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Ruthenium(II) polypyridyl complexes have gained significant interest as photochemotherapeutics (PCTs) due to their synthetic viability, strong light absorption, well understood excited state properties, and high phototoxicity indexes. Herein, we report the synthesis, characterization, electrochemical, spectrochemical, and preliminary cytotoxicity analyses of three series of ruthenium(II) polypyridyl complexes designed to mimic PCTs. The three series have the general structure of [Ru(bpy) 2 (N-N)] 2+ ( Series 1 ), [Ru(bpy)(dmb)(N-N)] 2+ ( Series 2 ), and [Ru(dmb) 2 (N-N)] 2+ ( Series 3 , where N-N is a bidentate polypyridyl ligand, bpy = 2,2'-bipyridine, and dmb = 6,6'-dimethyl-2,2'-bipyridine). In the three series, the N-N ligand was systematically modified to incorporate increased conjugation and/or electronegative heteroatoms to increase dπ-π* backbonding, red-shifting the lowest energy metal-to-ligand charge transfer (MLCT) absorptions from λ max = 454 to λ max = 580 nm, nearing the therapeutic window for PCTs (600-1100 nm). In addition, steric bulk was systematically introduced through the series, distorting the Ru(II) octahedra, making the dissociative 3 dd* state thermally accessible at room and body temperatures. This resulted in a 4 orders of magnitude increase in photoinduced ligand ejection kinetics, and demonstrates the ability to modulate both the MLCT* and dd* manifolds in the complexes, which is critical in PCT drug design. Preliminary cell viability assays suggest that the increased steric bulk to lower the 3 dd* states may interfere with the cytotoxicity mechanism, limiting photoinitiated toxicity of the complexes. This work demonstrates the importance of understanding both the MLCT* and dd* manifolds and how they impact the ability of a complex to act as a PCT agent.

The rapid recession of glaciers is exposing large zones to the development of embryonic phototrophic ecosystems and eventual ecological succession. Traditionally, succession patterns in glacial forefields have been seen as a response to time since deglaciation, but nowadays forefield exposure is so rapid that this theory may be less applicable. In this succession process, periphyton are potential pioneer organisms because of their role in modifying the local environment (e.g. access to water) to create conditions conducive to plant colonization. In this paper, we aim to decrypt the physical properties of the habitats that define the spatial and temporal assemblage of periphyton during the melt-season of an Alpine temperate glacier in the context of rapid climate change. We show that periphyton develop in glacial floodplains throughout the melt-season and could extend to cover significant surfaces. However, development is only possible when the combined conditions of stability and water accessibility are met. In glacial floodplains, stable zones exist and are typically located on terraces; but they can also be locally found for much shorter periods in the more active, glacial-stream reworked zone. On terraces, water accessibility can be a limit due to well-drained sediments, but when present, often aided by the role that biofilms play in creating an impermeable layer, it provides a stable and clear water source that biofilms could exploit. In the active part of the braid plain, whilst water availability is very high, the water is harsh (low temperature, high turbidity) and erosive. Therein, periphyton can rapidly exploit short windows of opportunity but the habitat conditions rarely remain stable for long enough for continuous periphyton cover to develop. Thus, the role of periphyton in ecosystem succession is strongly conditioned by the spatial extent of the active zone, itself a function of high rates of glacier melt and sediment supply associated with rapid glacier retreat., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Glacier shrinkage opens new proglacial terrain with pronounced environmental gradients along longitudinal and lateral chronosequences. Despite the environmental harshness of the streams that drain glacier forelands, their benthic biofilms can harbor astonishing biodiversity spanning all domains of life. Here, we studied the spatial dynamics of prokaryotic and eukaryotic photoautotroph diversity within braided glacier-fed streams and tributaries draining lateral terraces predominantly fed by groundwater and snowmelt across three proglacial floodplains in the Swiss Alps. Along the lateral chronosequence, we found that benthic biofilms in tributaries develop higher biomass than those in glacier-fed streams, and that their respective diversity and community composition differed markedly. We also found spatial turnover of bacterial communities in the glacier-fed streams along the longitudinal chronosequence. These patterns along the two chronosequences seem unexpected given the close spatial proximity and connectivity of the various streams, suggesting environmental filtering as an underlying mechanism. Furthermore, our results suggest that photoautotrophic communities shape bacterial communities across the various streams, which is understandable given that algae are the major source of organic matter in proglacial streams. Overall, our findings shed new light on benthic biofilms in proglacial streams now changing at rapid pace owing to climate-induced glacier shrinkage., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Brandani, Peter, Busi, Kohler, Fodelianakis, Ezzat, Michoud, Bourquin, Pramateftaki, Roncoroni, Lane and Battin.)

The Anthropocene has been proposed as a profound, globally synchronous rupture in the history of the Earth System with its current state fundamentally different to that of the Holocene and driven by the geological force of human activity. Here, we show how stratigraphy is being made in a lake that is heavily impacted upon by climate change and human activities. For one of the largest inner-Alpine catchments in the European Alps, we draw attention to how sedimentation rates are a product of non-stationary, reflexive, human actions. In Lake Geneva, we identify both a human-induced climate change (HCC) signature and the effects of a recent economic shock on sediment extraction upon sediment loading to and sedimentation rates in the lake. The HCC signature thus reflects the nature of climate change impacts in this basin, where sediment accumulation rates evolve with climate, but where economic conditions contribute to shifts in the supply of sediment to the lake. Following social theory, we call this glocalization because of the combined importance and inseparability of human impacts across different spatial scales. The nature of human impacts on sediment delivery to the lake mean that the influence of humans is unlikely to be captured in the long-term depositional record.

In Alpine streams, humans have strongly modified the interactions between hydraulic processes, geomorphology and aquatic life through dams, flow abstraction at water intakes and river channel engineering. To mitigate these impacts, research has addressed both minimum flows and flow variability to sustain aquatic ecosystems. Whilst such environmental flows might work downstream of dams, this may not be the case for water intakes. Intakes, generally much smaller than dams, are designed to abstract water and to leave sediment behind. Sediment accumulation then results in the need to flush intakes periodically, often more frequently than daily in some highly glaciated basins. Sediment delivery downstream is then maintained through short duration floods with very high sediment loads. Here we tested the hypothesis that sediment flushing, and the associated high frequency of bed disturbance, controls in-stream habitat and macroinvertebrate assemblages. We collected macroinvertebrates over a 17-month period from an Alpine stream as well as a set of lateral unperturbed tributaries that served as controls. In contrast to established conceptual models, our results showed that the stream is largely void of life during summer, but that populations recover rapidly as the frequency of intake flushing falls in early autumn, producing richer and larger populations in winter and early spring. The recovery in autumn may be due to the recruitment of individuals from tributaries. We conclude that intake flushing in summer inverts expected summer-winter macroinvertebrate abundances, and questions the extent to which environmental flows in intake-impacted Alpine streams will lead to improvements in instream macrofauna unless sediment also is managed., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Flooding is a very costly natural hazard in the UK and is expected to increase further under future climate change scenarios. Flood defences are commonly deployed to protect communities and property from flooding, but in recent years flood management policy has looked towards solutions that seek to mitigate flood risk at flood-prone sites through targeted interventions throughout the catchment, sometimes using techniques which involve working with natural processes. This paper describes a project to provide a succinct summary of the natural science evidence base concerning the effectiveness of catchment-based 'natural' flood management in the UK. The evidence summary is designed to be read by an informed but not technically specialist audience. Each evidence statement is placed into one of four categories describing the nature of the underlying information. The evidence summary forms the appendix to this paper and an annotated bibliography is provided in the electronic supplementary material.

Vegetation is a characteristic feature of shallow aquatic flows such as rivers, lakes and coastal waters. Flow through and above aquatic vegetation canopies is commonly described using a canopy mixing layer analogy which provides a canonical framework for assessing key hydraulic characteristics such as velocity profiles, large-scale coherent turbulent structures and mixing and transport processes for solutes and sediments. This theory is well developed for the case of semi-rigid terrestrial vegetation and has more recently been applied to the case of aquatic vegetation. However, aquatic vegetation often displays key differences in morphology and biomechanics to terrestrial vegetation due to the different environment it inhabits. Here we investigate the effect of plant morphology and biomechanical properties on flow-vegetation interactions through the application of a coupled LES-biomechanical model. We present results from two simulations of aquatic vegetated flows: one assuming a semi-rigid canopy and the other a highly flexible canopy and provide a comparison of the associated flow regimes. Our results show that while both cases display canopy mixing layers, there are also clear differences in the shear layer characteristics and turbulent processes between the two, suggesting that the semi-rigid approximation may not provide a complete representation of flow-vegetation interactions., (© The Author(s) 2016.)

Assessing the impact of glaciation on Earth's surface requires understanding glacial erosion processes. Developing erosion theories is challenging because of the complex nature of the erosion processes and the difficulty of examining the ice/bedrock interface of contemporary glaciers. We demonstrate that the glacial erosion rate is proportional to the ice-sliding velocity squared, by quantifying spatial variations in ice-sliding velocity and the erosion rate of a fast-flowing Alpine glacier. The nonlinear behavior implies a high erosion sensitivity to small variations in topographic slope and precipitation. A nonlinear rate law suggests that abrasion may dominate over other erosion processes in fast-flowing glaciers. It may also explain the wide range of observed glacial erosion rates and, in part, the impact of glaciation on mountainous landscapes during the past few million years., (Copyright © 2015, American Association for the Advancement of Science.)

The hydrological and biogeochemical processes that operate in catchments influence the ecological quality of freshwater systems through delivery of fine sediment, nutrients and organic matter. Most models that seek to characterise the delivery of diffuse pollutants from land to water are reductionist. The multitude of processes that are parameterised in such models to ensure generic applicability make them complex and difficult to test on available data. Here, we outline an alternative--data-driven--inverse approach. We apply SCIMAP, a parsimonious risk based model that has an explicit treatment of hydrological connectivity. We take a bayesian approach to the inverse problem of determining the risk that must be assigned to different land uses in a catchment in order to explain the spatial patterns of measured in-stream nutrient concentrations. We apply the model to identify the key sources of nitrogen (N) and phosphorus (P) diffuse pollution risk in eleven UK catchments covering a range of landscapes. The model results show that: 1) some land use generates a consistently high or low risk of diffuse nutrient pollution; but 2) the risks associated with different land uses vary both between catchments and between nutrients; and 3) that the dominant sources of P and N risk in the catchment are often a function of the spatial configuration of land uses. Taken on a case-by-case basis, this type of inverse approach may be used to help prioritise the focus of interventions to reduce diffuse pollution risk for freshwater ecosystems., (Copyright © 2012 Elsevier B.V. All rights reserved.)

The mantra that policy and management should be 'evidence-based' is well established. Less so are the implications that follow from 'evidence' being predictions of the future (forecasts, scenarios, horizons) even though such futures define the actions taken today to make the future sustainable. Here, we consider the tension between 'evidence', reliable because it is observed, and predictions of the future, unobservable in conventional terms. For flood risk management in England and Wales, we show that futures are actively constituted, and so imagined, through 'suites of practices' entwining policy, management and scientific analysis. Management has to constrain analysis because of the many ways in which flood futures can be constructed, but also because of commitment to an accounting calculus, which requires risk to be expressed in monetary terms. It is grounded in numerical simulation, undertaken by scientific consultants who follow policy/management guidelines that define the futures to be considered. Historical evidence is needed to deal with process and parameter uncertainties and the futures imagined are tied to pasts experienced. Reliance on past events is a challenge for prediction, given changing probability (e.g. climate change) and consequence (e.g. development on floodplains). So, risk management allows some elements of risk analysis to become unstable (notably in relation to climate change) but forces others to remain stable (e.g. invoking regulation to prevent inappropriate floodplain development). We conclude that the assumed separation of risk assessment and management is false because the risk calculation has to be defined by management. Making this process accountable requires openness about the procedures that make flood risk analysis more (or less) reliable to those we entrust to produce and act upon them such that, unlike the 'pseudosciences', they can be put to the test of public interrogation by those who have to live with their consequences., (© 2011 Royal Society)

Hydrologic transport of dissolved organic carbon (DOC) from peat soils may differ to organo-mineral soils in how they responded to changes in flow, because of differences in soil profile and hydrology. In well-drained organo-mineral soils, low flow is through the lower mineral layer where DOC is absorbed and high flow is through the upper organic layer where DOC is produced. DOC concentrations in streams draining organo-mineral soils typically increase with flow. In saturated peat soils, both high and low flows are through an organic layer where DOC is produced. Therefore, DOC in stream water draining peat may not increase in response to changes in flow as there is no switch in flow path between a mineral and organic layer. To verify this, we conducted a high-resolution monitoring study of soil and stream water at an upland peat catchment in northern England. Our data showed a strong positive correlation between DOC concentrations at -1 and -5 cm depth and stream water, and weaker correlations between concentrations at -20 to -50 cm depth and stream water. Although near surface organic material appears to be the key source of stream water DOC in both peat and organo-mineral soils, we observed a negative correlation between stream flow and DOC concentrations instead of a positive correlation as DOC released from organic layers during low and high flow was diluted by rainfall. The differences in DOC transport processes between peat and organo-mineral soils have different implications for our understanding of long-term changes in DOC exports. While increased rainfall may cause an increase in DOC flux from peat due to an increase in water volume, it may cause a decrease in concentrations. This response is contrary to expected changes in DOC exports from organo-mineral soils, where increase rainfall is likely to result in an increase in flux and concentration.

The ability of submerged macrophytes to moderate the structure of food webs with respect to lake eutrophication management has been intensively studied in recent years. Many lake managers have adopted the option of increasing macrophyte abundance in order to restore eutrophic waters, with a view to improve water quality, increase water transparency and reduce phytoplankton biomass. These studies are mostly based upon the comparison of macrophyte-rich and macrophyte-free waters. There is less quantitative information on how different levels of macrophyte abundance, in particular very low levels, influence ecosystem structure, or vice versa, within the same ecosystem. This paper takes a multivariate statistical approach to examine ecosystem function with low macrophyte abundance (ca. 5%) in the context of nutrient-phytoplankton-zooplankton interaction in a eutrophic shallow lake. It shows that with low levels of macrophyte coverage, phytoplankton biomass was only limited by nutrient (TP and Si) availability, whilst nutrient (Si) as well as grazing (zooplankton and Daphnia) factors were both limiting phytoplankton levels in macrophyte-free waters. With respect to interactions between Daphnia and chlorophyll-a, the results suggest that low macrophyte cover does not result in a reduction of phytoplankton biomass due to the presence of Daphnia. Rather, low macrophyte cover provides a refuge that maintains constant Daphnia predation, so reducing chlorophyll-a fluctuation. These results add credence to the causal interpretation of different interactions amongst nutrients, phytoplankton and zooplankton at very low macrophyte densities.

The focus of eutrophication research has tended to be upon short-term and experimental studies. However, given the range of factors that can influence eutrophication dynamics, and that these matter over a range of time scales, some discrete, some continuous, eutrophication dynamics may only be fully investigated when long-term, time-series data are available. The present study aims to evaluate the interacting effects of abiotic processes and biotic dynamics in explaining variations of phytoplankton biomass in a eutrophic shallow lake, Barton Broad (Norfolk, UK) using a long-term data set. Multivariate statistical analysis shows that the inter-relationships between phytoplankton variability, nutrient and grazing factors were highly sensitive to seasonal periodicity. In spring phytoplankton biomass was related to phosphorus, nitrogen and silicon. In summer phytoplankton biomass was associated with phosphorus, nitrogen and zooplankton. In autumn phytoplankton was related to phosphorus, nitrogen, silicon and zooplankton. In winter, no significant relationship could be established between phytoplankton and environmental variables. This paper improves our understanding of the governing role of nitrogen, phosphorus, silicon and zooplankton upon phytoplankton variability, and hence, improves management methods for eutrophic lakes.

Gold mining in the Portovelo-Zaruma district in southern Ecuador is causing considerable environmental impacts; the most important ones are related to the discharge of cyanide, mercury and metal rich tailings into rivers of the Puyango catchment area. Cyanide and metal levels in rivers regularly exceed environmental quality criteria. The contamination impacts biodiversity, with cyanide causing a direct lethal effect on biota close to source and metal contaminants considerably reducing aquatic biodiversity further downstream. It is shown that the prevailing neutral or slightly alkaline conditions of the rivers ensure that metals are mainly associated with sediment. However, elevated metal levels in bottom living larvae collected from contaminated sites suggest that these sediment bound metals are readily bioavailable. Leaching experiments indicate that the relative ease by which metals are taken up by larvae is related to the speciation of sediment associated metals. It is further shown that large amounts of metals, which are bound to suspended sediment under ambient pH conditions, enter the dissolved and directly bioavailable state in more acidic conditions. Metal levels in carnivorous fish were found to be modestly elevated only, with the exception of mercury. Mercury levels exceeded 0.5 mg/kg in fish from both contaminated and uncontaminated sites, showing that both methylation and bioaccumulation of mercury are occurring in the Puyango river basin.