutrophication. This model is simple and usable to assess system-wide effects of management policies, and can serve as a paving stone for future quantitative analyses of system dynamics at local scales.

In this paper we provide an overview of new knowledge on oxygen depletion (hypoxia) and related phenomena in aquatic systems resulting from the EU-FP7 project HYPOX ("In situ monitoring of oxygen depletion in hypoxic ecosystems of coastal and open seas, and landlocked water bodies", http://www.hypox.net). In view of the anticipated oxygen loss in aquatic systems due to eutrophication and climate change, HYPOX was set up to improve capacities to monitor hypoxia as well as to understand its causes and consequences.
Temporal dynamics and spatial patterns of hypoxia were analyzed in field studies in various aquatic environments, including the Baltic Sea, the Black Sea, Scottish and Scandinavian fjords, Ionian Sea lagoons and embayments, and Swiss lakes. Examples of episodic and rapid (hours) occurrences of hypoxia, as well as seasonal changes in bottom-water oxygenation in stratified systems, are discussed. Geologically driven hypoxia caused by gas seepage is demonstrated. Using novel technologies, temporal and spatial patterns of water-column oxygenation, from basin-scale seasonal patterns to meter-scale sub-micromolar oxygen distributions, were resolved. Existing multidecadal monitoring data were used to demonstrate the imprint of climate change and eutrophication on long-term oxygen distributions. Organic and inorganic proxies were used to extend investigations on past oxygen conditions to centennial and even longer timescales that cannot be resolved by monitoring. The effects of hypoxia on faunal communities and biogeochemical processes were also addressed in the project. An investigation of benthic fauna is presented as an example of hypoxia-devastated benthic communities that slowly recover upon a reduction in eutrophication in a system where naturally occurring hypoxia overlaps with anthropogenic hypoxia. Biogeochemical investigations reveal that oxygen intrusions have a strong effect on the microbially mediated redox cycling of elements. Observations and modeling studies of the sediments demonstrate the effect of seasonally changing oxygen conditions on benthic mineralization pathways and fluxes. Data quality and access are crucial in hypoxia research. Technical issues are therefore also addressed, including the availability of suitable sensor technology to resolve the gradual changes in bottom-water oxygen in marine systems that can be expected as a result of climate change. Using cabled observatories as examples, we show how the benefit of continuous oxygen monitoring can be maximized by adopting proper quality control. Finally, we discuss strategies for state-of-the-art data archiving and dissemination in compliance with global standards, and how ocean observations can contribute to global earth observation attempts.

Common pool resource experiments in the laboratory and the field have provided insights that have contrasted to those derived from conventional non-cooperative game theory. Contrary to predictions from non-cooperative game theory, participants are sometimes willing to restrain voluntarily from over extracting resources and use costly punishment to sanction other participants. Something as simple as face-to-face communication has been shown to increase average earnings significantly. In the next generation of experiments, both in the laboratory and in the field, we need to extract more information that provides insight concerning why people make the decisions they make. More information is needed concerning attributes of individuals as well as the social and social–ecological context in which they interact that may give rise to such deviations from theoretical predictions. In the process of extracting more information from participants and the contexts in which they interact, we face several methodological and ethical challenges which we address in this paper.

Nonlinear biodegradation in natural porous media is affected by the heterogeneity of the formation and dispersive mixing processes. We analyze these coupled effects by combining recent advances in analytical one-dimensional modeling of bioreactive transport with stochastic concepts of dispersive mixing in heterogeneous domains. Specifically, we model bioremediation of a sorbing contaminant undergoing nonlinear biodegradation in heterogeneous aquifers applying the stochastic-convective and the advective-dispersive stream tube approaches, in which we use a semianalytical traveling wave solution for one-dimensional reactive transport. The results of numerical simulations agree excellently with both models, which establishes that the traveling wave solution is an efficient and accurate way to evaluate the development of intrastream tube concentration distributions and that the advective-dispersive stream tube approach is suitable to describe nonlinear bioreactive transport in systems controlled by local-scale dispersion. In contrast with conservative transport the mean contaminant flux is shown to be significantly influenced by transverse dispersion, even for realistic Peclet values. Furthermore, asymptotic front shapes are shown to be neither Fickian nor constant ( traveling wave behavior), which raises questions about the current practice of upscaling bioreactive transport. The error caused by neglecting local dispersion was found to increase with time and to remain significant even for large retardation differences between electron acceptor and contaminant. This implies that, even if reaction rates are dominated by chromatographic mixing, the dispersive mixing process cannot be disregarded when predicting bioreactive transport.

Environmental processes have been modelled for decades. However, the need for integrated assessment and modeling (IAM) has grown as the extent and severity of environmental problems in the 21st Century worsens. The scale of IAM is not restricted to the global level as in climate change models, but includes local and regional models of environmental problems. This paper discusses various definitions of IAM and identifies five different types of integration that are needed for the effective solution of environmental problems. The future is then depicted in the form of two brief scenarios: one optimistic and one pessimistic. The current state of IAM is then briefly reviewed. The issues of complexity and validation in IAM are recognised as more complex than in traditional disciplinary approaches. Communication is identified as a central issue both internally among team members and externally with decision-makers, stakeholders and other scientists. Finally it is concluded that the process of integrated assessment and modelling is considered as important as the product for any particular project. By learning to work together and recognise the contribution of all team members and participants, it is believed that we will have a strong scientific and social basis to address the environmental problems of the 21st Century.